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CN112451753B - Nanofiber-reinforced absorbable intraosseous fixation material and preparation method thereof - Google Patents

Nanofiber-reinforced absorbable intraosseous fixation material and preparation method thereof Download PDF

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CN112451753B
CN112451753B CN202110114581.1A CN202110114581A CN112451753B CN 112451753 B CN112451753 B CN 112451753B CN 202110114581 A CN202110114581 A CN 202110114581A CN 112451753 B CN112451753 B CN 112451753B
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fibers
nanofiber
bone
fiber
lactide
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CN112451753A (en
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董文兴
赵树宇
杨腾飞
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Beijing Tianxing Medical Co ltd
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Beijing Tianxing Bomaidi Medical Equipment Co ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/12Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L31/125Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L31/127Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing fillers of phosphorus-containing inorganic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/12Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L31/125Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L31/129Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing macromolecular fillers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/146Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148Materials at least partially resorbable by the body
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0015Electro-spinning characterised by the initial state of the material
    • D01D5/003Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/24Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247Discontinuous hollow structure or microporous structure

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Abstract

The invention provides a nanofiber reinforced absorbable internal bone fixation material and a preparation method thereof. The nanofiber reinforced intraosseous fixing material is mainly formed by compounding a biodegradable high polymer material, nanofibers and an artificial bone material; wherein the surface of the nano fiber is modified, and the content of the nano fiber accounts for 10-20% of the total weight of the material; the content of the biodegradable high polymer material accounts for 60-80% of the total weight of the material; the artificial bone material accounts for 10-20% of the total weight of the material. The nanofiber reinforced absorbable intraosseous fixing material overcomes the characteristic that the common intraosseous fixing material is easy to fracture in multiple scales; the nanofiber has the characteristics of large specific surface, high porosity, strong modification capability and high elastic modulus, greatly improves the mechanical property of the absorbable bone internal fixation material, further promotes bone absorption and bone ingrowth, and accelerates the process of postoperative recovery.

Description

Nanofiber-reinforced absorbable intraosseous fixation material and preparation method thereof
Technical Field
The invention relates to the technical field of medical materials, in particular to a nanofiber reinforced absorbable bone internal fixation material and a preparation method thereof.
Background
With the iterative update of medical technology, although the traditional metal has higher mechanical strength and fatigue resistance and can meet the requirements of clinical operations on the performance of the metal, after the metal material is implanted into a human body, the metal material cannot be degraded in the human body, so that after the metal material is cured, a secondary operation is required to be performed to take out the metal material, and secondary damage is caused to a patient. In recent years, absorbable and fixed implants are widely concerned by virtue of unique advantages, but have a series of problems, but have certain limitations compared with other non-absorbable materials, and have the defects of poor anti-cracking capacity, low toughness, obvious brittleness, inconsistent degradation rate and bone ingrowth rate and the like, so that the appearance and the service life of the absorbable and fixed materials are influenced to a certain extent, and most importantly, the life safety of patients is seriously threatened. In order to reduce the accident problem caused by the defects of the absorbable and fixing material, the quality of the absorbable and fixing material needs to be improved completely.
In view of this, the present invention is proposed.
Disclosure of Invention
The invention aims to provide a nanofiber reinforced absorbable internal bone fixation material and a preparation method thereof. The nanofiber reinforced absorbable intraosseous fixing material overcomes the characteristic that the common intraosseous fixing material is easy to fracture in multiple scales; the nanofiber has the characteristics of large specific surface, high porosity, strong modification capability and high elastic modulus, greatly improves the mechanical property of the absorbable bone internal fixation material, further promotes bone absorption and bone ingrowth, and accelerates the process of postoperative recovery.
In order to achieve the above purpose of the present invention, the present invention adopts the following technical scheme:
in one aspect, a nanofiber-reinforced absorbable bone internal fixation material is provided, which is mainly compounded from a biodegradable high polymer material, nanofibers and an artificial bone material;
wherein the nanofiber surface is modified or modified; the content of the nano-fiber accounts for 10-20% of the total weight of the bone internal fixation material; the content of the biodegradable high polymer material accounts for 60-80% of the total weight of the bone internal fixation material; the artificial bone material accounts for 10-20% of the total weight of the material.
In one embodiment, the nanofiber is subjected to hydrophilic modification through a plasma surface treatment method, so that the biocompatibility and the interaction between the nanofiber and a biodegradable high polymer material and an artificial bone material are improved, and the elongation at break and the strength at break of the fiber can be enhanced; alternatively, a natural or synthetic substance for promoting bone in-growth is introduced, wherein the natural or synthetic substance for promoting bone in-growth comprises one or more substances which are beneficial to bone in-growth and bone absorption, such as chitosan, collagen, hyaluronic acid and growth factors.
In one embodiment, the nanofibers comprise one or more of polylactic acid, polyglycolide fibers, collagen fibers, polylactide fibers, polyglycolide-lactide copolymer fibers, polycaprolactone fibers, polyhydroxybutyrate fibers, polydioxanone fibers, polylactide-caprolactone copolymer fibers, lactide-hydroxybutyric acid copolymer fibers, lactide-glycolide-caprolactone copolymer fibers, chitosan fibers, cellulose nanofibers, and the like.
The type and physical and chemical properties of the nanofibers also affect the reinforcing effect, and a single type of fiber or different types of fibers may be used as the method of using the nanofibers.
In one embodiment, the diameter of the nanofibers is 50 to 1000 nm, preferably 50 to 500 nm; the porosity is 70-80%.
As a fiber component for reinforcing the performance of the absorbable bone internal fixation material by the nanofiber, the performance of the nanofiber can influence the reinforcing effect, for example, the diameter of the nanofiber is 50-500 nm, which is beneficial to the optimization of the reinforcing effect, further, the porosity of the nanofiber is 70-80%, the specific surface area of the nanofiber is large, the porosity is high, the tensile strength is high, and the reinforcing effect is beneficial to improvement.
In one embodiment, the biodegradable polymeric material is a conventional biodegradable polymeric material, including one or more of polylactic acid, polyglycolide, polylactide, polyglycolide-lactide copolymer, polycaprolactone, polyhydroxybutyric acid, polydioxanone, polylactide-caprolactone copolymer, lactide-hydroxybutyric acid copolymer, and lactide-glycolide-caprolactone copolymer.
In one embodiment, the artificial bone material comprises one or more of hydroxyapatite, fluorapatite, tricalcium phosphate, carbonic apatite, Calcium Sulfate Dihydrate (CSD), Calcium Sulfate Hemihydrate (CSH), Calcium Sulfate Anhydrite (CSA), and the like.
In another aspect, a method for preparing a nanofiber-reinforced absorbable bone internal fixation material is provided, the method comprising:
preparing nano fibers by using an electrostatic spinning technology, and performing surface modification on the nano fibers;
uniformly mixing the modified or modified nano-fibers with a biodegradable material and an artificial bone material to prepare blended particles;
and (3) preparing the blended particles into a profile through an injection molding process.
In one embodiment, the step of surface modifying the nanofibers comprises:
initiating acrylic acid surface grafting polymerization on the surface of the electrostatic nanofiber by using low-temperature plasma; wherein, the modification conditions are as follows: the vacuum degree is 50-70Pa, the gas flow is 1-3L/min, the discharge power is 50-200W, and the discharge time is 10-60 s.
In one embodiment, the specific steps of preparing nanofibers using electrospinning include: adding a high molecular polymer into a solvent, and magnetically stirring to obtain an electrostatic spinning solution; adding the electrostatic spinning solution into a spray head, and performing electrostatic spinning to obtain nano fibers;
preferably, the high molecular polymer is selected from one or more of polylactic acid, polyglycolide fiber, collagen fiber, polylactide fiber, polyglycolide-lactide copolymer fiber, polycaprolactone fiber, polyhydroxybutyrate fiber, polydioxanone fiber, polylactide-caprolactone copolymer fiber, lactide-hydroxybutyric acid copolymer fiber, lactide-glycolide-caprolactone copolymer fiber, chitosan fiber, cellulose nanofiber, etc.;
preferably, the solvent is selected from one or more of chloroform, acetone, methanol, tetrahydrofuran, benzene, N-dimethylformamide, and hexafluoroisopropanol.
In a specific embodiment, the concentration of the electrostatic spinning solution is 10-30%, the magnetic stirring time is not less than 6 hours, the electrostatic spinning voltage is 10-30 kV, the spinning solution advancing speed is 0.3-5 mL/h, the receiving distance from a spinning nozzle to a roller is 15-30 cm, the spinning environment temperature is 20-45 ℃, and the ambient relative humidity is 30-80%.
In one embodiment, the blended particles are made into a profile by an injection molding process comprising the steps of: uniformly mixing the blended particles with a nucleating agent dispersed in an organic solvent, removing the organic solvent, carrying out low-degree crystallization, and then carrying out injection molding in a mold. Wherein, the injection molding temperature is preferably 140 ℃ and 280 ℃, and the mold temperature is preferably 25-100 ℃.
Has the advantages that:
according to the nanofiber-reinforced absorbable bone internal fixation material provided by the invention, the thick holes are thinned by filling the hole structures among composite products through the nanofibers, so that the hole structures in the composite materials are improved, the microstructure is more compact, and the formation of harmful holes is effectively limited. The nanofiber-reinforced absorbable bone internal fixation material overcomes the characteristic of multi-scale fracture of common bone internal fixation, on one hand, the nanofiber with high elastic modulus on the surface greatly improves the mechanical property of the absorbable fixation material, and meanwhile, the nanofiber has the advantages of high porosity, strong embeddability and the like, so that the bone growth can be further promoted to enter the bone for absorption, the healing time is shortened, and the treatment effect is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an SEM micrograph of nanofibers prepared according to example 1 of the present invention;
FIG. 2 is the water contact angle of the unmodified nanofiber;
FIG. 3 is a water contact angle after nanofiber modification;
FIG. 4 is an SEM image of an unmodified composite material of comparative example 1;
FIG. 5 is an SEM image of a modified composite material of example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In this example 1, the nanofiber-reinforced absorbable bone internal fixation material is formed by compounding polyglycolide-lactide copolymer nanofibers, polyglycolide-lactide copolymer pellets, and β -tricalcium phosphate; wherein the dosage of the polyglycolide-lactide copolymer nano-fiber is 15g, the dosage of the polyglycolide-lactide copolymer granule is 65g, and the dosage of the beta-tricalcium phosphate is 20 g.
The preparation process comprises the following steps:
1. the preparation of the polyglycolide-lactide copolymer nanofiber by utilizing an electrostatic spinning technology specifically comprises the following steps: adding polyglycolide-lactide high-molecular polymer into a solvent, and performing magnetic stirring to obtain an electrostatic spinning solution; adding the prepared electrostatic spinning solution into a spray head, and carrying out electrostatic spinning to obtain polyglycolide-lactide copolymer nano-fibers;
the concentration of the electrostatic spinning solution is 20%, the magnetic stirring time is 6h, the electrostatic spinning voltage is 20kV, the advancing speed of the spinning solution is 0.5 mL/h, the receiving distance from a spinning nozzle to a roller is 20 cm, the spinning environment temperature is 25 ℃, and the ambient relative humidity is 30%.
2. Carrying out surface modification on the polyglycolide-lactide copolymer fiber prepared in the step 1, and comprising the following steps: initiating acrylic acid surface grafting polymerization on the surface of the electrostatic nanofiber by using low-temperature plasma; wherein, the modification conditions are as follows: the vacuum degree is 70Pa, the gas flow is 3L/min, the discharge power is 50-200W, and the discharge time is 10-60 s.
3. Blending the modified polyglycolide-lactide copolymer nano-fiber, the polyglycolide-lactide copolymer granules and the artificial bone material beta-tricalcium phosphate according to a proportion.
4. And (3) preparing the blended material obtained in the step (2) into a profile through an injection molding process, wherein the injection molding process comprises the following steps: uniformly mixing the blended particles with an alpha-type nucleating agent dispersed in an organic solvent, wherein the dosage of the alpha-type nucleating agent is 0.01 percent of the total amount of the blended particles, removing the organic solvent, carrying out low-degree crystallization, and then carrying out injection molding. Wherein, the injection molding temperature is preferably 160 ℃, and the mold temperature is preferably 25 ℃.
Fig. 1 is a morphology diagram of the hot glycolide-lactide copolymer nanofiber prepared in this example 1, and it can be seen from the diagram that the hot glycolide-lactide copolymer nanofiber prepared by the electrospinning method has uniform diameter distribution and smooth and regular fiber surface.
Example 2
The nanofiber reinforced absorbable bone internal fixation material is formed by compounding polylactic acid nanofibers, polyglycolide-lactide copolymer granules and beta-tricalcium phosphate artificial bone materials; wherein the dosage of the polylactic acid nano fiber is 15g, the dosage of the polyglycolide-lactide copolymer granules is 65g, and the dosage of the beta-tricalcium phosphate artificial bone material is 20 g.
The preparation process comprises the following steps:
1. the preparation of the polylactic acid nano fiber by utilizing the electrostatic spinning technology specifically comprises the following steps: adding a polylactic acid high molecular polymer into a chloroform solvent, and performing magnetic stirring to obtain an electrostatic spinning solution; adding the prepared electrostatic spinning solution into a spray head, and performing electrostatic spinning to obtain polylactic acid nano fibers;
the concentration of the electrostatic spinning solution is 20%, the magnetic stirring time is 6h, the electrostatic spinning voltage is 20kV, the advancing speed of the spinning solution is 0.5 mL/h, the receiving distance from a spinning nozzle to a roller is 20 cm, the spinning environment temperature is 25 ℃, and the ambient relative humidity is 30%.
2. Carrying out surface modification on the polyglycolide-lactide copolymer fiber prepared in the step 1, and comprising the following steps: initiating acrylic acid surface grafting polymerization on the surface of the electrostatic nanofiber by using low-temperature plasma; wherein, the modification conditions are as follows: the vacuum degree is 70Pa, the gas flow is 3L/min, the discharge power is 50-200W, and the discharge time is 10-60 s.
3. Mixing polylactic acid nanometer fiber, polyglycolide-lactide copolymer granule and beta-tricalcium phosphate artificial bone material according to a proportion.
4. And (3) preparing the blended material obtained in the step (2) into a profile through an injection molding process, wherein the injection molding process comprises the following steps: uniformly mixing the blended particles with an alpha-type nucleating agent dispersed in an organic solvent, wherein the dosage of the alpha-type nucleating agent is 0.01 percent of the total amount of the blended particles, removing the organic solvent, carrying out low-degree crystallization, and then carrying out injection molding. Wherein, the injection molding temperature is preferably 160 ℃, and the mold temperature is preferably 25 ℃.
Comparative example 1
The preparation method is the same as that of the example 1, except that: wherein the dosage of the polyglycolide-lactide copolymer nano-fiber is 5g, the dosage of the polyglycolide-lactide copolymer granule is 65g, and the dosage of the beta-tricalcium phosphate is 30 g.
Comparative example 2
The preparation method is the same as that of the example 1, except that: the polyglycolide-lactide copolymer nanofiber is not subjected to surface modification.
Examples of effects
1. The shape and appearance of the composite bone internal fixation material are as follows:
as can be seen from FIG. 1, the polyglycolide-lactide nanofibers prepared by the electrospinning method have uniform diameter distribution and smooth and regular fiber surfaces. The nanofiber is modified by the plasma technology, and a water contact angle comparison test before and after modification (fig. 2 is a water contact angle of the nanofiber under an unmodified condition, and fig. 3 is a water contact angle of the nanofiber after modification) shows that the water contact angle of the nanofiber after modification is obviously reduced, which indicates that the hydrophilicity of the surface of the nanofiber is obviously improved. Meanwhile, SEM representation is carried out on the composite material before and after modification (figure 4 is an SEM picture of the unmodified composite material in comparative example 1, and figure 5 is an SEM picture of the modified composite material in example 1), so that the microscopic surface of the modified composite material is more uniform, and the modification means is favorable for improving the acting force between the composite materials to ensure that the composite materials are uniformly mixed, thereby achieving the expected purpose.
2. The intrinsic viscosity (dL/g) and the mechanical properties of the absorbable bone fixation materials prepared in example 1 and comparative examples 1-2 were compared with the degradation time under different degradation time conditions.
TABLE 1 intrinsic viscosity (dL/g) of absorbable intraosseous fixation materials as a function of degradation time
Numbering 0 week 4 weeks For 12 weeks For 26 weeks
Example 1 1.84±0.05 1.76±0.05 1.54±0.05 1.10±0.05
Comparative example 1 1.74±0.05 1.56±0.05 1.20±0.05 0.81±0.05
Comparative example 2 1.80±0.05 1.63±0.05 1.25±0.05 0.90±0.05
TABLE 2 variation of mechanical Properties of absorbable intraosseous fixation Material with degradation time
Numbering 0 week 4 weeks For 12 weeks For 26 weeks
Example 1 >1200N >1000N >850N >650N
Comparative example 1 >900N >750N >500N >400N
Comparative example 2 >1000N >800N >550N >450N
From the above test results, it can be found from table 1 that the intrinsic viscosity of the nanofiber has a certain change under different degradation time conditions, which indicates that the nanofiber has a biodegradation performance, but the degradation rate of the intrinsic viscosity has a certain relationship with the ratio of the nanofiber to the beta-tricalcium phosphate and whether the nanofiber is modified, for example, the ratio of the beta-tricalcium phosphate is higher in comparative example 1, it can be found that the performance degradation speed of the axial extraction force is fast, and is only 400N after 26 weeks, which is lower than the clinical minimum use standard (450N), so that an appropriate ratio can be selected according to actual clinical needs.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (8)

1. The nanofiber-reinforced absorbable internal bone fixation material is characterized by being mainly formed by compounding a biodegradable high polymer material, nanofibers and an artificial bone material;
wherein the surface of the nanofiber is modified or modified; the content of the nano-fiber accounts for 10-20% of the total weight of the bone internal fixation material; the content of the biodegradable high polymer material accounts for 60-80% of the total weight of the bone internal fixation material; the artificial bone material accounts for 10-20% of the total weight of the bone internal fixation material;
the preparation method of the nanofiber reinforced absorbable bone internal fixation material comprises the following steps:
preparing nano fibers by using an electrostatic spinning technology, and performing surface modification on the nano fibers;
uniformly mixing the modified or modified nano-fibers with a biodegradable material and an artificial bone material to prepare blended particles; preparing the blended particles into a profile through an injection molding process;
the step of surface modifying the nanofibers comprises: initiating acrylic acid surface grafting polymerization on the surface of the electrostatic spinning nanofiber by using low-temperature plasma; wherein, the modification conditions are as follows: the vacuum degree is 50-70Pa, the gas flow is 1-3L/min, the discharge power is 50-200W, and the discharge time is 10-60 s.
2. The bone fixation material of claim 1, wherein the nanofibers comprise one or more of polylactic acid fibers, polyglycolide fibers, collagen fibers, polyglycolide-lactide copolymer fibers, polycaprolactone fibers, polyhydroxybutyrate fibers, polydioxanone fibers, polylactide-caprolactone copolymer fibers, lactide-hydroxybutyrate copolymer fibers, lactide-glycolide-caprolactone copolymer fibers, chitosan fibers, and cellulose nanofibers.
3. The intraosseous fixation material according to claim 1 or 2, wherein the diameter of the nanofiber is 50 to 1000 nm; the porosity of the nanofiber is 70-80%.
4. The bone fixation material of claim 1, wherein the biodegradable polymer material comprises one or more of polylactic acid, polyglycolide-lactide copolymer, polycaprolactone, polyhydroxybutyric acid, polydioxanone, polylactide-caprolactone copolymer, lactide-hydroxybutyric acid copolymer, and lactide-glycolide-caprolactone copolymer.
5. The intraosseous fixation material of claim 1, wherein the artificial bone material comprises one or more of hydroxyapatite, fluorapatite, tricalcium phosphate, carbonic apatite, calcium sulfate dihydrate, calcium sulfate hemihydrate, and calcium sulfate anhydrite.
6. The method for preparing the nanofiber reinforced absorbable bone internal fixation material as claimed in any one of claims 1 to 5, wherein the method comprises the following steps:
preparing nano fibers by using an electrostatic spinning technology, and performing surface modification on the nano fibers;
uniformly mixing the modified or modified nano-fibers with a biodegradable material and an artificial bone material to prepare blended particles;
preparing the blended particles into a profile through an injection molding process;
the step of surface modifying the nanofibers comprises: initiating acrylic acid surface grafting polymerization on the surface of the electrostatic spinning nanofiber by using low-temperature plasma; wherein, the modification conditions are as follows: the vacuum degree is 50-70Pa, the gas flow is 1-3L/min, the discharge power is 50-200W, and the discharge time is 10-60 s.
7. The method of claim 6, wherein the step of preparing the nanofibers using an electrospinning technique comprises: adding a high molecular polymer into a solvent, and magnetically stirring to obtain an electrostatic spinning solution; adding the electrostatic spinning solution into a spray head, and performing electrostatic spinning to obtain nano fibers;
the high molecular polymer is selected from one or more of polylactic acid fiber, polyglycolide fiber, collagen fiber, polyglycolide-lactide copolymer fiber, polycaprolactone fiber, polyhydroxy butyric acid fiber, poly-p-dioxanone fiber, polylactide-caprolactone copolymer fiber, lactide-hydroxybutyric acid copolymer fiber, lactide-glycolide-caprolactone copolymer fiber, chitosan fiber and cellulose nanofiber;
the solvent is one or more of chloroform, acetone, methanol, tetrahydrofuran, benzene, N-dimethylformamide and hexafluoroisopropanol;
the concentration of the electrostatic spinning solution is 10-30%, and the magnetic stirring time is not less than 6 hours; the voltage of electrostatic spinning is 10-30 kV, the advancing speed of the spinning solution is 0.3-5 mL/h, the receiving distance from a spinning nozzle to a roller is 15-30 cm, the temperature of the spinning environment is 20-45 ℃, and the relative humidity of the surrounding environment is 30-80%.
8. The method of claim 6, wherein the injection molding process comprises the steps of: uniformly mixing the blended particles with a nucleating agent dispersed in an organic solvent, removing the organic solvent, carrying out low-degree crystallization, and then carrying out injection molding in a mold; wherein the injection molding temperature is 140-280 ℃, and the mold temperature is 25-100 ℃.
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