CN111068106A - Medical degradable antibacterial composite material and preparation method and application thereof - Google Patents

Medical degradable antibacterial composite material and preparation method and application thereof Download PDF

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CN111068106A
CN111068106A CN201911181729.2A CN201911181729A CN111068106A CN 111068106 A CN111068106 A CN 111068106A CN 201911181729 A CN201911181729 A CN 201911181729A CN 111068106 A CN111068106 A CN 111068106A
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composite material
magnesium alloy
alloy
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白晶
张越
薛烽
程兆俊
周健
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Southeast University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
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    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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Abstract

The invention discloses a medical degradable antibacterial composite material and a preparation method and application thereof, the composite material takes a porous magnesium alloy (6) with a through hole as a reinforcement, a hole (1) of the reinforcement is filled with degradable high polymer materials of polycaprolactone and polylactic acid, and nano magnesium oxide powder is uniformly dispersed in the degradable high polymer materials. The preparation steps of the composite material are as follows: 1) preparing a porous magnesium alloy (6) reinforcement; 2) blending the nano magnesium oxide powder, polylactic acid and polycaprolactone and then molding into a polymer sheet (5); 3) and (3) placing the polymer sheet (5) above the porous magnesium alloy (6), and extruding and solidifying to obtain the magnesium alloy. The material has good biocompatibility, safe, stable and controllable degradation and good mechanical property, has an antibacterial function, is suitable for small orthopedic repair products in various shapes, can be used as a new generation of degradable material, and is used in the medical implantation fields of bone trauma surgery, bone defect repair surgery, plastic cosmetology and the like.

Description

Medical degradable antibacterial composite material and preparation method and application thereof
Technical Field
The invention relates to a medical degradable antibacterial composite material and a preparation method and application thereof, belonging to the field of orthopedic medical instruments, in particular to the field of medical instruments for bone trauma surgery, bone defect repair surgery and plastic cosmetology.
Background
The bone repair technology is a conventional means of bone trauma surgery, bone defect repair surgery and plastic cosmetology, is currently and most commonly made of pure titanium or titanium alloy clinically, provides good conditions for bone tissue healing due to stable repair effect and superior biocompatibility, but has the following problems: (1) the elastic modulus of titanium metal is 8 times of that of cortical bone, and stress shielding effect exists on normal bone tissues, so that osteoporosis and secondary fracture are easily caused; (2) can not be degraded and absorbed, needs to be taken out after a secondary operation, and causes secondary damage.
In recent years, the absorbable polymer materials gradually applied to clinical use partially overcome the defects, and the absorbable polymer materials applied to bone surgery are mainly absorbable polyester materials, monomers of which are mainly lactic acid and glycolic acid, and polylactide and polyglycolide are formed through polycondensation. However, the strength of the polymer material is insufficient compared to the metal material. If the absorbable polymer plate is fixed at the fracture end with larger stress, the fixing force is weakened along with the degradation of the absorbable plate, and secondary fracture may be caused. Secondly, the degradation products of the absorbable polymer plate are acidic, namely, the fracture area is always in a low pH value state during the degradation period of the absorbable polymer plate, and the environment is easy to cause local inflammatory reaction and influence the activity of osteoblasts. Thirdly, the absorbable plate does not block X-rays, which causes certain inconvenience for postoperative curative effect observation. In addition, polylactic acid materials degrade too quickly in vivo and, although they have good compressive properties, they are a great disadvantage of polylactic acid materials themselves because they are essentially non-tough.
Therefore, it is important to find a suitable absorbable biomaterial with high strength and low elastic modulus for orthopedic repair. The magnesium and the alloy thereof have excellent mechanical property and degradability. The material has good mechanical compatibility, the elastic modulus is about 41-45 GPa, and the material is closer to human bones than titanium metal; the density of the powder is 1.7 to 1.9g/cm3Left and right, the density is similar to the density of compact bone of human bone; the specific strength and specific stiffness of the material are high, and the tensile strength can be improved to more than 400MPa through proper alloying, cold-hot plastic deformation and heat treatment, so that the mechanical strength requirement of a bone repair material is met; is harmless to human body and has good biocompatibility. However, the magnesium alloy has poor corrosion resistance, the biodegradation speed in a human body is too high, the corrosion is often serious before the fracture is fixed and healed completely and is not stable, the mechanical strength is greatly reduced due to the too high corrosion degradation speed, and the bone dissolving phenomenon is caused by the rapidly released magnesium metal ions in a large amount. Although there are some current reports on the improvement of corrosion resistance by surface modification treatment, the effect is not ideal.
The invention content is as follows:
the technical problem is as follows: the invention aims to provide a medical degradable antibacterial composite material, a preparation method and application thereof, overcomes the defects of a bone repair device made of a pure medical titanium alloy, a pure magnesium alloy or a pure absorbable polylactic acid material, and has good application prospects in bone trauma surgery, bone defect repair surgery, plastic cosmetology and particularly high-stress fracture section internal fixation.
The technical scheme is as follows: the invention provides a medical degradable antibacterial composite material, which takes porous magnesium alloy with through holes as a reinforcement, the holes of the reinforcement are filled with degradable high polymer materials of polycaprolactone and polylactic acid, and nano magnesium oxide powder is uniformly dispersed in the degradable high polymer materials.
Wherein:
the degradable high polymer material in the composite material accounts for 19-49% of the total volume of the composite material, and the porous magnesium alloy accounts for 50-80% of the total volume of the composite material; the proportion of the nano magnesium oxide powder in the total volume of the composite material is not more than 1%, wherein the polylactic acid accounts for 10% -90% of the total volume of the degradable high polymer material, and the polycaprolactone accounts for 10% -90% of the total volume of the degradable high polymer material.
The porosity of the porous magnesium alloy in the composite material is 40-85%, the pore diameter is 200-3000 mu m, the pores are communicated, the shape of the pore body is polygonal or circular, and the thickness of the porous magnesium material is 0.5-10 mm.
The pore size of the porous magnesium alloy in the composite material is uniformly distributed, or gradually increased from the edge of the porous magnesium alloy to the core, or in gradient distribution in the vertical direction or the horizontal direction.
The porous magnesium alloy is a multi-element magnesium alloy formed by one or more of magnesium-aluminum alloy, magnesium-manganese alloy, magnesium-zinc alloy, magnesium-zirconium alloy, magnesium-rare earth alloy, magnesium-alkaline earth alloy, magnesium-lithium alloy, magnesium-calcium alloy or magnesium-silver alloy.
The molecular weight of the polylactic acid is 5-150 ten thousand, and the polylactic acid is a copolymer of lactic acid and glycollic acid, or a copolymer or a mixture of one or two of poly L-lactic acid and poly (D, L) -lactic acid; the polycaprolactone is poly epsilon-caprolactone with the molecular weight of 3-6 ten thousand.
The invention also provides a preparation method of the medical degradable antibacterial composite material, which comprises the following steps:
1) preparing a porous magnesium alloy reinforcement: determining the pore shape and the pore size of the porous magnesium alloy according to the actual requirements of the composite material, and preparing the porous magnesium alloy with the required pore size and structure by a negative pressure seepage method;
2) mixing the ingredients: determining the relative content of a magnesium alloy reinforcement and a degradable high polymer material in the composite material, determining the blending ratio of polylactic acid and polycaprolactone, determining the relative content of nano magnesium oxide powder, mixing the nano magnesium oxide powder and a polylactic acid solution according to a predetermined formula of each component, ultrasonically dispersing the mixture until the mixture is uniform, then blending the mixture with the polycaprolactone in proportion in a torque rheometer, and then molding the mixture into a high polymer sheet for later use;
3) hot-pressing to form a material: and (3) placing the high polymer sheet obtained in the step 2) above the porous magnesium alloy obtained in the step 1), placing the high polymer sheet and the porous magnesium alloy together in a mold of a hot press, heating and extruding in a unidirectional manner until the degradable high polymer material in the high polymer sheet permeates out of the bottom surface of the porous magnesium alloy, ensuring that the degradable high polymer material is fully filled in the holes of the porous magnesium alloy, taking out the high polymer sheet after complete solidification, and removing the redundant degradable high polymer material on the surface of the porous magnesium alloy.
Wherein:
and 2) proportionally blending the polycaprolactone with the mixture, and then molding the mixture into a sheet for later use, wherein the blending condition is that the blending is carried out for 10-30 min at 180-210 ℃, the molding condition is that the temperature is 180-210 ℃, the cooling temperature is 40-80 ℃, the pressure is 50-100N, and the thickness of the sheet is 1-5 mm.
The heating temperature rise unidirectional extrusion in the step 3) is 170-210 ℃, and the pressure is 10-20 MPa.
The invention also provides application of the medical degradable antibacterial composite material, which is applied to orthopedic repair with different shapes and sizes.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. mechanical enhancement: the porous magnesium alloy with excellent strength, plasticity and elastic modulus and through holes is used as a reinforcement, so that the toughness of the medical degradable antibacterial composite material can be obviously improved, and degradable macromolecules filled in the holes can be embedded into the communicated holes to form surrounding locking, thereby achieving a better reinforcement effect; in addition, polylactic acid and polycaprolactone are mixed, the defects of insufficient strength and insufficient toughness of the rubbery polycaprolactone are overcome, and the mechanical property of the high polymer material is adjusted by controlling the blending ratio of the two blends.
2. Acid-base neutralization: in the process of in vivo degradation, the composite material has little influence on the local acidity and alkalinity of the surrounding physiological environment, because the degradation of the reinforcement porous magnesium alloy presents the characteristic of alkalinity, the acidic environment of the degraded matrix polymer is well neutralized, and the characteristic that the local acidity is too high and too strong after the degradation of the traditional polymer orthopedic instrument is overcome.
3. And (3) healing promotion: the magnesium alloy is preferentially degraded to form a through hole porous structure, so that the climbing growth of bone cells is facilitated, the release of magnesium ions can promote the growth of the bone cells, and meanwhile, the antibacterial function of the nano magnesium oxide is beneficial to inhibiting the infection of surrounding tissues and enhancing the fixing effect.
4. The degradation rate is controllable: the degradation and absorption speed of the composite material in vivo is controllable, because the corrosion degradation speed of the magnesium alloy in a physiological environment is high, and the degradation speed of the degradable high polymer material is relatively low, the degradation rate of the composite material can be adjusted by adjusting the relative content of the polylactic acid matrix and the magnesium alloy reinforcement and the mixing ratio of the two degradable high polymer materials.
5. All components of the medical degradable antibacterial composite material can be completely biodegraded and absorbed in vivo: the composite material is composed of polylactic acid, polycaprolactone and magnesium alloy with good biocompatibility and degradability, has no side effect, and avoids the problem that the traditional antibacterial agent is retained in vivo through copper ions, silver ions, nickel ions and titanium dioxide.
Drawings
FIG. 1 is a schematic view of a porous magnesium alloy in a medical degradable antibacterial composite material provided by the invention, wherein the porosity is 83%, and holes are three-dimensionally communicated;
FIG. 2 is a schematic cross-sectional view of the medical degradable antibacterial composite material provided by the present invention, wherein 1 is a hole on the porous magnesium alloy, and 2 is a connection skeleton between the holes of the porous magnesium alloy;
fig. 3 is a schematic diagram of a hot pressing mode in the preparation process of the medical degradable antibacterial composite material provided by the invention, wherein 3 is an upper pressing head of a hot press, 4 is a lower pressing head of the hot press, 5 is a polymer sheet, and 6 is a porous magnesium alloy.
Detailed Description
Therefore, in order to solve the existing problems, the invention provides a medical degradable antibacterial composite material and a preparation method and application thereof, the composite material is formed by taking a through hole porous magnesium alloy with absorbability as a reinforcement and mixing polylactic acid and polycaprolactone matrix with nanometer magnesium oxide powder with antibacterial function, the performance of the composite material has the advantages of absorbable high molecular materials and degradable magnesium alloy, but the disadvantages of the absorbable high molecular materials and the degradable magnesium alloy can be overcome, the composite material has good application prospects in bone trauma surgery, bone defect repair surgery and plastic cosmetology, especially in internal fixation of high stress fracture sections, and relevant research reports are not found at home and abroad so far. The following examples are further illustrated.
Example 1
A medical degradable antibacterial composite material is characterized in that a ZX20(97.7 wt% Mg, 2 wt% Zn and 0.3 wt% Ca) porous magnesium alloy 6 with a through hole is used as a reinforcement (the porosity is 40% and the pore diameter is 200 mu m) to be communicated with each other, the shape of the hole is circular, the thickness of the porous magnesium material is 0.5mm, degradable high polymer materials polycaprolactone and polylactic acid are filled in the hole 1 of the reinforcement, the polylactic acid accounts for 10% of the volume of the high polymer materials, the polycaprolactone accounts for 90% of the total volume of the high polymer materials, and nano magnesium oxide powder is uniformly dispersed in the degradable high polymer materials. In the composite material, the degradable high polymer material accounts for 19% of the total volume of the composite material, the porous magnesium alloy 6 accounts for 80% of the total volume of the composite material, and the nano magnesium oxide powder accounts for 1% of the total volume of the composite material.
The pore size of the porous magnesium alloy 6 in the composite material is uniformly distributed.
The polylactic acid is poly L-lactic acid, the molecular weight of the polylactic acid is 30 ten thousand, and the polycaprolactone is poly epsilon-caprolactone, the molecular weight of the polycaprolactone is 3 ten thousand.
A preparation method of a medical degradable antibacterial composite material comprises the following steps:
1) preparing 10g of ZX20 porous magnesium alloy 6 reinforcement with porosity of 40% by adopting a negative pressure seepage method;
2) taking 6g of poly L-lactic acid with molecular weight of 30 ten thousand, preparing 15% polylactic acid solution by using dichloromethane, adding nano magnesium oxide powder, performing ultrasonic dispersion, volatilizing the dichloromethane, adding the polylactic acid and polycaprolactone into a torque rheometer together according to the proportion, blending for 10min at 180 ℃, then pressing into a macromolecular sheet 5 with thickness of 1mm at 180 ℃ and 50N, and cooling at 40 ℃ for later use;
3) cleaning the porous magnesium alloy 6 reinforcement prepared in the step 1), pickling the surface until the surface is bright, then padding the macromolecular sheet 5 obtained in the step 2) above the porous magnesium alloy 6, then placing the porous magnesium alloy between an upper pressing head 3 and a lower pressing head 4 of a hot press, carrying out hot pressing at 170 ℃ and 10MPa for 5min, repeating the process twice, cooling to room temperature, taking out the macromolecular material burrs on the outer surface, and processing the macromolecular material burrs into the required product by adopting a machining method.
An application of the medical degradable antibacterial composite material is applied to orthopedic repair with different shapes and sizes.
Example 2
A medical degradable antibacterial composite material is prepared by using AZ31(96 wt% Mg, 3 wt% Al and 1 wt% Zn) porous magnesium alloy 6 with through holes as reinforcement (porosity is 85%, aperture is 3000 μm, holes 1 are communicated with each other, shape of the hole is polygonal, thickness of the porous magnesium alloy is 5mm, degradable high polymer materials polycaprolactone and polylactic acid are filled in the holes 1 of the reinforcement, the polylactic acid accounts for 90% of volume of the high polymer materials, the polycaprolactone accounts for 10% of total volume of the high polymer materials, and nano magnesium oxide powder is uniformly dispersed in the degradable high polymer materials, wherein the degradable high polymer materials in the composite material account for 49% of total volume of the composite material, the porous magnesium alloy 6 accounts for 50% of total volume of the composite material, and the nano magnesium oxide powder accounts for 1% of the composite material.
The pore size of the porous magnesium alloy 6 in the composite material is distributed in a mode that the pore size gradually increases from the edge of the porous magnesium alloy to the core.
The polylactic acid is poly (D, L) -lactic acid of 5 ten thousand, the polycaprolactone is poly epsilon-caprolactone, and the molecular weight is 6 ten thousand.
A preparation method of a medical degradable antibacterial composite material comprises the following steps:
1) preparing 6g of AZ31 porous magnesium alloy 6 reinforcement with porosity of 85% by adopting a negative pressure seepage method;
2) preparing 8g of poly (D, L) -lactic acid with the molecular weight of 5 ten thousand into 15% polylactic acid solution by using dichloromethane, adding nano magnesium oxide powder, performing ultrasonic dispersion, volatilizing the dichloromethane, adding the polylactic acid and polycaprolactone into a torque rheometer together according to the proportion, blending for 30min at 210 ℃, then pressing into a 5mm high-molecular sheet 5 at 210 ℃ and 100N, and cooling at 80 ℃ for later use;
3) cleaning the porous magnesium alloy 6 reinforcement prepared in the step 1), pickling the surface until the surface is bright, then padding the macromolecular sheet 5 obtained in the step 2) above the porous magnesium alloy, then placing the porous magnesium alloy between an upper pressing head 3 and a lower pressing head 4 of a hot press, carrying out hot pressing at 210 ℃ and 20MPa for 5min, repeating the process twice, cooling the porous magnesium alloy to room temperature, taking out the macromolecular material burrs on the outer surface, and processing the macromolecular material burrs into the required product by adopting a machining method.
An application of a medical degradable antibacterial composite material in orthopedic repair with different shapes and sizes.
Example 3
A medical degradable antibacterial composite material is characterized in that holes 1 of a reinforcement (with the porosity of 50% and the pore diameter of 400 mu m) made of Mg2Zn (98 wt% Mg and 2 wt% Zn) porous magnesium alloy 6 with through holes are communicated, the shape of each hole is polygonal or circular, the thickness of the porous magnesium alloy is 2mm, degradable high polymer materials polycaprolactone and polylactic acid are filled in the holes 1 of the reinforcement, the polylactic acid accounts for 30% of the volume of the high polymer materials, the polycaprolactone accounts for 70% of the total volume of the high polymer materials, nano magnesium oxide powder is uniformly dispersed in the degradable high polymer materials, the degradable high polymer materials in the composite material account for 29.5% of the total volume of the composite material, the porous magnesium alloy 6 accounts for 70% of the total volume of the composite material, and the nano magnesium oxide powder accounts for 0.5% of the total volume of the composite material.
The pore size of the porous magnesium alloy 6 in the composite material presents gradient distribution of the pore size in the vertical direction.
The polylactic acid is poly L-lactic acid and poly (D, L) -lactic acid copolymer, the molecular weight of which is 10 ten thousand, and the polycaprolactone is poly epsilon-caprolactone, the molecular weight of which is 4 ten thousand.
A preparation method of a medical degradable antibacterial composite material comprises the following steps:
1) preparing 5g of Mg2Zn porous magnesium alloy 6 reinforcement with porosity of 50% by adopting a negative pressure seepage method;
2) preparing 9g of polylactic acid with the molecular weight of 10 ten thousand into 15% polylactic acid solution by using dichloromethane, adding nano magnesium oxide powder, performing ultrasonic dispersion, volatilizing the dichloromethane, adding the polylactic acid and the polycaprolactone into a torque rheometer together according to the proportion, blending for 15min at 190 ℃, then performing compression molding at 200 ℃ and 70N to obtain a 2mm high polymer sheet 5, and cooling at 60 ℃ for later use;
3) and (3) padding the high polymer sheet 5 obtained in the step 2) above the porous magnesium alloy 6, then placing the high polymer sheet between an upper pressing head 3 and a lower pressing head 4 of a hot press, carrying out mould pressing at 180 ℃ and 15MPa for 5min, repeating the process twice, cooling to room temperature, taking out the high polymer material burrs on the outer surface, and processing the high polymer material burrs into the required product by adopting a machining method.
An application of a medical degradable antibacterial composite material in orthopedic repair with different shapes and sizes.
Example 4
A medical degradable antibacterial composite material uses Mg4ZnY (95 wt% Mg, 4 wt% Zn, 1 wt% Zn) porous magnesium alloy 6 with through holes as a reinforcement (the porosity is 70%, the aperture is 800 mu m) and the holes 1 are communicated with each other, the shape of the holes is polygonal or circular, the thickness of the porous magnesium material is 4mm, degradable high polymer materials polycaprolactone and polylactic acid are filled in the holes 1 of the reinforcement, the polylactic acid accounts for 70% of the volume of the high polymer materials, the polycaprolactone accounts for 30% of the total volume of the high polymer materials, and nano magnesium oxide powder is uniformly dispersed in the degradable high polymer materials. In the composite material, the degradable high polymer material accounts for 39.2 percent of the total volume of the composite material, the porous magnesium alloy 6 accounts for 60 percent of the total volume of the composite material, and the nano magnesium oxide powder accounts for 0.8 percent of the total volume of the composite material.
The pore size of the porous magnesium alloy 6 in the composite material is uniformly distributed.
The polylactic acid is poly L-lactic acid with the molecular weight of 20 ten thousand, and the polycaprolactone is poly epsilon-caprolactone with the molecular weight of 5 ten thousand.
A preparation method of a medical degradable antibacterial composite material comprises the following steps:
1) preparing 8g of Mg2Zn porous magnesium alloy 6 reinforcement with porosity of 70% by adopting a negative pressure seepage method;
2) taking 6g of polylactic acid with the molecular weight of 20 ten thousand, preparing 15% polylactic acid solution by using dichloromethane, adding nano magnesium oxide powder, performing ultrasonic dispersion, volatilizing the dichloromethane, adding the polylactic acid and the polycaprolactone into a torque rheometer together according to the proportion, blending for 20min at 200 ℃, then pressing into a 3mm high polymer sheet 5 at 190 ℃ and 80N, and cooling at 70 ℃ for later use;
3) and (3) padding the high polymer sheet 5 obtained in the step 2) above the porous magnesium alloy 6, then placing the high polymer sheet between an upper pressing head 3 and a lower pressing head 4 of a hot press, carrying out mould pressing at 190 ℃ and 110MPa for 5min, repeating the process twice, cooling to room temperature, taking out the high polymer material burrs on the outer surface, and processing the high polymer material burrs into the required product by adopting a machining method.
An application of a medical degradable antibacterial composite material in orthopedic repair with different shapes and sizes.

Claims (10)

1. A medical degradable antibacterial composite material is characterized in that: the composite material takes a porous magnesium alloy (6) with a through hole as a reinforcement, a hole (1) of the reinforcement is filled with a degradable high polymer material polycaprolactone and polylactic acid, and nano magnesium oxide powder is uniformly dispersed in the degradable high polymer material.
2. The medical degradable antibacterial composite material of claim 1, wherein: in the composite material, the degradable high polymer material accounts for 19-49% of the total volume of the composite material, the porous magnesium alloy (6) accounts for 50-80% of the total volume of the composite material, and the nano magnesium oxide powder accounts for no more than 1% of the total volume of the composite material, wherein the polylactic acid accounts for 10-90% of the total volume of the degradable high polymer material, and the polycaprolactone accounts for 10-90% of the total volume of the degradable high polymer material.
3. The medical degradable antibacterial composite material of claim 1, wherein: the porosity of the porous magnesium alloy (6) in the composite material is 40-85%, the pore diameter is 200-3000 mu m, the pores (1) are communicated, the shape of the pore body is polygonal or circular, and the thickness of the porous magnesium alloy (6) material is 0.5-10 mm.
4. The medical degradable antibacterial composite material of claim 1, wherein: the pore size of the porous magnesium alloy (6) in the composite material is uniformly distributed, or the pore size is gradually increased from the edge of the porous magnesium alloy (6) to the core, or the pore size is distributed in a gradient change mode in the vertical direction or the horizontal direction.
5. The medical degradable antibacterial composite material of claim 1, wherein: the porous magnesium alloy (6) is a multi-element magnesium alloy formed by one or more of magnesium-aluminum alloy, magnesium-manganese alloy, magnesium-zinc alloy, magnesium-zirconium alloy, magnesium-rare earth alloy, magnesium-alkaline-earth alloy, magnesium-lithium alloy, magnesium-calcium alloy or magnesium-silver alloy.
6. The medical degradable antibacterial composite material of claim 1, wherein: the molecular weight of the polylactic acid is 5-150 ten thousand, and the polylactic acid is a copolymer of lactic acid and glycollic acid, or a copolymer or a mixture of one or two of poly L-lactic acid and poly (D, L) -lactic acid; the polycaprolactone is poly epsilon-caprolactone with the molecular weight of 3-6 ten thousand.
7. A preparation method of the medical degradable antibacterial composite material as claimed in any one of claims 1 to 6, characterized by comprising the following steps: the method comprises the following steps:
1) preparing a porous magnesium alloy (6) reinforcement: determining the pore shape and the pore size of the porous magnesium alloy (6) according to the actual requirements of the composite material, and preparing the porous magnesium alloy (6) with the required pore size and structure by a negative pressure seepage method;
2) mixing the ingredients: determining the relative content of a magnesium alloy reinforcement and a degradable high polymer material in the composite material, determining the blending ratio of polylactic acid and polycaprolactone, determining the relative content of nano magnesium oxide powder, mixing the nano magnesium oxide powder and a polylactic acid solution according to a predetermined formula of each component, ultrasonically dispersing the mixture until the mixture is uniform, then blending the mixture with the polycaprolactone in proportion, and then molding the mixture into a high polymer sheet (5) for later use;
3) hot-pressing to form a material: and (3) placing the polymer sheet (5) obtained in the step (2) above the porous magnesium alloy (6) obtained in the step (1), placing the polymer sheet and the porous magnesium alloy (6) into a mold of a hot press together, heating, extruding in a one-way mode to enable the degradable polymer material in the polymer sheet (5) to permeate out of the bottom surface of the porous magnesium alloy (6), ensuring that the degradable polymer material is fully filled in the holes (1) of the porous magnesium alloy (6), taking out after complete solidification, and removing the redundant degradable polymer material on the surface of the porous magnesium alloy (6).
8. The preparation method of the medical degradable antibacterial composite material as claimed in claim 7, characterized in that: and 2) proportionally blending the polycaprolactone with the mixture, and then molding the mixture into a sheet for later use, wherein the blending condition is that the blending is carried out for 10-30 min at 180-210 ℃, the molding condition is that the temperature is 180-210 ℃, the cooling temperature is 40-80 ℃, the pressure is 50-100N, and the thickness of the sheet is 1-5 mm.
9. The preparation method of the medical degradable antibacterial composite material as claimed in claim 7, characterized in that: the heating temperature rise unidirectional extrusion in the step 3) is 170-210 ℃, and the pressure is 10-20 MPa.
10. The use of the medical degradable antibacterial composite material as claimed in any one of claims 1 to 6, characterized in that: the medical degradable antibacterial composite material is used for orthopedic repair.
CN201911181729.2A 2019-11-27 2019-11-27 Medical degradable antibacterial composite material and preparation method and application thereof Pending CN111068106A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112076352A (en) * 2020-08-25 2020-12-15 云南科威液态金属谷研发有限公司 Medical liquid metal thermoplastic functional composite material and preparation method and application thereof
CN112479737A (en) * 2020-12-09 2021-03-12 南京航空航天大学 Controllable porous biological ceramic support and preparation method and application thereof
CN112755254A (en) * 2021-01-18 2021-05-07 河南农业大学 Preparation method of tracheal cannula with antibacterial effect
CN114807839A (en) * 2022-04-25 2022-07-29 南昌大学 Stepped degradation magnesium alloy barrier film for dentistry and preparation method thereof
CN115038470A (en) * 2020-12-28 2022-09-09 元心科技(深圳)有限公司 Medical equipment for internal fixation and implantation in orthopedics department
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

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090099670A (en) * 2008-03-18 2009-09-23 유앤아이 주식회사 Complex implants infilterated with biodegradable mg(alloys) inside porous structural materials and method for manufacturing the same
CN102397588A (en) * 2011-11-15 2012-04-04 东南大学 Porous magnesium alloy three-dimensional reinforced absorbable medical compound material and preparation method thereof
CN103768663A (en) * 2014-01-07 2014-05-07 东南大学 Long-acting antibacterial absorbable bone surgical appliance material and preparation method thereof
CN104127916A (en) * 2014-07-15 2014-11-05 东南大学 Absorbable orthopedic apparatus material having antibiosis and bone growth promotion functions, and preparation method thereof
CN106421891A (en) * 2016-11-14 2017-02-22 佛山科学技术学院 Preparation method of degradable magnesium alloy and degradable polymer composite
CN108619565A (en) * 2018-04-28 2018-10-09 天津理工大学 A kind of l-lactic acid/magnesia composite coating and the preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090099670A (en) * 2008-03-18 2009-09-23 유앤아이 주식회사 Complex implants infilterated with biodegradable mg(alloys) inside porous structural materials and method for manufacturing the same
CN102397588A (en) * 2011-11-15 2012-04-04 东南大学 Porous magnesium alloy three-dimensional reinforced absorbable medical compound material and preparation method thereof
CN103768663A (en) * 2014-01-07 2014-05-07 东南大学 Long-acting antibacterial absorbable bone surgical appliance material and preparation method thereof
CN104127916A (en) * 2014-07-15 2014-11-05 东南大学 Absorbable orthopedic apparatus material having antibiosis and bone growth promotion functions, and preparation method thereof
CN106421891A (en) * 2016-11-14 2017-02-22 佛山科学技术学院 Preparation method of degradable magnesium alloy and degradable polymer composite
CN108619565A (en) * 2018-04-28 2018-10-09 天津理工大学 A kind of l-lactic acid/magnesia composite coating and the preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李强等: "《生物医用多孔金属材料的制备及表面改性》", 31 August 2016 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112076352A (en) * 2020-08-25 2020-12-15 云南科威液态金属谷研发有限公司 Medical liquid metal thermoplastic functional composite material and preparation method and application thereof
CN112076352B (en) * 2020-08-25 2022-03-29 云南迈特力医疗技术有限公司 Medical liquid metal thermoplastic functional composite material and preparation method and application thereof
CN112479737A (en) * 2020-12-09 2021-03-12 南京航空航天大学 Controllable porous biological ceramic support and preparation method and application thereof
CN112479737B (en) * 2020-12-09 2022-04-22 南京航空航天大学 Controllable porous biological ceramic support and preparation method and application thereof
CN115038470A (en) * 2020-12-28 2022-09-09 元心科技(深圳)有限公司 Medical equipment for internal fixation and implantation in orthopedics department
CN112755254A (en) * 2021-01-18 2021-05-07 河南农业大学 Preparation method of tracheal cannula with antibacterial effect
CN112755254B (en) * 2021-01-18 2022-03-15 河南农业大学 Preparation method of tracheal cannula with antibacterial effect
CN114807839A (en) * 2022-04-25 2022-07-29 南昌大学 Stepped degradation magnesium alloy barrier film for dentistry and preparation method thereof
CN114807839B (en) * 2022-04-25 2023-03-14 南昌大学 Stepped degradation magnesium alloy barrier film for dentistry and preparation 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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Application publication date: 20200428