CN106421891A - Preparation method of degradable magnesium alloy and degradable polymer composite - Google Patents
Preparation method of degradable magnesium alloy and degradable polymer composite Download PDFInfo
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- CN106421891A CN106421891A CN201611001200.4A CN201611001200A CN106421891A CN 106421891 A CN106421891 A CN 106421891A CN 201611001200 A CN201611001200 A CN 201611001200A CN 106421891 A CN106421891 A CN 106421891A
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- 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
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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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
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
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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
- 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
- A61L27/58—Materials at least partially resorbable by the body
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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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Abstract
The invention provides a preparation method of a degradable magnesium alloy and degradable polymer composite. Degradable magnesium or a degradable magnesium alloy is taken as a metal substrate and processed, and three-dimensional through pores in different shapes and with different porosity are densely formed in the metal substrate adopting the degradable magnesium or the degradable magnesium alloy. The degradable magnesium or the degradable magnesium alloy is taken as a substrate material and tightly combined with a degradable polymer through the crossed through three-dimensional pores, the overall mechanical properties of the composite are far higher than those of a single degradable polymer, the composite can meet requirements of most applications such as bone filling, bone repair, bone transplantation and the like, the medical magnesium or the medical magnesium alloy is degraded in a human body fluid corrosion environment, calcium deposition and osteocyte formation can be promoted, bone healing can be accelerated, and the biological activity is improved; the composite can form porous tissue automatically in a degradation process, ingrowth of new bone tissue and propagation of osteocytes are facilitated, and rehabilitation time of bone tissue is shortened.
Description
Technical field
The present invention relates to a kind of biology medical material technical field, especially a kind of degradable magnesium alloy are polymerized with degradable
The preparation method of thing composite.
Background technology
Orthopedic implanting material has become bone collection, the indispensable material of the filling of Cranial defect and prosthesis institute at present,
Rustless steel, cochrome and titanium alloy are most popular body bone tissue substitution material at present, these Strength of Metallic Materials
High, be easy to preserve, processing technique maturation, be readily processible to the variously-shaped appearance profile to adapt to bone.Research shows, biological material
The elastic modelling quantity of material is implanted into most important for bone.As these metal implant materials are present in terms of elastic modelling quantity with people's bone
Larger difference, i.e. its elastic modelling quantity (110～220GPa) are mismatched with the modulus (10～40GPa) of people's bone, therefore biological material
Material can cause " stress shielding " phenomenon with the mismatch of people's biomechanics of bone performance, may cause osteoporosises or implantation during life-time service
The premature failure of body.Additionally, as material such as bone immobilizing material is temporarily implanted, as these metal materials cannot be dropped in human body
Solution, after osseous tissue heals, needs to take out by second operation, therefore increased patient suffering and medical expense burden.In order to
This problem is solved, needs the medical metal material of low elastic modulus is obtained, the porous of solid material can significantly reduce material
The elastic modelling quantity of material, reaches the mating on elastic modelling quantity with people's bone.
POROUS TITANIUM or titanium alloy are with people's bone very close to mechanical property is adjustable, with preferable bone in terms of elastic modelling quantity
Section's application potential, but as its elastic modelling quantity and intensity are relatively low, it is impossible to meet the bone high to mechanical property requirements and needs be implanted into,
But mainly the intensity of composite being adjusted by changing titanium silk diameter and porosity, turns to large aperture and macroporosity
During skeleton, its low intensity, the composite material strength for causing which to make is limited.
The degradable polymer mechanical property of Clinical practice is low at present, may be only available for the fracture of spongy bone and non-bearing bone
Or the interior fixation in osteotomy, clinical needs of human Cortex's bone or heavy burden bone fixation completely are not met by, therefore application model
Enclose narrow.
For the problem that above-mentioned material and clinical practice are present, we prepare on the basis of numerous studies work
The composite material of degradable magnesium alloy and degradable polymer.
Content of the invention
For the deficiencies in the prior art, the present invention provides a kind of degradable magnesium alloy and degradable polymer composite material
Preparation method.
The technical scheme is that：A kind of preparation method of degradable magnesium alloy and degradable polymer composite material,
Characterized in that, comprising the following steps：
1) using degradable metal magnesium or magnesium alloy as metal basal board, and the metal basal board of degradable magnesium or magnesium alloy is entered
Row is processed, and is covered with the hole of the three-dimensional insertion of different shape and porosity on the metal basal board for making degradable metal magnesium or magnesium alloy
Gap；
2) metal basal board for being covered with the hole that three-dimensional runs through is put in the mould of closing, is 80～250 DEG C of bars in temperature
In the hole under part running through the three-dimensional of the degradable polymer press-in degradable magnesium of melting or magnesium alloy；
3), it is 80～250 DEG C in temperature, pressure is for being kept for 0.3～15 minute under conditions of 10～150MPa, and the demoulding is cooled down
Afterwards, the polymer of the residual outside the metal basal board hole of magnesium or magnesium alloy is cut off, obtains degradable magnesium or magnesium alloy and degradable
The composite of polymer.
Described degradable magnesium or magnesium alloy are 80～250MPa with the compressive strength of the composite of degradable polymer,
10～40GPa of elastic modelling quantity, and the composite is as the rehabilitation of osseous tissue is progressively degraded under human body fluid corrosion, finally
It is absorbed by the body and excludes and be external, it is not necessary to which second operation takes out.
In technique scheme, step 2) in degradable polymer be polylactic acid (PLA), Poly-L-lactic acid (PLLA), poly-
Hydroxyacetic acid (PGA), poly- lactone (PCL), copolymer of poly lactic acid (PLGA), poly- to any one in dioxy cyclohexanone (PDO)
Plant or several mixing.
The aperture of the metal basal board of the degradable metal magnesium or magnesium alloy be 0.2～5mm, porosity be 21%～
70%.
In technique scheme, step 1) in, to gold by way of laser boring or 3D printing pore-forming or digital control hole drilling
Category substrate is processed, and obtains the metal basal board of the hole full of three-dimensional insertion.
Beneficial effects of the present invention are：
1st, using the higher degradable metal magnesium of mechanical property or magnesium alloy as matrix material, and degradable magnesium or magnesium alloy
It is closely linked by intersecting the three-dimensional cellular structure of insertion between degradable polymer, adhesion therebetween is relatively
By force, therefore its overall mechanical properties is far above single degradable polymer, can meet human Cortex's bone or heavy burden bone completely is solid
Fixed clinical needs；
2nd, due to magnesium and magnesium alloy, each degradation speed is different from polymer, under human body fluid corrosive environment medical magnesium or
Magnesium alloy is realized degraded, separates out magnesium ion, can promote the deposition of calcium and the formation of osteocyte, accelerate symphysis, increased
Biological activity, is met the clinical needs of cortical bone or heavy burden bone fixation completely, is finally absorbed by the body and excludes by polymer
In vitro, it is not necessary to which second operation takes out；
3rd, composite can also automatically form porous organization in degradation process, be conducive to growing into and bone for new bone tissue
The increment procreation of cell, shortens the rehabilitation duration of osseous tissue；
4th, the auxiliary materials such as any bonding agent or organic solvent is not used in manufacturing process, and composite is maintained inherently
Good biocompatibility, by modes such as 3D printings, metal basal board is processed so that the three-dimensional on metal basal board runs through
Porosity and shape accurately control, so as to further increase the intensity of composite.
Description of the drawings
Fig. 1 is the structural representation of the metal basal board for being covered with the hole that three-dimensional runs through of the present invention.
Specific embodiment
To combining accompanying drawing, the specific embodiment of the present invention is described further below：
As shown in figure 1, making degradable magnesium or magnesium alloy by way of laser boring or 3D printing pore-forming or digital control hole drilling
The hole for running through full of three-dimensional on metal basal board, its pore size and steric configuration can be adjustable according to demand, and regulative mode is simple,
Pore size is accurate, is pumped the polymer in hole by extrusion or injection or press moulding mode, so as to accurately control composite
Intensity, with meet diverse bone types implantation requirement.
Embodiment 1
The preparation method of a kind of degradable magnesium alloy and degradable polymer composite material, it is characterised in that including following
Step：
1), using degradable metal magnesium as metal basal board, and 3D punching process is carried out to degradable metal magnesium, makes degradable
It is covered with hole of the aperture for three-dimensional insertion that 0.3mm, porosity are 35% on magnesium metal metal basal board；
2), the metal basal board for being covered with the hole that three-dimensional runs through is put in the injection mold of closing, is 180 DEG C in temperature
Under the conditions of by melting degradable polymer polylactic acid (PLA) by injection molding manner press-in degradable magnesium metal basal board three-dimensional
In the hole for running through；
3), it is 180 DEG C in temperature, pressure cuts off metal for placing 3～10 minutes under conditions of 20MPa after demoulding cooling
Polylactic acid (PLA) outside magnesio plate hole, obtains the composite of degradable metal magnesium and degradable polymer.
The compressive strength of the degradable metal magnesium that the present embodiment is obtained and the composite of degradable polymer up to
100MPa, elastic modelling quantity 25GPa.
Embodiment 2
A kind of preparation method of degradable magnesium alloy and the composite of degradable high polymer, it is characterised in that include with
Lower step：
1), using degradable magnesium alloy Mg-0.5Zr-1Ca as metal basal board, and degradable magnesium alloy is processed, makes
It is covered with hole of the aperture for three-dimensional insertion that 0.35mm, porosity are 45% on the metal basal board of degradable magnesium alloy；
2), the metal basal board for being covered with the degradable magnesium alloy Mg-0.5Zr-1Ca of the hole that three-dimensional runs through is put into closing
Injection mold in, under the conditions of temperature is 240 DEG C by melting degradable polymer polyglycolic acid (PGA) pass through extruding side
In the hole that the three-dimensional of the metal basal board of formula press-in degradable magnesium alloy Mg-0.5Zr-1Ca runs through；
3), it is 240 DEG C in temperature, pressure after demoulding cooling, is cut off magnesium and closes for placing 3～10 minutes under conditions of 20MPa
Polymer poly hydroxyacetic acid (PGA) outside auri plate hole, obtains the composite of degradable magnesium alloy and degradable polymer.
The compressive strength of the degradable magnesium alloy that the present embodiment is obtained and the composite of degradable polymer is 130MPa,
Elastic modelling quantity is 30GPa.
Embodiment 3
The preparation method of a kind of degradable magnesium alloy and degradable polymer composite material, it is characterised in that including following
Step：
1), using degradable magnesium alloy Mg-1Mn-2Zn-1Nd alloy as metal basal board, and degradable magnesium alloy is carried out
3D punching is processed, make to be covered with the metal basal board of degradable magnesium alloy aperture be 0.2mm, porosity be 21% three-dimensional insertion
Hole；
2), the metal basal board for being covered with the hole that three-dimensional runs through is put in the injection molding of closing, is 200 DEG C in temperature
Under the conditions of will melting degradable polymer Poly-L-lactic acid (PLLA), by injection system be pressed into degradable magnesium alloy three-dimensional
In the hole for running through；
3), it is 200 DEG C in temperature, 100MPa pressure is placed 0.3～1 minute under conditions of being, after demoulding cooling, cuts off magnesium
Polymer Poly-L-lactic acid (PLLA) outside alloy-based plate hole, obtains the composite wood of degradable magnesium alloy and degradable polymer
Material.
The compressive strength of the degradable magnesium alloy that the present embodiment is obtained and the composite of degradable polymer is 220MPa,
Elastic modelling quantity is 40GPa.
Embodiment 4
A kind of preparation method of degradable magnesium alloy and the composite of degradable high polymer, it is characterised in that include with
Lower step：
1), using degradable magnesium alloy as metal basal board, and degradable magnesium alloy is processed, makes degradable magnesium alloy
Metal basal board on be covered with hole of the aperture for three-dimensional insertion that 0.5mm, porosity are 55%；
2), the metal basal board for being covered with the hole that three-dimensional runs through is put in the injection mold of closing, is 80 DEG C in temperature
Under the conditions of will melting degradable polymer copolymer of poly lactic acid (PLGA), by injection molding manner be pressed into degradable magnesium alloy three
In the hole that dimension runs through；
3), it is 80 DEG C in temperature, pressure cuts off metal for placing 3～10 minutes under conditions of 10MPa after demoulding cooling
Excess polymer outside substrate aperture, just forms the composite of the degradable magnesium alloy and degradable polymer.
The compressive strength of the degradable magnesium alloy that the present embodiment is obtained and the composite of degradable polymer is 85MPa,
Elastic modelling quantity is 10GPa.
Merely illustrating the principles of the invention described in above-described embodiment and description and most preferred embodiment, without departing from this
On the premise of spirit and scope, the present invention also has various changes and modifications, and these changes and improvements both fall within requirement and protect
In the scope of the invention of shield.
Claims (5)
1. the preparation method of a kind of degradable magnesium alloy and degradable polymer composite material, it is characterised in that including following step
Suddenly：
1) using degradable metal magnesium or magnesium alloy as at metal basal board, and the metal basal board to degradable magnesium or magnesium alloy
Reason, is covered with the hole of the three-dimensional insertion of different shape and porosity on the metal basal board for making degradable metal magnesium or magnesium alloy；
2) metal basal board for being covered with the hole that three-dimensional runs through is put in the mould of closing, under the conditions of temperature is 80～250 DEG C
In the hole that the three-dimensional of the degradable polymer press-in degradable magnesium of melting or magnesium alloy is run through；
3), it is 80～250 DEG C in temperature, pressure is holding 0.3～15 minute under conditions of 10～150MPa, after demoulding cooling,
The polymer of the residual outside the metal basal board hole of magnesium or magnesium alloy is cut off, is obtained degradable magnesium or magnesium alloy is polymerized with degradable
The composite of thing.
2. the preparation method of a kind of degradable magnesium alloy according to claim 1 and degradable polymer composite material, its
It is characterised by：The compressive strength of described degradable magnesium or magnesium alloy and the composite of degradable polymer is 80～
250MPa, elastic modelling quantity is 10～40GPa.
3. the preparation method of a kind of degradable magnesium alloy according to claim 1 and degradable polymer composite material, its
It is characterised by：Step 2) in degradable polymer be polylactic acid (PLA), Poly-L-lactic acid (PLLA), polyglycolic acid (PGA),
Poly- lactone (PCL), copolymer of poly lactic acid (PLGA), poly- to any one or a few the mixing in dioxy cyclohexanone (PDO).
4. the preparation method of a kind of degradable magnesium alloy according to claim 1 and degradable polymer composite material, its
It is characterised by：The aperture of the metal basal board of the degradable metal magnesium or magnesium alloy be 0.2～5mm, porosity be 21%～
70%.
5. the preparation method of a kind of degradable magnesium alloy according to claim 1 and degradable polymer composite material, its
It is characterised by：Step 1) in, by way of laser boring or 3D printing pore-forming or digital control hole drilling, metal basal board is processed,
Obtain the metal basal board of the hole full of three-dimensional insertion.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611001200.4A CN106421891A (en) | 2016-11-14 | 2016-11-14 | Preparation method of degradable magnesium alloy and degradable polymer composite |
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| CN201611001200.4A CN106421891A (en) | 2016-11-14 | 2016-11-14 | Preparation method of degradable magnesium alloy and degradable polymer composite |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108478881A (en) * | 2018-03-22 | 2018-09-04 | 西安交通大学 | A kind of 3D printing method of magnesium alloy-polymer composite degradable biological support |
| CN110025409A (en) * | 2019-04-17 | 2019-07-19 | 东南大学 | A kind of elastic Invasive lumbar fusion device and preparation method thereof of magnesium powder function enhancing high molecular material porous structure |
| CN110665067A (en) * | 2018-07-03 | 2020-01-10 | 中南大学 | Magnesium/polylactic acid composite bone scaffold and preparation method thereof |
| CN111068106A (en) * | 2019-11-27 | 2020-04-28 | 东南大学 | Medical degradable antibacterial composite material and preparation method and application thereof |
| CN115501386A (en) * | 2022-09-28 | 2022-12-23 | 北京科技大学 | Full-degradable high-toughness bionic gradient composite material and additive manufacturing method thereof |
| CN115591015A (en) * | 2022-10-25 | 2023-01-13 | 季华实验室（Cn） | Degradable metal/polymer composite bone fracture plate and preparation method thereof |
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| CN101455862A (en) * | 2007-12-12 | 2009-06-17 | 中国科学院金属研究所 | Preparation method of polyporous material for biological medicine tissue engineering scaffold |
| CN102908672A (en) * | 2012-10-30 | 2013-02-06 | 东南大学 | High-strength absorbable magnesium substrate composite orthopedic fixing device and preparation method thereof |
-
2016
- 2016-11-14 CN CN201611001200.4A patent/CN106421891A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101455862A (en) * | 2007-12-12 | 2009-06-17 | 中国科学院金属研究所 | Preparation method of polyporous material for biological medicine tissue engineering scaffold |
| CN102908672A (en) * | 2012-10-30 | 2013-02-06 | 东南大学 | High-strength absorbable magnesium substrate composite orthopedic fixing device and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108478881A (en) * | 2018-03-22 | 2018-09-04 | 西安交通大学 | A kind of 3D printing method of magnesium alloy-polymer composite degradable biological support |
| CN110665067A (en) * | 2018-07-03 | 2020-01-10 | 中南大学 | Magnesium/polylactic acid composite bone scaffold and preparation method thereof |
| CN110025409A (en) * | 2019-04-17 | 2019-07-19 | 东南大学 | A kind of elastic Invasive lumbar fusion device and preparation method thereof of magnesium powder function enhancing high molecular material porous structure |
| CN111068106A (en) * | 2019-11-27 | 2020-04-28 | 东南大学 | Medical degradable antibacterial composite material and preparation method and application thereof |
| CN115501386A (en) * | 2022-09-28 | 2022-12-23 | 北京科技大学 | Full-degradable high-toughness bionic gradient composite material and additive manufacturing method thereof |
| CN115591015A (en) * | 2022-10-25 | 2023-01-13 | 季华实验室（Cn） | Degradable metal/polymer composite bone fracture plate and preparation method thereof |
| CN115591015B (en) * | 2022-10-25 | 2024-01-26 | 季华实验室 | Degradable metal/polymer composite bone fracture plate and preparation method thereof |
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