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CN-121987854-A - High-solid-content modified hydroxyapatite photosensitive resin material and application thereof in bone repair material

CN121987854ACN 121987854 ACN121987854 ACN 121987854ACN-121987854-A

Abstract

The invention discloses a high-solid-content modified hydroxyapatite photosensitive resin material and application thereof in bone repair materials. The modified hydroxyapatite material comprises, by mass, 50-90 parts of modified hydroxyapatite, 10-30 parts of a photosensitive resin matrix, 0-20 parts of an active diluent and 0.1-0.5 part of a photoinitiator, and is subjected to photocuring 3D printing to prepare a high-content modified hydroxyapatite photosensitive resin product, and then is sintered at a high temperature to prepare the hydroxyapatite bone repair product. The hydroxyapatite bone repair product prepared by the method has the advantages of small dimensional shrinkage, high precision, good mechanical property, biocompatibility and the like, and provides a new solution for the application of the hydroxyapatite in the bone repair product.

Inventors

  • Zhuo dongxian
  • LUO JINXI
  • RAO JIUPING
  • WANG RUI
  • CHEN SHAOYUN
  • LIU XIAOYING
  • CAI CUIFANG
  • GAO JIANHONG

Assignees

  • 福建农林大学
  • 泉州师范学院

Dates

Publication Date
20260508
Application Date
20251222

Claims (10)

  1. 1. The high-solid-content modified hydroxyapatite photosensitive resin material is characterized by comprising the following raw materials in parts by mass: 50-90 parts of modified hydroxyapatite 10-30 Parts of photosensitive resin matrix 0-20 Parts of reactive diluent 0.1-0.5 Part of photoinitiator The preparation method of the modified hydroxyapatite comprises the following steps: (1) Under the protection of nitrogen, reacting hydroxyl-containing acrylic acid monomer, diisocyanate, solvent and catalyst for 2.8-3.5 hours in an environment of 83-88 ℃, and carrying out suction filtration after the reaction is finished to obtain a prepolymer A; (2) Under the protection of nitrogen, the prepolymer A, the hydroxyapatite, the solvent and the catalyst react for 1.8-2.5 hours in an environment of 83-88 ℃, and after the reaction is finished, the modified hydroxyapatite is obtained by suction filtration.
  2. 2. The high-solid-content modified hydroxyapatite photosensitive resin material according to claim 1, wherein the mass ratio of the hydroxy acrylic acid-containing monomer and the diisocyanate in the step (1) is 0.7-0.8:1, and the mass ratio of the prepolymer A and the hydroxyapatite in the step (2) is 1:9.5-10.5.
  3. 3. The high-solid-content modified hydroxyapatite photosensitive resin material according to claim 1, wherein said diisocyanate in the step (1) is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and lysine diisocyanate.
  4. 4. The high-solid content modified hydroxyapatite photosensitive resin material according to claim 1, wherein the hydroxyl group-containing acrylic monomer in the step (1) is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate, polyethylene glycol monoacrylate, and N-hydroxyethyl acrylamide.
  5. 5. The high-solid-content modified hydroxyapatite photosensitive resin material according to claim 1, wherein said catalyst in the steps (1) and (2) is dibutyltin dilaurate, and said solvent is ethyl acetate.
  6. 6. The high-solid-content modified hydroxyapatite photosensitive resin material according to claim 1, wherein said photosensitive resin matrix is at least one of methyl methacrylate, lauryl methacrylate, 1, 6-hexanediol diacrylate, tetrahydrofuranacrylate, tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol a diacrylate, trimethylolpropane triacrylate, pentaerythritol acrylate, isobornyl acrylate, and cyclotrimethylolpropane methylal acrylate; the reactive diluent comprises at least one of o-phenylphenoxyethyl acrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate and isobornyl acrylate; the photoinitiator is 1-hydroxycyclohexyl phenyl ketone.
  7. 7. The use of a high-solid-content modified hydroxyapatite photosensitive resin material according to any one of claims 1 to 6 in bone repair materials.
  8. 8. The method according to claim 7, wherein the high-solid content modified hydroxyapatite photosensitive resin material is subjected to pretreatment to obtain slurry, the slurry is subjected to photocuring 3D printing to obtain a photosensitive resin product, and finally the photosensitive resin product is subjected to high-temperature sintering to obtain the hydroxyapatite bone repair product.
  9. 9. The method for pretreatment of the ceramic foam material, which is characterized by comprising the steps of adding a high-solid-content modified hydroxyapatite photosensitive resin material into a flask, mechanically stirring for 15+/-2 min at 400+/-10 rpm in a constant-temperature water bath at 85+/-1 ℃, magnetically stirring for 15+/-2 min at the same rotating speed, and carrying out vacuum defoaming for 10+/-2 min to obtain the foam slurry.
  10. 10. The method according to claim 8, wherein the parameters of the photo-curing 3D printing are that the light source has a wavelength of 405 nm, the light power is 4.0 Mw/cm -2 , the exposure time of the bottom layer is 30s, the exposure time of the other layers is 12s, and the thickness of each printing layer is 80 μm; The high-temperature sintering process comprises the steps of heating to 500+/-20 ℃ at 0.5 ℃ per minute, preserving heat for 30+/-5 minutes, heating to 1500+/-50 ℃ at 5 ℃ per minute, preserving heat for 1+/-0.1 hour, and finally cooling to room temperature at 5 ℃ per minute.

Description

High-solid-content modified hydroxyapatite photosensitive resin material and application thereof in bone repair material Technical Field The invention belongs to the field of 3D printing materials, and particularly relates to a high-solid-content modified hydroxyapatite photosensitive resin material and application thereof in a bone repair material. Background With the aggravation of global aging, the bone diseases are high, and the elderly have vigorous demands on bone instruments. Although autologous bone grafting is "gold standard", it has the defects of regional complications, pain, blood loss, long operation time, limited materials and the like, and allogeneic bone has good usability, but has low osteoinductive property, easy infection, immune rejection and poor healing. Therefore, development of new bone repair techniques to improve the therapeutic effect is urgent. In recent years, bioactive ceramics have been attracting attention among many biological materials because their compositions are highly similar to natural bones. Hydroxyapatite (HA) is a representative of bioactive ceramics, HAs relatively stable performance in human physiological environments, HAs excellent biocompatibility, and in addition, HA scaffolds generally have suitable and ideal microstructure, mechanical properties and biological properties, and are considered to be ideal bone repair materials. Patent application CN105712735A provides a preparation method of a porous hydroxyapatite material for bone repair, which is prepared by a template method and is difficult to realize personalized customization, and patent application CN113509592A provides a porous hydroxyapatite polyurethane bone scaffold material and a preparation method thereof, which are used for preparing a scaffold by foaming and molding in a mold. However, due to differences in individual skeletal structures, conventional manufacturing processes have difficulty meeting the requirements of customization. In contrast, 3D printing technology can enable highly customized stent fabrication, meeting individual needs from person to person, and from injury to injury. Major additive manufacturing techniques include laser sintering (SLS), fused deposition techniques (FDM), photo-curing forming techniques (SLA), direct ink writing techniques (DIW), and the like. Among them, FDM was first widely used for the preparation of polymer/HA composite scaffolds because of its simple equipment and low cost. Zhang et al adopts FDM technology to prepare PCL/HA composite scaffold, and HA content upper limit is only 20wt%, and after sintering the linear shrinkage rate reaches 12.4%, and scaffold elastic modulus is an order of magnitude lower than natural cortical bone, can't satisfy the demand of bearing bone repair (Frontiers in Bioengineering and Biotechnology,2023, 11:1252636). Liu et al tried to increase HA content to 40wt% by microfluidic co-extrusion FDM technique, and although formation was realized barely, the stent porosity deviation reached + -7%, which could not meet the clinical grade dimensional accuracy (+ -0.2 mm) requirements (Bio-DESIGN AND Manufacturing,2024,7 (1): 89-102). The bone repair product with high HA content (more than or equal to 50 wt%) is closer to the inorganic component proportion of natural bone (HA in the natural bone accounts for 60-70% of the inorganic component), the biocompatibility and bone conductivity are more excellent, the material density after sintering is higher, the dimensional accuracy is higher, the mechanical strength is closer to the cortical bone (elastic modulus is 20-40GPa, breaking strength is 40-70 MPa) of a human body, the degradation rate is more gentle, the support can be provided for bone tissue regeneration for a long time, and the premature failure of a bracket is avoided. However, research shows that the stable preparation of the composite scaffold with high HA content (more than or equal to 50 wt%) is difficult to realize by the existing technology, and three main core problems are that HA is used as inorganic ceramic powder, surface hydroxyl groups are easy to cause agglomeration and are weak in interface combination with an organic matrix, the viscosity of slurry or silk material is obviously increased by the high HA content to influence the molding smoothness, and the scaffold is easy to have the problems of high shrinkage rate, insufficient dimensional accuracy and substandard mechanical property after molding. Meanwhile, the low HA content stent HAs serious shrinkage after sintering, remarkably reduces the dimensional accuracy, and HAs difficult full play of biocompatibility and bone conductivity. Disclosure of Invention Based on the preparation problem of the high-content HA bone repair product, the invention aims to provide a high-solid-content modified hydroxyapatite photosensitive resin material and application thereof in bone repair materials. In order to achieve the above purpose, the invention adopts the following