CN112451753B - Nanofiber-reinforced absorbable intraosseous fixation material and preparation method thereof - Google Patents
Nanofiber-reinforced absorbable intraosseous fixation material and preparation method thereof Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- fibers
- nanofiber
- bone
- fiber
- lactide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002121 nanofiber Substances 0.000 claims abstract description 88
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 51
- 230000004048 modification Effects 0.000 claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002861 polymer material Substances 0.000 claims abstract description 7
- 238000013329 compounding Methods 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 53
- 229920001577 copolymer Polymers 0.000 claims description 42
- 238000010041 electrostatic spinning Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 22
- 238000001746 injection moulding Methods 0.000 claims description 17
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 239000004626 polylactic acid Substances 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 12
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 11
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000002667 nucleating agent Substances 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 5
- 102000008186 Collagen Human genes 0.000 claims description 5
- 108010035532 Collagen Proteins 0.000 claims description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 5
- 229920000954 Polyglycolide Polymers 0.000 claims description 5
- 229920001436 collagen Polymers 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 229920002463 poly(p-dioxanone) polymer Polymers 0.000 claims description 5
- 239000000622 polydioxanone Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000001523 electrospinning Methods 0.000 claims description 4
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 3
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims description 3
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052925 anhydrite Inorganic materials 0.000 claims description 2
- 229910052586 apatite Inorganic materials 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910052587 fluorapatite Inorganic materials 0.000 claims description 2
- 229940077441 fluorapatite Drugs 0.000 claims description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 2
- 229920002988 biodegradable polymer Polymers 0.000 claims 1
- 239000004621 biodegradable polymer Substances 0.000 claims 1
- 229920000117 poly(dioxanone) Polymers 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000002980 postoperative effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000008187 granular material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000001976 improved effect Effects 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- 239000007769 metal material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L31/00—Materials 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
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L31/127—Composite 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L31/00—Materials 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
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L31/129—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing macromolecular fillers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L31/00—Materials 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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L31/00—Materials 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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/146—Porous materials, e.g. foams or sponges
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L31/00—Materials 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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
- D01D5/247—Discontinuous hollow structure or microporous structure
Landscapes
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Heart & Thoracic Surgery (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Epidemiology (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
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
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 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110114581.1A CN112451753B (en) | 2021-01-28 | 2021-01-28 | Nanofiber-reinforced absorbable intraosseous fixation material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110114581.1A CN112451753B (en) | 2021-01-28 | 2021-01-28 | Nanofiber-reinforced absorbable intraosseous fixation material and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112451753A CN112451753A (en) | 2021-03-09 |
CN112451753B true CN112451753B (en) | 2021-04-27 |
Family
ID=74802730
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110114581.1A Active CN112451753B (en) | 2021-01-28 | 2021-01-28 | Nanofiber-reinforced absorbable intraosseous fixation material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112451753B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115305582B (en) * | 2022-07-15 | 2024-05-24 | 武汉理工大学 | Preparation method and application of a neurovascularized double-sided bionic periosteum |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100471912C (en) * | 2004-04-06 | 2009-03-25 | 石宗利 | A controllable degradable absorbent bioactive composite material and its preparation method |
JP5218951B2 (en) * | 2006-05-25 | 2013-06-26 | 株式会社ビーエムジー | High strength and high modulus biodegradable bone anchoring material |
CN101209355B (en) * | 2007-12-25 | 2011-06-15 | 暨南大学 | Preparation of material for bone plate, bone peg and bone block |
BR112013000962B1 (en) * | 2010-07-14 | 2020-06-23 | The Curators Of The University Of Missouri | POLYMER COMPOSITE |
CN103877621B (en) * | 2014-04-08 | 2015-07-08 | 广东药学院 | An electrospun fiber reinforced calcium phosphate bone cement composite material and its application |
-
2021
- 2021-01-28 CN CN202110114581.1A patent/CN112451753B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN112451753A (en) | 2021-03-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Park et al. | Fabrication of strong, bioactive vascular grafts with PCL/collagen and PCL/silica bilayers for small-diameter vascular applications | |
Chen et al. | Gas foaming of electrospun poly (L-lactide-co-caprolactone)/silk fibroin nanofiber scaffolds to promote cellular infiltration and tissue regeneration | |
Abedalwafa et al. | Biodegradable poly-epsilon-caprolactone (PCL) for tissue engineering applications: A review | |
CN101781815B (en) | Preparation method of porous fiber with controllable degradation rate for tissue engineering scaffold | |
Cirillo et al. | A comparison of the performance of mono-and bi-component electrospun conduits in a rat sciatic model | |
US20210402065A1 (en) | Functionally Gradient Material for Guided Periodontal Hard and Soft Tissue Regeneration and A Preparation Method Thereof | |
Zhang et al. | Degradation of electrospun SF/P (LLA-CL) blended nanofibrous scaffolds in vitro | |
Thomas et al. | Electrospinning of Biosyn®-based tubular conduits: Structural, morphological, and mechanical characterizations | |
CN105457096A (en) | Preparation method of a kind of good biocompatibility and degradable tussah silk fibroin tissue engineering scaffold material | |
CN101773689A (en) | Surgical repairing patch | |
CN101143941A (en) | Cellulose/soybean protein composite sponge and preparation method thereof | |
CN112451753B (en) | Nanofiber-reinforced absorbable intraosseous fixation material and preparation method thereof | |
KR100953366B1 (en) | Nanofiber scaffold for tissue regeneration and preparation method thereof | |
Bhattacharyya et al. | Electrospinning of poly [bis (ethyl alanato) phosphazene] nanofibers | |
Dai et al. | Biomimetic electrospun PLLA/PPSB nanofibrous scaffold combined with human neural stem cells for spinal cord injury repair | |
CN105420848B (en) | Superfine polyglycolide fiber, preparation method and device thereof, application thereof and patch | |
Balusamy et al. | Electrospun Nanofibers for Wound Dressing and Tissue Engineering Applications | |
CN114949353B (en) | Biological function differentiated adaptive musculoskeletal system prosthesis and preparation method thereof | |
CN112675363A (en) | 3D polylactic acid scaffold for bone tissue engineering and preparation method thereof | |
CN114949343B (en) | A kind of musculoskeletal system prosthesis with controllable gradient degradation and promoting tissue repair and preparation method thereof | |
Yuan et al. | Physicochemical and in vitro degradation behaviors of fibrous membranes with different polycaprolactone and gelatin proportions | |
Wang et al. | Poly (L-lactide-co-ε-caprolactone) Nanofiber Morphology Control and Influence of Properties | |
CN108434536B (en) | Lacrimal passage repair stent and preparation method thereof | |
Paletta et al. | Influence of Poly‐(L‐Lactic Acid) Nanofiber Functionalization on Maximum Load, Young′ s Modulus, and Strain of Nanofiber Scaffolds Before and After Cultivation of Osteoblasts: An In Vitro Study | |
Grumezescu et al. | Materials for Biomedical Engineering: Biopolymer Fibers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CP01 | Change in the name or title of a patent holder |
Address after: A018, 1st floor, building 1, 25 Jinghai 2nd Road, Beijing Economic and Technological Development Zone, Beijing Patentee after: Beijing Tianxing Medical Co.,Ltd. Address before: A018, 1st floor, building 1, 25 Jinghai 2nd Road, Beijing Economic and Technological Development Zone, Beijing Patentee before: BEIJING TIANXING BOMAIDI MEDICAL EQUIPMENT Co.,Ltd. |
|
CP01 | Change in the name or title of a patent holder |