CN100381182C - Biomedical degradation-absorption-controllable macromolecule metal composite implantation material and use thereof - Google Patents
Biomedical degradation-absorption-controllable macromolecule metal composite implantation material and use thereof Download PDFInfo
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- CN100381182C CN100381182C CNB2005100470934A CN200510047093A CN100381182C CN 100381182 C CN100381182 C CN 100381182C CN B2005100470934 A CNB2005100470934 A CN B2005100470934A CN 200510047093 A CN200510047093 A CN 200510047093A CN 100381182 C CN100381182 C CN 100381182C
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Abstract
The invention discloses a biological medical planting material and composite material and application of controllable decomposable macromolecular metal, which is characterized by the following: adopting decomposable macromolecular material as base and pure magnenium and alloy with bulk percentage at 5-50% from board, rod, pipe, filament, whisker and porous material as reinforcer, improving dynamical property in the composite material, controlling decomposing period effectively.
Description
Technical field
The present invention relates to bio-medical composition and metal implant material, specifically biomedical degradation-absorption-controllable macromolecule metal composite implantation material and application thereof.
Background technology
After many medical embedded devices (as angiocarpy bracket, nail and blade plate etc.) are completed the term of service, can not stay in the body for a long time, need operation once more to take out.The degradable medical material can progressively be degraded under the physiological environment in vivo and be absorbed metabolism by body, thereby is more suitable in implant into body.Being used for clinical biodegradation material at present mainly is macromolecular material, just like collagen protein, polylactic acid etc., with the commercializations such as spicule, medicine sustained release carrier and support of their making.
Biodegradable polymer material finds to exist many problems through clinical application for many years
[1-3]: (1) intensity is low, and hardness and rigidity are low; (2) degraded poor controllability, degradation time and intensity, rigidity do not match, thus intensity decreases makes the device premature failure soon in the degradation process; (3) local acid degradation product gathers and causes non-special inflammatory, the influence healing; (4) gamma-rays or go back oxidative ethane (EO) sterilization and disinfecting process in, the mechanical property reduction; (5) processing stability and storage stability are poor.Therefore improve the shortcoming of existing degradation material, or development novel degradable absorbing material, for the demand that satisfies clinical practice and patient, and the development of biomaterial etc. is all significant.
The corrosion resisting property of magnesium and magnesium alloy is relatively poor, and the normal potential of pure magnesium is-2.37V especially to contain Cl
-All the more so in the ionic Human Physiology environment, pure magnesium commonly used and magnesium alloy are in simulated body fluid, the corrosion degradation rate can reach 0.1-5mm/year, the alloy element of the corrosion rate of pure magnesium and magnesium alloy and material itself, microstructure (grain size, precipitate etc.), factors such as impurity content, machining state and apparent condition are closely related, therefore pure magnesium and magnesium alloy can be used to develop controlled etching degradation biological medical metal embedded material.
Degradable high polymer material has good biology performance, and pure magnesium and magnesium alloy have excellent mechanical property as degradable absorbing material contrast degradable high polymer material, therefore utilize the mechanical property of degradable magnesium and magnesium alloy and the good biocompatibility of degradable high polymer material, the development degradable absorbs macromolecule metal composite implantation material will have great advantage.
Summary of the invention
The purpose of this invention is to provide biological medical polymer metal composite implantation material and application thereof that a kind of controlled degradation absorbs, make it in the corrosion degradation process, degradation rate and implant devices active time are complementary, and guarantee implant devices good mechanical performance and biology performance during one's term of military service simultaneously.
For achieving the above object, the technical solution used in the present invention is:
The biomedical degradation-absorption-controllable macromolecule metal composite implantation material, with the degradable high polymer material is matrix, pure magnesium or magnesium alloy materials are as filler and strengthen body, pure magnesium and magnesium alloy can adopt plate, pipe, silk, rod, bits, whisker and porous state etc., metal strengthens the volume ratio of body and can adjust between 5% to 50% as required, improve the mechanical property of composite integral body in the degradation process by the intensity of adjusting pure magnesium and magnesium alloy, by the degradation cycle of adjustment degradable high polymer material and the corrosion rate of pure magnesium and magnesium alloy, reach the purpose of controlled degradation.
Described pure magnesium is medical pure magnesium or high-purity magnesium; Magnesium alloy is, the alloy system that magnalium series alloy, magnesium manganese series alloy, magnesium zinc series alloy, magnesium zirconium series alloy, magnesium rare earth metal alloy, magnesium lithium series alloy, magnesium calcium series alloy or magnesium silver series alloy etc. are different a kind of or the ternary system and the polynary system magnesium alloy that are formed by these system combinations.
The content of alloying element should satisfy the requirement of bio-medical basically in the above-mentioned magnesium alloy, makes its degradation amount in degradation process should be in not causing the dosage range of tissue toxicity reaction; Related pure magnesium and magnesium alloy mainly comprise: pure magnesium (weight content is more than 99%), magnalium series (mainly comprises Mg-Al-Zn except that binary system, Mg-Al-Mn, Mg-Al-Si, four ternary systems of Mg-Al-RE and other multicomponent systems, alloy representative such as AZ31, AZ61, AM60, AM50, AE21, AS21 etc., wherein the aluminum weight content requires less than 10%, Zn, Mn, Si and/or RE weight content content are less than 5%), magnesium manganese series (mainly is binary Mg-0.1～2.5%Mn and adds a small amount of rare earth, calcium, ternary system that zinc etc. are elementary composition or polynary system, represent alloy such as domestic trade mark MB1 and MB8), magnesium zinc series (mainly comprises Mg-Zn-Zr and Mg-Zn-Cu series except that binary system, alloy representative such as ZK21, ZK60, ZC62 etc.), magnesium zirconium series (mainly is binary Mg-0.1～1%Zr and adds a small amount of rare earth, ternary system that zinc etc. are elementary composition or polynary system, represent alloy such as K1A etc.), the magnesium rare earth metal (mainly is binary Mg-0.1～5%RE and interpolation small amount of aluminum, zirconium, calcium, ternary system that zinc etc. are elementary composition or polynary system,), magnesium lithium series (mainly is binary Mg-1～15%Li and interpolation small amount of aluminum, rare earth, ternary system that zinc and silicon etc. are elementary composition or polynary system, represent alloy such as LA91, LAZ933 etc.), magnesium calcium series (mainly is binary Mg-0.1～3%Ca and adds a small amount of rare earth, zirconium, ternary system that zinc etc. are elementary composition or polynary system), magnesium silver series (mainly is binary Mg-0.1～12%Ag and adds a small amount of rare earth, zirconium, ternary system that zinc etc. are elementary composition or polynary system are represented alloy such as QE22 etc.) etc. different alloy system a kind of or the ternary system and the polynary system magnesium alloy that form by these system combinations.For pure magnesium and magnesium alloy, its corrosion degradation rate can be by changing the composition of material itself, and conditions such as crystallite dimension and condition of heat treatment are controlled at 0.01-5mm/year.
Degradable high polymer material involved in the present invention can be selected the biodegradation material that is usually used at present clinically for use, mainly comprise collagen protein, gelatin, natural degradable macromolecular material and polylactide (polylactic acid such as chitin, PLA), poly-Acetic acid, hydroxy-, bimol. cyclic ester (polyglycolic acid, PGA), polybutylcyanoacrylate (PACA), polycaprolactone (PCL), poly-anhydride (comprises the aliphatic poly anhydride, fragrance adoption anhydride, heterocycle adoption anhydride, the poly-anhydride of polyamides anhydride and crosslinkable etc.), copolymer between synthesized degradable such as poe and/or polyphosphazene macromolecular material and the above-mentioned polymer etc.The research of above-mentioned degradable high polymer material is very ripe, with the part commercializations such as spicule, medicine sustained release carrier and support that their are made, its degradation rate in body fluid and simulated body fluid can be controlled at easily from a week by several years.
Controlled degradation organism-absorbing medical high polymer metal composite implantation material of the present invention can be used for the temporary transient or short-term medical bio implant devices of preparation, as internal fixation blade plate and nail and tissue engineering rack material etc.
The present invention has following advantage:
1. specific strength and specific rigidity height.Degradable high polymer material after the enhancing of magnesium metal alloy, has improved the intensity of integral material relatively; Not matching of degradation time and intensity takes place in degradable high polymer material easily in degradation process, premature loss intensity, and degradable absorb composite material of the present invention is in the degradation process process, the magnesium metal alloy material that strengthens usefulness can be adjusted intensity etc. as required, makes the interim under arms effective maintenance good mechanical performance of whole composite.Pure magnesium and magnesium alloy materials have the elastic modelling quantity approaching with people's bone simultaneously, if the devices relevant with skeleton such as making bone fixture can be avoided the stress barrier effectively, are very beneficial for symphysis.
2. degradation rate is easily controlled.The advantage of the abundant combination of the present invention and the performance pure magnesium of degradable and magnesium alloy and degradable macromolecule, can solve the fast problem of intensity decreases in the low and degradation process of degradable high polymer material intensity, utilize the easy control of degradable high polymer material degradation rate simultaneously, and pure magnesium and magnesium alloy materials excellent mechanical property and high corrosion rate, by the mechanical property of magnesium metal material and the degradation cycle of corrosion rate and degradable macromolecule matrix material, can obtain to satisfy the pure magnesium of biological medical degradable and the magnesium alloy materials of different clinical demands.
3. safe, practical property is good.Pure magnesium and magnesium alloy have many advantages as embedded material: 1. magnesium resource is abundant, low, the wide material sources of relative cost; 2. the density of magnesium and magnesium alloy is 1.74g/cm
3About, with the Compact bone density (1.75g/cm of people's bone
3) very approaching; 3. magnesium and magnesium alloy have high specific strength and specific stiffness; 4. the Young's modulus of elasticity of magnesium and magnesium alloy is about 45GP, about the elastic modelling quantity 20GPa near people's bone, can avoid stress-shielding effect as implant; 5. magnesium is the macroelement that is only second to calcium, sodium and potassium in the human body, and everyone the daily requirement amount of being grown up is greater than 350mg, and it participates in a series of metabolic processes in the body.Finally be corroded under the physiological environment in vivo degraded and absorbed or metabolism of degradable magnesium and magnesium alloy by body, its catabolite mainly is the magnesium ion of needed by human body, magnesium is the needed by human body macroelement, contained other alloying element contents are all within the bio-medical scope, selected degradable high polymer material also is commonly used clinically at present, therefore it is safe that the macromolecule metal composite implantation material after adopting the present invention to handle prepares the medical embedded device of controlled degradation, has very big advantage and application prospect.
The specific embodiment
Embodiment 1:
Adopt 99.95% pure magnesium filament some (after polishing, the silk footpath is at 0.5mm), ultrasonic cleaning 5 minutes in acetone, ethanol respectively, at the vacuum drying oven inner drying, put into the model of customization then, add molten state polylactic acid (PLA), the shared volume ratio of pure magnesium silk is about 30%, the cooling post-treatment becomes specimen (30mm * 20mm * 3mm), be immersed in by corroding degraded fully in the simulation plasma solutions of table 1 preparation after about 6 months.
Because the corrosion rate of pure magnesium material can be adjusted by factors such as impurity content and crystallite dimension and heat treatments, the degradation rate of polylactic acid also can be controlled according to the molecular weight of polylactic acid and the thickness of coating, so can be optimized adjustment from pure magnesium and polylactic acid two aspects according to the degradation rate of the pure magnesium lactic acid composite material of medical controlled degradation that passes through above prepared.
Table 1: artificial blood plasma is formed
| Chemical compound | NaCl | CaCl 2 | KCl | MgSO4 | NaHCO 3 | Na 2HPO 4 | NaH 2PO 4 |
| Concentration, mg/L | 6800 | 200 | 400 | 100 | 2200 | 126 | 26 |
Embodiment 2
With 12 of as cast condition AZ31B magnesium alloy 2mm rods after polishing, ultrasonic cleaning 5 minutes in acetone, ethanol respectively, at the vacuum drying oven inner drying, make composite with polyglycolic acid (PGA) then, AZ31B magnesium alloy bar proportion about 30%, make test sample (40mm * 30mm * 6mm), be immersed in the 0.9%NaCl solution and after about 9 months, corrode degraded fully.
Because the corrosion rate of AZ31B magnesium alloy materials can be adjusted by factors such as impurity content and crystallite dimension and heat treatments, the degradation rate of polyglycolic acid also can be controlled according to the thickness of molecular weight and coating, thus according to can be through the degradation rate of the medical controlled degradation magnesium alloy materials of above prepared from alloy substrate and surperficial polyglycolic acid two aspects and ratio be optimized adjustment.
Embodiment 3
High-purity magnesium (99.99%) is considered to be worth doing, ultrasonic cleaning 5 minutes in acetone, ethanol respectively, at the vacuum drying oven inner drying, compound with the copolymer (PLGA) of polylactic acid and polyglycolic acid then, the magnesium chips ratio is about 40%, make test sample (35mm * 20mm * 3mm), be immersed in the 0.9%NaCl solution and after about 4 months, corrode degraded fully.
Because the corrosion rate of pure magnesium material can be adjusted by factors such as impurity content and crystallite dimension and heat treatments, the degradation rate of the copolymer of polylactic acid and polyglycolic acid also can be controlled according to the thickness of the two proportioning and coating, so according to being optimized adjustment from alloy substrate and surperficial polylactic acid and polyglycolic acid two aspects through the degradation rate of the medical controlled degradation magnesium alloy materials of above prepared.
Embodiment 4
With 5 of AM60 magnesium alloy sheets (1mm thick * 5mm is wide), ultrasonic cleaning 5 minutes in acetone, ethanol respectively, at the vacuum drying oven inner drying, compound with polylactic acid molten state liquid then, the magnesium alloy ratio is about 20%, suitable mould is put in the material taking-up cooled off, and the demoulding is after the finishing use, make test sample (40mm * 30mm * 4mm), be immersed in by after about 7 months, corroding degraded fully in the simulation plasma solutions of table 1 preparation.
Because the corrosion rate of AM60 magnesium alloy materials can be adjusted by factors such as impurity content and crystallite dimension and heat treatments, the degradation rate of polylactic acid also can be controlled according to the thickness of molecular weight and coating, so can be optimized adjustment from alloy substrate and surperficial polylactic acid two aspects according to the degradation rate of the medical controlled degradation magnesium alloy materials that passes through above prepared.
Embodiment 5
With ZK60 magnesium alloy plate (45mm * 10mm * 3mm) polishing after laser boring (porosity is 50%), ultrasonic cleaning 5 minutes in acetone, ethanol respectively, then and polycaprolactone (PCL) compound, the magnesium alloy ratio is about 45%, make test sample (50mm * 25mm * 8mm), be immersed in the 0.9%NaCl solution and after about 10 months, corrode degraded fully.
Because the corrosion rate of ZK60 magnesium alloy materials can be adjusted by factors such as impurity content and crystallite dimension and heat treatments, the degradation rate of polycaprolactone also can be controlled according to the thickness of molecular weight and coating, so can be optimized adjustment from alloy substrate and surperficial polycaprolactone two aspects according to the degradation rate of the medical controlled degradation magnesium alloy materials that passes through above prepared.
Embodiment 6
Difference from Example 5 is:
Magnesium alloy is MB1 rod ( 3mm), and degradable high polymer material is a collagen protein, and the magnesium alloy ratio is about 30%.
Embodiment 7
Difference from Example 5 is:
Magnesium alloy is K1A plate (0.8mm thick * 4mm is wide), and degradable high polymer material is isopyknic gelatin and chitin, and the magnesium alloy ratio is about 20%.
Embodiment 8
Difference from Example 5 is:
Magnesium alloy is as cast condition LA91 bits, and degradable high polymer material is a poe, and the magnesium alloy ratio is 50%.
Embodiment 9
Difference from Example 5 is:
Magnesium alloy is QE22 plate (1.2mm thick * 5mm is wide), and degradable high polymer material is a polybutylcyanoacrylate, and the magnesium alloy ratio is about 30%.
Claims (7)
1. biomedical degradation-absorption-controllable macromolecule metal composite implantation material is characterized in that: be matrix with the degradable high polymer material, it is built-in with magnesium alloy materials as strengthening body, and the percent by volume of magnesium alloy materials is 5～50%;
One of adopt in plate, pipe, silk, rod, bits, whisker and the porous material or their combination as the magnesium alloy of the built-in enhancing body of composite.
2. according to the described biomedical degradation-absorption-controllable macromolecule metal composite implantation material of claim 1, it is characterized in that: described magnesium alloy is a kind of of magnalium, magnesium-manganese alloy, magnesium-zinc alloy, magnesium zircaloy, magnesium-rare earth alloy, magnesium lithium alloy, magnesium calcium alloy, magnesium silver alloy or the ternary system or the polynary system magnesium alloy that are formed by these system combinations.
3. according to the described biomedical degradation-absorption-controllable macromolecule metal composite implantation material of claim 1, it is characterized in that: the weight content of aluminum＜10% in the described magnesium alloy, the weight content of Zn, Mn, Si or Re＜5%, the weight content of Zr≤1%, the weight content of Li≤15%, the weight content of Ca≤3%, the weight content of Ag≤12%.
4. according to the described biomedical degradation-absorption-controllable macromolecule metal composite implantation material of claim 1, it is characterized in that: described degradable high polymer material is: the natural degradable macromolecular material, or polylactide, poly-Acetic acid, hydroxy-, bimol. cyclic ester, polybutylcyanoacrylate, polycaprolactone, poly-anhydride, poe and/or these synthesized degradable macromolecular materials of polyphosphazene, or the copolymer between the above-mentioned polymer.
5. according to the described biomedical degradation-absorption-controllable macromolecule metal composite implantation material of claim 4, it is characterized in that: described natural degradable macromolecular material is collagen protein, gelatin and/or chitin; Poly-anhydride is the poly-anhydride of aliphatic poly anhydride, fragrant adoption anhydride, heterocycle adoption anhydride, polyamides anhydride or crosslinkable.
6. the application of the described biomedical degradation-absorption-controllable macromolecule metal composite implantation material of claim 1 is characterized in that: the high-molecule metal composite is used for the temporary transient or short-term bio-medical implant devices of preparation.
7. according to the application of the described biomedical degradation-absorption-controllable macromolecule metal composite implantation material of claim 6, it is characterized in that: described implant devices is an internal fixation with blade plate, internal fixation with nail or used in tissue engineering support.
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| CN115591015B (en) * | 2022-10-25 | 2024-01-26 | 季华实验室 | Degradable metal/polymer composite bone fracture plate and preparation method thereof |
| CN115671399B (en) * | 2022-11-22 | 2024-01-30 | 同光(昆山)生物科技有限公司 | Medical magnesium-containing implant with double protective layers and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020120348A1 (en) * | 2000-12-21 | 2002-08-29 | Melican Mora Carolynne | Reinforced tissue implants and methods of manufacture and use |
| CN1141980C (en) * | 2002-05-10 | 2004-03-17 | 清华大学 | Nano carbon tube reinforced high-molecular composition for repairing bone |
-
2005
- 2005-08-26 CN CNB2005100470934A patent/CN100381182C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020120348A1 (en) * | 2000-12-21 | 2002-08-29 | Melican Mora Carolynne | Reinforced tissue implants and methods of manufacture and use |
| CN1141980C (en) * | 2002-05-10 | 2004-03-17 | 清华大学 | Nano carbon tube reinforced high-molecular composition for repairing bone |
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