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CN-121991140-A - Ferrocenyl dynamic covalent network monomer, 3D printing resin containing ferrocenyl dynamic covalent network monomer and application of ferrocenyl dynamic covalent network monomer

CN121991140ACN 121991140 ACN121991140 ACN 121991140ACN-121991140-A

Abstract

The ferrocenyl dynamic covalent network monomer is introduced into the monomer, so that the ferrocenyl dynamic covalent network monomer can endow a material with paramagnetism, reversible fracture and recombination characteristics are endowed through dynamic covalent bonds, and the monomer is introduced into a polymer network, so that the material has photocuring activity, paramagnetism and dynamic responsiveness, and has a remarkable application prospect when being used for photocuring 3D printing to prepare intelligent functional devices.

Inventors

  • CHEN JIAN
  • MENG LONG
  • LIU HUAN
  • HAN TIANCHENG
  • LIN JINRUI

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 ferrocenyl dynamic covalent network monomer is characterized in that the structural formula is shown in formula I: ; In formula I, R 1 、R 4 is each a carbon-carbon double bond containing group, and R 2 、R 3 is each independently selected from an acylhydrazone bond, a disulfide bond, or a borate bond.
  2. 2. A ferrocenyl dynamic covalent network monomer according to claim 1, wherein in formula I, R 1 、R 4 is each independently selected from acryl or methacryl.
  3. 3. A ferrocenyl dynamic covalent network monomer according to claim 1, wherein in formula I, R 1 、R 4 is the same functional group and/or R 2 、R 3 is the same functional group.
  4. 4. A method for preparing a ferrocenyl dynamic covalent network monomer according to any one of claims 1-3, characterized in that the steps comprise: S1, taking ferrocenylamine compounds and dynamic covalent bond precursor compounds containing aldehyde groups to perform condensation reaction under the action of a solvent to form intermediates containing ferrocene units and dynamic covalent bonds, wherein the precursor compounds are at least one compound containing acylhydrazone bonds, disulfide bonds or boric acid ester bonds as dynamic covalent bonds; S2, acylating the intermediate with an acyl chloride compound containing a photocuring double bond under the action of a catalyst, and separating and purifying the reaction liquid to obtain the ferrocenyl dynamic covalent network monomer with the structure shown in the formula I.
  5. 5. The method according to claim 4, wherein in step S1, the molar ratio of the ferrocenylamine compound to the aldehyde group-containing dynamic covalent bond precursor compound is 1 (1-3); and/or, the condensation reaction condition is that the reaction is carried out for 2-4 hours at 40-60 ℃; and/or the solvent is ethanol or dichloromethane.
  6. 6. The method according to claim 4, wherein in the step S2, the molar amount of the acid chloride compound containing a photo-curable double bond is 1 to 2 times that of the ferrocenylamine compound; and/or the reaction is catalyzed by triethylamine for 1-3h at 20-30 ℃.
  7. 7. A3D printing resin is characterized by comprising, by mass, 20-50 parts of ferrocenyl dynamic covalent network monomer, 10-20 parts of acrylic acid oligomer, 20-50 parts of photo-curing reactive diluent, 1-5 parts of photoinitiator and 0-5 parts of auxiliary agent, wherein the ferrocenyl dynamic covalent network monomer is the ferrocenyl dynamic covalent network monomer according to any one of claims 1-3.
  8. 8. The 3D printing resin of claim 7, wherein the acrylic oligomer is selected from at least one of a difunctional acrylate, a polyurethane acrylate, or an epoxy acrylate; and/or the photo-curing reactive diluent is at least one selected from trimethylolpropane triacrylate, tripropylene glycol diacrylate and 1, 6-hexanediol diacrylate; And/or the photoinitiator is at least one selected from 2,4, 6-trimethylbenzoyl phosphorus oxide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone and benzophenone; And/or, the auxiliary agent comprises an antifoaming agent, a leveling agent and a stabilizer.
  9. 9. A 3D printed article obtained by 3D printing photo-curing the 3D printing resin of claims 7-8.
  10. 10. Use of the 3D printing resin of claims 7-8 or the 3D printed article of claim 9, the use comprising at least one of: 1) Preparing a shape memory product; 2) And preparing a magnetic control device.

Description

Ferrocenyl dynamic covalent network monomer, 3D printing resin containing ferrocenyl dynamic covalent network monomer and application of ferrocenyl dynamic covalent network monomer Technical Field The invention relates to the technical field of 3D printing functional materials, in particular to a ferrocenyl dynamic covalent network monomer, a 3D printing resin containing the ferrocenyl dynamic covalent network monomer and application of the ferrocenyl dynamic covalent network monomer. Background The 3D printing technology has wide application prospect in the fields of aerospace, electronic devices, biomedical treatment and the like by virtue of the advantages of high precision and personalized customization. Among them, photo-curing 3D printing is one of the current mainstream 3D printing technologies because of its fast molding speed and high resolution, and its core is the development of high-performance photo-curing resin. Most of polymer networks formed after the traditional photo-curing resins such as epoxy resin, acrylic ester and the like are of static covalent structures, and the defects of large brittleness, fixed shape, single function and the like exist, so that the requirements of intelligent devices on dynamic response of materials and multifunctional integration are difficult to meet. The shape memory polymer is used as an intelligent material, and can recover a preset shape under external stimulus (such as heat, light, magnetism, electricity and the like), but the traditional preparation mode is mostly dependent on heat curing, has poor compatibility with photo-curing 3D printing, and most products lack of functionality, so that the application of the shape memory polymer in manufacturing precision devices is limited. Smart functional devices generally refer to devices (Lendlein & Gould, 2019) that deform or respond functionally to external stimuli (e.g., heat, magnetism, light), and their performance often meets the requirements of shape memory efficiency (ASTM F3062-20), magnetic response strength (IEEE MAGNETICS Society, 2019), and high precision manufacturing (ISO/ASTM 52902:2019). In the biomedical field, in particular orthopedics, the need for implanted devices is evolving from "static fixation" to "dynamic repair and intelligent regulation". The next generation of intelligent bone fixation devices, such as bone nails or bone plates with shape memory and magnetic control deformation capability, have become an important direction for promoting medical intelligence. Currently, the research of combining ferrocenyl with a dynamic covalent network and adapting light-curing 3D printing technology is still in a blank stage. The existing ferrocenyl polymers are mostly prepared through thermal polymerization, the molding efficiency is low, and the dynamic covalent network materials lack paramagnetic and other functionalities and cannot realize magnetic control shape programming. Therefore, developing a 3D printing resin with photo-curing formability, paramagnetism, thermal shape memory effect and magnetic programmability has important significance for promoting the efficient manufacture of intelligent functional devices. Disclosure of Invention The invention provides a ferrocenyl dynamic covalent network monomer and a photo-curing resin composition containing the ferrocenyl dynamic covalent network monomer, which are used for forming covalent network materials by 3D printing, realize the functions of thermal shape memory effect and paramagnetism, and can meet the requirement of magnetic control shape programming so as to meet the application of intelligent functional devices. The technical scheme of the invention is realized as follows: in a first aspect, the invention provides a ferrocenyl dynamic covalent network monomer, which is characterized by having a structural formula as shown in formula I: ; In formula I, R 1、R4 is each a carbon-carbon double bond containing group, and R 2、R3 is each independently selected from an acylhydrazone bond, a disulfide bond, or a borate bond. Further, in formula I, R 1、R4 is each independently selected from acryl or methacryl. Further, in formula I, R 1、R4 is the same functional group, and/or R 2、R3 is the same functional group. In a second aspect of the present invention, there is provided a method for preparing the ferrocenyl dynamic covalent network monomer of the first aspect, comprising the steps of: S1, taking ferrocenylamine compounds and dynamic covalent bond precursor compounds containing aldehyde groups to perform condensation reaction under the action of a solvent to form intermediates containing ferrocene units and dynamic covalent bonds, wherein the precursor compounds are at least one compound containing acylhydrazone bonds, disulfide bonds or boric acid ester bonds as dynamic covalent bonds; S2, acylating the intermediate with an acyl chloride compound containing a photocuring double bond under the action of a catalyst, and separating and purif