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CN-122012080-A - Long-life room-temperature phosphorescent material capable of being subjected to stereolithography and preparation and application thereof

CN122012080ACN 122012080 ACN122012080 ACN 122012080ACN-122012080-A

Abstract

The invention belongs to the technical field of polymers and luminescent materials, and particularly relates to a room-temperature phosphorescent material with long service life capable of being subjected to stereolithography, and preparation and application thereof. The long-life room-temperature phosphorescent material comprises poly (propylene fumarate), hyperbranched polyester acrylate and phosphorescent molecule LAD, wherein the number average molecular weight of the poly (propylene fumarate) is 2800-4000 g/mol, the mass ratio of the poly (propylene fumarate) is more than or equal to 58% and the mass ratio of the phosphorescent molecule is 0.08-0.15% based on the total amount of the poly (propylene fumarate) and the hyperbranched polyester acrylate. According to the invention, the LAD is matched with the polypropylene fumarate and hyperbranched polyester acrylate resin system, so that the phosphorescence service life of the LAD is obviously prolonged.

Inventors

  • WANG SHANFENG
  • Zhou Jiuhao
  • YANG ZHIYONG

Assignees

  • 中山大学

Dates

Publication Date
20260512
Application Date
20260414

Claims (10)

  1. 1. The long-life room temperature phosphorescent material is characterized by comprising poly propylene fumarate, hyperbranched polyester acrylate and phosphorescent molecules; the structural formula of the phosphorescence molecule is as follows: ; the number average molecular weight of the poly propylene fumarate is 2800-4000 g/mol; the mass ratio of the poly propylene glycol fumarate is more than or equal to 58 percent based on the total amount of the poly propylene glycol fumarate and the hyperbranched polyester acrylate; the mass ratio of phosphorescent molecules is 0.08-0.15% based on the total amount of the poly propylene fumarate and the hyperbranched polyester acrylate.
  2. 2. The long-life room temperature phosphorescent material of claim 1, comprising, by weight, 60-100 parts of poly propylene fumarate, 0.1-40 parts of hyperbranched polyester acrylate and 0.05-0.5 part of phosphorescent molecule.
  3. 3. The long life room temperature phosphorescent material according to claim 1, characterized in that the number average molecular weight of the poly propylene fumarate is 3000-3500 g/mol, and/or The mass ratio of phosphorescent molecules is 0.1-0.12% based on the total amount of the poly propylene fumarate and the hyperbranched polyester acrylate.
  4. 4. The long life room temperature phosphorescent material according to claim 1, further comprising 0.1 to 3 parts of a photoinitiator.
  5. 5. The long-life room temperature phosphorescent material according to claim 1, wherein the preparation method of the poly propylene fumarate comprises the steps of mixing the poly propylene fumarate, 1, 2-propylene glycol, a catalyst and a polymerization inhibitor in a nitrogen atmosphere, carrying out polymerization reaction to obtain bis (hydroxypropyl) fumaric diester, and then further carrying out reaction to obtain the poly propylene fumarate.
  6. 6. The method for preparing the long-life room temperature phosphorescent material according to any one of claims 1 to 5, which is characterized in that the long-life room temperature phosphorescent material is prepared by uniformly mixing poly propylene fumarate, hyperbranched polyester acrylate, phosphorescent molecules and other components contained in a system.
  7. 7. A long-life room temperature phosphorescent film, which is characterized in that the long-life room temperature phosphorescent material of any one of claims 1-5 is adopted for ultraviolet light curing to prepare and obtain the long-life room temperature phosphorescent film.
  8. 8. The long-life room temperature phosphor film of claim 7, wherein the long-life room temperature phosphor film has a thickness of 0.05 to 0.5mm and/or the ultraviolet light curing time is not less than 30 minutes.
  9. 9. The 3D printing workpiece is characterized in that the 3D printing workpiece is prepared by adopting a first light-cured resin and a second light-cured resin; The first photo-curing resin is the long-life room temperature phosphorescent material of any one of claims 1-5; The phosphorescence lifetime of the first light-cured resin is 350-450ms, and the phosphorescence lifetime of the second light-cured resin is 210-310 mu s.
  10. 10. Use of the long-life room temperature phosphorescent material of any one of claims 1 to 5, the long-life room temperature phosphorescent film of any one of claims 7 to 8 or the 3D printed article of claim 9 in the field of information encryption and anti-counterfeiting.

Description

Long-life room-temperature phosphorescent material capable of being subjected to stereolithography and preparation and application thereof Technical Field The invention belongs to the technical field of polymers and luminescent materials, and particularly relates to a room-temperature phosphorescent material with long service life capable of being subjected to stereolithography, and preparation and application thereof. Background The organic room temperature phosphorescent material has great application potential in the fields of information encryption, high-end product anti-counterfeiting and the like by virtue of the advantages of long luminous life, large Stokes displacement, adjustable structure, good flexibility and the like, and is easier to realize functional molding by being compounded with a polymer matrix compared with the traditional inorganic phosphorescent material. However, the phosphorescence performance of most organic room temperature phosphorescence materials is easily affected by molecular aggregation and oxygen quenching, the polymer matrix is needed to realize performance enhancement, and how to combine the phosphorescence small molecules with the formable polymer matrix to realize the integrated preparation of phosphorescence function and fine structure becomes a key difficult problem for the application of the phosphorescence material in the anti-counterfeiting field. The 3D printing technology can accurately construct an object with any complex geometric shape according to a digital model, wherein the surface projection micro-stereoscopic photoetching technology is used as a micron-level high-precision photo-curing 3D printing method, can realize high-fidelity manufacturing of a complex fine structure, and provides design freedom for application of functional materials in the anti-counterfeiting field. The combination of the organic room temperature phosphorescent material and the high-precision 3D printing technology is expected to realize the direct manufacture of the anti-counterfeiting device with integrated structure-phosphorescence function, and the selection of a proper polymer matrix is the core for realizing the aim. Document "Time-Dependent Multicolor Afterglow from Dual Persistent Luminescence of Fluorescence and Phosphorescence in a UV-Cured Polyurethane Matrix（Siyang Jiang,Danman Guo,ACS Materials Lett,https://doi.org/10.1021/acsmaterialslett.3c01498）" discloses a time-dependent polychromatic afterglow polyurethane system, which has a phosphorescent lifetime of up to 217ms at 626 nm by means of a rapid UV-curing copolymerization of pyrene-1-carboxylate derivatives (PyC) with poly- ε -caprolactone (PCL) prepolymers. By means of the colorful afterglow change characteristic and the rapid ultraviolet curing preparation process, the material has wide application prospect in the fields of time-dependent three-level information encryption and anti-counterfeiting. However, the problem of shorter phosphorescent lifetime of the polymer system provided by the above solution still exists, and how to further improve the phosphorescent lifetime of the polymer system based on phosphorescent molecules and apply the same in the 3D printing field is a technical problem to be solved in the art. Disclosure of Invention In view of the above-mentioned problems of the prior art, it is a primary object of the present invention to provide a long-life room temperature phosphorescent material. The second object of the invention is to provide a preparation method of the long-life room temperature phosphorescent material. A third object of the present invention is to provide a long-life room temperature phosphorescent film. A fourth object of the present invention is to provide a 3D printed article. The fifth object of the invention is to provide a long-life room temperature phosphorescent material, a long-life room temperature phosphorescent film or a 3D printing part, which are applied to the fields of information encryption and anti-counterfeiting. In order to achieve the above purpose, the present invention is realized by the following technical scheme: the invention discloses a long-life room temperature phosphorescent material, which comprises poly propylene fumarate, hyperbranched polyester acrylate and phosphorescent molecules; the structural formula of the phosphorescence molecule is as follows: ; the number average molecular weight of the poly propylene fumarate is 2800-4000 g/mol; the mass ratio of the poly propylene glycol fumarate is more than or equal to 58 percent based on the total amount of the poly propylene glycol fumarate and the hyperbranched polyester acrylate; the mass ratio of phosphorescent molecules is 0.08-0.15% based on the total amount of the poly propylene fumarate and the hyperbranched polyester acrylate. In the invention, the phosphorescent molecule (LAD) is a pyrene cyclic organic small molecule with excellent room temperature phosphorescent emission characteristic,