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CN-122011870-A - Photoluminescent organic-inorganic hybrid photochromic coating and preparation method thereof

CN122011870ACN 122011870 ACN122011870 ACN 122011870ACN-122011870-A

Abstract

The invention relates to the technical field of photoluminescence, in particular to a photoluminescence organic-inorganic hybridization photochromic coating and a preparation method thereof, wherein the coating comprises an organic polymer network, heteropolyanions and rare earth ions dispersed in the organic polymer network; the organic polymer network comprises structural units derived from ethylenically unsaturated monomers and boron-containing monomers. The coating is prepared by photopolymerization and an in-situ growth method, and the heteropolyanion and the rare earth ion are anchored in a polymer network through coordination. The coating provided by the invention has high visible light transmittance in an initial state, and can be subjected to rapid and reversible color change under ultraviolet light or sunlight irradiation, and meanwhile, the characteristic fluorescence intensity of rare earth ions can be reversibly regulated and controlled along with the color change. The invention has the dual functions of photochromism and photoluminescence, has good environmental stability and mild preparation process, and can be used in the fields of intelligent windows, safety information encryption and the like.

Inventors

  • YANG ZHENGWEN
  • ZHANG YUETENG
  • HUANG ANJUN
  • ZHAO HEPING
  • QIU JIANBEI
  • SONG ZHIGUO

Assignees

  • 昆明理工大学

Dates

Publication Date
20260512
Application Date
20260326

Claims (10)

  1. 1. A photoluminescent organic-inorganic hybrid photochromic coating, comprising: An organic polymer network comprising structural units derived from an ethylenically unsaturated monomer and a boron-containing monomer; and a heteropolyanion dispersed in the organic polymer network; The coating exhibits a reversible color change upon irradiation with ultraviolet light or sunlight.
  2. 2. The coating of claim 1, further comprising rare earth ions dispersed in the organic polymer network, wherein the coating emits a characteristic fluorescence upon excitation by ultraviolet light, and wherein the intensity of the characteristic fluorescence varies with the reversible color change.
  3. 3. The coating of claim 1 or 2, wherein the ethylenically unsaturated monomers comprise acrylate monomers or methacrylate monomers, and acrylic monomers or methacrylic monomers.
  4. 4. The coating of claim 3, wherein the molar ratio of the acrylic monomer or methacrylic monomer to the boron-containing monomer is (6-10): (1-3): (0.5-2).
  5. 5. The coating of claim 4, wherein the molar ratio is 8:2:1.
  6. 6. The coating of claim 1 or 2, wherein the boron-containing monomer is vinylphenylboronic acid.
  7. 7. The coating of claim 1 or 2, wherein the heteropolyanion is derived from phosphotungstic acid.
  8. 8. The coating of claim 2, wherein the rare earth ions are europium ions.
  9. 9. The coating of claim 1, wherein the coating has a visible light transmission of not less than 80% in an initial state.
  10. 10. A method of preparing the coating of any one of claims 1 to 9, comprising the steps of: s1, mixing an ethylenically unsaturated monomer and a boron-containing monomer with a photoinitiator, and carrying out polymerization reaction under ultraviolet light irradiation to form an organic polymer network; s2, mixing the organic polymer network and the heteropoly acid in a solvent, and stirring for 3-5 hours at 100-120 ℃ to form a uniform solution; s3, when the coating contains rare earth ions, rare earth salts are further added in the step S2, so that the rare earth salts and the heteropoly acid are dissolved in the solvent together; and S4, coating the uniform solution obtained in the step S2 or the step S3 on a substrate by adopting a knife coating method, and sequentially carrying out evaporation of the solvent at 50-70 ℃ and vacuum drying at 80-120 ℃ to obtain the coating.

Description

Photoluminescent organic-inorganic hybrid photochromic coating and preparation method thereof Technical Field The invention relates to the technical field of photoluminescence, in particular to a photoluminescence organic-inorganic hybridization photochromic coating and a preparation method thereof. Background Photochromic and photoluminescent play a vital role in security, smart windows or information storage. However, the traditional inorganic photochromic material is usually synthesized under the high-temperature condition, is difficult to realize effective color change under the irradiation of sunlight, and remarkably restricts the application of the inorganic photochromic material in practical scenes such as intelligent windows and the like. Although the organic photochromic and photoluminescent materials can be processed by a solution method at low temperature, the inherent toxicity and poor environmental stability of the organic photochromic and photoluminescent materials severely restrict the popularization of the organic photochromic and photoluminescent materials in practical application. The photochromic function and the photoluminescence function are integrated in a single material system, so that the reversible regulation and control of photoluminescence can be realized, and the information encryption grade is further improved. However, the current research of this technology is mainly focused on inorganic material systems, which are generally limited by higher uv response thresholds, longer uv response times, and lower visible light transmittance. In view of the bottleneck, the invention prepares the photoluminescence organic-inorganic hybridization photochromic coating (BAV-W-Eu) through photopolymerization and an in-situ growth method. The coating has the excellent performances of no toxicity, good stability, high visible light transmittance, low ultraviolet response threshold, quick light response and the like, and compared with the conventional method, the preparation process is more energy-saving and environment-friendly, and has obvious comprehensive advantages. Importantly, the photochromic process can realize reversible regulation and control of luminous intensity. The multifunctional organic-inorganic photochromic hybrid not only has potential application prospect in the fields of intelligent windows, safety information encryption and the like, but also provides a new design thought for a system with photochromic and photoluminescent functions integrated in a single material. Disclosure of Invention The invention aims to provide a photoluminescence organic-inorganic hybridization photochromic coating and a preparation method thereof, wherein the coating comprises an organic polymer network, heteropolyanions and rare earth ions dispersed in the organic polymer network, and the coating can show reversible color change and reversible regulation and control of fluorescence intensity under ultraviolet light or sunlight irradiation. In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme: A photoluminescent organic-inorganic hybrid photochromic coating comprising: An organic polymer network comprising structural units derived from an ethylenically unsaturated monomer and a boron-containing monomer; and a heteropolyanion dispersed in the organic polymer network; The coating exhibits a reversible color change upon irradiation with ultraviolet light or sunlight. Further, the coating further comprises rare earth ions dispersed in the organic polymer network, the coating emits characteristic fluorescence under ultraviolet light excitation, and the intensity of the characteristic fluorescence changes along with the reversible color change. Further, the ethylenically unsaturated monomer includes an acrylic monomer or a methacrylic monomer, and an acrylic monomer or a methacrylic monomer. Further, the molar ratio of the acrylic acid ester monomer or the methacrylic acid ester monomer to the acrylic acid monomer or the methacrylic acid monomer to the boron-containing monomer is (6-10): (1-3): (0.5-2). Further, the molar ratio is 8:2:1. Further, the boron-containing monomer is vinyl phenylboronic acid. Further, the heteropolyanion is derived from phosphotungstic acid. Further, the rare earth ions are europium ions. Further, the visible light transmittance of the coating in the initial state is not lower than 80%. In another aspect, the present invention provides a method of preparing the above-described coating, comprising the steps of: s1, mixing an ethylenically unsaturated monomer and a boron-containing monomer with a photoinitiator, and carrying out polymerization reaction under ultraviolet light irradiation to form an organic polymer network; s2, mixing the organic polymer network and the heteropoly acid in a solvent, and stirring for 3-5 hours at 100-120 ℃ to form a uniform solution; s3, when the coating contains rare earth