CN108219360B - Medical polyether-ether-ketone composite material and preparation method thereof - Google Patents
Medical polyether-ether-ketone composite material and preparation method thereof Download PDFInfo
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- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a medical polyether-ether-ketone composite material and a preparation method thereof, wherein the medical polyether-ether-ketone composite material is prepared from the following raw materials in parts by weight: 45-55 parts of polyether-ether-ketone, 30-45 parts of hydroxyapatite, 3-6 parts of polyvinyl alcohol, 2-5 parts of polyurethane and 2-5 parts of polyamino acid; the composite material has the advantages that hydroxyapatite is treated by polyamino acid and polyether ether ketone is subjected to micro-crosslinking modification by polyvinyl alcohol, so that the amount of the added hydroxyapatite is larger on the premise that the mechanical property of the composite material is not remarkably reduced; the orthopedic implant made of the composite material has better biological activity and mechanical property, and has positive effect on solving the clinical problem of the implant in medicine.
Description
Technical Field
The invention relates to the field of medical materials, in particular to a medical polyether-ether-ketone composite material and a preparation method thereof.
Background
With the wide clinical application of orthopedic implants made of different materials, the performance of various materials in biological tissues is more clearly understood: orthopedic implants made of traditional materials (such as cobalt-chromium alloy, titanium, stainless steel, etc.) have a much higher elastic modulus than bone, but are less biocompatible; the high molecular polymer made bone implant has good biocompatibility, but can not bear the load of physiological level and can not be used as the implant for bearing load for a long time, so the development of the biological material with the structure and the mechanical property matched with bones is the key for solving the clinical problems.
The elastic modulus of Polyetheretherketone (PEEK) is close to that of cortical bone, and the PEEK has the advantages of good biocompatibility and radiation permeability, no artifact caused by magnetic resonance scanning, and the like, and is always the key point of research of bone science experts and materials science experts for many years. Although the biocompatibility research (cytotoxicity, cell proliferation rate, mutagenicity, adhesiveness, cell biological function and the like of materials by methods such as in vitro cell culture, implantation in animals and the like) on the PEEK proves that the PEEK has good biocompatibility and stable chemical properties, in order to provide a base material with better biocompatibility for a clinical implant, the bioactivity of the PEEK and the PEEK composite material needs to be further improved.
Hydroxyapatite (HAP) has a molecular structure and a calcium-phosphorus ratio very similar to those of inorganic components in normal bones, has good biocompatibility and osteoconductivity with bones, is aggregated and grown with osteoblasts when being cultured with the osteoblasts, and is widely applied to the medical field, particularly to the support or implantation of bones. Therefore, in order to further improve the biological activity of PEEK, HAP and PEEK are compounded to prepare a PEEK-HAP compound body, and experimental analysis proves that the biological activity of the PEEK-HAP compound body is enhanced along with the increase of the volume fraction of the HAP, but the tensile strength and fatigue time of the PEEK-HAP compound material are reduced along with the increase of the content of the HAP, so that the wide application of the PEEK-HAP compound body orthopedic implant in clinic is limited. Although the defects of the PEEK-HAP complex are improved by the application of the HAP whiskers and the carbon fibers, the mechanical properties of the PEEK are reduced by the addition of a large amount of HAP whiskers, the increase of the bioactivity of the PEEK-HAP complex is limited, and the bioactivity of the carbon fibers is poor, and the existence of the carbon fibers or the influence on the bioactivity of the PEEK-HAP complex is caused.
Disclosure of Invention
The invention aims to overcome the defects of poor bioactivity and mechanical property of the existing PEEK-HAP complex, and provides a medical polyether-ether-ketone composite material and a preparation method thereof; according to the invention, hydroxyapatite is treated by polyamino acid and the polyvinyl alcohol is used for modifying polyether-ether-ketone through micro-crosslinking, so that the amount of the added hydroxyapatite is larger on the premise that the mechanical property of the composite material is not remarkably reduced, and the orthopedic implant prepared from the composite material has better biological activity and mechanical property, and has a positive effect on solving the clinical problem of the implant in medicine.
In order to realize the aim, the invention provides a medical polyether-ether-ketone composite material which is prepared from the following raw materials in parts by weight: 45-55 parts of polyether ether ketone, 30-45 parts of hydroxyapatite, 3-6 parts of polyvinyl alcohol, 2-5 parts of polyurethane and 2-5 parts of polyamino acid.
A medical polyether-ether-ketone composite material utilizes the principle that hydroxyapatite can obviously increase the bioactivity of polyether-ether-ketone, not only the hydroxyapatite is treated by polyamino acid, so that the hydroxyapatite has better compatibility, but also the bioactivity of the hydroxyapatite is ensured; the polyvinyl alcohol is used for modifying the micro-crosslinking of the polyether-ether-ketone, so that the polyether-ether-ketone has better toughness and mechanical property; therefore, on the premise that the mechanical property of the composite material is not remarkably reduced, the amount of the added hydroxyapatite is larger, the biological activity of the composite material is better, and the orthopedic implant made of the composite material has better biological activity and mechanical property and has positive effect on solving the clinical problem of the implant in medicine.
According to the medical polyether-ether-ketone composite material, the polyether-ether-ketone is used as a base material and provides basic performance for the composite material, so that the polymerization degree of the polyether-ether-ketone directly influences the basic performance of the composite material, the larger the polymerization degree of the polyether-ether-ketone is within a certain range, the better the mechanical property of the polyether-ether-ketone is, but the partial performance of the polyether-ether-ketone is reduced along with the increase of the polymerization degree; preferably, the polymerization degree of the polyether-ether-ketone is 120-250; most preferably, the polymerization degree of the polyether-ether-ketone is 150-220; through optimization, the obtained polyether-ether-ketone composite material has the best comprehensive performance.
According to the medical polyether-ether-ketone composite material, the hydroxyapatite is used as a filler, so that the bioactivity of the composite material can be obviously improved, the higher the addition amount is, the better the bioactivity of the composite material is, but the poorer the mechanical property of the composite material is, and the particle size of the composite material also influences the distribution of the composite material in a matrix material and influences the performance of the composite material; preferably, the particle size of the hydroxyapatite is 0.01-10 μm; the larger the particle size, the poorer the bioactivity, the greater the effect on the properties of the composite material, and the smaller the particle size, the more difficult the dispersion.
According to the medical polyether-ether-ketone composite material, the polyvinyl alcohol is a cross-linking agent, and hydroxyl groups on a chain can perform addition reaction with ketone groups, so that polyether-ether-ketone is slightly cross-linked, and the mechanical property of the composite material is improved; the polymerization degree of the polyvinyl alcohol influences the toughness and the strength of the composite material, and the higher the polymerization degree is, the better the toughness is and the lower the strength is; preferably, the polymerization degree of the polyvinyl alcohol is 300-500; most preferably, the polymerization degree of the polyvinyl alcohol is 350-450; through optimization, the obtained composite material has good toughness and high strength.
According to the medical polyether-ether-ketone composite material, the polyurethane is a fatigue-resistant modifier and a compatibilizer, so that the fatigue resistance of the composite material can be improved, meanwhile, the compatibility of hydroxyapatite subjected to polyamino acid modification treatment can be improved, the influence of the hydroxyapatite on the performance of the composite material is reduced, the addition amount of the hydroxyapatite is increased, and the bioactivity of the composite material is improved while the performance of the composite material is ensured.
The polyamino acid is a coupling agent and a compatibilizer, and carboxyl groups on the polyamino acid can react with hydroxyl groups on hydroxyapatite, so that the compatibility of the hydroxyapatite in a high polymer material is improved, the influence of the hydroxyapatite on the performance of the composite material is reduced, the addition amount of the hydroxyapatite is increased, and the biological activity of the composite material is improved while the performance of the composite material is ensured; however, excessive carboxyl and hydroxyl can reduce the bioactivity of the hydroxyapatite, so that the carboxyl activity on the polyamino acid needs to be limited, and the bioactivity of the hydroxyapatite is ensured while the compatibility of the hydroxyapatite is improved; preferably, the polymerization degree of the polyamino acid is 5-20; most preferably, the polymerization degree of the polyamino acid is 8-15; through optimization, the polyamino acid has the best modification effect on the compatibility and the bioactivity of hydroxyapatite, and has the best improvement effect on the bioactivity of the composite material.
Preferably, the medical polyether-ether-ketone composite material is prepared from the following raw materials in parts by weight: 50 parts of polyether ether ketone, 40 parts of hydroxyapatite, 4 parts of polyvinyl alcohol, 3 parts of polyurethane and 3 parts of polyamino acid.
In order to achieve the above object, the present invention further provides a method for preparing a medical polyetheretherketone composite material, comprising the following steps:
(1) dissolving the polyamino acid into water to form a solution, mixing the solution with hydroxyapatite, heating the solution for reaction, and drying the reaction product after the reaction is finished;
(2) uniformly mixing the treated hydroxyapatite in the step (1) with polyether-ether-ketone, polyvinyl alcohol and polyurethane to obtain a mixture;
(3) and carrying out composite treatment on the mixture to obtain the medical polyether-ether-ketone composite material.
A method for preparing medical polyether-ether-ketone composite material, firstly modifying hydroxyapatite with polyamino acid to increase compatibility of hydroxyapatite and polyether-ether-ketone; polyvinyl alcohol is used for micro-crosslinking of polyether-ether-ketone, and polyurethane is used for compatibilization and fatigue-resistant modification, so that the addition amount of hydroxyapatite is increased, the bioactivity of the composite material is increased, and the mechanical property is increased; the preparation method is simple and reliable, and is suitable for large-scale and industrial production of the medical polyether-ether-ketone composite material.
According to the preparation method of the medical polyether-ether-ketone composite material, the reaction temperature of the heating reaction in the step (1) is too high, the influence on the bioactivity of hydroxyapatite is large, the reaction temperature is too low, and the reaction time is long; preferably, the reaction temperature is 50-80 ℃, and the reaction time is 0.5-3 h.
The preparation method of the medical polyether-ether-ketone composite material comprises the following steps of (1) carrying out composite treatment in the step (3) by adopting a double-screw extruder; in the extrusion process of the double-screw extruder, crosslinking reaction can be carried out, and the obtained composite material has excellent performance, good stability and convenient operation.
Compared with the prior art, the invention has the beneficial effects that:
1. the composite material of the invention treats the hydroxyapatite through the polyamino acid, so that the hydroxyapatite has better compatibility, and simultaneously, the bioactivity of the hydroxyapatite is ensured, the addition amount of the hydroxyapatite in the composite material is increased, and the bioactivity of the composite material is better.
2. The composite material of the invention enables the polyether-ether-ketone to have better toughness and mechanical property by the micro-crosslinking modification of the polyvinyl alcohol to the polyether-ether-ketone, the amount of hydroxyapatite which can be added is larger, and the biological activity of the composite material is better.
3. The polyurethane in the composite material can improve the fatigue resistance of the composite material, can increase the compatibility of hydroxyapatite after polyamino acid modification treatment, reduces the influence of the hydroxyapatite on the performance of the composite material, and improves the addition amount of the hydroxyapatite.
4. The preparation method of the composite material is simple and reliable, and is suitable for large-scale and industrial production of the medical polyether-ether-ketone composite material.
Detailed Description
The present invention will be described in further detail with reference to test examples and specific embodiments. It should be understood that the scope of the above-described subject matter is not limited to the following examples, and any techniques implemented based on the disclosure of the present invention are within the scope of the present invention.
Example 1
(1) Dissolving 3 parts of polyamino acid with the polymerization degree of 12 in water to form a solution, mixing the solution with 40 parts of hydroxyapatite with the particle size of 1 mu m, reacting at the temperature of 70 ℃ for 1.5 hours, and drying after the reaction is finished;
(2) uniformly mixing the hydroxyapatite treated in the step (1) with 50 parts of polyether-ether-ketone with the polymerization degree of 200, 4 parts of polyvinyl alcohol with the polymerization degree of 400 and 3 parts of polyurethane to obtain a mixture;
(3) and (3) crosslinking and extruding the mixture by using a double-screw extruder to obtain the medical polyether-ether-ketone composite material.
Example 2
(1) Dissolving 2 parts of polyamino acid with the polymerization degree of 5 into water to form a solution, mixing the solution with 45 parts of hydroxyapatite with the particle size of 0.01 mu m, reacting at the temperature of 80 ℃ for 0.5h, and drying after the reaction is finished;
(2) uniformly mixing the hydroxyapatite treated in the step (1) with 55 parts of polyetheretherketone with the polymerization degree of 250, 3-6 parts of polyvinyl alcohol with the polymerization degree of 500 and 2 parts of polyurethane to obtain a mixture;
(3) and (3) crosslinking and extruding the mixture by using a double-screw extruder to obtain the medical polyether-ether-ketone composite material.
Example 3
(1) Dissolving 5 parts of polyamino acid with the polymerization degree of 20 into water to form a solution, mixing the solution with 30 parts of hydroxyapatite with the particle size of 10 mu m, reacting for 3 hours at the temperature of 60 ℃, and drying after the reaction is finished;
(2) uniformly mixing the hydroxyapatite treated in the step (1) with 45 parts of polyether-ether-ketone with a polymerization degree of 120, 3-6 parts of polyvinyl alcohol with a polymerization degree of 300 and 5 parts of polyurethane to obtain a mixture;
(3) and (3) crosslinking and extruding the mixture by using a double-screw extruder to obtain the medical polyether-ether-ketone composite material.
Example 4
(1) Dissolving 3 parts of polyamino acid with the polymerization degree of 15 into water to form a solution, mixing the solution with 35 parts of hydroxyapatite with the particle size of 0.1 mu m, reacting at the temperature of 65 ℃ for 2.5 hours, and drying after the reaction is finished;
(2) uniformly mixing the hydroxyapatite treated in the step (1) with 50 parts of polyether-ether-ketone with the polymerization degree of 180, 5 parts of polyvinyl alcohol with the polymerization degree of 450 and 2 parts of polyurethane to obtain a mixture;
(3) and (3) crosslinking and extruding the mixture by using a double-screw extruder to obtain the medical polyether-ether-ketone composite material.
Comparative example 1
(1) Uniformly mixing 40 parts of hydroxyapatite, 50 parts of polyether-ether-ketone with the polymerization degree of 200, 4 parts of polyvinyl alcohol with the polymerization degree of 400 and 3 parts of polyurethane to obtain a mixture;
(2) and (3) crosslinking and extruding the mixture by using a double-screw extruder to obtain the medical polyether-ether-ketone composite material.
Comparative example 2
(1) Dissolving 3 parts of polyamino acid with the polymerization degree of 12 in water to form a solution, mixing the solution with 40 parts of hydroxyapatite with the particle size of 1 mu m, reacting at the temperature of 70 ℃ for 1.5 hours, and drying after the reaction is finished;
(2) uniformly mixing the hydroxyapatite treated in the step (1), 50 parts of polyether-ether-ketone with the polymerization degree of 200 and 3 parts of polyurethane to obtain a mixture;
(3) and (3) crosslinking and extruding the mixture by using a double-screw extruder to obtain the medical polyether-ether-ketone composite material.
Comparative example 3
(1) Dissolving 3 parts of polyamino acid with the polymerization degree of 12 in water to form a solution, mixing the solution with 40 parts of hydroxyapatite with the particle size of 1 mu m, reacting at the temperature of 70 ℃ for 1.5 hours, and drying after the reaction is finished;
(2) uniformly mixing the hydroxyapatite treated in the step (1) with 50 parts of polyether-ether-ketone with the polymerization degree of 200 and 4 parts of polyvinyl alcohol with the polymerization degree of 400 to obtain a mixture;
(3) and (3) crosslinking and extruding the mixture by using a double-screw extruder to obtain the medical polyether-ether-ketone composite material.
Comparative example 4
(1) Dissolving 3 parts of polyamino acid with the polymerization degree of 12 in water to form a solution, mixing the solution with 40 parts of hydroxyapatite with the particle size of 1 mu m, reacting at the temperature of 70 ℃ for 1.5 hours, and drying after the reaction is finished;
(2) uniformly mixing the hydroxyapatite treated in the step (1) with 50 parts of polyether-ether-ketone with the polymerization degree of 200, 4 parts of polyvinyl alcohol with the polymerization degree of 600 and 3 parts of polyurethane to obtain a mixture;
(3) and (3) crosslinking and extruding the mixture by using a double-screw extruder to obtain the medical polyether-ether-ketone composite material.
Comparative example 5
(1) Dissolving 3 parts of polyamino acid with the polymerization degree of 2 in water to form a solution, mixing the solution with 40 parts of hydroxyapatite with the particle size of 1 mu m, reacting at the temperature of 70 ℃ for 1.5 hours, and drying after the reaction is finished;
(2) uniformly mixing the hydroxyapatite treated in the step (1) with 50 parts of polyether-ether-ketone with the polymerization degree of 200, 4 parts of polyvinyl alcohol with the polymerization degree of 400 and 3 parts of polyurethane to obtain a mixture;
(3) and (3) crosslinking and extruding the mixture by using a double-screw extruder to obtain the medical polyether-ether-ketone composite material.
The composites of examples 1-4 and comparative examples 1-5 were tested for performance and the data reported were as follows:
| performance of | Modulus of elasticity (GPa) | Tensile Strength (MPa) | Biological activity |
| Example 1 | 11.6 | 52.6 | +++++ |
| Example 2 | 12.3 | 48.7 | ++++++ |
| Example 3 | 9.2 | 54.5 | ++++ |
| Example 4 | 10.8 | 51.3 | +++++ |
| Comparative example 1 | 20.9 | 34.8 | +++++ |
| Comparative example 2 | 17.6 | 46.9 | +++++ |
| Comparative example 3 | 16.5 | 45.2 | +++++ |
| Comparative example 4 | 8.4 | 41.3 | +++++ |
| Comparative example 5 | 9.2 | 48.7 | ++ |
Note: the more "+" the better the performance.
Analysis of the experimental data shows that the medical polyether-ether-ketone composite material prepared in the embodiments 1-4 has good mechanical properties and high biological activity; in the comparative example 1, the hydroxyapatite is not treated by the polyamino acid, so that the compatibility of the hydroxyapatite and the polyether-ether-ketone is poor, and the mechanical property of the composite material is obviously reduced; in the comparative example 2, polyvinyl alcohol is not added to carry out micro-crosslinking on polyether-ether-ketone, so that the toughness of the composite material is poor, the elastic modulus is obviously increased, the brittleness is increased, and the tensile strength is reduced to a certain extent; in the comparative example 3, polyurethane is not added, and the compatibility of the modified hydroxyapatite in the composite material is reduced, so that the mechanical property of the composite material is reduced to a greater extent; the polyvinyl alcohol used in the comparative example 4 has high polymerization degree, the molecular chain of the crosslinked polyether-ether-ketone is easy to move, the elastic modulus is small, the toughness is good, but the tensile strength of the composite material is also obviously reduced; the polyamino acid used in comparative example 5 has too low a degree of polymerization, and a large number of reactive carboxyl groups, which affects the bioactivity of hydroxyapatite, resulting in a significant decrease in the bioactivity of the composite material.
Claims (4)
1. The medical polyether-ether-ketone composite material is characterized by being prepared from the following raw materials in parts by weight: 50 parts of polyether ether ketone with the polymerization degree of 200, 40 parts of hydroxyapatite, 4 parts of polyvinyl alcohol with the polymerization degree of 400, 3 parts of polyurethane and 3 parts of polyamino acid with the polymerization degree of 12.
2. The composite material according to claim 1, wherein the hydroxyapatite has a particle size of 0.01 to 10 μm.
3. A method for preparing the medical polyetheretherketone composite material according to any of claims 1-2, comprising the steps of:
(1) dissolving the polyamino acid into water to form a solution, mixing the solution with hydroxyapatite, heating the solution for reaction, and drying the reaction product after the reaction is finished;
(2) uniformly mixing the hydroxyapatite treated in the step (1) with polyether-ether-ketone, polyvinyl alcohol and polyurethane to obtain a mixture;
(3) and carrying out composite treatment on the mixture to obtain the medical polyether-ether-ketone composite material.
4. The method according to claim 3, wherein the reaction temperature in the step (1) is 50 to 80 ℃ and the reaction time is 0.5 to 3 hours.
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