CN106267361A - A kind of medical gradient porous composite of medicine-carried metal-polymer - Google Patents
A kind of medical gradient porous composite of medicine-carried metal-polymer Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/443—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with carbon fillers
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
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- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction
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Abstract
The present invention relates to a kind of medical gradient porous composite of medicine-carried metal-polymer, the gradient porous composite of this metal-polymer is with medical macromolecular materials as matrix, being wound around the porous material woven with medical metal wire is enhancing phase, and wherein, matrix material mark is 10 90%；The gradient porous composite of described metal-polymer is to be squeezed into matrix strengthening in phase hole, then utilizes chemical corrosion method to remove reinforced partly phase metal, forms porous surface, the gradient porous material of internal entity.Compared with prior art, material of the present invention has an excellent mechanical performance, good bone transmission and inducibility, and top layer porous layer thickness, pore size and porosity can control.Surface porous layer can be loaded into medicine as required, play prevention and infect, promote osteogenesis and the effect of healing.This preparation method has that operation is simple, low cost and other advantages.
Description
Technical field
The invention belongs to biomedical materials field, be specifically related to a kind of medical medicine-carried metal-polymer gradient porous
Composite, the material of preparation is mainly used in the aspect such as Bone Defect Repari and bone collection.
Background technology
Medical macromolecular materials have the features such as good mechanical property, chemical stability.Therefore medical macromolecular materials
Obtain clinical practice widely.But the general biological activity of medical macromolecular materials is poor, it is difficult to form bone with skeleton and melt
Close, limit its application as bone renovating material.Hole in medical material can be bone cell growth and body fluid transmission offer
The combination of passage, beneficially material and osteocyte.But porous material mechanical property is relatively low, it is not enough to apply in stress load feelings
Bone under condition is implanted.So design one had both had loose structure, there are again the medical macromolecular materials of good mechanical property
Tool is of great significance.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and a kind of medical medicine-carried gold is provided
Genus-polymer gradient is composite porous, and the loose structure of this material surface is conducive to bone cell growth and body fluid transmission, internal
Entity structure can provide intensity support so that it is mechanical property is mated with bone photo.Can be as required in this material surface porous layer
It is loaded into medicine, plays prevention and infect, promote osteogenesis and the effect of healing.This material can meet artificial joint, spinal fusion material
Material and bone support repair materials etc. and implant needs.
The purpose of the present invention can be achieved through the following technical solutions: a kind of medical medicine-carried metal-polymer gradient
It is composite porous, it is characterised in that this metal-polymer gradient is composite porous with medical macromolecular materials as matrix,
Being wound around the porous material woven with medical metal wire is enhancing phase, and wherein matrix material mark is 10-90%；Described gold
Genus-polymer gradient is composite porous is to be entered by melted matrix in the hole strengthening phase by compression casting, then profit
Remove reinforced partly phase metal with chemical corrosion method, form porous surface, the gradient porous material of internal entity.Chemical attack
Agent selects according to the chemical characteristic strengthening phase and matrix material of required removing.The thickness forming surface porous layer can basis
The concentration by control corrosion rate liquid and etching time is needed to control.Thus regulate the structure of this medical material, mechanics, physics etc.
Performance, meets the demand of different situations.
Described medical macromolecular materials are polyurethane, silicone rubber, polyester fiber, polyvinyl pyrrolidone, polyethers ether
Ketone, polymethyl methacrylate, polyvinyl alcohol, polylactic acid or polyethylene.
Described medical macromolecular materials can be added as needed on short fiber reinforced phase or particulates reinforcements.
Described short fiber reinforced is mutually selected from carbon fiber, oxide whisker or biological glass fiber, and described granule strengthens
Mutually selected from bioglass particles, tantalum powder or hydroxylapatite powder.
The tinsel that described enhancing uses mutually includes titanium silk, tantalum wire, zirconium silk or stainless steel silk, described wire diameter
For 0.05-2mm, preferably 0.1-0.5mm, strengthening phase porosity and control by being wound around braiding, porosity change scope is 10%-
90%, preferably 55-90%.
Surface porous layer and internal entity stratum proportion that described metal-polymer gradient is composite porous are passed through to control
Corrosive liquid concentration and etching time control, to regulate the composite porous structure of metal-polymer gradient and mechanical property, full
Use demand under foot different situations, surface porous layer volume fraction changes between 1-90%, preferably 5-40%.
The composite porous compressive yield strength scope of described metal-polymer gradient is 1MPa-200MPa, preferably
50-150MPa, elastic modelling quantity scope is 0.1GPa-80GPa, preferably 5-50GPa.
The composite porous contained medicine of described metal-polymer gradient includes the material of good biocompatibility, prevention
The medicine of postoperative infection, the element of promotion bone cell growth, anti-tumor drug or somatomedin；
The material of described good biocompatibility includes tantalum powder, hydroxyapatite, calcium silicates, calcium phosphate or calcium sulfate；
The medicine of described prevention of postoperative infection includes silver ion, gentamycin sulfate or vancomycin；
The described element promoting bone cell growth includes strontium, zinc, lithium, calcium.
The chemical mordant used includes Fluohydric acid., hydrochloric acid, nitric acid, sulphuric acid or chloroazotic acid.
Described medical medicine-carried metal-polymer gradient is composite porous disclosure satisfy that the overwhelming majority is to requirement of strength
Higher bone filling, bone collection, the needs of Bone Defect Repari, the most all kinds of artificial jointes, spinal fusion material, bone supports repair materials
Etc. the application of aspect.
Compared with prior art, the porous surface polyether-ether-ketone that prepared by the present invention has the advantage that
1. there is excellent mechanical property, bone transmission and self-bone grafting ability；
The most easy and simple to handle, low cost of manufacture；
3. can be controlled by control corrosion rate liquid concentration and etching time, compound to regulate metal-polymer gradient porous
The structure of material and mechanical property, it is achieved the adjustable purpose of mechanical property；
4. porous surface layer thickness, pore size and porosity can regulate as required；
5. material shape and size are easily controlled, and can need design according to implantation；
6. can meet the filling of most of bone, Bone Defect Repari, the demand of bone collection.
Accompanying drawing explanation
Fig. 1 is the gradient porous structure schematic diagram within the present invention.
Detailed description of the invention
Elaborating embodiments of the invention below, the present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following enforcement
Example.
Embodiment 1
Using the titanium silk of a diameter of 0.05mm of medical grade, be wound around and be woven into setting shape, its porosity is 90%, passes through
Melted polyether-ether-ketone is injected in the hole of POROUS TITANIUM by compression casting, then is corroded 5 minutes by the Fluohydric acid. that concentration is 10%,
Forming the gradient porous titanium-polyether-ether-ketone composite material of surface porous layer 2%, the compression yield strength of this material is 130MPa,
Elastic modelling quantity is 25GPa, it is adaptable to Bone Defect Repari and bone in the case of stress load are implanted.
Embodiment 2
Using the titanium silk of a diameter of 0.2mm of medical grade, be wound around and be woven into setting shape, its porosity is 70%, passes through
Melted polyether-ether-ketone is injected in the hole of POROUS TITANIUM by compression casting, then corrodes 15 points by the Fluohydric acid. that concentration is 10%
Clock, forms the gradient porous titanium-polyether-ether-ketone composite material of surface porous layer 10%.Surface porous layer utilize laser melting coating carry
Entering tantalum powder, tantalum has excellent biocompatibility, can be effectively improved the synosteosis ability of material.The compression yield strength of this material
For 150MPa, elastic modelling quantity is 30GPa, it is adaptable to Bone Defect Repari and bone in the case of stress load are implanted.
Embodiment 3
Using the titanium silk of a diameter of 0.4mm of medical grade, be wound around and be woven into setting shape, its porosity is 50%, passes through
Melted polyether-ether-ketone is injected in the hole of POROUS TITANIUM by compression casting, then corrodes 30 points by the Fluohydric acid. that concentration is 10%
Clock, forms the gradient porous titanium-polyether-ether-ketone composite material of surface porous layer 20%.Hydroxyapatite slurry it is loaded in surface holes
Then body solidifies, and hydroxyapatite has excellent biocompatibility, can promote that implant is firmly combined with bone formation.This material
The compression yield strength of material is 140MPa, and elastic modelling quantity is 32GPa, it is adaptable to Bone Defect Repari and bone in the case of stress load are planted
Enter.
Embodiment 4
Using the titanium silk of a diameter of 1mm of medical grade, be wound around and be woven into setting shape, its porosity is 30%, by pressure
Melted polyether-ether-ketone is injected in the hole of POROUS TITANIUM by power casting, then is corroded 60 minutes by the Fluohydric acid. that concentration is 10%,
Form the gradient porous titanium-polyether-ether-ketone composite material of surface porous layer 40%.Porous surface utilized osmosis in hole in once
Being loaded into gentamycin sulfate, gentamycin sulfate can effectively suppress staphylococcus aureus and escherichia coli etc., can be with prevention of postoperative
Infect, reduce the probability that implant surgery is failed.The compression yield strength of this material is 100MPa, and elastic modelling quantity is 22GPa, is suitable for
Bone Defect Repari and bone in the case of stress load are implanted.
Embodiment 5
Using the titanium silk of a diameter of 2mm of medical grade, be wound around and be woven into setting shape, its porosity is 20%, by pressure
Melted polyether-ether-ketone is injected in the hole of POROUS TITANIUM by power casting, then is corroded 80 minutes by the Fluohydric acid. that concentration is 15%,
Forming the gradient porous titanium-polyether-ether-ketone composite material of surface porous layer 60%, the compression yield strength of this material is 80MPa,
Elastic modelling quantity is 18GPa, it is adaptable to Bone Defect Repari and bone in the case of stress load are implanted.
Embodiment 6
Using the titanium silk of a diameter of 0.4mm of medical grade, be wound around and be woven into setting shape, its porosity is 50%, passes through
Melted polyether-ether-ketone is injected in the hole of POROUS TITANIUM by compression casting, then corrodes 120 points by the Fluohydric acid. that concentration is 20%
Clock, forms the gradient porous titanium-polyether-ether-ketone composite material of surface porous layer 100%, and the compression yield strength of this material is
20MPa, elastic modelling quantity is 3.5GPa, it is adaptable to Bone Defect Repari and bone in the case of stress load are implanted.
Embodiment 7
Using the zirconium silk of a diameter of 0.2mm of medical grade, be wound around and be woven into setting shape, its porosity is 40%, passes through
Melted polyether-ether-ketone is injected in the hole of POROUS TITANIUM by compression casting, then corrodes 30 points by the Fluohydric acid. that concentration is 20%
Clock, forms the gradient porous zirconium-polyether-ether-ketone composite material of surface porous layer 20%, and the compression yield strength of this material is
110MPa, elastic modelling quantity is 26GPa, it is adaptable to Bone Defect Repari and bone in the case of stress load are implanted.
Embodiment 8
Using the stainless steel silk of a diameter of 0.4mm of medical grade, be wound around and be woven into setting shape, its porosity is 20%,
By compression casting by the hole of liquid polylactic acid injection POROUS TITANIUM, after solidification, then it is the hcl corrosion of 30% by concentration
30 minutes, form the gradient porous rustless steel-lactic acid composite material of surface porous layer 5%, the compression yield strength of this material
For 160MPa, elastic modelling quantity is 70GPa, it is adaptable to Bone Defect Repari and bone in the case of stress load are implanted.
Embodiment 9
Using the titanium silk of a diameter of 0.2mm of medical grade, be wound around and be woven into setting shape, its porosity is 60%, passes through
Methyl methacrylate is injected in the hole of POROUS TITANIUM by compression casting, after polymerizing curable, then by hydrogen fluorine that concentration is 10%
Acid corrosion 30 minutes, forms the gradient porous titanium-composite material of polymethyl methacrylate of surface porous layer 20%, this material
Compression yield strength is 110MPa, and elastic modelling quantity is 25GPa, it is adaptable to Bone Defect Repari and bone in the case of stress load are implanted.
Embodiment 10
Using the titanium silk of a diameter of 2mm of medical grade, be wound around and be woven into setting shape, its porosity is 10%, by pressure
Methyl methacrylate is injected in the hole of POROUS TITANIUM by power casting, after polymerizing curable, then by Fluohydric acid. corruption that concentration is 5%
Losing 3 minutes, form the gradient porous titanium-composite material of polymethyl methacrylate of surface porous layer 1%, the compression of this material is bent
Taking intensity is 200MPa, and elastic modelling quantity is 80GPa, it is adaptable to Bone Defect Repari and bone in the case of stress load are implanted.
Embodiment 11
Using the stainless steel silk of a diameter of 0.05mm of medical grade, be wound around and be woven into setting shape, its porosity is 90%,
By compression casting by the hole of liquid polylactic acid injection POROUS TITANIUM, after solidification, then it is the hcl corrosion of 37% by concentration
600 minutes, forming the gradient porous rustless steel-lactic acid composite material of surface porous layer 90%, the compression yield of this material is strong
Degree is 1MPa, and elastic modelling quantity is 0.1GPa, it is adaptable to Bone Defect Repari and bone under non-stress load condition are implanted.
Claims (8)
1. medical medicine-carried metal-polymer gradient is composite porous, it is characterised in that this metal-polymer gradient
Composite porous with medical macromolecular materials as matrix, it is wound around the porous material of braiding for strengthening with medical metal wire
Phase, wherein matrix material mark is 10-90%；Described metal-polymer gradient is composite porous is to be squeezed into by matrix
Strengthen in phase hole, then utilize chemical corrosion method to remove reinforced partly phase metal, form porous surface, the ladder of internal entity
Degree porous material.
Medical medicine-carried metal-polymer gradient the most according to claim 1 is composite porous, it is characterised in that institute
The medical macromolecular materials stated are polyurethane, silicone rubber, polyester fiber, polyvinyl pyrrolidone, polyether-ether-ketone, poly-methyl-prop
E pioic acid methyl ester, polyvinyl alcohol, polylactic acid or polyethylene.
Medical medicine-carried metal-polymer gradient the most according to claim 1 is composite porous, it is characterised in that institute
The medical macromolecular materials stated can be added as needed on short fiber reinforced phase or particulates reinforcements.
Medical medicine-carried metal-polymer gradient the most according to claim 1 is composite porous, it is characterised in that institute
The short fiber reinforced stated is mutually selected from carbon fiber, oxide whisker or biological glass fiber, and described particulates reinforcements is selected from biology
Glass particle, tantalum powder or hydroxylapatite powder.
Medical medicine-carried metal-polymer gradient the most according to claim 1 is composite porous, it is characterised in that institute
The tinsel that the enhancing stated uses mutually includes titanium silk, tantalum wire, zirconium silk or stainless steel silk, and described wire diameter is 0.05-
2mm, preferably 0.08-0.5mm, strengthen phase porosity and control by being wound around braiding, and porosity change scope is 10%-90%, excellent
Select 55-90%.
Medical medicine-carried metal-polymer gradient the most according to claim 1 is composite porous, it is characterised in that institute
Surface porous layer that metal-polymer gradient of stating is composite porous and internal entity stratum proportion are by control corrosion rate liquid concentration
With etching time control, to regulate the composite porous structure of metal-polymer gradient and mechanical property, meet different situations
Under use demand, surface porous layer volume fraction changes between 0-90%, preferably 5-40%.(thickness before said divided by
Radius is bad, because the material of preparation should not be pole shape surely, that saying limits too many, or by volume fraction).
Medical medicine-carried metal-polymer gradient the most according to claim 1 is composite porous, it is characterised in that institute
The composite porous compressive yield strength scope of metal-polymer gradient of stating is 1MPa-200MPa, preferably 50-150MPa,
Elastic modelling quantity scope is 0.1GPa-80GPa, preferably 5-50GPa.
Medical medicine-carried metal-polymer gradient the most according to claim 1 is composite porous, it is characterised in that institute
The composite porous contained medicine of metal-polymer gradient stated includes the material of good biocompatibility, prevention of postoperative infection
Medicine, the element of promotion bone cell growth, anti-tumor drug or somatomedin；
The material of described good biocompatibility includes tantalum powder, hydroxyapatite, calcium silicates, calcium phosphate or calcium sulfate；
The medicine of described prevention of postoperative infection includes silver ion, gentamycin sulfate or vancomycin；
The described element promoting bone cell growth includes strontium, zinc, lithium, calcium.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107374760A (en) * | 2017-07-24 | 2017-11-24 | 芜湖微云机器人有限公司 | A kind of gradient porous planting body with medicine carrying function |
| CN109111178A (en) * | 2017-06-23 | 2019-01-01 | 高雄医学大学 | Ceramic material with active slow release effect, method for its manufacture and system comprising such ceramic material |
| CN109172865A (en) * | 2018-06-15 | 2019-01-11 | 南京市第医院 | Gradient distribution 3D printing Ti-PDA-BMP-2 bone defect repair support and preparation method thereof |
| CN109260513A (en) * | 2018-09-03 | 2019-01-25 | 南京冬尚生物科技有限公司 | A kind of 3D printing Ti-PMMA- vancomycin Anti-infective bone bracket and preparation method and application |
| CN109395158A (en) * | 2018-09-03 | 2019-03-01 | 南京市第医院 | A kind of 3D printing PCL-PMMA- vancomycin Anti-infective bone bracket and preparation method and application |
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