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CN-121991370-A - Zirconium-based metal-organic framework fluorescence sensing material, 3D printing product containing zirconium-based metal-organic framework fluorescence sensing material and application of zirconium-based metal-organic framework fluorescence sensing material

CN121991370ACN 121991370 ACN121991370 ACN 121991370ACN-121991370-A

Abstract

The invention provides a zirconium-based metal-organic framework fluorescent sensing material, a 3D printing product containing the same and application thereof; the zirconium-based metal-organic framework fluorescent sensing material is obtained by coordination of zirconium tetrachloride and an organic ligand with a plurality of amino groups, and has a metal-organic framework with a three-dimensional hole structure. On the other hand, the material can embed MOF with specific chemical recognition function into a 3D printing structure body to realize the integration of a sensing-color developing function and a complex three-dimensional structure, and has the advantages of good mechanical strength, stable active site and difficult loss of a 3D printing device, and has remarkable application prospect in harmful gas detection.

Inventors

  • HAN TIANCHENG
  • MENG LONG
  • LIU HUAN
  • LIN JINRUI
  • QIU XIANXING

Assignees

  • 信联聚科(上海)新材料有限公司

Dates

Publication Date
20260508
Application Date
20260123

Claims (10)

  1. 1. The zirconium-based metal-organic framework fluorescent sensing material is characterized by being prepared by a coordination reaction of zirconium tetrachloride and an organic ligand, wherein the structural formula of the organic ligand is shown as formula I: 。
  2. 2. The preparation method of the zirconium-based metal-organic framework fluorescent sensing material is characterized in that zirconium tetrachloride and an organic ligand shown in a formula I are subjected to coordination reaction in a solvent by a solvothermal method or a stirring method to obtain a crude product, and then the crude product is washed and dried to obtain the zirconium-based metal-organic framework fluorescent sensing material.
  3. 3. The method according to claim 2, wherein the solvent is one selected from the group consisting of N, N-dimethylformamide and methylene chloride.
  4. 4. The preparation method according to claim 2, wherein the organic ligand represented by formula I is prepared by the steps of: S1.2, carrying out cyclization reaction on 3-diamino terephthalic acid and monomethyl adipate under an acidic condition to obtain an intermediate I; S2, placing the intermediate I in a mixed solution of hexamethyldisilazane and/or trimethylhalosilane, and heating and refluxing the mixed solution to react to generate an intermediate II; s3, reacting the intermediate II with 5-benzyl halide 1.3-diamine under a reflux condition to obtain an organic ligand shown in a formula I; The reaction route of the preparation method is as follows: 。
  5. 5. the process according to claim 4, wherein in step S3, the 5-halogenated benzyl 1.3-diamine is obtained by amino-protecting 5-toluene-1, 3-diamine, halogenating with a halogenating agent, and deprotecting the amino group.
  6. 6. The method according to claim 5, wherein the amino-protecting reagent is di-t-butyl dicarbonate; and/or the halogenating agent is N-chlorosuccinimide or N-bromosuccinimide.
  7. 7. The 3D printing resin composition is characterized by comprising, by weight, 3-10 parts of a metal organic framework Zr-MOF, 50-60 parts of an acrylic ester monomer, 10-30 parts of a reactive diluent, 1-3 parts of a photoinitiator, 0-1 part of a defoaming agent and 0-1 part of a polymerization inhibitor, wherein the metal organic framework Zr-MOF is the zirconium-based metal organic framework fluorescent sensing material according to claim 1 or the zirconium-based metal organic framework fluorescent sensing material prepared by the preparation method according to any one of claims 2-6.
  8. 8. The resin composition of claim 7, wherein the acrylate monomer is at least one of bisphenol a type epoxy diacrylate or polyester acrylate; And/or the reactive diluent is tripropylene glycol diacrylate or 1, 6-hexanediol diacrylate; and/or the photoinitiator is phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide; And/or, the defoamer is BYK-UV 3500; and/or the polymerization inhibitor is hydroquinone monomethyl ether.
  9. 9. A 3D printed article, characterized by being obtained by curing the 3D printed resin composition according to claim 7 or 8 by 3D printing.
  10. 10. Use of the 3D printing resin composition of claim 7 or 8, or the 3D printed article of claim 9 in formaldehyde detection.

Description

Zirconium-based metal-organic framework fluorescence sensing material, 3D printing product containing zirconium-based metal-organic framework fluorescence sensing material and application of zirconium-based metal-organic framework fluorescence sensing material Technical Field The invention relates to the technical field of metal-organic frame fluorescent materials, in particular to a zirconium-based metal-organic frame fluorescent sensing material, a 3D printing product containing the same and application thereof. Background With the development of industry and city, the monitoring requirement of harmful substances in the air (such as formaldehyde CH 2 O and the like) is increasingly urgent. The traditional detection method, such as gas chromatography-mass spectrometry technology, has the defects of high equipment cost, complex operation, professional requirement, difficulty in real-time and in-situ monitoring and the like, although the precision is high. Chemical sensors based on color change have been widely studied in order to achieve rapid, on-site detection of specific gases. The metal organic frame material has ultrahigh specific surface area, adjustable pore channel structure and surface chemical property, can interact with specific gas molecules in high selectivity and high sensitivity, and is often accompanied by macroscopic color change, so the metal organic frame material is regarded as an ideal gas sensing material. Currently, researchers often coat MOF materials on the surface of paper, fabric or solid substrates to make simple test strips or sensing devices. However, such devices suffer from limitations such as poor mechanical strength, easy removal of the MOF layer, single function, uncontrollable shape, and difficulty in integration into complex systems. On the other hand, 3D printing (additive manufacturing) techniques, particularly based on photo-curing techniques, provide unprecedented flexibility in manufacturing devices of complex structures. Currently, there have been studies on attempts to compound some functional nanomaterials (e.g., carbon nanotubes, graphene, nano metal particles) with 3D printing resins to produce structural members having conductivity or mechanical reinforcement. However, the application of these materials to the field of gas detection, especially with their color change properties, still faces significant challenges. The main problems are that: 1. The dispersibility problem is that the MOF material is micro-nano powder, is difficult to stably and uniformly disperse in resin, and is easy to agglomerate, so that the smoothness of a printing process and the mechanical property of a formed part are affected, the active sites of the formed part are seriously shielded, and the sensing performance is obviously reduced. 2. The functional retention challenge is that the resin matrix may encapsulate the MOF particles, impeding their contact with the target gas molecules, and that uv light irradiation or high temperature during printing may damage the structure of the MOF, resulting in inactivation of its sensing activity. 3. The device has single function, most 3D printing researches are focused on manufacturing mechanical structural parts at present, and the printed object is 'passive'. How to directly assign a sensitive chemical recognition function (such as color change characteristics of MOF) to a 3D printing structural member, so that the 3D printing structural member becomes an intelligent device with 'active' and perception capability, which is a leading-edge problem in the field at present. Therefore, there is an urgent need in the art for a new technology capable of solving the above problems, which not only can realize uniform dispersion and function retention of MOFs in printing materials, but also can utilize the technical advantages of 3D printing to manufacture intelligent devices that have complex structures, good mechanical properties, and can intuitively and rapidly detect harmful substances in the air through color changes. Disclosure of Invention The invention provides a zirconium-based metal-organic framework fluorescent sensing material, which is used for meeting the material performance requirement for detecting harmful gas after 3D printing. The technical scheme of the invention is realized as follows: the first aspect of the invention provides a zirconium-based metal-organic framework fluorescent sensing material, which is obtained by a coordination reaction between zirconium tetrachloride and an organic ligand, wherein the structural formula of the organic ligand is shown as formula I: 。 the second aspect of the invention provides a preparation method of the zirconium-based metal-organic framework fluorescent sensing material in the first aspect, wherein zirconium tetrachloride and an organic ligand shown in a formula I are subjected to coordination reaction in a solvent by a solvothermal method or a stirring method to obtain a crude product, and