CN115120781A - Medical composite high polymer material and preparation method thereof - Google Patents

Medical composite high polymer material and preparation method thereof Download PDF

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CN115120781A
CN115120781A CN202210812783.8A CN202210812783A CN115120781A CN 115120781 A CN115120781 A CN 115120781A CN 202210812783 A CN202210812783 A CN 202210812783A CN 115120781 A CN115120781 A CN 115120781A
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polymer material
calcium
preparing
medical composite
composite polymer
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付家鹏
刘继强
赵学东
吕心建
张明振
陈峥嵘
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Yunyi Beijing Medical Devices Co ltd
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Yunyi Beijing Medical Devices Co ltd
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Priority to PCT/CN2023/106599 priority patent/WO2024012411A1/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/04—Conditioning or physical treatment of the material to be shaped by cooling
    • B29B13/045—Conditioning or physical treatment of the material to be shaped by cooling of powders or pellets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion

Abstract

The invention relates to a preparation method of a medical composite high polymer material, wherein the medical composite high polymer material comprises polyaryletherketone and a calcium-phosphorus material, and the preparation method comprises the following steps: cooling the polyaryletherketone raw material to below the embrittlement temperature; finely processing the polyaryletherketone raw material under a freezing condition to obtain polyaryletherketone powder; and (3) co-extruding and molding polyaryletherketone powder and calcium-phosphorus material powder to form the medical composite high polymer material.

Description

Medical composite high polymer material and preparation method thereof
Technical Field
The invention relates to a preparation method of a medical composite high polymer material, in particular to a preparation method of a medical composite high polymer material containing polyaryletherketone and calcium-phosphorus materials.
Background
The elastic modulus of the thermoplastic special engineering plastic Polyetheretherketone (PEEK) is close to that of cortical bone, and especially the elastic modulus of carbon fiber reinforced PEEK (CFR-PEEK) is more matched with that of cortical bone. This close or matching modulus of elasticity reduces or eliminates stress shielding effects to some extent, thereby reducing or avoiding bone resorption, and facilitating osteointegration between the implant and the bone tissue. Therefore, from the 80 s in the 20 th century, PEEK has received increasing attention from researchers in materials science and bone science, and has the possibility of replacing metal materials in the field of hard tissue repair and replacement. PEEK is transparent to X-rays, and produces no artifacts upon CT or MRI scans, thus making it easier to monitor bone growth and healing processes. In addition, PEEK also has the characteristics of good biocompatibility, wear resistance, fatigue resistance, corrosion resistance, easy processing and the like. The advantages enable PEEK to be widely applied to the fields of wounds, spines, joints and the like. However, PEEK has no bioactivity and cannot form osseointegration with bone tissues, which limits the application of PEEK in the field of tissue repair and replacement to a certain extent.
In the face of the deficiency, research is mainly focused on improving the bioactivity and biocompatibility of the PEEK by changing the surface structure of the PEEK or adding active materials (such as hydroxyapatite, bioactive glass and the like), so as to provide a material which meets the requirements of biological performance for the implant.
Hydroxyapatite [ Ca ] 10 (PO 4 ) 6 (OH) 2 ]Is the best known CaP material, the Ca/P ratio is 1.67, the hydroxyapatite crystal is in a hexagonal system, and OH on the surface of the microcrystal - Can adsorb PO in vacancy 43 - Or phosphate radical or hydroxyl radical on macromolecule, can adsorb Sr when Ca ion position is vacant 3 + 、K + Iso-cation and protein molecular group, PO 43 - When it is on the surface of the crystal, H 2 O can be connected toHydrogen peroxide bonding with PO 43 - And (4) ion combination. Tricalcium phosphate [ Ca ] 3 (PO4) 2 ]The Ca/P ratio of (A) is 1.5, the calcium-phosphorus ratio of the calcium phosphate is close to that of hydroxyapatite, and the solubility of the calcium phosphate is higher under physiological conditions. The natural bone mineral composition is also a main component in natural bone mineral components, and researches show that the natural bone mineral composition also has the functions of being a carrier for drug or ion transfer and promoting the regeneration of new bones and new blood vessels, so that the natural bone mineral composition becomes one of the first-choice materials for repairing bone defects. In addition to the excellent biological performance, hydroxyapatite is relatively easy and inexpensive to produce and can be relatively easily developed for clinical applications, bringing great promise for the further development of bone tissue engineering. Other useful calcium phosphorus materials include tetracalcium phosphate, calcium oxide, and the like.
The hydroxyapatite powder may be prepared by a dry method, a chemical precipitation method, a sol-gel method, a hydrothermal synthesis method, a biomimetic solution growth synthesis method, and the like.
At present, PEEK mainly appears in the form of powder and granules in the production and processing process, commercially available medical PEEK only has granule products, and the granular products are mixed with hydroxyapatite for extrusion or injection molding, so that the problem of uniform dispersibility of hydroxyapatite particles in a PEEK matrix is difficult to solve, the particles are greatly agglomerated in the matrix, and the mechanical property, particularly the tensile strength, of the composite material is seriously reduced, potential safety hazards exist in clinical application, and the actual requirements of the clinical application are difficult to meet. Meanwhile, the commercially available PEEK powder is of an industrial grade and cannot meet the requirements of medical instruments.
PEEK bars containing 20% of hydroxyapatite are produced in the industry at present, the line diameter is about 16mm, and machining and cutting are needed to expose the hydroxyapatite in the PEEK bars, so that the line diameter and the processing means of the PEEK bars limit the PEEK bars from entering the field of sports medicine.
CN 080814638A provides a preparation method and application of a nano material/polyetheretherketone composite material, which adopts the processes of solution dispersion, grinding dispersion, high-speed dispersion and post-injection blending. Firstly, uniformly dispersing the nano material and the polyether-ether-ketone by using a dispersion liquid to obtain a blend, then drying, grinding and dispersing by using grinding equipment, and uniformly mixing with the rest polyether-ether-ketone by using a high-speed mixer to perform extrusion processing to obtain the plastic particles of the novel polyether-ether-ketone composite material. In the method, substances such as coupling agents and the like are introduced in the step of solution dispersion, so that the risk of materials is increased, the application in the field of medical instruments is not facilitated, the process is complex, and the time cost is high.
CN 110152068A provides a method for uniformly dispersing nano-hydroxyapatite in polyetheretherketone by ball-milling pretreatment, and then, after uniform mixing, the mixture of nano-hydroxyapatite and polyetheretherketone is melted in a double screw extruder for secondary mixing, thereby further improving the dispersibility of nano-hydroxyapatite in polyetheretherketone. However, the method utilizes a ball milling method to grind and mix the PEEK and the hydroxyapatite, on one hand, the ball milling method is difficult to sufficiently reduce the particle size of the PEEK so as to achieve the purpose of sufficiently mixing with the hydroxyapatite, and the problem of uneven dispersion still exists in the extrusion process; on the other hand, the ball milling process can cause the PEEK temperature to be obviously increased, and the color, the mechanical property and the like of the material are changed to a certain extent.
Therefore, it is desired to provide a method for preparing a medical composite polymer material, which can refine and sufficiently mix a commercially available medical grade PEEK pellet product and hydroxyapatite, realize uniform dispersion, sufficiently expose the surface, and have excellent product performance without introducing other impurities.
Disclosure of Invention
Therefore, the invention provides a preparation method of a medical composite high polymer material, wherein the medical composite high polymer material comprises polyaryletherketone and a calcium-phosphorus material, and the preparation method comprises the following steps:
cooling the polyaryletherketone raw material to below the embrittlement temperature;
finely processing the polyaryletherketone raw material under the freezing condition to obtain polyaryletherketone powder;
and (3) co-extruding and molding polyaryletherketone powder and calcium-phosphorus material powder to form the medical composite high polymer material.
The polyaryletherketone raw material is refined under the freezing condition, so that polyaryletherketone powder meeting the requirement of fine size can be obtained on the basis of a commercially available polyaryletherketone granular product, and then the polyaryletherketone powder and the calcium-phosphorus material powder respectively enter an extruder through two feeding ports of the extruder, are mixed in the extruder and are subjected to co-extrusion molding.
If the material is not frozen in the grinding process, the color of the obtained grinding powder can be changed into grey due to heat generated by friction between the polyaryletherketone material and a cutter, so that the appearance of the product is influenced.
Preferably, the polyaryletherketone is Polyetheretherketone (PEEK). The embrittlement temperature of polyetheretherketone is generally between-80 ℃ and-60 ℃, for example. It is further preferred that the calcium phosphate material comprises one or more of hydroxyapatite, alpha-tricalcium phosphate, beta-tricalcium phosphate, tetracalcium phosphate and calcium oxide. Preferably, the calcium phosphate material is hydroxyapatite, or tricalcium phosphate, or a mixture of hydroxyapatite and tricalcium phosphate, or a mixture of one or more of alpha-tricalcium phosphate, beta-tricalcium phosphate, tetracalcium phosphate and calcium oxide with hydroxyapatite. When the mixture contains hydroxyapatite, the mass percentage of the hydroxyapatite in the mixture is more than 80 percent. More preferably, the calcium-phosphorus ratio of the calcium-phosphorus material is preferably in the range of 1.65 to 1.82 specified in ISO 13779-3. Still preferably, the mass percentage of the calcium phosphorus material in the total mass of the polyaryletherketone and the calcium phosphorus material is 10-30%, preferably 15-20%. Alternatively or additionally, the polyaryletherketones may also be Polyetherketones (PEK), Polyetherketoneketones (PEKK), Polyetheretherketoneketones (PEEKK) and Polyetherketoneetherketoneketones (PEKEKK).
Preferably, the refining under freezing conditions is freeze grinding. For example, the rotational speed of the grinding in the freeze grinding is 15000rpm to 20000rpm, and the grinding time is 2 to 5 minutes.
Preferably, the particle size of the calcium-phosphorus material for mixing with the polyaryletherketone powder is 0.5-50 microns.
The low-temperature cooling of the polyaryletherketone raw material is preferably carried out by adopting a cooling medium which is easy to volatilize, has no residue and is harmless to a human body. According to a preferred embodiment of the present invention, the cooling medium is liquid nitrogen, and the polyaryletherketone raw material is cooled in the liquid nitrogen for 1-5 minutes to cool the polyaryletherketone raw material to the embrittlement temperature. Then, the refining treatment is carried out under the freezing condition of the temperature range of-150 ℃ to-110 ℃ (preferably-130 ℃). Refining to obtain polyaryletherketone powder. In this case, depending on the characteristics of the cooling medium used, it is conceivable to remove the cooling medium and water by vacuum-drying the polyaryletherketone powder obtained by the refinement treatment. And carrying out vacuum drying at the temperature of 120-180 ℃ for 4-8 hours.
Alternatively or additionally, it is also possible to cool the polyaryletherketone starting material to its embrittlement temperature, for example between-80 ℃ and-60 ℃, by selecting a residue-free and harmless to the human body combination among the substances employed in the common laboratory cooling baths listed in table 1 below:
TABLE 1 Cooling temperature of common laboratory cooling baths
Figure BDA0003739891200000041
Figure BDA0003739891200000051
According to a preferred embodiment of the preparation method of the medical composite polymer material, polyaryletherketone powder and calcium-phosphorus material powder are co-extruded and molded through an extruder, and the polyaryletherketone powder and the calcium-phosphorus material powder enter the extruder through different feeding ports. In the prior art, a single feeding port is adopted in a double-screw extruder. However, the difference between the particle size of the calcium phosphorus material and the particle size of the ground polyaryletherketone powder is very large (the particle size of the calcium phosphorus material is about 10 microns, and the particle size of the polyaryletherketone powder is about 400 microns), so that the mixed powder is difficult to uniformly mix, and the calcium phosphorus material with small particle size enters the feeding opening first, so that the calcium phosphorus material agglomeration phenomenon exists on the particle surface of the obtained calcium phosphorus material-polyaryletherketone, the appearance is influenced, and the mechanical property is reduced. In contrast, polyaryletherketone powder obtained by finely processing polyaryletherketone raw materials under a freezing condition and calcium phosphorus material powder enter an extruder through different feeding ports, so that the dispersion uniformity of a calcium phosphorus material in polyaryletherketone is facilitated, and calcium phosphorus material-polyaryletherketone particles with stable and consistent performance are obtained. The composite modification process enables hydroxyapatite to be uniformly dispersed in the polyetheretherketone, thereby solving the technical problem that the mechanical property of the composite material is reduced due to stress concentration caused by the agglomeration effect of the hydroxyapatite, and further improving the mechanical property of the polyetheretherketone/hydroxyapatite composite material while improving the biological activity.
The polyaryletherketone powder and the calcium-phosphorus material powder with proper particle sizes can be obtained by using the preparation method of the medical composite polymer material, so that the polyaryletherketone powder and the calcium-phosphorus material powder can be directly injected, and when hydroxyapatite and polyetheretherketone are used as raw materials, the hydroxyapatite powder and the polyetheretherketone are uniformly mixed and exposed on the surface of hydroxyapatite-polyetheretherketone (HA-PEEK) composite particles, so that a product obtained by directly injecting the Hydroxyapatite (HA) and the Polyetheretherketone (PEEK) is prevented from forming a hydrophobic layer on the surface, and the hydrophobic layer limits the hydroxyapatite to play a role of bioactivity on the surface.
According to another aspect of the present invention, there is also provided a medical composite polymer material prepared by the above method for preparing a medical composite polymer material.
Drawings
Fig. 1 is a flow chart schematically showing an embodiment of a method for producing a medical composite polymer material according to the present invention.
Detailed Description
The invention is described in detail below with reference to the attached drawing figures, which are only for explaining the invention and are not to be construed as limiting the invention.
Example one
As shown in fig. 1, first, commercially available medical grade Polyetheretherketone (PEEK) raw material pellet particles are cryogenically cooled to an embrittlement temperature or lower using liquid nitrogen as a cooling medium. And continuously taking liquid nitrogen as a cooling medium, and carrying out freezing grinding on the PEEK raw material at the temperature of-150 to-110 ℃ to realize refining treatment so as to obtain PEEK powder with the particle size of 50-800 micrometers. And then, carrying out vacuum drying on the obtained PEEK powder for 4-8 hours at the temperature of 120-180 ℃. Meanwhile, calcium phosphate material powder containing Hydroxyapatite (HA) and/or beta-tricalcium phosphate (beta-TCP) and/or alpha-tricalcium phosphate and/or tetracalcium phosphate and/or calcium oxide with a calcium-phosphorus ratio of 1.65-1.82 is provided, and the calcium phosphate material powder HAs a particle size of 0.5-50 microns. And then, co-extruding and molding the calcium-phosphorus material powder and PEEK powder by an extruder to form the medical composite polymer material.
The test proves that the performance parameters of the medical composite polymer material (HA-PEEK) prepared by the method completely reach the relevant material standards of PEEK, and the detailed parameters are shown in a table 2:
TABLE 2 measured HA-PEEK data
Performance of Require that HA-PEEK test data
Tensile strength at yield, Mpa ≥90 99
Tensile strength at break, Mpa ≥70 75
Elongation at break,% ≥5 15
Flexural strength, Mpa ≥110 170
Flexural modulus, Gpa ≥3 5
Notched impact strength (cantilever beam), J/m ≥50 70
Here, as the cutters used in the grinding process are all made of 316 stainless steel, and the temperature is controlled by liquid nitrogen in the grinding process, no new substance is generated or introduced in the grinding process, and no auxiliary agent or other substance is introduced in other production processes, the biocompatibility of the raw materials is not changed in the whole production process of the medical composite polymer material, so that the biocompatibility of the medical grade HA-PEEK material produced by the method completely meets the national standard GB/T16886.1-2011 part 1 of biological evaluation of medical devices: risk management assessments & tests "have associated with them the regulations and requirements of cytotoxicity, sensitization, irritation or intradermal response, acute systemic toxicity, subchronic toxicity, genotoxicity and implantation tests.
Example two
First, commercially available medical-grade Polyaryletherketone (PAEK) raw material pellet particles are cryogenically cooled to below the embrittlement temperature using liquid nitrogen as a cooling medium. And continuously taking liquid nitrogen as a cooling medium, and carrying out freeze grinding on the PAEK raw material at the temperature of-130 ℃ to obtain PAEK powder with the particle size of 50-800 micrometers. And then, carrying out vacuum drying on the PAEK powder for 4-8 hours at the temperature of 120-180 ℃. Then, calcium-phosphorus material powder with the calcium-phosphorus ratio of 1.65-1.82 and the particle size of 0.5-50 microns is provided, and the calcium-phosphorus material powder and the PAEK powder are co-extruded and molded through an extruder to form the medical composite polymer material.
EXAMPLE III
First, commercially available medical grade Polyetheretherketone (PEEK) raw material pellet particles were cryogenically cooled to below the embrittlement temperature using dry ice as a cooling medium. And continuously taking dry ice as a cooling medium, and carrying out freeze grinding on the PEEK raw material at the temperature of-78.5-57 ℃ to realize refining treatment so as to obtain PEEK powder with the particle size of 50-800 micrometers. And then, carrying out vacuum drying on the obtained PEEK powder for 4-8 hours at the temperature of 120-180 ℃. Then, calcium-phosphorus material powder with the calcium-phosphorus ratio of 1.65-1.82 and the particle size of 0.5-50 microns is provided, and the calcium-phosphorus material powder and PEEK powder are co-extruded and molded through an extruder to form the medical composite polymer material.
Example four
First, commercially available medical grade Polyetheretherketone (PEEK) raw material pellet particles are cryogenically cooled to an embrittlement temperature or lower using liquid nitrogen as a cooling medium. Then, using dry ice as a cooling medium, and carrying out freeze grinding on the PEEK raw material at the temperature of-78.5 to-57 ℃ to obtain PEEK powder with the particle size of 50-800 microns. And then, carrying out vacuum drying on the obtained PEEK powder for 4-8 hours at the temperature of 120-180 ℃. Meanwhile, calcium phosphate material powder containing Hydroxyapatite (HA) and/or beta-tricalcium phosphate (beta-TCP) and/or alpha-tricalcium phosphate and/or tetracalcium phosphate and/or calcium oxide with a calcium-phosphorus ratio of 1.65-1.82 is provided, and the calcium phosphate material powder HAs a particle size of 0.5-50 microns. And then, co-extruding and molding the calcium-phosphorus material powder and PEEK powder by an extruder to form the medical composite polymer material.
EXAMPLE five
First, commercially available medical grade Polyetheretherketone (PEEK) raw material pellet particles were cryogenically cooled to an embrittlement temperature or lower using dry ice as a cooling medium. Then, using liquid nitrogen as a cooling medium, and carrying out freeze grinding on the PEEK raw material at the temperature of-150 ℃ to-110 ℃ to obtain PEEK powder with the particle size of 50-800 microns. Then, the obtained PEEK powder is subjected to vacuum drying for 4 to 8 hours at a temperature of 120 to 180 ℃. Then, calcium-phosphorus material powder with the calcium-phosphorus ratio of 1.65-1.82 and the particle size of 0.5-50 microns is provided to form the medical composite polymer material.
In the above embodiments, the calcium-phosphorus material powder and the PAEK powder are respectively supplied into the extruder through one feeding port and are co-extruded by the extruder. The method avoids the agglomeration phenomenon caused by the fact that the calcium phosphorus material with relatively smaller particle size is easier to enter the extruder in the extruder structure with a single feeding port, thereby being beneficial to the dispersion uniformity of the calcium phosphorus material in the polyaryletherketone and ensuring that calcium phosphorus material-polyaryletherketone particles with stable and consistent performance are obtained
In each of the above examples, the cryogrinding process was incubated. The low temperature cooling and the freeze grinding are both carried out in the sealed container, and the input quantity of the used cooling medium is controlled according to the real-time monitoring result of the temperature in the sealed container, so as to ensure the temperature condition.
The embodiments described above may also be practiced with variations in that no cooling medium is added during the freeze-grinding process. However, this results in insufficient material freezing during the grinding process, which may result in the color of the resulting ground powder becoming gray due to frictional heat generation between the polyaryletherketone material and the grinding tools, thereby affecting the appearance of the product.
The foregoing describes preferred embodiments of the present invention, but the spirit and scope of the present invention is not limited to the specific disclosure herein. Those skilled in the art can freely combine and expand the above-described embodiments in accordance with the teachings of the present invention to make further embodiments and applications within the spirit and scope of the present invention. The spirit and scope of the present invention are not to be limited by the specific embodiments but by the appended claims.

Claims (24)

1. A preparation method of a medical composite high polymer material comprises polyaryletherketone and a calcium phosphorus material, and comprises the following steps:
cooling the polyaryletherketone raw material to below the embrittlement temperature;
refining the polyaryletherketone raw material under a freezing condition to obtain polyaryletherketone powder;
and co-extruding and molding the polyaryletherketone powder and calcium-phosphorus material powder to form the medical composite high polymer material.
2. The method for preparing the medical composite polymer material according to claim 1, wherein the polyaryletherketone is polyetheretherketone.
3. The method for preparing a medical composite polymer material according to claim 2, wherein the calcium-phosphorus material comprises one or more of hydroxyapatite, α -tricalcium phosphate, β -tricalcium phosphate, tetracalcium phosphate, and calcium oxide.
4. The method for preparing the medical composite polymer material according to claim 3, wherein the calcium phosphate material is hydroxyapatite or β -tricalcium phosphate.
5. The method for preparing a medical composite polymer material according to claim 3, wherein the calcium-phosphorus material is a mixture of one or more of α -tricalcium phosphate, β -tricalcium phosphate, tetracalcium phosphate and calcium oxide with hydroxyapatite.
6. The method for preparing a medical composite polymer material according to claim 5, wherein the calcium phosphate material is a mixture of hydroxyapatite and β -tricalcium phosphate.
7. The method for preparing the medical composite polymer material according to claim 5 or 6, wherein the mass percentage of the hydroxyapatite in the mixture is more than 80%.
8. The method for preparing the medical composite polymer material according to any one of claims 1 to 3, wherein the polyaryletherketone powder obtained by the refining treatment is vacuum-dried.
9. The method for preparing the medical composite polymer material according to claim 8, wherein the vacuum drying is performed at 120-180 ℃ for 4-8 hours.
10. The method for preparing a medical composite polymer material according to claim 8 or 9, wherein polyaryletherketone powder and calcium-phosphorus material powder are co-extruded by an extruder, and enter the extruder through different feeding ports.
11. The method for preparing the medical composite high molecular material according to any one of claims 1 to 3, wherein a volatile, residue-free and harmless cooling medium is used in the step of performing low-temperature cooling and fine processing on the polyaryletherketone raw material.
12. The method for preparing the medical composite polymer material according to claim 11, wherein the cooling medium is liquid nitrogen or dry ice, and the cooling time of the polyaryletherketone raw material which is cooled to the brittle temperature below in the cooling medium is 1-5 minutes.
13. The method for preparing the medical composite polymer material according to claim 12, wherein the cooling medium is liquid nitrogen, and the refinement treatment under the freezing condition is performed at a temperature ranging from-150 ℃ to-110 ℃.
14. The method for preparing the medical composite polymer material according to claim 13, wherein the refinement treatment under the freezing condition is performed at a temperature of-130 ℃.
15. The method for preparing the medical composite polymer material according to claim 12, wherein the cooling medium is dry ice, and the refinement treatment under the freezing condition is performed at a temperature range of-78.5 ℃ to-57 ℃.
16. The method according to any one of claims 1 to 3, wherein the refinement treatment is freeze grinding.
17. The method for preparing a medical composite polymer material according to claim 16, wherein the rotational speed of the freeze-grinding is 15000rpm to 20000rpm, and the grinding time is 2 to 5 minutes.
18. The method for preparing the medical composite polymer material according to any one of claims 1 to 3, wherein the particle size of the calcium-phosphorus material powder is 0.5 to 50 μm.
19. The method for preparing the medical composite polymer material according to any one of claims 1 to 3, wherein the calcium-phosphorus material accounts for 10-30% of the total mass of the polyaryletherketone and the calcium-phosphorus material.
20. The method for preparing the medical composite polymer material according to claim 19, wherein the calcium-phosphorus material accounts for 15-20% of the total mass of the polyaryletherketone and the calcium-phosphorus material.
21. The method for preparing the medical composite polymer material according to any one of claims 1 to 3, wherein the calcium-phosphorus ratio of the calcium-phosphorus material is in a range of 1.65 to 1.82.
22. The method for producing a medical composite polymer material according to any one of claims 1 to 3, wherein the refinement treatment under the freezing condition is performed under the heat-retaining condition.
23. The method for preparing a composite polymer material for medical use according to claim 22, wherein the cryogenic cooling and the refinement under the freezing condition are both performed in a sealed container, and the input amount of the cooling medium used is controlled according to the result of monitoring the temperature in the sealed container in real time.
24. A medical composite polymer material, characterized in that it is prepared by the method for preparing a medical composite polymer material according to any one of claims 1 to 23.
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