CN1460526A - Porous bone prosthesis containing hydroxy apatite component and its preparation method - Google Patents
Porous bone prosthesis containing hydroxy apatite component and its preparation method Download PDFInfo
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Abstract
The porous bnoe prosthesis with good biological compatibility and biological activity is formed from nano hydroxyapatite and polyamide component with weight ratio of 1/1-0.3, and has mutual through pores whose pore size is 1-300 micrometers, and its total porosity is 30-70%. Its preparation method includes the following steps: according to the described ratio mixing fine hydroxyapatite powder and polyamide fine powder, then mixing them with ethyl alcohol solution containing calcium chloride to make solidifiation, and using water to dissolve the above-mentioned obtained material to remove water solubility component from solidified material and form porous structure in the bone prosthesis material.
Description
Technical Field
The invention relates to a porous bone restoration containing a hydroxyapatite component, in particular to a composite porous bone restoration in the form of a nano or non-nano hydroxyapatite/polyamide component and a preparation method thereof.
Background
Bone repair is a new cross field of material science and life science, and provides a promising new method for repairing bone defects, bone tumors and refractory fractures, wherein the porous prosthesis is one of key technologies of bone repair engineering. The porous prosthesis aims to provide a three-dimensional scaffold for the cells of the constructed tissue and provide a proper environment for the growth of the cells. The porous material is the basic framework and metabolic site for cell attachment, provides a scaffold for the new tissue, and is maintained for a certain time until the new tissue has own biomechanical properties. The porous material plays a supporting role in bone repair engineering, keeps the shape of the original tissue, and also plays a template role, provides a place for cells to lodge, grow, differentiate and proliferate, thereby guiding the regeneration of damaged tissues.
The calcium-phosphorus material is the main component of inorganic matter constituting hard tissue of human body, has natural affinity with human body tissue, and can form firm biological bond with soft and hard tissue of human body. The principle and advantages of using nano-hydroxyapatite as a bone substitute are self-evident, since the inorganic substance of natural bone is mainly composed of nano-hydroxyapatite, which accounts for about 65% by weight of natural bone. Further studies have shown that cortical bone is composed primarily of bone units, or harvard's system, which areheld together by a hard tissue matrix or matrix. It is known that the exchange of substances between bone units is performed through the fochmann's canal crossing the bone space, which allows blood to flow to the deepest bone unit to maintain the physiological activity of the bone. To design an osteoconductive implant, it should logically resemble matrix or interstitial bone. Because the diameter of the bone unit is about 190-230 microns and the material exchange is carried out through Fockmann's tubes, the ideal bone graft substitute is a system of interpenetrated and small-diameter pore channels simulating cortical bone.
Calcium-phosphorus bioactive ceramic substitute materials such as hydroxyapatite ceramics and the like which are used at present are widely used for repairing and reconstructing a muscular-skeletal system in a block form and a particle form clinically. Because the inorganic substance has similar component composition with the inorganic substance of human hard tissue (such as bone, tooth, etc.), the block ceramic has good biocompatibility and bioactivity, but the block ceramic has large brittleness, difficult processing and easy fracture; the granular ceramics have the defects of wandering and displacement, and the mechanical properties of the calcium phosphate bioactive materials are not satisfactory, the indexes of the breaking strength and the fracture toughness are both lower than those of human compact bones, and the elastic modulus is greatly higher than that of natural bones, so the clinical application of the granular ceramics is limited.
The polyamide has good compatibility with human tissues due to the molecular structure of the polyamide is very similar to that of human collagen, is an excellent medical polymer material, has higher toughness and strength, and has wide and long-term clinical application.
The natural bone is an inorganic/organic composite material composed of hydroxyapatite and macromolecular collagen fibers, and has good mechanical properties. How to prepare the bone repair material with similar material and fine structure according to the composition structure of natural bone, so that the bone repair material has good bone conduction and bone induction performance, and has very important significance in theory and clinical practice. In order to improve the flexibility and the processability of the calcium-phosphorus material and imitate the composition structure characteristics of natural bones, the inorganic/organic composite biological material with good biological activity and mechanical property is increasingly widely regarded as the main body of bone repair and substitution materials of hard tissues and bone restoration materials of tissue engineering.
Disclosure of Invention
In view of the above situation, the present application firstly provides a method for constructing an excellent porous bone repair material by compounding a polyamide organic material having good toughness and an elastic modulus close to that of human bone with an inorganic material having bioactivity so as to simulate natural bone components. The material can be processed into a three-dimensional porous structure, can support adhesion and proper growth of new cells and tissues in a matrix besides meeting the biocompatibility requirement, induces the expression of normal morphology and functions of the cells, and supports the tissues or transmits stress through proper mechanical strength of the material, so that the cells can grow on a three-dimensional shape scaffold according to the pre-design.
On the basis, the invention further provides a preparation method for preparing the porous bone prosthesis.
The current research result shows that the Hydroxyapatite (HA) material HAs good biological activity and can form firm bonding with bone tissues; the medical polyamide component (PA) of the high polymer material has higher toughness and strength, contains a plurality of repeated polar groups on the main chain, has good compatibility with polar inorganic materials, and can be used for improving the toughness of hydroxyapatite. The experimental result also shows that the higher the content of HA in the composite material is, the better the bioactivity of the composite material is. After the hydroxyapatite and the polyamide are compounded, the excellent performances of the hydroxyapatite and the polyamide can be fully combined, so that the bone repair and reconstruction bone repair material with biocompatibility and bioactivity can be obtained.
Accordingly, the porous bone restoration body is composed of hydroxyapatite/medical polyamide components with the weight ratio of 1/(1-0.3), the bone restoration body also comprises mutually communicated pores with the pore diameter of 1-300 microns, and the total volume of the pores accounts for 30-70% of the total volume of the bone restoration body material.
In the above-described bone prosthesis of the present invention, the pores preferably include pore structures in the form of pores having different sizes. For example, it is preferable to include both micropores having a pore size of 1 to 50 μm and macropores having a pore size of 100 and 300. mu.m; also, micropores are mainly present on the wall of the pore of the macropores.
Because the content of the hydroxyapatite in the natural bone of a human body is 65-70 percent of the equivalent, the content of the hydroxyapatite in the composition of the bone repair body is also 65-70 percent of the optimal proportion, so as to realize the aim and the effect of improving the bioactivity of the porous composite material to the maximum extent, and become a more ideal bone repairbody material.
In the above-mentioned composition of the bone prosthesis material, the medical polyamide-based component may be selected from the currently used types of materials such as polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide MXD-6, and the like. Among them, polyamide 66 is preferable. For example, compared with Polyamide (PA)66, the strength and the elastic modulus of PA6 of Polyamide (PA)6 are lower than those of PA66, and the water absorption is larger than that of PA66, but the HA/PA6 composite material obtained by compounding with hydroxyapatite HAs a higher degradation speed in vivo than that of HA/PA66, and is superior to PA66 in bone tissue repair and tissue engineering which require a higher degradation speed, such as bone defect filling repair. Further, PA6 is superior in elongation at break and impact strength (toughness) to PA66 and is slightly better in processing fluidity. And PA66 has good heat resistance, high strength and hardness, high molding speed and low water absorption. The HA/PA66 composite material HAs low degradation in vivo and is superior to PA6 in the aspect of bone repair requiring no degradation, such as vertebras, craniums and the like. The PA11 and PA12 materials have low water absorption, and the physical properties and the product size change after water absorption are small; the density is small and the weight is light; the impact resistance is good; the anti-bending fatigue property is excellent, and the drug resistance is excellent; good wear resistance and flexibility, and is more suitable for being used as prosthesis of facet joint, artificial eye platform (artificial eyeball), jaw bone, etc. Compared with PA6 and PA66, the polyamide MXD-6 has high tensile strength, bending strength, elastic modulus, hardness and other properties, excellent fatigue resistance, good wear resistance, excellent oxygen and moisture barrier properties, can be co-extruded or co-injected with various thermoplastic polymers, has good processing performance, and is suitable for being used as a prosthesis at bearing force positions of various joints, artificial vertebral plates, vertebral bodies and the like. Therefore, in the porous bone repair material of the present invention, the medical polyamide-based component may be selected according to the specific use requirements.
The preparation of the porous bone restoration can adopt the steps of mixing fine powder of medical polyamide components and fine powder of hydroxyapatite according to the proportion, mixing the mixture with ethanol solution containing 14-70% of calcium chloride in weight/volume ratio according to the proportion of 1 g/(0.5-1) ml, then solidifying, and fully dissolving and removing water-soluble components in a solidified material by using water, thereby forming a porous structure in the solidified body.
In the above-mentioned preparation method, the hydroxyapatite component can be prepared by a method reported at present. For example, it is preferable to use hydroxyapatite powder of nanometer size obtained by reacting calcium salt with phosphate. Among them, it is preferable to use the molar ratio of calcium to phosphorus in the hydroxyapatite component.
The fine powder of the medical polyamide-based component can be obtained commercially or prepared by a method reported at present. For the latter, one preparation method that may be used as reference is: the polyamide composition is prepared by dissolving a polyamide component selected according to use requirements in a dimethylformamide or dimethylacetamide solution containing calcium chloride, pouring the mixed solution into water to form fine powder, and centrifugally cleaning and drying the obtained fine powder. Wherein the weight/volume content of the calcium chloride in the dimethylformamide or dimethylacetamide solution containing the calcium chloride can be 18-20%, and the weight/volume ratio of the polyamide component to the dimethylformamide or dimethylacetamide in the solution is 1/(15-40).
In the preparation method of the porous bone prosthesis, a specific mode for reference in implementation is that fine powder of the mixed hydroxyapatite component and polyamide component is mixed with calcium chloride/ethanol solution, and then is cured in the air, so that the composite material body is cured along with the volatilization of ethanol, and the metal salt is continuously remained in a cured material. Then putting the calcium chloride solution into water to further dissolve and remove water-soluble calcium chloride components. In the curing process in the air, along with the volatilization of ethanol, a plurality of micropores can be left in the composite material body, but metal components such as calcium chloride and the like are still left in the composite material; after being placed in water, the calcium chloride component may be further leached from the material, leaving many new micropores and/or further forming macropores in the composite body.
Another embodiment, to which reference may be made in practice, is to mix said fine powder of the mixed hydroxyapatite component and polyamide component with a calcium chloride/ethanol solution, i.e. to place it in water, so that the solidification of the composite material and the dissolution and leaching of the ethanol and calcium chloride components of the material from the composite material take place simultaneously, leaving large and small pores in the composite material.
The composite material solidified body after water dissolving treatment is taken out, and is dried in the shade at room temperature and then dried at 50-70 ℃ to obtain the porous bone restoration body which has good biocompatibility and bone conduction performance and can be used for replacing and repairing bone tissue defects.
The experimental results show that the two different methods of solidification and water treatment can have certain influence on the pore size of the pores formed in the porous bone prosthesis. Firstly, the mixture is solidified in the air, and the formed micropores are very small and are usually 1-20 microns; and cured directly in water, the pores may have a pore size of 1-50 microns or greater. Therefore, in order to obtain smaller micropores (1-20 microns), ethanol is solidified in air for a long time to allow ethanol to be substantially completely volatilized, and then the ethanol is placed in water to further dissolve and remove calcium chloride, so that larger pores with the size of more than 100 microns can be obtained, and a plurality of penetrating micropores can be formed on the walls of the large pores. In order to obtain larger pores (100-.
Since the function of the bone prosthesis is to guide the growth or proliferation of the implanted cells or cells migrating around the scaffold, it should first be a supporting substrate enabling the cells to adhere, differentiate, proliferate or migrate and be easily processed into a three-dimensional porous structure. The porosity of the prosthesis is very important, and a suitable pore size and/or porosity is beneficial for osteoblast growth, as it enables cell migration or proliferation. Pore size affects the ingrowth of cells and the internal surface area of the scaffold. Scaffolds with larger internal surface areas can culture more cells, providing sufficient numbers of cells for regenerating organs.
The porous structure in the bone repair body can provide a larger adhesion surface for cells, is favorable for the adhesion of the cells and allows the ingrowth of vascular tissues. The material with high porosity has large specific surface area, can provide a large amount of sufficient space for cell growth and extracellular matrix secretion, can provide gas and nutrient exchange environment necessary for cell growth, and is beneficial to nutrient exchange and waste discharge of cells. Pore size has been shown to be an important parameter affecting fibrovascular tissue ingrowth. The pore size has a major influence on the ingrowth of new bone tissue into the carrier. Research shows that the pore size is 15-40 microns, and fibrous tissues are allowed to grow in; the smaller micropores can allow body fluid and tissue fluid to enter, form the whole body fluid circulation, enter nutrient substances and oxygen and discharge metabolites; the pore size is 40-100 microns, and non-mineral bone tissues can be allowed to grow in; the pore size is larger than 100 microns, and the vascular tissue is allowed to grow in. In order to maintain the viability and health of the tissue, the pore size must be larger than 100-200 microns, and the large pore size not only can increase the contact area and increase the anti-moving capacity, but also can provide blood supply for the connective tissue growing into the biological implant material. The wall of the big hole is rich in microporous porous materials, and can adsorb cell factors, growth factors, proteins and other induction factors beneficial to tissue growth. The porous scaffold material and the structure prepared by the traditional process are difficult to ensure the complete communication between pores.
The results measured by the archimedes method also show that, in the above-mentioned preparation method, the amount of calcium chloride component and/or ethanol in the raw materials and/or reagents used in the preparation process is also related to the pore size and porosity in the produced porous bone prosthesis. The total amount of the calcium chloride component and/or the ethanol is small, so that the porosity in the formed porous bone restoration can be obviously reduced. Therefore, the adjustment and control of the pore size and/or porosity of the prepared porous bone prosthesis within a desired or required range can be realized by changing the calcium chloride concentration in the calcium chloride/ethanol solution used in the preparation process and/or the solid/liquid ratio used when the hydroxyapatite/polyamide-based component composite material powder is mixed with the calcium chloride/ethanol solution.
Since the hydroxyapatite component accounting for about 65% of the natural bone weight is mainly nano-hydroxyapatite, in order to achieve a better uniform mixing degree of the fine powder of the hydroxyapatite component and the polyamide component of the present invention, it is a preferable measure that the hydroxyapatite component as an important raw material is optimally nano-hydroxyapatite in the above preparation process.
The experimental result shows that in the composition of the bone prosthesis, the hydroxyapatite, especially the nano hydroxyapatite/polyamide component in the weight ratio of 1/(1-0.3) is increased, and the obtained composite material not only has correspondingly improved bioactivity, but also has correspondingly increased compressive strength along with the increase of the proportion of the (nano) hydroxyapatite component. Therefore, during preparation, the composition ratio of the (nano) hydroxyapatite to the polyamide component is changed, so that the performance effects of the porous bone restoration in various aspects such as biological activity, mechanical property and the like can be improved, and the aim of comprehensively adjusting different clinical requirements can be fulfilled.
Further experimental results also confirm that the mixed curing liquid of calcium chloride/ethanol is a necessary condition in the curing process of the porous bone prosthesis of the above-mentioned form of the present invention. After mixing of ethanol alone or an aqueous solution of calcium chloride alone with the hydroxyapatite/polyamide component composite powder, the composite doesnot cure. The fine powder of the composite material can form a material body in a solidified state only after being mixed with the calcium chloride/ethanol mixed solidification liquid.
Recent research on porous biomaterials has largely focused on the pore structure of porous implants, particularly the effect of the pore size and the interrelationship between porous bodies and tissues. And gradually realize the control of the pore diameter of the porous body, thereby preparing the implant with different pore diameters according to different implantation requirements and improving the mechanical strength of the porous body as much as possible on the premise of meeting the biological performance. The bone restoration structure has a pore structure with the pore diameter of about 1-300 microns and the porosity of 30-70 percent, and is communicated with each other, so that the bone restoration structure is very favorable for tissue growth and nutrient substance transportation and is a good carrier for cell growth. Therefore, the bone repair body with the complex microstructure shape can well meet various requirements on the aspect of forming a porous cell carrier framework structure, and is a bone repair material with a very promising development prospect.
Based on the above description, according to the common technical knowledge and conventional means in the field, various modifications, substitutions or changes can be made without departing from the basic technical idea of the present invention.
The foregoing and other objects, features, and advantages of the invention will be apparent from the following more particular description of the embodiments of the invention, as illustrated in the accompanying drawings. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realizedbased on the above contents of the present invention belong to the scope of the present invention.
Drawings
Fig. 1 is a scanning electron microscope observation result of the nano hydroxyapatite slurry synthesized by the porous composite bone prosthesis prepared by the invention.
FIGS. 2 to 5 are scanning electron micrographs of porous composite bone repair materials of different forms according to the present invention.
Fig. 6 is a result of a canine mandibular bone defect repairing experiment using the porous bone prosthesis of the present invention.
Detailed Description
(1) Composite material powder:
preparing nano hydroxyapatite: feeding calcium nitrate and ammonium phosphate according to the calcium/phosphorus molar ratio of 1.60-1.67, and obtaining hydroxyapatite through the following reactions:
Fine powder of polyamide-based component: the polyamide powder can be prepared by using the current commercial polyamide 66 or other corresponding polyamide fine powder or according to the current reportedmethod.
Preparing fine powder of the composite material: mixing the nano hydroxyapatite fine powder and polyamide fine powder such as polyamide 66 according to the weight ratio of 1/(1-0.3), grinding, washing with distilled water for 2 times, drying, grinding again, and sieving with 400 meshes for later use. The hydroxyapatite content in the composite material fine powder can be about 60 percent.
(2) Mixing liquid:
preparing slurry with calcium chloride content of 14 g/100 ml, 20 g/100 ml, 30 g/100 ml and 60 g/100 ml with calcium chloride and anhydrous ethanol, and sealing in bottle.
(3) Preparing a porous composite bone restoration body:
preparation method 1
Mixing the composite material fine powder and the mixed liquid with the calcium chloride content of 14 g/100 ml and 20 g/100 ml respectively according to the proportion of the solid fine powder to the mixed liquid (S/L) of 1/0.5 and 1/0.7, and fully blending in a mortar for 2-5 minutes to obtain a cured material. Placing the mixture into a mold with a certain shape for forming, curing at room temperature, taking out the cured body after 1 day, then placing the cured body into water for soaking for 1-2 days, taking out the cured body, and drying in an oven at 50-70 ℃ to obtain two porous materials respectively. The Scanning Electron Microscope (SEM) results are shown in fig. 2 and 3. The SEM picture reflects the microstructure of the sample, and the pore size is observed through the picture. The porosity was measured by Archimedes analysis.
FIG. 2 shows the morphology of the micropores of a sample obtained from a slurry of calcium chloride/ethanol at 14 g/100 ml and S/L of 1/0.5, the majority of the micropores having a pore size in the range of 1-10 microns and a porosity of only around 30%.In FIG. 3, the sample obtained from 20 g/100 ml of a calcium chloride/ethanol slurry at S/L of 1/0.7 had a pore size of substantially 100 μm or more, and in addition to these larger pore sizes, had pores having a pore size of 1 to 10 μm and a porosity of about 40%. As can be seen from SEM pictures, the porous material has irregular pore shapes and a uniform distribution state, the pores (macroscopic pores) are formed by leaching and solidifying calcium chloride, abundant micropores exist on the walls of the pores and are formed by volatilizing ethanol (microscopic pores), and the existence of the micropores enables the macroscopic pores to be communicated with one another.
These results demonstrate that the amount of calcium chloride affects the pore size and porosity of the cured body, with a corresponding increase in both calcium chloride and ethanol content.
Preparation method 2
Mixing the composite material fine powder and the mixed liquid with the calcium chloride content of 30 g/100 ml and 60 g/100 ml respectively according to the proportion that the S/L is 1/0.7 and 1/1, and fully blending in a mortar for 2-5 minutes to obtain a cured material. Placing the porous material in a mold for forming, curing the porous material for 1 hour at room temperature, placing the cured material and the mold in water, soaking for 2 days, taking out, and drying in an oven at 50-70 ℃ to obtain two porous materials. The scanning results of the electron microscope are shown in fig. 4 and 5.
In the pore morphology in FIG. 4, the large pore diameter is about 100-200 microns, the micropores are about 5-20 microns, and the porosity is 55%. As can be seen from FIG. 5, the pore size of the macropores is substantially 100-300. mu.m, and in addition to these larger pore sizes, there are micropores with a pore size of 5-20 μm and a porosity of 70%. As can be seen from fig. 4and 5, the porous material has irregular pore morphology but a uniform distribution, and the pores (macroscopic pores) are formed by leaching solidified calcium chloride, and the micropores on the walls of the pores are formed by dissolving ethanol in water, and the existence of the micropores enables the more macroscopic pores to be communicated with each other.
The above results also show that the content of calcium chloride will affect the pore size and porosity of the cured body. FIG. 4 is a composite material cured with a slurry having a calcium chloride content of 30 g/100 ml at an S/L ratio of 1/0.7. FIG. 5 is a composite material cured with a slurry having a calcium chloride content of 60 grams per 100ml at an S/L ratio of 1/1. As the calcium chloride and ethanol content increased, the pore size and porosity of the cured body increased accordingly.
The following experiment for repairing the dog mandibular bone defect was performed with the porous nano-hydroxyapatite/polyamide bone prosthesis to observe the tissue repair process after the porous nano-hydroxyapatite/polyamide bone prosthesis was implanted into the dog mandibular cortex defect:
the method comprises the following steps: two box-like defects of 15X 10X 5mm were designed on the mandible of 9 healthy male hybrid dogs, and one of them was implanted with a prefabricated block of corresponding size made of a porous block-shaped prefabricated product hydroxyapatite/polyamide 66(HA/PA66) bone prosthesis (pore size substantially 100-200 microns, in addition to these larger pore sizes, micropores with a pore size of 5-20 microns, porosity 55%) prepared by the above-described method 2 of the present invention. Animals were sacrificed at 2, 4, 8, 12, 16 weeks post-surgery, tissue specimens were excised and histologically observed.
As a result: the wound of the operation area is well healed, obvious rejection reaction isnot seen, the porous material is implanted to be exposed, and the soft tissue coverage is good.
The periphery of the implanted porous material is wrapped by the gradually thickened fibrous connective tissue in 2-8 weeks, the membranous osteogenesis sign appears on the bone restoration-tissue interface in 12 weeks, and the HA/PA66 bone restoration body is completely wrapped by the new bone tissue and is combined with the artificial bone in an osteogenic way in 16 weeks. At this time, the bone formation between tissues of the wrapping material is obvious, the new bone tissue seals the marrow cavity of the mandible at the defect position and grows into the surface pores of the material, and no connective tissue interval exists between the material and the bone tissue to form complete osseous combination. The morphological structure of the material itself is not obviously changed, and the surrounding tissues do not phagocytose the material particles by macrophages. No active remodeling was seen in the bone tissue of the control defect, which had been replaced by fibrous connective tissue. The results are shown in FIG. 6. Fig. 6 shows that 16 weeks after implantation, the bone tissue spikes ('←' indicates) grown into the porous material have been substantially matured '#' to be a porous prosthesis.
As can be seen by observing the biological characteristics of the HA/PA66 bone repair body, the porous bone repair body used in the experiment HAs no toxicity and foreign body reaction after being implanted into an animal body, the wound is normally healed, and wound infection, material exposure and tissue necrosis do not occur; after the bone restoration body is implanted into the body, blood clots are formed in the tissue and inside the pores, capillary blood vessels and proliferated fibroblast grow into the pores, and the capillary blood vessels and the proliferated fibroblast are covered with soft tissue in the periphery. A dynamic balance exists between the mechanical stress and the bone tissue, and the stress change of the bone tissue in a certain physiological stress range has positive significance for the formation and reconstruction of the bone. The conventional HA material HAs crisp texture, is fragile under the action of external force, is not easy to shape, cannot repair long-section and large-range bone defects, is difficult to cut and form in an operation, and HAs poor clinical operability, while the HA/PA66 material HAs mechanical properties similar to that of cortical bone, can conduct normal biological force after the material at the large-range cortical bone defect is repaired, and is beneficial to the formation and reconstruction of new bone, thereby laying a foundation for the complete recovery of the function and the shape of the defect.
At 16 weeks of the above experiment, the defect at the implant material was substantially repaired by new bone, indicating that the porous bone repair material as a barrier can mechanically prevent the rapid growth of surrounding connective tissues such as fibroblasts to the defect, and exclude them from the defect area, and guide the migration of osteoblasts with slower migration speed to the defect area, thereby forming new bone. In the process, the main function of the HA/PA66 bone repair material is the function of a three-dimensional structure bracket, which is beneficial to the growth of blood vessels and osteoblasts of the bone grafting bed. The HA/PA66 bone repair material in the experiment is coated by fibrous connective tissue in the early stage of repair after being implanted into the defect, and then the membranous osteogenesis process is started in the coated tissue, and finally mature bone tissue is formed. In tissue that grows into the pores of the surface of the material, it is observed that membranous osteogenesis often begins from the site of interface with the material, rather than growing gradually from the more blood-rich periphery.This indicates that the surface biological properties of the material favour the formation of new bone. At 12 weeks, new bone began to form at the tissue-bone interface of the wrapping material, but the new bone was less calcified. At 16 weeks, the range and calcification degree of new bones are increased, the callus density is increased, the porous restoration material and the surrounding bone tissues are completely fused together, and the boundary between the porous restoration material and the surrounding bone tissues is not obvious; the bone tissue wrapping material with good calcification can form bone combination at the interface between the two materials.
And (4) conclusion: the porous nano hydroxyapatite/polyamide bone restoration body has good biocompatibility, the restoration tissue is membranous osteogenesis, the artificial bone and the bone tissue form osseous combination at 16 weeks, and the material also has bone guiding and potential bone induction functions.
Claims (9)
1. A porous bone restoration body containing a hydroxyapatite component is characterized by comprising the hydroxyapatite/medical polyamide component in a weight ratio of 1/(1-0.3), the bone restoration body material also comprises mutually communicated pores with the pore diameter of 1-300 microns, and the total volume of the pores accounts for 30-70% of the total volume of the bone restoration body material.
2. The porous bone prosthesis according to claim 1, wherein the pores in said bone prosthesis comprise micropores with a pore size of less than 50 microns and macropores with a pore size of 100 and 300 microns, and the micropores are mainly present on the walls of the macropores.
3. The porous bone prosthesis according to claim 1, wherein the hydroxyapatite component in said bone prosthesis is a nano-sized hydroxyapatite powder obtained by reacting a calcium salt with a phosphate.
4. The porous bone prosthesis according to claim 1, wherein the calcium/phosphorus molar ratio in the hydroxyapatite component of said material composition is 1.60 to 1.67.
5. The porous bone prosthesis according to any one of claims 1 to 4, wherein said material is composed of a medical polyamide component selected from the group consisting of polyamide 6, polyamide 66, polyamide 11, polyamide 12 and polyamide MXD-6.
6. The porous bone prosthesis according to claim 5, wherein said material composition comprises polyamide 66 as the medical polyamide component.
7. A method for preparing the porous bone prosthesis of claim 1, wherein the method comprises mixing medical polyamide fine powder and hydroxyapatite fine powder according to the above ratio, mixing with ethanol solution containing 14-70% by weight/volume of calcium chloride at a solid/liquid ratio of 1 g/(0.5-1) ml, solidifying, and dissolving with water to remove water-soluble components in the solidified material to form a pore structure in the bone prosthesis material.
8. The method according to claim 7, wherein the finely divided mixture of the hydroxyapatite component and the polyamide component is mixed with a calcium chloride/ethanol solution, and then the mixture is solidified in air, and then placed in water to dissolve and remove the water-soluble component therein to form the void structure.
9. The method according to claim 7, wherein the finely divided mixture of the hydroxyapatite component and the polyamide component is mixed with a calcium chloride/ethanol solution, and the mixture is placed in water, and the solidification and dissolution of the mixed material to remove water-soluble components are carried out simultaneously.
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