CN110624136B - Degradable medical composite material and preparation method and application thereof - Google Patents
Degradable medical composite material and preparation method and application thereof Download PDFInfo
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- CN110624136B CN110624136B CN201910949265.9A CN201910949265A CN110624136B CN 110624136 B CN110624136 B CN 110624136B CN 201910949265 A CN201910949265 A CN 201910949265A CN 110624136 B CN110624136 B CN 110624136B
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- composite material
- degradable medical
- medical composite
- tricalcium phosphate
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- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title abstract description 22
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 83
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 60
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 32
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 53
- 238000002156 mixing Methods 0.000 claims description 39
- 238000001746 injection moulding Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
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- 239000002245 particle Substances 0.000 claims description 24
- 229920001400 block copolymer Polymers 0.000 claims description 22
- 239000007943 implant Substances 0.000 claims description 21
- 230000000399 orthopedic effect Effects 0.000 claims description 20
- 239000011812 mixed powder Substances 0.000 claims description 16
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- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 9
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- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 claims description 6
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- 229940074391 gallic acid Drugs 0.000 claims description 3
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 claims description 3
- 235000005875 quercetin Nutrition 0.000 claims description 3
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- 239000011256 inorganic filler Substances 0.000 abstract description 28
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- 229910052698 phosphorus Inorganic materials 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000004071 biological effect Effects 0.000 description 4
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- 229940079593 drug Drugs 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
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Classifications
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L31/127—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing fillers of phosphorus-containing inorganic materials
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L31/129—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing macromolecular 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a degradable medical composite material, and a preparation method and application thereof. The degradable medical composite material provided by the invention comprises the following raw materials in percentage by mass: 55-80% of polylactic acid-glycolic acid copolymer; 15-40% of beta-tricalcium phosphate; 0.5-2% of plant polyphenol; 3-10% of PLGA-b-PEG-b-PLGA. The composite material provided by the invention takes polylactic acid-glycolic acid copolymer (PLGA) as a degradable organic base material, takes beta-tricalcium phosphate as an inorganic filler, adopts plant polyphenol as a coupling agent, and adopts PLGA-b-PEG-b-PLGA as a compatilizer, and the composite material has strong interfacial bonding force between an organic phase and an inorganic phase and excellent mechanical property. Experimental results show that the tensile strength of the degradable medical composite material is more than 53MPa, and the bending strength of the degradable medical composite material is more than 115 MPa.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a degradable medical composite material, and a preparation method and application thereof.
Background
In recent years, more fracture fixtures made of absorbable materials are used clinically, and achieve better internal fixation effect. Compared with the metal internal fixation, the device has the most clinical attraction advantage that the device does not need to be taken out again after fracture healing in the case of internal fixation of fracture by receiving the high molecular biodegradable material device.
Although polylactic acid and other absorbable implanted products prepared from single degradable high polymer materials are generally applied clinically, certain problems still exist in practical application, mainly because the material has low bone bonding capability and no osteoconductivity, and an acid product generated by degradation after the product is implanted into a human body can cause aseptic inflammatory reaction and even aseptic osteonecrosis, and meanwhile, the acid product can promote the material to undergo self-accelerated degradation.
PLGA is formed by random polymerization of two monomers, namely lactic acid and glycolic acid, is a degradable functional polymer organic compound, has better mechanical strength and elastic modulus, good biocompatibility, no toxicity and good encapsulation and film forming performance, and is widely applied to the fields of pharmacy, medical engineering materials and modern industry.
The beta-tricalcium phosphate is mainly composed of calcium and phosphorus, and the components of the beta-tricalcium phosphate are similar to the inorganic components of the bone matrix and are well combined with the bone. Animal or human somatic cells can normally grow, differentiate and propagate on beta-tricalcium phosphate material. The calcium/phosphorus ratio in tricalcium phosphate (TCP) is 1.5:1, the calcium/phosphorus ratio is close to that of normal bone tissues, TCP HAs different biological properties from Hydroxyapatite (HA), and the biggest difference is that after TCP is implanted into a human body, the TCP can be degraded in vivo to provide rich Ca and P for the formation of new bones. Meanwhile, the TCP has good bone conduction performance and biocompatibility, and after the material is implanted into an animal body, bones and the material can be directly fused. And the degradation product of the beta-TCP is alkalescent, can neutralize lactic acid and glycolic acid generated by PLGA degradation, but has poor toughness, brittleness and poor load bearing performance.
TCP and PLGA are compounded, so that the composite material has excellent mechanical and biological properties, and acidic degradation products of PLGA can be buffered by beta-TCP alkalescence, so that the occurrence of inflammation of tissues around an implant is reduced or even avoided; the beta-TCP provides high-quality calcium and phosphorus sources for the bone healing or repairing process, improves the bone bonding capability of the material, and provides a good bone cell adhesion growth environment for bone induction.
The composite material has various preparation processes, and different preparation methods influence the mechanical property and the biological property of the material. The conventional preparation methods include a melt blending method, a solvent volatilization method and an in-situ polymerization method, wherein the solvent volatilization method is commonly used in laboratory research, and comprises the steps of dissolving a high polymer material in an organic solvent, adding an inorganic material, and uniformly dispersing inorganic particles in a high polymer solution by a mechanical stirring or ultrasonic oscillation method. Removing the solvent, drying at a certain temperature and vacuum degree to obtain the composite material, and performing post-processing. The solvent evaporation method has the advantages that the two materials are uniformly mixed, and has the defects that a large amount of organic solvent is needed, the environmental pollution and the health hazard are caused, and the method is not suitable for industrial production and use. The in-situ polymerization method is to mix inorganic materials before the polymerization of monomers and then initiate the polymerization by an initiator under a certain temperature and high vacuum state. The inorganic filler in the prepared composite material is uniformly dispersed in a polymer matrix, the interface combination is good, but the method has strict requirements on polymerization monomers and polymerization reaction conditions, if the control is not good, the polymerization is incomplete, the monomers can be dissociated, the molecular weight of the composite material obtained by the method is difficult to increase, and the application is limited. The melt blending method is simple, the inorganic filler is directly added into the high molecular material, and is blended under the condition of the melting temperature higher than that of the high molecular material, and the inorganic filler is dispersed in the polymer matrix by virtue of mechanical action force. The preparation method has the advantages that the shape and the size of the particles can be controlled in the preparation process, the difficulty is the dispersion problem of the inorganic particles, and the agglomeration is easy to form.
Research shows that the strength loss of the composite material of the high molecular material and the inorganic filler occurs at the two-phase interface of the high molecular material and the inorganic material firstly, because the surface properties of the inorganic material and the organic polymer have larger difference and the interface bonding force is weaker. Therefore, how to improve the interfacial bonding force between the polymer material and the inorganic material in the composite material is the key to improve the mechanical property of the composite material.
Disclosure of Invention
In view of the above, the present invention provides a degradable medical composite material, and a preparation method and an application thereof, and the degradable medical composite material provided by the present invention has strong interface bonding force between an organic phase and an inorganic phase, and excellent material mechanical properties.
The invention provides a degradable medical composite material which comprises the following raw materials in percentage by mass:
preferably, the molar ratio of lactide structures in the polylactic acid-glycolic acid copolymer is 70-90%, and the molar ratio of glycolide structures in the polylactic acid-glycolic acid copolymer is 10-30%;
the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 20-55 ten thousand.
Preferably, the particle size of the beta-tricalcium phosphate is 10-200 mu m.
Preferably, the plant polyphenol comprises one or more of tannic acid, gallic acid and quercetin.
Preferably, the mass ratio of the PLGA block to the PEG block in the PLGA-b-PEG-b-PLGA block copolymer is 1: (0.5 to 2);
the weight average molecular weight of the PLGA-b-PEG-b-PLGA block copolymer is 1000-10000.
The invention provides a preparation method of the degradable medical composite material in the technical scheme, which comprises the following steps:
a) mixing plant polyphenol and beta-tricalcium phosphate in a liquid phase medium for reaction to obtain a beta-tricalcium phosphate solution treated by the plant polyphenol;
b) mixing and reacting PLGA-b-PEG-b-PLGA block copolymer and the beta-tricalcium phosphate solution treated by the plant polyphenol to obtain modified beta-tricalcium phosphate;
c) and melting and blending the polylactic acid-glycolic acid copolymer and the modified beta-tricalcium phosphate to obtain the degradable medical composite material.
Preferably, step c) specifically comprises:
c1) mixing polylactic acid-glycolic acid copolymer and the modified beta-tricalcium phosphate, and then freezing and grinding to obtain mixed powder;
c2) and carrying out melt blending on the mixed powder to obtain the degradable medical composite material.
The invention provides an absorbable orthopedic implant product, which is made of the degradable medical composite material in the technical scheme.
Preferably, the absorbable orthopedic implant product is an absorbable interface screw, an absorbable anchor or an absorbable bone plate.
The invention provides a preparation method of an absorbable orthopedic implant product, which comprises the following steps:
the degradable medical composite material of the technical scheme is subjected to injection molding to obtain an absorbable orthopedic implant product.
Compared with the prior art, the invention provides a degradable medical composite material and a preparation method and application thereof. The degradable medical composite material provided by the invention comprises the following raw materials in percentage by mass: 55-80% of polylactic acid-glycolic acid copolymer; 15-40% of beta-tricalcium phosphate; 0.5-2% of plant polyphenol; 3-10% of PLGA-b-PEG-b-PLGA block copolymer. The degradable medical composite material provided by the invention takes polylactic acid-glycolic acid copolymer (PLGA) as a degradable organic base material, takes beta-tricalcium phosphate as an inorganic filler, adopts plant polyphenol as a coupling agent, and adopts PLGA-b-PEG-b-PLGA block copolymer as a compatilizer. In the invention, a plurality of ortho-phenolic hydroxyl groups in the plant polyphenol can be used as a polybase ligand to carry out complexation reaction with calcium ions in tricalcium phosphate to form a stable chelate; meanwhile, phenolic hydroxyl of the plant polyphenol can also form hydrogen bonds with hydroxyl in a PEG chain segment in a compatilizer PLGA-b-PEG-b-PLGA block copolymer; the tail end of the PLGA chain segment of the PLGA-b-PEG-b-PLGA segmented copolymer can be connected with the PLGA base material in a physical entanglement mode through the van der Waals force and other actions, so that the interface action between the inorganic filler tricalcium phosphate and the PLGA base material is improved, the compatibility of the composite material and the dispersibility of the filler are improved, and the mechanical property of the composite material is further improved. Experimental results show that the tensile strength of the degradable medical composite material is more than 53MPa, and the bending strength of the degradable medical composite material is more than 115 MPa.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a degradable medical composite material which comprises the following raw materials in percentage by mass:
the degradable medical composite material provided by the invention is prepared from raw materials comprising polylactic acid-glycolic acid copolymer, beta-tricalcium phosphate, plant polyphenol and PLGA-b-PEG-b-PLGA block copolymer. The polylactic acid-glycolic acid copolymer (PLGA) is a degradable high polymer material and is used as an organic base material in the composite material. In the present invention, the molar ratio of the lactide structure in the PLGA is preferably 70 to 90%, and specifically may be 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%; the mole ratio of the glycolide structure in the PLGA is preferably 10-30%, and specifically can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%; the sum of the ratio of the lactide structure to the glycolide structure is 100 percent. In the present invention, the weight average molecular weight (Mw) of PLGA is preferably 20 to 55 ten thousand, specifically 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54 or 55 ten thousand; the intrinsic viscosity of the PLGA (at 25 ℃, the solvent is chloroform) is preferably 1.5-3.3 dl/g, and specifically can be 1.5dl/g, 1.6dl/g, 1.7dl/g, 1.8dl/g, 1.9dl/g, 2dl/g, 2.1dl/g, 2.2dl/g, 2.3dl/g, 2.4dl/g, 2.5dl/g, 2.6dl/g, 2.7dl/g, 2.8dl/g, 2.9dl/g, 3dl/g, 3.1dl/g, 3.2dl/g or 3.3 dl/g. In the present invention, the content of PLGA in the raw material is 55 to 80 wt%, specifically 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt% or 80 wt%.
In the invention, the beta-tricalcium phosphate is used as an inorganic filler in the composite material, and the particle size of the beta-tricalcium phosphate is preferably 10-200 μm, and specifically can be 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm or 200 μm. In the present invention, the content of the β -tricalcium phosphate in the raw material is 15 to 40 wt%, specifically 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, or 40 wt%.
In the present invention, the plant polyphenol (plant polyphenol) serves as a coupling agent of the organic base material and the inorganic filler. Plant polyphenol is a secondary metabolite with a polyphenol structure widely existing in plants, polyphenol substances are called as 'seventh nutrient', the polyphenol substances mainly comprise flavonoids, tannins, phenolic acids, anthocyanin and the like in the plants, and the plant polyphenol has the biological activity functions of removing free radicals in organisms, resisting lipid oxidation, delaying organism aging, preventing cardiovascular diseases, preventing cancers, resisting radiation and the like. The applications of plant polyphenols in the traditional industry mainly include tanning, oil extraction and wood processing. Besides being widely applied in the traditional industry, the plant polyphenol compound is the main application direction of plant polyphenol in the aspects of daily chemical products, medicines, agriculture, food additives, functional polymer materials and the like. The plant polyphenol has obvious inhibition effect on various bacteria, fungi and saccharomycetes, especially has strong inhibition capability on common pathogenic bacteria such as cholera bacteria, staphylococcus aureus, escherichia coli and the like, and does not influence the growth and development of organisms. Plant polyphenols can be selectively bound to the connective tissue of the joint to prevent joint swelling, help heal damaged tissue, and relieve pain. Therefore, the plant polyphenol has obvious effect on various types of arthritis. In 2006, 10 months, the U.S. Food and Drug Administration (FDA) approved tea polyphenols as a new prescription drug for the topical (external) treatment of genital warts caused by human papilloma virus. This is the first approved plant (herbal) drug by the FDA on the market according to the 1962 drug amendments. In the invention, a plurality of ortho-phenolic hydroxyl groups in the plant polyphenol can be used as a polybase ligand to carry out complexation reaction with calcium ions in tricalcium phosphate to form a stable chelate; meanwhile, phenolic hydroxyl of the plant polyphenol can also form hydrogen bonds with hydroxyl in a PEG chain segment in a compatilizer PLGA-b-PEG-b-PLGA segmented copolymer, so that the interface action between tricalcium phosphate as an inorganic filler and PLGA as an organic base material is improved, and the mechanical property of the composite material is improved.
In the present invention, the plant polyphenol preferably includes one or more of tannic acid, gallic acid, and quercetin. In the present invention, the content of the plant polyphenol in the raw material is 0.5 to 2 wt%, specifically 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, or 2 wt%.
In the present invention, the PLGA-b-PEG-b-PLGA block copolymer (PLGA-PEG-PLGA block copolymer) is used as a compatibilizer, the hydroxyl groups of the PEG segments in the block copolymer can react with the hydroxyl groups of the plant polyphenol through a large number of hydrogen bonds to form chemisorption, and the ends of the PLGA segments in the block copolymer can be physically entangled with the PLGA substrate through van der waals force, etc., thereby enhancing the interfacial bonding between the two phases. In the present invention, the mass ratio of the PLGA block to the PEG block in the PLGA-b-PEG-b-PLGA block copolymer is preferably 1: (0.5-2), specifically 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1: 2; the weight average molecular weight of the PLGA-b-PEG-b-PLGA block copolymer is preferably 1000-10000, and specifically can be 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 5727, 6000, 6288, 6500, 7000, 7500, 8000, 8500, 9000, 9500 or 10000. In the present invention, the content of the PLGA-b-PEG-b-PLGA block copolymer in the raw material is 3 to 10 wt%, specifically 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt% or 10 wt%.
The invention also provides a preparation method of the degradable medical composite material in the technical scheme, which comprises the following steps:
a) mixing plant polyphenol and beta-tricalcium phosphate in a liquid phase medium for reaction to obtain a beta-tricalcium phosphate solution treated by the plant polyphenol;
b) mixing and reacting PLGA-b-PEG-b-PLGA block copolymer and the beta-tricalcium phosphate solution treated by the plant polyphenol to obtain modified beta-tricalcium phosphate;
c) and melting and blending the polylactic acid-glycolic acid copolymer and the modified beta-tricalcium phosphate to obtain the degradable medical composite material.
In the preparation method of the degradable medical composite material provided by the invention, plant polyphenol and beta-tricalcium phosphate are mixed in a liquid phase medium. The liquid phase medium is preferably a phosphoric acid aqueous solution, and the phosphoric acid volume concentration in the phosphoric acid aqueous solution is preferably 0.5 to 1 vol%, and specifically may be 0.5 vol%, 0.6 vol%, 0.7 vol%, 0.8 vol%, 0.9 vol%, or 1 vol%. In the invention, the specific process of mixing is preferably to mix the plant polyphenol and the liquid-phase medium to obtain the plant polyphenol solution; and mixing the plant polyphenol solution with beta-tricalcium phosphate. In the invention, the mixing of the plant polyphenol and the liquid phase medium is preferably carried out under an ultrasonic condition, the mixing temperature is preferably 40-60 ℃, specifically 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, the mixing time is not particularly limited, and the plant polyphenol can be completely dissolved in the liquid phase medium. In the invention, the mixing of the plant polyphenol solution and the beta-tricalcium phosphate is preferably carried out under an ultrasonic condition, the mixing temperature is preferably 40-60 ℃, specifically 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, and the mixing time is 1-3 hours, specifically 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours. In the invention, after plant polyphenol and beta-tricalcium phosphate are mixed in a liquid phase medium, hydroxyl of the plant polyphenol and calcium ions of the beta-tricalcium phosphate react to generate a complex, and after the mixing reaction is finished, the beta-tricalcium phosphate solution treated by the plant polyphenol is obtained.
In the preparation method of the degradable medical composite material, after the beta-tricalcium phosphate solution treated by the plant polyphenol is obtained, the PLGA-b-PEG-b-PLGA segmented copolymer is mixed with the beta-tricalcium phosphate solution treated by the plant polyphenol. The mixing is preferably carried out under the ultrasonic condition, the mixing temperature is preferably 40-60 ℃, specifically 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, and the mixing time is 1-3 hours, specifically 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours. In the invention, after the PLGA-b-PEG-b-PLGA block copolymer and the beta-tricalcium phosphate solution treated by the plant polyphenol are mixed, the-O-in the PEG chain segment in the PLGA-b-PEG-b-PLGA block copolymer reacts with the-OH in the plant polyphenol to generate hydrogen bonds, and after the mixing reaction is finished, the modified beta-tricalcium phosphate solution is obtained. Drying the modified beta-tricalcium phosphate solution, wherein the drying mode is preferably blast drying and vacuum drying; the drying temperature is preferably 50-70 ℃, specifically 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, and the drying time is preferably 6-12 h, specifically 6h, 7h, 8h, 9h, 10h, 11h or 12 h. And after drying, obtaining the modified beta-tricalcium phosphate in a powder state.
In the preparation method of the degradable medical composite material, provided by the invention, after the modified beta-tricalcium phosphate is obtained, PLGA and the modified beta-tricalcium phosphate are melted and blended to obtain the degradable medical composite material. In the invention, as the medical PLGA raw materials sold in the market are all granular (the particle diameter is generally 0.5-4 mm), a supplier cannot provide powdery raw materials, and the inorganic filler beta-tricalcium phosphate is micron or nano-scale powdery particles, the particle size difference between the two is too large, the inorganic filler is not uniformly distributed in PLGA, and meanwhile, in the process of preparing the medical composite material in a melting and blending device such as a double-screw extruder, the phenomenon of nonuniform blanking can occur because the beta-tricalcium phosphate has high density and small particle size and the blanking speed is higher than that of the PLGA material, and the content of the beta-tricalcium phosphate in the composite material at the front section of granulation is higher than that in the composite material at the rear section of granulation. Therefore, in order to avoid the above problems, the present invention preferably performs freeze grinding of PLGA and modified β -tricalcium phosphate to obtain micron-sized mixed powder, and then performs melt blending of the mixed powder to prepare the degradable medical composite material. In the present invention, on the one hand, the freeze-grinding process does not cause degradation of PLGA and a reduction in mechanical strength; on the other hand, the PLGA and the modified beta-tricalcium phosphate can be uniformly mixed by grinding, so that the phenomenon of nonuniform blanking caused by the difference of the particle size and the density of the composite material particles in the process of melt blending is avoided. More specifically, the polylactic acid-glycolic acid copolymer and the modified beta-tricalcium phosphate are prepared into the degradable medical composite material according to the following steps:
c1) mixing polylactic acid-glycolic acid copolymer and the modified beta-tricalcium phosphate, and then freezing and grinding to obtain mixed powder;
c2) and carrying out melt blending on the mixed powder to obtain the degradable medical composite material.
In the above step provided by the present invention, in step c1), the temperature of the freeze-grinding is preferably-196 ℃; the cooling time of the material is preferably 10-60 min, and specifically can be 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60 min; the grinding time is preferably 10-60 min, and specifically may be 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60 min.
In the above step provided by the present invention, in step c2), the melt blending is performed in an extruder, the temperature from a feed port of the extruder to a die is preferably 140 to 210 ℃, and the temperature of the die is preferably 190 to 200 ℃.
The invention provides a degradable medical composite material and a preparation method thereof, wherein polylactic acid-glycolic acid copolymer (PLGA) is used as a degradable organic base material, beta-tricalcium phosphate is used as an inorganic filler, plant polyphenol is used as a coupling agent, and PLGA-b-PEG-b-PLGA block copolymer is used as a compatilizer. In the invention, a plurality of ortho-phenolic hydroxyl groups in the plant polyphenol can be used as a polybase ligand to carry out complexation reaction with calcium ions in tricalcium phosphate to form a stable chelate; meanwhile, phenolic hydroxyl of the plant polyphenol can also form hydrogen bonds with hydroxyl in a PEG chain segment in a compatilizer PLGA-b-PEG-b-PLGA block copolymer; the tail end of the PLGA chain segment of the PLGA-b-PEG-b-PLGA segmented copolymer can be connected with the PLGA base material in a physical entanglement mode through the van der Waals force and other actions, so that the interface action between the inorganic filler tricalcium phosphate and the PLGA base material is improved, the compatibility of the composite material and the dispersibility of the filler are improved, and the mechanical property of the composite material is further improved.
In the preparation method of the optimized degradable medical composite material, the freeze grinding technology is adopted, so that the degradation of the degradable high polymer material in the grinding process is avoided, the PLGA and the inorganic filler can be uniformly mixed during grinding, and the phenomenon of nonuniform blanking caused by the difference of the particle size and the density of the composite material particles in the melting and blending process is avoided.
The invention also provides an absorbable orthopedic implant product, the material of the absorbable orthopedic implant product is the degradable medical composite material in the technical scheme, and the absorbable orthopedic implant product comprises but is not limited to an absorbable interface screw, an absorbable anchor or an absorbable bone plate. The absorbable orthopedic implant product provided by the invention adopts the degradable medical composite material provided by the invention, and has excellent mechanical properties.
The invention also provides a preparation method of the absorbable orthopedic implant product, which comprises the following steps:
the degradable medical composite material of the technical scheme is subjected to injection molding to obtain an absorbable orthopedic implant product.
In the preparation method of the absorbable orthopedic implant product provided by the invention, the degradable medical composite material is directly subjected to injection molding to obtain the absorbable orthopedic implant product. Wherein the injection molding temperature is preferably 170-220 ℃, and specifically can be 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃ or 220 ℃; the injection molding pressure is preferably 1600-2000 bar, and specifically can be 1600bar, 1650bar, 1700bar, 1750bar, 1800bar, 1850bar, 1900bar, 1950bar or 2000 bar; the dwell time of the injection molding is preferably 10-50 s, and specifically can be 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s or 50 s; the temperature of the injection molding mold is preferably 30-45 ℃, and specifically can be 30 ℃, 35 ℃, 40 ℃ or 45 ℃.
The preparation method of the absorbable orthopedic implant product provided by the invention takes the degradable medical composite material provided by the invention as a raw material to prepare the absorbable orthopedic implant product, and the product has excellent mechanical properties.
For the sake of clarity, the following examples are given in detail.
Example 1
Adding 15g of tannic acid (molecular weight of 1701.2) into 500mL of 0.7% (volume fraction) phosphoric acid solution, performing ultrasonic dispersion and dissolution for 30 minutes at 50 ℃ to obtain solution A, adding 270g of beta-tricalcium phosphate (particle size of 10-200 mu m) into the solution A, and performing ultrasonic dispersion and mixing for 2 hours at 50 ℃ to obtain plant polyphenol surface treatment beta-tricalcium phosphate solution B;
adding 80g of PLGA-B-PEG-B-PLGA (block mass ratio PLGA: PEG: 1:1, Mw: 6288) into the solution B, and ultrasonically stirring for 2 hours at 50 ℃ to dissolve the solution B to obtain a solution C;
drying the solution C in a 60 ℃ forced air drying oven for 8 hours, and then placing the solution C in a 50 ℃ vacuum drying oven for drying until the moisture content is less than 500ppm to obtain modified inorganic filler powder D;
the modified inorganic filler powder D and 630 g of PLGA pellets (particle diameter 0.5-4 mm, lactide: glycolide molar ratio 82:18, intrinsic viscosity 2.0dl/g, Mw: 221000) were mechanically stirred in a flask for 30 minutes. And (3) after uniform stirring, adding the mixture into a grinding tank of a freezing grinder (protected by liquid nitrogen at the temperature of-196 ℃), putting the collider into the grinding tank, pre-cooling the sample in the grinder for 30 minutes, and taking out the sample after the grinding time is 30 minutes to obtain PLGA and modified inorganic filler mixed powder E.
Adding PLGA and modified inorganic filler mixed powder E into a Haake micro co-rotating twin-screw extruder PROCESS 11, setting the temperature of a feed inlet of the extruder to be 140-200 ℃, the temperature of an opening die to be 190 ℃, the rotating speed of a screw to be 80rpm, extruding a sample strip through the opening die, air-cooling, granulating, drying in vacuum until the moisture content is below 500ppm, and packaging in vacuum by using an aluminum plastic bag to obtain the degradable medical composite material.
The degradable medical composite material is subjected to product injection molding on a butterfield micro-injection molding machine, wherein the injection molding temperature is 170-200 ℃, the injection molding pressure is 1600-2000 bar, the pressure maintaining time is 21s, and the mold temperature is 30-45 ℃.
Example 2
Adding 10g of tannic acid (molecular weight of 1701.2) into 500mL of 0.7% (volume fraction) phosphoric acid solution, performing ultrasonic dispersion and dissolution for 30 minutes at 50 ℃ to obtain solution A, adding 282g of beta-tricalcium phosphate (particle size of 10-200 mu m) into the solution A, and performing ultrasonic dispersion and mixing for 2 hours at 50 ℃ to obtain plant polyphenol surface treatment beta-tricalcium phosphate solution B;
adding 50g of PLGA-B-PEG-B-PLGA (block mass ratio PLGA: PEG: 1:1.5, Mw: 5727) into the solution B, and ultrasonically stirring for 2 hours at 50 ℃ to dissolve the solution B to obtain a solution C;
drying the solution C in a 60 ℃ forced air drying oven for 8 hours, and then placing the solution C in a 50 ℃ vacuum drying oven for drying until the moisture content is less than 500ppm to obtain modified inorganic filler powder D;
the modified inorganic filler powder D and 658 g of PLGA pellets (particle diameter 0.5-4 mm, lactide: glycolide molar ratio 82:18, intrinsic viscosity 2.0dl/g, Mw: 221000) were mechanically stirred in a flask for 30 minutes. And (3) after uniform stirring, adding the mixture into a grinding tank of a freezing grinder (protected by liquid nitrogen at the temperature of-196 ℃), putting the collider into the grinding tank, pre-cooling the sample in the grinder for 30 minutes, and taking out the sample after the grinding time is 30 minutes to obtain PLGA and modified inorganic filler mixed powder E.
Adding the mixed powder E into a Haake micro co-rotating double-screw extruder PROCESS 11, setting the temperature of a feed inlet of the extruder to be 140-200 ℃, the temperature of a mouth mold to be 190 ℃, the rotating speed of a screw to be 80rpm, extruding a sample strip through the mouth mold, air-cooling, granulating, drying in vacuum to the moisture content of below 500ppm, and packaging in vacuum by using an aluminum plastic bag to obtain the degradable medical composite material.
The degradable medical composite material is subjected to product injection molding on a butterfield micro-injection molding machine, wherein the injection molding temperature is 170-200 ℃, the injection molding pressure is 1600-2000 bar, the pressure maintaining time is 21s, and the mold temperature is 30-45 ℃.
Example 3
Adding 15g of tannic acid (molecular weight of 1701.2) into 500mL of 0.7% (volume fraction) phosphoric acid solution, performing ultrasonic dispersion and dissolution for 30 minutes at 50 ℃ to obtain solution A, adding 270g of beta-tricalcium phosphate (particle size of 10-200 mu m) into the solution A, and performing ultrasonic dispersion and mixing for 2 hours at 50 ℃ to obtain plant polyphenol surface treatment beta-tricalcium phosphate solution B;
adding 80g of PLGA-B-PEG-B-PLGA (block mass ratio PLGA: PEG: 1:1, Mw: 6288) into the solution B, and ultrasonically stirring for 2 hours at 50 ℃ to dissolve the solution B to obtain a solution C;
drying the solution C in a 60 ℃ forced air drying oven for 8 hours, and then placing the solution C in a 50 ℃ vacuum drying oven for drying until the moisture content is less than 500ppm to obtain modified inorganic filler powder D;
the modified inorganic filler powder D and 630 g of PLGA pellets (particle diameter 0.5-4 mm, lactide: glycolide molar ratio 85:15, intrinsic viscosity 3.1dl/g, Mw: 485358) were mechanically stirred in a flask for 30 minutes. And (3) after uniform stirring, adding the mixture into a grinding tank of a freezing grinder (protected by liquid nitrogen at the temperature of-196 ℃), putting the collider into the grinding tank, pre-cooling the sample in the grinder for 30 minutes, and taking out the sample after the grinding time is 30 minutes to obtain PLGA and modified inorganic filler mixed powder E.
Adding the mixed powder E into a Haake micro co-rotating double-screw extruder PROCESS 11, setting the temperature of a feed inlet of the extruder to be 150-210 ℃, the temperature of a neck ring mold to be 200 ℃, the rotating speed of a screw to be 80rpm, extruding a sample strip through the neck ring mold, air-cooling, granulating, vacuum-drying until the moisture content is below 500ppm, and vacuum-packaging an aluminum-plastic bag to obtain the degradable medical composite material.
The degradable medical composite material is subjected to product injection molding on a butterfield micro-injection molding machine, wherein the injection molding temperature is 180-220 ℃, the injection molding pressure is 1600-2000 bar, the pressure maintaining time is 25s, and the mold temperature is 30-45 ℃.
Example 4
Adding 10g of tannic acid (molecular weight of 1701.2) into 500mL of 0.7% (volume fraction) phosphoric acid solution, performing ultrasonic dispersion and dissolution for 30 minutes at 50 ℃ to obtain solution A, adding 282g of beta-tricalcium phosphate (particle size of 10-200 mu m) into the solution A, and performing ultrasonic dispersion and mixing for 2 hours at 50 ℃ to obtain plant polyphenol surface treatment beta-tricalcium phosphate solution B;
adding 50g of PLGA-B-PEG-B-PLGA (block specific mass PLGA: PEG: 1:1.5, Mw: 5727) into the solution B, and ultrasonically stirring for 2 hours at 50 ℃ to dissolve the solution B to obtain a solution C;
drying the solution C in a 60 ℃ forced air drying oven for 8 hours, and then placing the solution C in a 50 ℃ vacuum drying oven for drying until the moisture content is less than 500ppm to obtain modified inorganic filler powder D;
the modified inorganic filler powder D and 658 g of PLGA pellets (particle diameter 0.5-4 mm, lactide: glycolide molar ratio 85:15, intrinsic viscosity 3.1dl/g, Mw: 485358) were mechanically stirred in a flask for 30 minutes. And (3) after uniform stirring, adding the mixture into a grinding tank of a freezing grinder (protected by liquid nitrogen at the temperature of-196 ℃), putting the collider into the grinding tank, pre-cooling the sample in the grinder for 30 minutes, and taking out the sample after the grinding time is 30 minutes to obtain PLGA and modified inorganic filler mixed powder E.
Adding the mixed powder E into a Haake micro co-rotating double-screw extruder PROCESS 11, setting the temperature of a feed inlet of the extruder to be 150-210 ℃, the temperature of a neck ring mold to be 200 ℃, the rotating speed of a screw to be 80rpm, extruding a sample strip through the neck ring mold, air-cooling, granulating, vacuum-drying until the moisture content is below 500ppm, and vacuum-packaging an aluminum-plastic bag to obtain the degradable medical composite material.
The degradable medical composite material is subjected to product injection molding on a butterfield micro-injection molding machine, wherein the injection molding temperature is 180-220 ℃, the injection molding pressure is 1600-2000 bar, the pressure maintaining time is 25s, and the mold temperature is 30-45 ℃.
Comparative example 1
700g of PLGA pellets (particle diameter 0.5-4 mm, lactide/glycolide molar ratio 82:18, intrinsic viscosity 2.0dl/g, Mw: 221000) and 300g of beta-tricalcium phosphate (particle size 10-200 μm) were weighed and mechanically stirred in a flask for 30 minutes. And after uniformly stirring, adding the mixed composite material into a PROCESS 11 of a Haake micro co-rotating double-screw extruder, setting the temperature of a feed inlet of the extruder to be 140-200 ℃, the temperature of a neck mold to be 190 ℃, the rotating speed of a screw to be 80rpm, extruding a sample strip through the neck mold, air-cooling, granulating, drying in vacuum to the moisture content of below 500ppm, and packaging in vacuum through an aluminum plastic bag to obtain the degradable medical composite material.
The degradable medical composite material is subjected to product injection molding on a butterfield micro-injection molding machine, wherein the injection molding temperature is 170-200 ℃, the injection molding pressure is 1600-2000 bar, the pressure maintaining time is 25s, and the mold temperature is 30-45 ℃.
Comparative example 2
700g of PLGA pellets (particle diameter 0.5-4 mm, lactide-glycolide molar ratio 85:15, intrinsic viscosity 3.1dl/g, Mw: 485358) and 300g of beta-tricalcium phosphate (particle size 10-200 μm) were weighed and mechanically stirred in a flask for 30 minutes. And after uniformly stirring, adding the mixed composite material into a PROCESS 11 of a Haake micro co-rotating double-screw extruder, setting the temperature of a feed inlet of the extruder to be 150-210 ℃, the temperature of a neck mold to be 200 ℃, the rotating speed of a screw to be 80rpm, extruding a sample strip through the neck mold, air-cooling, granulating, drying in vacuum until the moisture content is below 500ppm, and packaging in vacuum through an aluminum plastic bag to obtain the degradable medical composite material.
The degradable medical composite material is subjected to product injection molding on a butterfield micro-injection molding machine, wherein the injection molding temperature is 180-220 ℃, the injection molding pressure is 1600-2000 bar, the pressure maintaining time is 25s, and the mold temperature is 30-45 ℃.
Example 5
Performance testing
The performance test results of the degradable medical composite materials and the interface screws prepared in the embodiments 1 to 4 and the comparative examples 1 to 2 are shown in table 1, and table 1 is a data table of the performance test of the degradable medical composite materials and the interface screws provided by the present invention.
TABLE 1 degradable medical composites and interfacial screw Performance test data sheet
The performance tests show that the tensile strength and the bending strength of the modified beta-TCP/PLGA composite material are obviously improved and are far higher than those of the unmodified beta-TCP/PLGA, the intrinsic viscosity of the interface screw which is injected by the modified beta-TCP/PLGA composite material is not obviously reduced compared with that of the interface screw which is injected by the unmodified beta-TCP/PLGA composite material, which indicates that the PLGA material is not obviously degraded in the freeze grinding process, the modified beta-TCP and the matrix PLGA are physically or chemically combined, the interface combination between the two phases is enhanced, and the strength of the material and the pull-out strength of the interface screw are obviously improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A degradable medical composite material comprises the following raw materials in percentage by mass:
the raw materials are prepared into the degradable medical composite material according to the following steps:
a) mixing plant polyphenol and beta-tricalcium phosphate in a liquid phase medium for reaction to obtain a beta-tricalcium phosphate solution treated by the plant polyphenol;
b) mixing and reacting PLGA-b-PEG-b-PLGA block copolymer and the beta-tricalcium phosphate solution treated by the plant polyphenol to obtain modified beta-tricalcium phosphate;
c) and melting and blending the polylactic acid-glycolic acid copolymer and the modified beta-tricalcium phosphate to obtain the degradable medical composite material.
2. The degradable medical composite material as claimed in claim 1, wherein the molar ratio of lactide structure in the polylactic acid-glycolic acid copolymer is 70-90%, and the molar ratio of glycolide structure is 10-30%;
the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 20-55 ten thousand.
3. The degradable medical composite material of claim 1, wherein the β -tricalcium phosphate has a particle size of 10 to 200 μm.
4. The degradable medical composite of claim 1, wherein the plant polyphenol comprises one or more of tannic acid, gallic acid, and quercetin.
5. The degradable medical composite of claim 1, wherein the mass ratio of the PLGA block to the PEG block in the PLGA-b-PEG-b-PLGA block copolymer is 1: (0.5 to 2);
the weight average molecular weight of the PLGA-b-PEG-b-PLGA block copolymer is 1000-10000.
6. The degradable medical composite according to claim 1, wherein step c) specifically comprises:
c1) mixing polylactic acid-glycolic acid copolymer and the modified beta-tricalcium phosphate, and then freezing and grinding to obtain mixed powder;
c2) and carrying out melt blending on the mixed powder to obtain the degradable medical composite material.
7. An absorbable orthopedic implant product, wherein the material of the absorbable orthopedic implant product is the degradable medical composite material according to any one of claims 1-6.
8. The absorbable orthopedic implant product of claim 7, wherein the absorbable orthopedic implant product is an absorbable interface screw, an absorbable anchor, or an absorbable bone plate.
9. A method for preparing an absorbable orthopedic implant product, comprising the following steps:
the degradable medical composite material as claimed in any one of claims 1 to 6 is subjected to injection molding to obtain an absorbable orthopedic implant product.
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| CN115120781A (en) * | 2022-07-11 | 2022-09-30 | 运怡（北京）医疗器械有限公司 | Medical composite high polymer material and preparation method thereof |
| CN115058109A (en) * | 2022-08-20 | 2022-09-16 | 北京天星博迈迪医疗器械有限公司 | Degradable composite material with mixed particle size and preparation method and application thereof |
| CN116139327B (en) * | 2023-04-18 | 2023-06-27 | 北京艾方德科技有限公司 | Medical polyurethane foam material for improving compliance cavity hemostasis |
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