Search

CN-121991380-A - Hydrogel with X-ray radiation luminescence performance and preparation method thereof

CN121991380ACN 121991380 ACN121991380 ACN 121991380ACN-121991380-A

Abstract

The invention discloses a hydrogel with X-ray radiation luminescence property and a preparation method thereof, which belong to the technical field of hydrogel materials, the invention firstly synthesizes vinyl monomers containing stilbene units, and (3) carrying out copolymerization reaction on vinyl monomers containing stilbene units and water-soluble monomers through free radical polymerization reaction to obtain the polymer A. Then synthesizing vinyl monomer containing cyclodextrin unit, and copolymerizing vinyl monomer containing cyclodextrin unit with water-soluble monomer by free radical polymerization reaction to obtain polymer B. The polymer A and the host-guest interaction of the polymer B are utilized to synthesize the supermolecule hydrogel with X-ray radiation luminescence property. The hydrogel prepared by the invention emits green visible fluorescence under the radiation of X rays, does not contain metal elements, has high water content and is environment-friendly.

Inventors

  • ZHANG HAILEI
  • CHEN YUJIE
  • CHEN HUABIAO
  • SONG WEIHUA

Assignees

  • 河北大学

Dates

Publication Date
20260508
Application Date
20260131

Claims (10)

  1. 1. A method for preparing a hydrogel with X-ray radiation luminescence property, which is characterized by comprising the following steps: (1) Reacting p-aldehyde benzoic acid, N-dimethylformamide and thionyl chloride under a heating condition, removing unreacted thionyl chloride after the reaction is finished, adding hydroxyethyl methacrylate, tetrahydrofuran and triethylamine into an ice water bath, continuously reacting to obtain a crude product, and separating by column chromatography to obtain a compound 1; (2) Stirring and reacting the compound 1, sodium hydride, N-dimethylformamide and diethyl 4-bromobenzyl phosphite to obtain a crude product, and separating the crude product by column chromatography to obtain a compound 2; (3) Reacting the compound 2, N-methylolacrylamide, azodiisobutyronitrile and N, N-dimethylformamide under a heating condition, and performing reverse precipitation treatment by using a precipitant after the reaction is finished to obtain a polymer A; (4) Dissolving cyclodextrin and potassium hydroxide in water, adding acryloyl chloride into ice water bath, stirring for reaction, and performing reverse precipitation treatment by using a precipitant after the reaction is finished to obtain a compound CD-Ac; (5) Reacting the compound CD-Ac, acrylamide, potassium persulfate and dimethyl sulfoxide under a heating condition, and performing reverse precipitation treatment by using a precipitant after the reaction is finished to obtain a polymer B; (6) Mixing the polymer A and the polymer B in water, uniformly stirring, and standing to form hydrogel; wherein, the structural formulas of the compound 1, the compound 2, the polymer A, the compound CD-Ac and the polymer B are respectively as follows: 、 、 、 And ; N and m represent the number of repeating units on the left and right sides of the polymer A, respectively, and x and y represent the number of repeating units on the left and right sides of the polymer B, respectively.
  2. 2. The process according to claim 1, wherein in the step (1), the mass ratio of p-aldehyde benzoic acid to thionyl chloride is 1: (4-20), and/or, The dosage of the N, N-dimethylformamide is 1-5% of the mass of the p-aldehyde benzoic acid and/or, The heating is at a temperature of 50-80 ℃ for a time of 1-5 hours, and/or, The mass ratio of the p-aldehyde benzoic acid to the hydroxyethyl methacrylate to the tetrahydrofuran to the triethylamine is 1:0.5-4:4-20:0.5-4, and/or, The temperature of the continuous reaction is 50-80 ℃ and the time is 8-15 hours.
  3. 3. The process according to claim 1, wherein in the step (2), the mass ratio of the compound 1, sodium hydride, N-dimethylformamide and diethyl 4-bromobenzylphosphite is 1: (0.05-0.3): (10-30): (0.5-4), and/or, The stirring reaction time is 8-15 hours.
  4. 4. The process according to claim 1, wherein in the step (3), the mass ratio of the compound 2, N-methylolacrylamide, azobisisobutyronitrile and N, N-dimethylformamide is 1:1-5:0.01-0.20:20-60, and/or, The heating temperature is 50-80 ℃ and the heating time is 8-15 hours.
  5. 5. The process according to claim 1, wherein in the step (4), the mass ratio of cyclodextrin to potassium hydroxide is 1: (0.1-0.5), and/or, The cyclodextrin is one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin, and/or, The mass ratio of the cyclodextrin to the acrylic chloride is 1:0.1-0.5, and/or, The temperature of the stirring reaction is 20-40 ℃ and the time is 3-12 hours.
  6. 6. The process according to claim 1, wherein in the step (5), the mass ratio of the compound CD-Ac, acrylamide, potassium persulfate and dimethyl sulfoxide is 1: (0.01-0.5): (10-50), and/or, The heating temperature is 50-80 ℃ and the heating time is 8-15 hours.
  7. 7. The preparation method according to claim 1, wherein in the step (3), the step (4) and the step (5), the precipitants are selected from one of acetone, methanol, diethyl ether and petroleum ether.
  8. 8. The process according to claim 1, wherein in the step (6), the mass ratio of the polymer A, the polymer B and the water is 1: (0.5-4): (4-30), and/or, The standing time is 8-15 hours.
  9. 9. A hydrogel prepared by the method of any one of claims 1-8.
  10. 10. Use of the hydrogel of claim 9 in the field of flexible X-ray imaging.

Description

Hydrogel with X-ray radiation luminescence performance and preparation method thereof Technical Field The invention belongs to the technical field of hydrogel materials, and particularly relates to a hydrogel with X-ray radiation luminescence performance and a preparation method thereof. Background X-ray imaging is one of the core technologies in the field of modern medical diagnosis, and the core principle is that an X-ray signal is converted into a visual image through a rigid X-ray scintillator screen, so that a key basis is provided for clinical diagnosis. However, the conventional rigid scintillator screen has significant limitations in that the adhesion to non-planar objects is poor, the imaging quality is poor, and the actual requirements of dynamic imaging of the non-planar objects cannot be met. Therefore, the development of the flexible X-ray scintillator screen becomes a research hot spot in the related field in recent years, the flexible X-ray scintillator screen can be processed into any shape according to requirements and is adaptive to the characteristics of a non-planar object, and a new solution is provided for dynamic real-time monitoring. Currently, the predominant X-ray scintillator materials are based on inorganic crystals. The material has excellent luminous performance, but is in a rigid structure, is difficult to process into a flexible form, has poor water solubility and poor compatibility with a polymer material, and is difficult to realize uniform dispersion and finally influences imaging effect if the material is tried to be doped into hydrogel. The prior art still fails to break through the bottleneck, patent CN 118027968 discloses a Y 2MgTiO6 modified material doped with trivalent bismuth and trivalent europium ions, the material can emit yellow-red visible light under the irradiation of X rays, has good stability, still belongs to a rigid crystal material and cannot be processed into a flexible radiation luminescent material, patent CN 118407136 discloses a lead-containing organic-inorganic hybrid material Bmpip 2PbBr4 which can convert various radiation signals such as X rays, gamma rays and the like into visible light, has excellent stability, but is difficult to apply to the biomedical field due to the fact that the lead-containing inorganic scintillator nano particles are contained in the polymer film, and the technology reported in Nature (2021,590,410-415) proves the imaging advantage of the flexible material on an aspheric object, but the composite imaging screen belongs to a heterogeneous material, and the imaging effect is easily influenced by component compatibility. In summary, the existing X-ray radiation luminescent material generally has two main core problems that the existing X-ray radiation luminescent material contains toxic metal elements, limits the application of biomedical scenes, or cannot adapt to the dynamic imaging requirement of non-planar objects because a rigid structure is difficult to process into a flexible form. Therefore, developing a material that does not contain metal elements, has flexible bonding characteristics, and has X-ray radiation luminescence properties, is an important point and difficulty to be solved in the field. The hydrogel is used as a high-molecular three-dimensional network material with high water content, has good shape self-adaption capability, biocompatibility and high transparency, and just meets the substrate requirement of a flexible X-ray scintillator screen, thereby providing an ideal path for solving the problems. Disclosure of Invention Aiming at the technical problems, the invention provides hydrogel with X-ray radiation luminescence performance and a preparation method thereof. In order to achieve the above purpose, the present invention provides the following technical solutions: one of the purposes of the present invention is to provide a method for preparing a hydrogel with X-ray radiation luminescence, comprising the following steps: (1) Reacting p-aldehyde benzoic acid, N-dimethylformamide and thionyl chloride under a heating condition, removing unreacted thionyl chloride after the reaction is finished, adding hydroxyethyl methacrylate, tetrahydrofuran and triethylamine into an ice water bath, continuously reacting to obtain a crude product, and separating by column chromatography to obtain a compound 1; (2) Stirring and reacting the compound 1, sodium hydride, N-dimethylformamide and diethyl 4-bromobenzyl phosphite to obtain a crude product, and separating the crude product by column chromatography to obtain a compound 2; (3) Reacting the compound 2, N-methylolacrylamide, azodiisobutyronitrile and N, N-dimethylformamide under a heating condition, and performing reverse precipitation treatment by using a precipitant after the reaction is finished to obtain a polymer A; (4) Dissolving cyclodextrin and potassium hydroxide in water, adding acryloyl chloride into ice water bath, stirring for reaction, and per