CN111388752B - PVA fiber/polyamino acid/hydroxyapatite bone supporting material and preparation thereof - Google Patents
PVA fiber/polyamino acid/hydroxyapatite bone supporting material and preparation thereof Download PDFInfo
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Abstract
The invention relates to a medical composite material, in particular to a PVA fiber polyamino acid hydroxyapatite composite bone supporting material and a preparation method thereof. The invention provides a composite bone repair material, which consists of a polybasic amino acid polymer, polyvinyl alcohol fiber, calcium phosphate salt and a coupling agent, wherein the mass ratio of the raw materials is as follows: 20-50% of calcium phosphate salt, 15-30% of polyvinyl alcohol fiber, 20-55% of polybasic amino acid polymer and 1-5% of coupling agent. The PVA fiber polyamino acid calcium phosphate composite material has high strength, high toughness and high elastic modulus, and can be prepared into the supporting bone repair implant through injection molding rapid forming or hot press forming, wherein the bending strength of the obtained supporting bone repair implant is 120-160 MPa, the bending modulus is 5-15 GPa, the compressive strength of the obtained supporting bone repair implant is 120-180 MPa, and the biomechanical property of the obtained supporting bone repair implant is close to that of human bone tissues.
Description
Technical Field
The invention relates to a medical composite material capable of being used for load-bearing bone repair and reconstruction, in particular to a high-strength PVA fiber polyamino acid hydroxyapatite composite bone supporting material and a preparation method thereof.
Background
Bones are the support system of the human body, and bear the core system of the weight, movement and activities of the human body. Main bone body injuries of load-bearing bones caused by various factors need to be repaired and replaced in time to maintain the normal supporting function of the load-bearing bones. The forming period is generally 26-28 weeks, and then the complete bone tissue is formed through multiple reconstructions to complete the functional repair. Thus, a slightly larger lesion module (greater than 3cm diameter \ greater than 5cm length) during the bone formation cycle makes it difficult to form a complete new bone module to replace the implanted bone material entirely, both in allogenic and synthetic materials, with the difficulty of completely matching the new bone formation rate, strength and performance with the pre-traumatic bone, and surrounding interface. In most cases, the materials with close biomechanical properties and good compatibility and capable of forming a firm interface are selected for replacing and recovering to obtain the functions of the bone supporting system. The single material is difficult to meet the requirements in the aspects of density, biomechanical property, compatibility and stability, so that the formation of the multifunctional high-performance composite material bone support body by comprehensively utilizing the properties of various components is one of effective ways for solving the problems. The main components of human bone tissue include water, organic substances, inorganic salts, etc., and the content of water in the bone is small compared to other tissues and organs. Of the remaining solid matter, about 40% is organic matter (collagen), 60% is inorganic salt (apatite), and bone tissue can be regarded as a composite material composed of organic matter and inorganic salt. The inorganic salts in the bone are mainly crystalline hydroxyapatite, amorphous calcium phosphate and the like, and the inorganic salt components determine the hardness of the bone. Most of the organic substances are collagen, and the rest are other protein peptides and lipids such as glycosamine, glycan and the like, and the organic substances determine the elasticity and toughness of bones.
Biomechanics is one of the determining factors for the function of bone repair materials and repaired tissues. The traditional ceramic materials and metal materials are far different from bone tissue in mechanical strength, hardness, rigidity and elastic modulus, so that stress shielding is often caused, and the problems of loosening of repair materials, abrasion and necrosis of bone tissues, separation and the like often occur.
Therefore, the single-component ceramic, metal or polymer materials cannot meet the clinical requirements for hard tissue repair and reconstruction. The biomedical composite material not only has the properties and advantages of each component material, but also can obtain new characteristics which are not possessed by a single-component material. Among many bone repair composite materials, the nano-hydroxyapatite/polymer composite material simulates the composition or structural composition of inorganic to organic phases of natural bone, can combine the bioactivity of hydroxyapatite and the toughness of polymers, and is widely researched.
The subject group in the last decade is dedicated to the research on amino acid bone tissue repair materials, such as molecular chain design, inorganic filler selection, and full organic filling of polyamino acid, etc., such as polymer tissue repair materials and preparation methods (CN 101342383B), multi-component amino acid polymer tissue repair materials and preparation methods (CN 101385869B), degradable bioactive composite materials containing calcium phosphate components and preparation methods (CN 101417149B), amino acid copolymer-calcium sulfate composite materials and preparation methods (CN 101560326B), multi-component amino acid polymer-hydroxyapatite bone repair materials, support implants and preparation methods (CN104324415B), controllable degradable multi-component amino acid copolymer-organic calcium/phosphorus salt filling type composite bone implants and preparation methods (CN 104307048B), etc., but the prosthesis and bone graft thereof which are really similar to bone tissue structure and performance need deeper research, summarizing the research results, the design and preparation of the high-strength PVA fiber polyamino acid hydroxyapatite composite bone supporting material are provided, and the high-strength PVA fiber polyamino acid hydroxyapatite composite bone supporting material has a more stable interface, more approaches to the biomechanical property of a human supporting bone, has excellent biological safety and biological activity, and more approaches to the bionic structure and performance of human bone tissues and clinical requirements.
Disclosure of Invention
In order to solve the above problems, the invention designs and prepares the high-strength PVA fiber polybasic amino acid high polymer calcium phosphate salt composite bone supporting material by using a bionic structure starting from the composition and the structure of human bone tissues; coupling modification is carried out on the surfaces of the high-strength PVA fiber and the hydroxyapatite by using a coupling agent (such as titanate) which has good biocompatibility and no toxicity, so that the activity of the coupling agent is increased, and a stable interface is formed between the coupling agent and the polyamino acid.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a polyvinyl alcohol fiber/polybasic amino acid polymer/calcium phosphate salt composite bone repair material, which consists of a polybasic amino acid polymer, polyvinyl alcohol fibers, calcium phosphate salt and a coupling agent, wherein the mass of the calcium phosphate salt is 20-50% of that of the bone repair material, the mass of the polyvinyl alcohol fibers is 15-30% of that of the bone repair material, the mass of the polybasic amino acid polymer is 20-55% of that of the bone repair material, and the mass of the coupling agent is 1-5% of that of the bone repair material.
Furthermore, the elastic modulus of the polyvinyl alcohol fiber is more than or equal to 35GPa, and the breaking strength is more than or equal to 1500 MPa.
Further, the polyvinyl alcohol fiber satisfies: the fiber diameter is less than 15 mu m, the breaking elongation is 6-11%, the hot water resistance is more than or equal to 98 ℃, and the dry heat softening point is more than or equal to 216 ℃.
Further, the calcium phosphate salt is selected from: one of Hydroxyapatite (HA), MCP, CPI, CPP, DCP, ADCP, OCP, TCP, FA, TTCP or XOA; preferably HA.
Further, the polybasic amino acid polymer is a polybasic amino acid polymer formed by polymerizing linear chain amino acid and other alpha amino acid, wherein the molar ratio of the linear chain amino acid in the polybasic amino acid polymer is not less than 70%.
Further, the straight-chain amino acid is at least one of glycine, beta-alanine, gamma-aminobutyric acid, delta-aminopentanoic acid, epsilon-aminocaproic acid, zeta-aminoheptanoic acid, eta-aminocaprylic acid, theta-aminononanoic acid, iota-aminodecanoic acid, kappa-aminoundecanoic acid or lambda-aminododecanoic acid.
Further, the other alpha amino acids are human acceptable amino acids; still further, the additional amino acid is selected from the group consisting of: at least one of alanine, phenylalanine, glycine, gamma-aminobutyric acid, tryptophan, proline, hydroxyproline, lysine, arginine, threonine, aspartic acid or glutamic acid. The degradation product of the multi-amino acid polymer is micromolecular oligopeptide or amino acid monomer, is non-toxic and non-irritant to human bodies, has high biological safety, and can regulate and control the mechanical property of the multi-amino acid polymer by regulating and controlling the variety and the content of amino acid.
Further, the number of amino acids in the polyamino acid polymer is 2 to 8.
In the invention, a coupling agent with good biocompatibility and no toxicity can be selected, and a titanate coupling agent is preferred.
Further, the titanate coupling agent is selected from: one of isopropyl trioleate acyloxy titanate coupling agent HY-105, isopropyl tri (dioctyl phosphate acyloxy) titanate HY-102, tetraisopropyl di (dioctyl phosphite acyloxy) titanate coupling agent HY-401, triisostearic acid isopropyl titanate coupling agent HY-101 or isopropyl tri (dodecyl benzene sulfonyl) titanate coupling agent HY-109.
Further, the polyvinyl alcohol fiber/polybasic amino acid polymer/calcium phosphate salt composite bone repair material is prepared by connecting the polybasic amino acid polymer, the polyvinyl alcohol fiber and the calcium phosphate salt through a coupling agent.
Further, the method for obtaining the composite bone repair material with stable interface by connecting the polybasic amino acid polymer, the polyvinyl alcohol fiber and the calcium phosphate salt through the titanate coupling agent comprises the following steps: firstly, respectively carrying out surface coupling treatment on polyvinyl alcohol fibers (PVA fibers) and calcium phosphate salts by using a coupling agent; then carrying out in-situ copolymerization on the calcium phosphate salt subjected to surface coupling treatment, linear chain amino acid and other alpha amino acids at 180-250 ℃ to obtain a calcium phosphate salt/polybasic amino acid polymer in-situ composite material; and then carrying out melt blending (such as extrusion molding through a double-screw extruder) on the coupled polyvinyl alcohol fiber, the coupled calcium phosphate salt and the calcium phosphate salt/polybasic amino acid polymer in-situ composite material at the temperature of 180-250 ℃ to obtain the polyvinyl alcohol fiber/polybasic amino acid polymer/calcium phosphate salt composite bone repair material which has stable interface, adjustable calcium phosphate salt content, high strength, high modulus and high biological activity.
The second technical problem to be solved by the present invention is to provide a preparation method of the above polyvinyl alcohol fiber/polyamino acid polymer/hydroxyapatite composite bone repair material, wherein the preparation method comprises: preparing the polyvinyl alcohol fiber, the calcium phosphate salt and the polybasic amino acid polymer into the composite material with stable interface by a coupling agent.
Further, the preparation method of the bone repair material comprises the following steps: firstly, respectively carrying out surface coupling treatment on polyvinyl alcohol fibers (PVA fibers) and calcium phosphate salts by using a coupling agent; then carrying out in-situ copolymerization on the calcium phosphate salt subjected to surface coupling treatment, linear chain amino acid and other alpha amino acids at 180-250 ℃ to obtain a calcium phosphate salt/polybasic amino acid polymer in-situ composite material; and then carrying out melt blending (such as extrusion molding through a double-screw extruder) on the coupled polyvinyl alcohol fiber, the coupled calcium phosphate salt and the calcium phosphate salt/polybasic amino acid polymer in-situ composite material at the temperature of 180-250 ℃ to obtain the polyvinyl alcohol fiber/polybasic amino acid polymer/calcium phosphate salt composite bone repair material which has stable interface, adjustable calcium phosphate salt content, high strength, high modulus and high biological activity.
Further, the preparation method of the polyvinyl alcohol fiber/polybasic amino acid polymer/hydroxyapatite composite bone repair material comprises the following steps:
1) respectively mixing the coupling agent with calcium phosphate salt and polyvinyl alcohol fiber in a spraying manner, fully stirring in the mixing process, and then carrying out vacuum drying to obtain coupling agent-treated calcium phosphate salt and coupling agent-treated polyvinyl alcohol fiber;
2) mixing the linear chain amino acid and other alpha amino acids, gradually heating to 180-210 ℃ under the protection of inert gas, then preserving heat at 210-230 ℃ for 1-5 hours, gradually heating to 215-250 ℃, and keeping the temperature in the temperature range for 0.5-3.5 hours to obtain a multi-element amino acid polymer; then adding the calcium phosphate treated by the coupling agent obtained in the step 1), and continuously reacting for 1-5 hours at the temperature; obtaining a calcium phosphate salt/polybasic amino acid polymer in-situ composite material (a polybasic amino acid polymer containing calcium phosphate salt);
3) fully mixing the calcium phosphate salt/polybasic amino acid polymer in-situ composite material obtained in the step 2), the polyvinyl alcohol fiber treated by the coupling agent obtained in the step 1) and the calcium phosphate salt treated by the coupling agent, and then melting and blending at 150-210 ℃ to obtain the composite bone repair material.
Further, in the step 1), the content of the coupling agent is 1-5 wt% of the mass of the polyvinyl alcohol fiber, and the content of the coupling agent is 0.5-7.5 wt% of the mass of the calcium phosphate salt.
Further, in the step 2), the mass of the calcium phosphate is 20-50% of that of the polybasic amino acid polymer.
Further, in the step 3), the mixture ratio of each component is as follows: 100-200 parts of calcium phosphate salt/polybasic amino acid polymer in-situ composite material, 30-100 parts of coupling agent treated calcium phosphate salt and 30-100 parts of coupling agent treated polyvinyl alcohol fiber.
Further, in step 3), the calcium phosphate salt-containing polyamino acid polymer is pulverized to a particle size of less than 3mm before use.
Further, in the step 3), a double-screw extruder is adopted for extrusion granulation in the melt blending.
A third technical problem to be solved by the present invention is to provide a supporting bone repair implant made of the above bone repair material.
Furthermore, the bending strength of the support type bone repair implant is 120-160 MPa, the bending modulus is 5-15 GPa, and the compressive strength is 120-180 MPa.
Further, the thermal deformation temperature range of the support type bone repair implant is 50-120 ℃, and the melting point of the support type bone repair implant is 160-220 ℃.
Further, the cytotoxicity of the supporting type bone repair implant is less than or equal to grade 1.
The fourth technical problem to be solved by the present invention is to provide a preparation method of the above-mentioned supporting bone repair implant, the preparation method comprising: the polyvinyl alcohol fiber/polybasic amino acid polymer/calcium phosphate salt composite bone repair material is used as a raw material and is obtained by injection molding or hot press molding at the temperature of 150-210 ℃.
A fifth technical problem to be solved by the present invention is to indicate the use of the above-mentioned distraction-type bone repair implant as a bone supporting material, a bone supporting instrument, a cervical fusion cage, a thoracolumbar fusion cage, a vertebral body, a vertebral plate or an irregular bone wound support.
The invention has the beneficial effects that:
the invention provides a high-strength PVA fiber polyamino acid calcium phosphate composite bone supporting material and a preparation method thereof, the composite material has high strength, high toughness and high elastic modulus, can be rapidly molded by injection molding or hot press molding, has a stable interface, good biomechanical compatibility and bioactivity, can be selected according to different purposes, and is suitable for supporting substitution, repairing and reconstruction of clinical bone bearing bones and instant plastic supporting repair of some complex irregular wounds. The bending strength of the obtained support type bone repair implant is 120-160 MPa, the bending modulus is 5-15 GPa, the compression strength is 120-180 MPa, the compression modulus is 6-20 GPa, and the biomechanical property of the implant is close to that of human bone tissues. The thermal deformation temperature range of the obtained support type bone repair implant is 50-120 ℃, the melting point is 160-220 ℃, and the thermal decomposition starting temperature is more than 350 ℃; the cytotoxicity of the obtained bone supporting material is less than or equal to 1 grade, and the bone supporting material is non-toxic and non-irritant; has good biological activity and biological safety.
Compared with the existing implanted bone repair material, the high-strength PVA fiber polyamino acid hydroxyapatite composite bone support material has good biocompatibility and can provide proper mechanical strength; the curing liquid has high selectivity, no toxicity, no stimulation and no heat source reaction; the product formed by the composite material has no obvious influence on the acidity of the surrounding environment, and the in vitro test result shows that the pH value of the product can be maintained at 7.0-7.5; the PVA fiber has high strength and modulus and good biocompatibility; the polybasic amino acid polymer is nontoxic, and calcium phosphate salt such as hydroxyapatite has good living activity; the composite material has the advantages that the deformation temperature and the elastic modulus of the bone repair material can be regulated and controlled by regulating and controlling the content of each component; in addition, the method can be used for rapid molding through injection molding, the obtained bone repair material has good biomechanical compatibility and bioactivity, the required thermal deformation temperature and mechanical property can be selected according to different purposes, and the bone repair material is suitable for supporting clinical orthopedic bone repair and reconstruction and instant molding support and repair of some complex irregular wounds.
Detailed Description
The invention provides a high-strength PVA fiber polyamino acid hydroxyapatite composite bone supporting material and a preparation method thereof; the PVA fiber is polyvinyl alcohol with high polymerization degree, the fiber strength is more than or equal to 1500MPa, the modulus is more than 35GPa, the calcium phosphate salt (hydroxyapatite) is synthesized by a thermodynamic synthesis method, and the amino acid is alpha amino acid or straight-chain amino acid. Carrying out surface coupling treatment on PVA fibers and calcium phosphate salt by using a coupling agent in the first step, and carrying out in-situ copolymerization on the calcium phosphate salt, alpha amino acid and straight-chain amino acid at 180-250 ℃ in the second step to obtain a PAA-HA in-situ composite material containing a certain amount of calcium phosphate salt; thirdly, extruding the coupled PVA fiber, the coupled calcium phosphate salt and the PAA-HA in-situ composite material at 180-250 ℃; therefore, the PVA fiber polyamino acid hydroxyapatite composite bone supporting material which has stable interface, adjustable calcium phosphate salt content, high strength, high modulus and high biological activity is obtained, the bending strength is more than or equal to 100MPa, the compressive strength is more than or equal to 120MPa, the bending modulus is 5-20 GPa, the biomechanical requirements of compact bone are met, and the PVA fiber polyamino acid hydroxyapatite composite bone supporting material is an ideal bone supporting material.
The above-mentioned contents of the present invention will be further described in detail by the following specific embodiments of examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. Various substitutions and alterations according to the general knowledge and conventional practice in the art are intended to be included within the scope of the present invention without departing from the technical spirit of the present invention as described above.
In the following examples of the invention, the polyvinyl alcohol fibers selected satisfied: the diameter of the fiber is less than 15 μm, the smaller the diameter of the fiber, the larger the surface area of the fiber with the same weight, the larger the contact area with calcium phosphate and a coupling agent, and the more stable the interface; the breaking strength is more than or equal to 1500MPa, the elastic modulus is more than or equal to 35GPa, the breaking elongation (namely the breaking productivity, namely the maximum elongation percentage when breaking is achieved) is 6-11%, the hot water resistance is more than or equal to 98 ℃, the dry heat softening point is more than or equal to 216 ℃, and the length: 4. 6, 9, 12 and 15 mm.
Example 1
Preparation of a supporting bone repair implant comprising the steps of:
(1) weighing 1000g of hydroxyapatite and 30g of isopropyl trioleate acyloxy titanate (titanate coupling agent HY-105), putting the hydroxyapatite into a 5L reaction bottle with stirring, putting the titanate coupling agent HY-105 into an atomizer, spraying while stirring, completing atomization for 30 minutes, continuing stirring for one hour, pouring out the hydroxyapatite, and performing vacuum drying at 80 ℃ for 6 hours to obtain C4;
(2) weighing 1000g of high-strength PVA fiber (the diameter is 15 mu m, the length is 6mm), 50g of isopropyl trioleate acyloxy titanate (titanate coupling agent HY-105), putting the PVA fiber into a 5L reaction bottle with stirring, putting the titanate coupling agent HY-105 into an atomizer, spraying while stirring, completing atomization within 30 minutes, continuously stirring for one hour, then taking out the high-strength PVA fiber, and performing vacuum drying with the temperature of 80 ℃ for 6 hours to obtain C3;
(3) 111.35g of epsilon-aminocaproic acid [ straight chain amino acid ], 6.55g of hydroxyproline [ alpha amino acid ], 8.26g of phenylalanine [ alpha amino acid ] and 7.31g of lysine [ alpha amino acid ] are respectively weighed, added into a 250ml three-necked bottle, added with 50ml of distilled water, introduced with nitrogen for protection, stirred and heated to 180 ℃ for dehydration (whether the dehydration treatment is finished can be judged by observing whether the amino acid starts to melt or not); after the dehydration is finished, continuously heating to 210 ℃, carrying out prepolymerization for 1 hour in a molten state, then continuously heating to 220 ℃ for carrying out polymerization reaction for 3 hours to obtain polyamino acid (C2); then under the protection of nitrogen, 60g of hydroxyapatite (C4) treated by titanate coupling agent is added, and polymerization reaction is continued for 1 hour at 220-250 ℃ to obtain 180g of in-situ polymerization polyamino acid hydroxyapatite composite material (calcium phosphate salt/polybasic amino acid polymer in-situ composite material) (X);
(4) crushing 180g of the in-situ polymerized polyamino acid hydroxyapatite composite material (X) into particles with the particle size of 5-10 meshes, adding 40g of treated high-strength PVA fiber (C3) and 30g of coupled hydroxyapatite (C4), mixing at 190 ℃ by a Haake rheometer, and performing extrusion molding to obtain a mechanical spline of the high-strength PVA fiber polyamino acid hydroxyapatite composite bone supporting material; wherein the injection molding temperature is 185 ℃ and the pressure is 120 MPa.
Tests show that the compressive strength of the obtained supporting material is 150MPa, the bending strength is 125MPa, the bending modulus is 7.5GPa, and the compressive strength is slightly higher than that of compact bones (supporting main dry bones) of a human body; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 95 ℃ and the melting point was 185 ℃. After firing at 800 ℃ for 6 hours, the residual amount of hydroxyapatite was 89.5g, which was 36% of the composite material.
The support material is cut into
After disinfection and sterilization, the wafer is subjected to cytotoxicity test, and the result is grade 0; when the mouse osteoblasts are cultured, the increment rate of the mouse osteoblasts is 119% in 72 hours, and the mouse osteoblasts have good osteogenic performance.
The support material is taken to carry out a degradation experiment in SBF (SBF solution adopted by in-vitro simulation solution), the weight loss in the first week is 3.15%, the weight loss in the second week is 3.68%, the weight gain in the third week is 1.52%, and the weight gain in the fourth week is 1.11%, which shows that the material has good in-vitro bioactivity and stability.
Example 2
Preparation of a supporting bone repair implant comprising the steps of:
(1) weighing 1000g of hydroxyapatite, 45g of isopropyl tri (dioctyl phosphate acyloxy) titanate and a titanate coupling agent HY-102, putting the hydroxyapatite into a 5L reaction bottle with stirring, putting the titanate coupling agent HY-102 into an atomizer, spraying while stirring, completing atomization within 45 minutes, continuing stirring for one hour, pouring out the hydroxyapatite, and performing vacuum drying at 80 ℃ for 6 hours to obtain C4;
(2) weighing 1000g of high-strength PVA fiber (with the diameter of 15 mu m and the length of 6mm), 50g of isopropyl tri (dioctyl phosphate acyloxy) titanate and titanate coupling agent HY-102, putting the PVA fiber into a 5L reaction bottle with stirring, putting the titanate coupling agent HY-102 into an atomizer, spraying while stirring, completing atomization within 45 minutes, continuously stirring for one hour, then taking out the high-strength PVA fiber, and performing vacuum drying at 80 ℃ for 6 hours to obtain C3;
(3) 123.42g of zeta-aminoheptanoic acid [ straight chain amino acid ], 6.55g of (131.1) [ alpha amino acid ], 8.26g of phenylalanine [ alpha amino acid ] and 7.31g of lysine [ alpha amino acid ] are respectively weighed and added into a 250ml three-necked bottle, 50ml of distilled water is added, nitrogen protection is introduced, stirring is carried out, the temperature is increased to 180 ℃ for dehydration (whether dehydration treatment is finished can be judged by observing whether the amino acid starts to melt or not); after the dehydration is finished, continuously heating to 210 ℃, carrying out prepolymerization for 1 hour in a molten state, then continuously heating to 220 ℃ for carrying out polymerization reaction for 3 hours to obtain polyamino acid (C2); then under the protection of nitrogen, adding 42.5g of hydroxyapatite (C4) treated by titanate coupling agent, and continuing polymerization reaction for 1 hour at 220-250 ℃ to obtain 170g of in-situ polymerized polyamino acid hydroxyapatite composite material (X);
(4) and (3) crushing 170g of the in-situ polymerized polyamino acid hydroxyapatite composite material (X) into particles with the granularity of 5-10 meshes, adding 50g of treated high-strength PVA fiber (C3) and 80g of coupled hydroxyapatite (C4), mixing at 190 ℃ by a Haake rheometer, and extruding to obtain the mechanical spline of the high-strength PVA fiber polyamino acid hydroxyapatite composite bone supporting material.
Tests show that the compressive strength of the obtained supporting material is 150MPa, the bending strength is 135MPa, the bending modulus is 9.0GPa, and the compressive strength is slightly higher than that of compact bones (supporting main dry bones) of a human body; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 96 ℃ and the melting point was 182 ℃. By firing at 800 ℃ for 6 hours, the residual amount of hydroxyapatite was 122.5g, 41% of the composite.
The support material is cut into
After disinfection and sterilization, the wafer is subjected to cytotoxicity test, and the result is grade 0; when the mouse osteoblasts are cultured, the proliferation rate is 120% in 72 hours, and the bone forming performance is good.
The supporting material and SBF are taken to carry out degradation experiments, the weight loss in the first week is 2.15%, the weight loss in the second week is 3.15%, the weight gain in the third week is 1.26%, and the weight gain in the fourth week is 1.05%, which shows that the material has good in vitro bioactivity and stability.
Example 3
Preparation of a supporting bone repair implant comprising the steps of:
(1) weighing 1000g of hydroxyapatite and 35g of tetraisopropyl di (dioctyl phosphite acyloxy) titanate coupling agent HY-401, putting the hydroxyapatite into a 5L reaction bottle with stirring, putting the titanate coupling agent HY-401 into an atomizer, spraying while stirring, completing atomization within 25 minutes, continuing stirring for one hour, pouring out the hydroxyapatite, and performing vacuum drying at 80 ℃ for 6 hours to obtain C4;
(2) weighing 1000g of high-strength PVA fiber (with the diameter of 15 mu m and the length of 9mm), 45g of tetraisopropyl di (dioctyl phosphite acyloxy) titanate coupling agent HY-401, putting the PVA fiber into a 5L reaction bottle with stirring, putting the titanate coupling agent HY-401 into an atomizer, spraying while stirring, completing atomization within 25 minutes, continuously stirring for one hour, then taking out the high-strength PVA fiber, and performing vacuum-pumping drying at 80 ℃ for 6 hours to obtain C3;
(3) respectively weighing 117.9g of epsilon-aminocaproic acid [ straight chain amino acid ], 7.31g of lysine [ alpha amino acid ], 4.13g of phenylalanine [ alpha amino acid ] and 2.23g of alanine [ alpha amino acid ], adding the weighed materials into a 250ml three-necked bottle, adding 50ml of distilled water, introducing nitrogen for protection, stirring, heating to 180 ℃ for dehydration (whether the dehydration treatment is finished can be judged by observing whether the amino acid starts to melt or not); after the dehydration is finished, continuously heating to 210 ℃, carrying out prepolymerization for 1 hour in a molten state, then continuously heating to 220 ℃ for carrying out polymerization reaction for 3 hours to obtain polyamino acid (C2); then under the protection of nitrogen, 30.0g of hydroxyapatite (C4) treated by titanate coupling agent is added, and polymerization reaction is continued for 1 hour at 220-250 ℃ to obtain 144g of in-situ polymerized polyamino acid hydroxyapatite composite material (X);
(4) and (2) crushing 144g of the in-situ polymerized polyamino acid hydroxyapatite composite material (X) into particles with the particle size of 5-10 meshes, adding 50g of treated high-strength PVA fiber (C3) and 50g of coupled hydroxyapatite (C4), mixing by a Haake rheometer at 190 ℃, and extruding to obtain the mechanical spline of the high-strength PVA fiber polyamino acid hydroxyapatite composite bone supporting material.
The compressive strength is 138MPa, the bending strength is 130MPa, the bending modulus is 8.0GPa, and the bending strength is slightly higher than that of compact bones (supporting main dry bones) of a human body; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 86 ℃ and the melting point was 185 ℃. By firing at 800 ℃ for 6 hours, the residual amount of hydroxyapatite was 80.5g, representing 33% of the composite.
The composite material is cut into
After disinfection and sterilization, the wafer is subjected to cytotoxicity test, and the result is grade 0; when the mouse osteoblasts are cultured, the proliferation rate is 120% in 72 hours, and the bone forming performance is good.
The composite material and SBF are subjected to degradation experiments, the weight loss in the first week is 1.85%, the weight loss in the second week is 3.03%, the weight gain in the third week is 1.32%, and the weight gain in the fourth week is 0.75%, which shows that the material has good in vitro biological activity and stability.
Example 4
Preparation of a supporting bone repair implant comprising the steps of:
(1) weighing 1000g of hydroxyapatite, 45g of isopropyl tri (dioctyl phosphate acyloxy) titanate and a titanate coupling agent HY-102, putting the hydroxyapatite into a 5L reaction bottle with stirring, putting the titanate coupling agent HY-102 into an atomizer, spraying while stirring, completing atomization within 45 minutes, continuing stirring for one hour, pouring out the hydroxyapatite, and performing vacuum drying at 80 ℃ for 6 hours to obtain C4;
(2) weighing 1000g of high-strength PVA fiber (with the diameter of 15 mu m and the length of 6mm), 50g of isopropyl tri (dioctyl phosphate acyloxy) titanate and a titanate coupling agent HY-102, putting the PVA fiber into a 5L reaction bottle with stirring, putting the titanate coupling agent HY-102 into an atomizer, spraying while stirring, completing the atomization within 45 minutes, continuously stirring for one hour, taking out the high-strength PVA fiber, and carrying out vacuum drying at 80 ℃ for 6 hours to obtain C3;
(3) respectively weighing 43.56 g of zeta-aminoheptanoic acid [ linear amino acid ], 78.66g of epsilon-aminocaproic acid [ linear amino acid ], 6.55g of hydroxyproline [ alpha amino acid ], 2.92g of lysine [ alpha amino acid ] and 4.96g of phenylalanine [ alpha amino acid ], adding into a 250ml three-necked bottle, adding 50ml of distilled water, introducing nitrogen for protection, stirring, heating to 180 ℃ for dehydration (whether the dehydration treatment is finished can be judged by observing whether the amino acid starts to melt or not); after the dehydration is finished, continuously heating to 210 ℃, carrying out prepolymerization for 1 hour in a molten state, then continuously heating to 220 ℃ for carrying out polymerization reaction for 3 hours to obtain polyamino acid (C2); then under the protection of nitrogen, adding 42.5g of hydroxyapatite (C4) treated by titanate coupling agent, and continuing polymerization reaction for 1 hour at 220-250 ℃ to obtain 160g of in-situ polymerized polyamino acid hydroxyapatite composite material (X);
(4) and (2) crushing 160g of the in-situ polymerized polyamino acid hydroxyapatite composite material (X) into particles with the granularity of 5-10 meshes, adding 60g of treated high-strength PVA fiber (C3) and 80g of coupled hydroxyapatite (C4), mixing at 190 ℃ by a Haake rheometer, and extruding to obtain the mechanical spline of the high-strength PVA fiber polyamino acid hydroxyapatite composite bone supporting material.
The compressive strength is 145MPa, the bending strength is 138MPa, the bending modulus is 9.5GPa, and the bending strength is slightly higher than that of compact bones (supporting main and trunk bones) of a human body; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 90 ℃ and the melting point was 180 ℃. By firing at 800 ℃ for 6 hours, the residual amount of hydroxyapatite was 126.5g, representing 42% of the composite.
The composite material is cut into
After disinfection and sterilization, the wafer is subjected to cytotoxicity test, and the result is grade 0; when the mouse osteoblasts are cultured, the increment rate of the mouse osteoblasts is 115% in 72 hours, and the mouse osteoblasts have good osteogenic performance.
The composite material and SBF are subjected to degradation experiments, the weight loss in the first week is 3.15%, the weight loss in the second week is 3.93%, the weight gain in the third week is 1.55%, and the weight gain in the fourth week is 0.55%, which shows that the material has good in vitro biological activity and stability.
Example 5
Preparation of a supporting bone repair implant comprising the steps of:
(1) weighing 1000g of hydroxyapatite, 35g of isopropyl triisostearate and a titanate coupling agent HY-101, putting the hydroxyapatite into a 5L reaction bottle with stirring, putting the titanate coupling agent HY-102 into an atomizer, spraying while stirring, completing the atomization within 45 minutes, continuing stirring for one hour, pouring out the hydroxyapatite, and carrying out vacuum-pumping drying at 80 ℃ for 6 hours to obtain C4;
(2) weighing 1000g of high-strength PVA fiber (with the diameter of 15 mu m and the length of 12mm), 45g of isopropyl triisostearate, and HY-101 as a titanate coupling agent, putting the PVA fiber into a 5L reaction bottle with stirring, putting HY-102 as the titanate coupling agent into an atomizer, spraying while stirring, completing atomization within 45 minutes, continuing stirring for one hour, then taking out the high-strength PVA fiber, and performing vacuum drying at 80 ℃ for 6 hours to obtain C3;
(3) 130.68g of zeta-aminoheptanoic acid, 6.55g of alpha amino acid, 4.13g of phenylalanine, 3.66g of lysine and 3.66g of alpha amino acid are respectively weighed and added into a 250ml three-necked bottle, 50ml of distilled water is added, nitrogen is introduced for protection, stirring is carried out, the temperature is raised to 180 ℃ for dehydration (whether dehydration treatment is finished can be judged by observing whether the amino acid starts to melt or not); after the dehydration is finished, continuously heating to 210 ℃, carrying out prepolymerization for 1 hour in a molten state, then continuously heating to 220 ℃ for carrying out polymerization reaction for 3 hours to obtain polyamino acid (C2); then under the protection of nitrogen, 43.0g of hydroxyapatite (C4) treated by titanate coupling agent is added, and polymerization reaction is continued for 1 hour at 220-250 ℃ to obtain 170g of in-situ polymerized polyamino acid hydroxyapatite composite material (X);
(4) and (3) crushing 170g of the in-situ polymerized polyamino acid hydroxyapatite composite material (X) into particles with the granularity of 5-10 meshes, adding 70g of treated high-strength PVA fiber (C3) and 90g of coupled hydroxyapatite (C4), mixing at 190 ℃ by a Haake rheometer, and extruding to obtain the mechanical spline of the high-strength PVA fiber polyamino acid hydroxyapatite composite bone supporting material.
The compressive strength is 150MPa, the bending strength is 145MPa, the bending modulus is 10.0GPa, and the bending strength is higher than that of compact bones (supporting main bones) of a human body; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 95 ℃ and the melting point was 180 ℃. By firing at 800 ℃ for 6 hours, the residual amount of hydroxyapatite was 132.5g, which was 40% of the composite.
The composite material is cut into
After disinfection and sterilization, the wafer is subjected to cytotoxicity test, and the result is grade 0; when the mouse osteoblasts are cultured, the increment rate of the mouse osteoblasts is 110 percent in 72 hours, and the mouse osteoblasts have good osteogenic performance.
The composite material and SBF are subjected to degradation experiments, the weight loss in the first week is 2.92%, the weight loss in the second week is 3.26%, the weight gain in the third week is 1.72%, and the weight gain in the fourth week is 0.49%, which shows that the material has good in vitro biological activity and stability.
Example 6
Preparation of a supporting bone repair implant comprising the steps of:
(1) weighing 1000g of hydroxyapatite, 45g of isopropyl tri (dioctyl phosphate acyloxy) titanate and a titanate coupling agent HY-102, putting the hydroxyapatite into a 5L reaction bottle with stirring, putting the titanate coupling agent HY-102 into an atomizer, spraying while stirring, completing atomization within 45 minutes, continuing stirring for one hour, pouring out the hydroxyapatite, and performing vacuum drying at 80 ℃ for 6 hours to obtain C4;
(2) weighing 1000g of high-strength PVA fiber (with the diameter of 15 mu m and the length of 6mm), 50g of isopropyl tri (dioctyl phosphate acyloxy) titanate, a titanate coupling agent HY-102, hydroxyapatite into a 5L reaction bottle with stirring, putting the titanate coupling agent HY-102 into an atomizer, spraying while stirring, completing atomization within 45 minutes, continuously stirring for one hour, then taking out the high-strength PVA fiber, and performing vacuum drying at 80 ℃ for 6 hours to obtain C3;
(3) 152.5g of theta-amino nonanoic acid [ straight chain amino acid ], 6.55g of (131.1) [ alpha amino acid ], 3.30g of phenylalanine [ alpha amino acid ] and 5.85g of lysine [ alpha amino acid ] are respectively weighed, added into a 250ml three-necked bottle, added with 50ml of distilled water, introduced with nitrogen for protection, stirred and heated to 180 ℃ for dehydration (whether the dehydration treatment is finished can be judged by observing whether the amino acid starts to melt or not); after the dehydration is finished, continuously heating to 210 ℃, carrying out prepolymerization for 1 hour in a molten state, then continuously heating to 220 ℃ for carrying out polymerization reaction for 3 hours to obtain polyamino acid (C2); then under the protection of nitrogen, adding 42.5g of hydroxyapatite (C4) treated by titanate coupling agent, and continuing polymerization reaction for 1 hour at 220-250 ℃ to obtain 170g of in-situ polymerized polyamino acid hydroxyapatite composite material (X);
(4) and (3) crushing 170g of the in-situ polymerized polyamino acid hydroxyapatite composite material (X) into particles with the granularity of 5-10 meshes, adding 50g of treated high-strength PVA fiber (C3) and 80g of coupled hydroxyapatite (C4), mixing at 190 ℃ by a Haake rheometer, and extruding to obtain the mechanical spline of the high-strength PVA fiber polyamino acid hydroxyapatite composite bone supporting material.
The compressive strength is 150MPa, the bending strength is 135MPa, the bending modulus is 9.0GPa, and the bending strength is slightly higher than that of compact bones (supporting main dry bones) of a human body; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 96 ℃ and the melting point was 182 ℃. By firing at 800 ℃ for 6 hours, the residual amount of hydroxyapatite was 122.5g, 41% of the composite.
The composite material is cut into
After disinfection and sterilization, the wafer is subjected to cytotoxicity test, and the result is grade 0; when the mouse osteoblasts are cultured, the proliferation rate is 120% in 72 hours, and the bone forming performance is good.
The composite material and SBF are subjected to degradation experiments, the weight loss in the first week is 2.15%, the weight loss in the second week is 3.15%, the weight gain in the third week is 1.26%, and the weight gain in the fourth week is 1.05%, which shows that the material has good in vitro biological activity and stability.
Example 7
In the same way as the embodiment 1, isopropyl tris (dodecyl benzenesulfonyl) titanate and titanate coupling agent HY-109 are used for replacing isopropyl triolein acyloxy titanate and titanate coupling agent HY-105; the others are the same.
The compressive strength is 150MPa, the bending strength is 125MPa, the bending modulus is 7.5GPa, and the compressive strength is slightly higher than that of compact bones (supporting main and trunk bones) of a human body; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 95 ℃ and the melting point was 185 ℃. By firing at 800 ℃ for 6 hours, the residual amount of hydroxyapatite was 89.5g, representing 36% of the composite.
The composite material is cut into
After disinfection and sterilization, the wafer is subjected to cytotoxicity test, and the result is grade 0; when the mouse osteoblasts are cultured, the increment rate of the mouse osteoblasts is 119% in 72 hours, and the mouse osteoblasts have good osteogenic performance.
The composite material and SBF are subjected to degradation experiments, the weight loss in the first week is 3.15%, the weight loss in the second week is 3.68%, the weight gain in the third week is 1.52%, and the weight gain in the fourth week is 1.11%, which shows that the material has good in vitro biological activity and stability.
Example 8
As in example 1, the high strength PVA fiber diameter was replaced by PVA fibers having a diameter of 15 μm and a length of 15 mm. The others are the same. The compressive strength is 160MPa, the bending strength is 155MPa, and the bending modulus is 9.5 GPa; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 95 ℃ and the melting point was 181 ℃. By firing at 800 ℃ for 6 hours, the residual amount of hydroxyapatite was 122.5g, 41% of the composite.
The composite material is cut into
After disinfection and sterilization, the wafer is subjected to cytotoxicity test, and the result is grade 0; when the mouse osteoblasts are cultured, the proliferation rate is 120% in 72 hours, and the bone forming performance is good.
The composite material and SBF are subjected to degradation experiments, the weight loss in the first week is 2.15%, the weight loss in the second week is 3.15%, the weight gain in the third week is 1.26%, and the weight gain in the fourth week is 1.05%, which shows that the material has good in vitro biological activity and stability.
Comparative example 1
Weighing 131g of epsilon-aminocaproic acid, adding the epsilon-aminocaproic acid into a 250ml three-necked bottle, adding 50ml of distilled water, introducing nitrogen for protection, stirring, heating to 180 ℃ for dehydration, raising the temperature to 202 ℃ until all water is removed, continuously heating to 210 ℃, carrying out prepolymerization for 1 hour in a molten state, and then continuously heating to 220 ℃ for carrying out polymerization for 4 hours.
At the temperature and under the protection of nitrogen, 50g of dried nano hydroxyapatite is added, the temperature is kept at 220 ℃, the mixture is slowly stirred for 1 hour under the protection of nitrogen, the whole reaction is finished, and the mixture is cooled to room temperature under the protection of nitrogen, and 162g of the composite material is obtained.
Crushing the nano-hydroxyapatite and polyamino acid composite bone graft material into granules with the granularity of 5-10 meshes, extruding and molding the granules by a Haake rheometer to prepare a mechanical sample strip, and measuring the compressive strength of the mechanical sample strip to be 90MPa, the bending strength to be 75MPa and the bending modulus to be 5 GPa; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 82 ℃ and the melting point was 201 ℃. By firing at 800 ℃ for 6 hours, the residual amount of hydroxyapatite was 55.1g, representing 30% of the composite.
The polymer in the composite material is PA6 (poly-6-aminocaproic acid is formed after 6-aminocaproic acid is polymerized), the activity is poor, and the strength and the modulus of the composite material are not matched with those of compact bones of a human body after hydroxyapatite is added.
Comparative example 2
Adding 105.25g, 8.9g, 8.25g and 7.3g of 6-aminocaproic acid, alanine, phenylalanine and lysine into a 250ml three-necked bottle, adding 50ml of distilled water, heating to 200 ℃ under electric stirring, introducing nitrogen for protection, continuously heating to 210 ℃ after the dehydration is finished to melt the mixture, heating to 220 ℃ again, carrying out polymerization reaction for 2 hours (111.7), adding 50g of hydroxyapatite, and continuously reacting at 220 ℃ for 2 hours to obtain 161g of the hydroxyapatite/polyamino acid composite material.
Crushing the hydroxyapatite and polyamino acid composite bone graft material into particles with the granularity of 5-10 meshes, and performing extrusion molding by using a Haake rheometer to obtain a mechanical sample strip with the compressive strength of 80MPa, the bending strength of 65MPa and the bending modulus of 3 GPa; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 50 ℃, the thermal deformation temperature was 55 ℃ and the melting point was 177 ℃.
Although the material contains various amino acids, the main chain structure is disordered, no chemical bond for linking molecular chains is formed, the flexibility is too high, the deformability is too large, the thermal deformation temperature is low, the modulus is low, and the material is not suitable for the load-bearing bone repair.
Comparative example 3
Adding 117.9g, 4.45g, 3.28g and 3.65g of 6-aminocaproic acid, alanine, hydroxyproline and lysine into a 250ml three-necked bottle, adding 50ml of distilled water, heating to 200 ℃ under electric stirring, introducing nitrogen for protection, continuously heating to 210 ℃ after the dehydration is finished to melt the mixture, heating to 220 ℃ again, carrying out polymerization reaction for 2 hours (129.28), adding 70g of hydroxyapatite, and continuously reacting at 220 ℃ for 2 hours to obtain 199g of composite material, namely the inorganic matter content is 35%.
Crushing the hydroxyapatite and polyamino acid composite bone graft material into particles with the granularity of 5-10 meshes, and performing extrusion molding by using a Haake rheometer to obtain a mechanical sample strip with the compressive strength of 90MPa, the bending strength of 75MPa and the bending modulus of 4 GPa; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 60 ℃ and the melting point was 182 ℃.
Although the material contains a plurality of amino acids, the main chain active amino acid group does not form effective linkage, does not form chemical bonds for linking molecular chains, has too high flexibility and too large deformability, and is not suitable for load-bearing bone repair.
Comparative example 4
Adding 98.25g, 8.9g, 8.25g, 6.55g and 7.3g of 6-aminocaproic acid, alanine, phenylalanine, hydroxyproline and lysine into a 250ml three-necked bottle, adding 50ml of distilled water, heating to 200 ℃ under electric stirring, introducing nitrogen for protection, continuously heating to 210 ℃ after the dehydration is finished to melt the mixture, heating to 220 ℃ again, performing polymerization reaction for 2 hours (111.25), adding 80g of hydroxyapatite, and continuously reacting for 2 hours at 220 ℃ to obtain 190g of composite material, namely the inorganic matter content is 40%.
Crushing the hydroxyapatite and polyamino acid composite bone graft material into particles with the granularity of 5-10 meshes, and performing extrusion molding by using a Haake rheometer to obtain a mechanical sample strip, wherein the compressive strength is 95MPa, the bending strength is 82MPa, and the bending modulus is 5.5 GPa; the glass transition temperature and the melting point were measured by DSC, and the glass transition temperature was 61 ℃ and the melting point was 185 ℃.
Although the material contains a plurality of amino acids, the main chain active amino acid group does not form effective linkage, does not form chemical bonds for linking molecular chains, has too high flexibility and too large deformability, and is not suitable for load-bearing bone repair.
Claims (13)
1. The polyvinyl alcohol fiber/polybasic amino acid polymer/calcium phosphate salt composite bone repair material is characterized by comprising a polybasic amino acid polymer, polyvinyl alcohol fibers, a calcium phosphate salt and a coupling agent, wherein the mass of the calcium phosphate salt is 20-50% of that of the bone repair material, the mass of the polyvinyl alcohol fibers is 15-30% of that of the bone repair material, the mass of the polybasic amino acid polymer is 20-55% of that of the bone repair material, and the mass of the coupling agent is 1-5% of that of the bone repair material; wherein the polyvinyl alcohol fibers satisfy: the elastic modulus is more than or equal to 35GPa, the breaking strength is more than or equal to 1500MPa, the fiber diameter is less than 15 mu m, the breaking elongation is 6-11%, the hot water resistance is more than or equal to 98 ℃, and the dry heat softening point is more than or equal to 216 ℃;
the polybasic amino acid polymer is a polybasic amino acid polymer formed by polymerizing linear chain amino acid and other alpha amino acid, wherein the molar ratio of the linear chain amino acid in the polybasic amino acid polymer is not less than 70%;
and the polyvinyl alcohol fiber/polybasic amino acid polymer/calcium phosphate salt composite bone repair material is prepared by adopting the following method: firstly, respectively carrying out surface coupling treatment on polyvinyl alcohol fibers and calcium phosphate salt by using a coupling agent; then carrying out in-situ copolymerization on the calcium phosphate salt subjected to surface coupling treatment, linear chain amino acid and other alpha amino acids at 180-250 ℃ to obtain a calcium phosphate salt/polybasic amino acid polymer in-situ composite material; and then carrying out melt blending on the polyvinyl alcohol fiber subjected to coupling treatment, the calcium phosphate salt subjected to coupling treatment and the calcium phosphate salt/polybasic amino acid polymer in-situ composite material at the temperature of 180-250 ℃ to obtain the polyvinyl alcohol fiber/polybasic amino acid polymer/calcium phosphate salt composite bone repair material.
2. The polyvinyl alcohol fiber/polyamino acid polymer/calcium phosphate composite bone repair material according to claim 1,
the calcium phosphate salt is selected from: HA. One of MCP, CPP, DCP, ADCP, OCP, TCP, FA, TTCP or XOA; or:
the coupling agent is a non-toxic coupling agent with good biocompatibility.
3. The polyvinyl alcohol fiber/polyamino acid polymer/calcium phosphate salt composite bone repair material according to claim 2, wherein the calcium phosphate salt is HA; or:
the straight-chain amino acid is at least one of glycine, beta-alanine, gamma-aminobutyric acid, delta-aminopentanoic acid, epsilon-aminocaproic acid, zeta-aminoheptanoic acid, eta-aminocaprylic acid, theta-aminononanoic acid, iota-aminodecanoic acid, kappa-aminoundecanoic acid or lambda-aminododecanoic acid; the other alpha amino acids are human acceptable amino acids; or:
the coupling agent is a titanate coupling agent.
4. The polyvinyl alcohol fiber/polyamino acid polymer/calcium phosphate salt composite bone repair material according to claim 3, wherein the other alpha amino acid is selected from the group consisting of: at least one of alanine, phenylalanine, glycine, tryptophan, proline, hydroxyproline, lysine, arginine, threonine, aspartic acid, or glutamic acid; the variety of amino acids in the polybasic amino acid polymer is 2-8; or:
the titanate coupling agent is selected from: one of an isopropyl trioleate acyloxy titanate coupling agent, an isopropyl tri (dioctyl phosphate acyloxy) titanate coupling agent, a tetraisopropyl di (dioctyl phosphite acyloxy) titanate coupling agent, a triisostearic acid isopropyl titanate coupling agent or an isopropyl tri (dodecyl benzene sulfonyl) titanate coupling agent.
5. The preparation method of the polyvinyl alcohol fiber/polybasic amino acid polymer/hydroxyapatite composite bone repair material according to any one of claims 1 to 4, characterized in that the preparation method comprises the following steps: firstly, respectively carrying out surface coupling treatment on polyvinyl alcohol fibers and calcium phosphate salt by using a coupling agent; then carrying out in-situ copolymerization on the calcium phosphate salt subjected to surface coupling treatment, linear chain amino acid and other alpha amino acids at 180-250 ℃ to obtain a calcium phosphate salt/polybasic amino acid polymer in-situ composite material; and then carrying out melt blending on the polyvinyl alcohol fiber subjected to coupling treatment, the calcium phosphate salt subjected to coupling treatment and the calcium phosphate salt/polybasic amino acid polymer in-situ composite material at the temperature of 180-250 ℃ to obtain the polyvinyl alcohol fiber/polybasic amino acid polymer/calcium phosphate salt composite bone repair material.
6. The method for preparing the polyvinyl alcohol fiber/polybasic amino acid polymer/hydroxyapatite composite bone repair material according to claim 5, wherein the method for preparing the polyvinyl alcohol fiber/polybasic amino acid polymer/hydroxyapatite composite bone repair material comprises the following steps:
1) respectively mixing the coupling agent with calcium phosphate salt and polyvinyl alcohol fiber in a spraying manner, fully stirring in the mixing process, and then carrying out vacuum drying to obtain coupling agent-treated calcium phosphate salt and coupling agent-treated polyvinyl alcohol fiber;
2) mixing the linear chain amino acid and other alpha amino acids, gradually heating to 180-210 ℃ under the protection of inert gas, then preserving heat at 210-230 ℃ for 1-5 hours, gradually heating to 215-250 ℃, and keeping the temperature in the temperature range for 0.5-3.5 hours to obtain a multi-element amino acid polymer; then adding the calcium phosphate treated by the coupling agent obtained in the step 1), and continuously reacting for 1-5 hours in the temperature interval; obtaining the calcium phosphate salt/polybasic amino acid polymer in-situ composite material;
3) fully mixing the calcium phosphate salt/polybasic amino acid polymer in-situ composite material obtained in the step 2), the polyvinyl alcohol fiber treated by the coupling agent obtained in the step 1) and the calcium phosphate salt treated by the coupling agent, and then melting and blending at 180-250 ℃ to obtain the composite bone repair material.
7. The method for preparing the polyvinyl alcohol fiber/polybasic amino acid polymer/hydroxyapatite composite bone repair material according to claim 6,
in the step 1), the content of the coupling agent accounts for 1-5 wt% of the mass of the polyvinyl alcohol fiber, and the content of the coupling agent accounts for 0.5-7.5 wt% of the mass of the calcium phosphate salt; or:
in the step 2), the mass of the calcium phosphate is 20-50% of that of the polybasic amino acid polymer; or:
in the step 3), the mixture ratio of each component is as follows: 100-200 parts of calcium phosphate salt/polybasic amino acid polymer in-situ composite material, 30-100 parts of coupling agent treated calcium phosphate salt and 30-100 parts of coupling agent treated polyvinyl alcohol fiber.
8. A supporting bone repair implant, characterized in that it is made of a bone repair material, which is a composite bone repair material according to any one of claims 1 to 4, or a bone repair material made by the preparation method according to any one of claims 5 to 6.
9. The supporting bone repair implant of claim 8, wherein the supporting bone repair implant has a flexural strength of 120 to 160MPa, a flexural modulus of 5 to 15GPa, and a compressive strength of 120 to 180 MPa.
10. The supporting bone repair implant of claim 9, wherein the supporting bone repair implant has a thermal deformation temperature in the range of 50 ℃ to 120 ℃ and a melting point in the range of 160 ℃ to 220 ℃.
11. The supporting bone repair implant of claim 9, wherein the supporting bone repair implant has a cytotoxicity of grade 1 or less.
12. A method of making a supported bone repair implant according to claim 8, wherein the method comprises: the supporting bone repair implant is obtained by injection molding or hot press molding of a polyvinyl alcohol fiber/polybasic amino acid polymer/calcium phosphate salt composite bone repair material serving as a raw material at 150-210 ℃.
13. The supporting bone repair implant according to any one of claims 8 to 11 for use as a cervical cage, thoracolumbar cage, vertebral body or vertebral plate.
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