A polyetheretherketone composite material, a preparation method thereof, and its application in 3D printing artificial skull prosthesis

Abstract

The present invention relates to a polyetheretherketone (PEEK) composite material, a preparation method thereof, and its application in 3D-printed artificial skull prostheses, and relates to the technical field of PEEK materials. The PEEK composite material comprises the following raw materials, measured by weight: 50-60 parts of PEEK, 40-50 parts of modified hydroxyapatite, and 4-9 parts of chitosan. Based on the existing PEEK / hydroxyapatite system, the present invention effectively addresses the problem of decreased tensile strength caused by excessive addition of hydroxyapatite by modifying hydroxyapatite with a carboxyl-containing cage-type polysilsesquioxane and introducing chitosan with an appropriate degree of deacetylation. This improves the material's flexibility, resulting in a PEEK composite material with a high hydroxyapatite content, excellent tensile strength, and good flexibility, which can fully meet the application requirements of bone implants such as artificial skull prostheses.

Description

Technical Field

[0001] The present invention relates to the technical field of polyetheretherketone materials, and in particular to a polyetheretherketone composite material, a preparation method thereof, and an application thereof in 3D-printed artificial skull prostheses. Background Art

[0002] In the field of bone implant materials, finding materials that combine good biocompatibility, excellent mechanical properties, and physical and chemical properties compatible with human bone has always been a key challenge for researchers. Artificial skull prostheses, as a key application area for bone implants, place stringent material requirements on their properties. They must be able to withstand certain external impacts, possess good flexibility to adapt to the complex physiological environment of the human body, and be compatible with surrounding tissues to promote bone growth and repair.

[0003] Polyetheretherketone (PEEK), a high-performance specialty engineering plastic, demonstrates significant potential for bone implants due to its outstanding mechanical properties, good biocompatibility, chemical resistance, and excellent radiation resistance. It is increasingly becoming a candidate material for artificial cranial prostheses. However, pure PEEK also has significant limitations. Its relatively low bioactivity and significant differences in composition and structure from human bone make it difficult to directly induce the attachment, proliferation, and differentiation of osteoblasts, hindering the rapid integration and repair of bone tissue. To improve the performance of PEEK, researchers have attempted to composite it with inorganic materials with excellent bioactivity. Hydroxyapatite (HA), a major inorganic component of human bone and teeth, possesses excellent bioactivity and osteoconductivity, providing a suitable microenvironment for osteoblast growth and promoting new bone formation and regeneration. Therefore, incorporating HA into a PEEK matrix to prepare PEEK / HA composites has become an effective approach to enhance the bioactivity and mechanical properties of PEEK.

[0004] However, the existing research on polyetheretherketone / hydroxyapatite systems faces some urgent problems. On the one hand, in order to obtain sufficient biological activity, a higher content of hydroxyapatite needs to be added. However, as the amount of hydroxyapatite added increases, the tensile strength of the composite material will decrease significantly. This is because the interfacial bonding strength between hydroxyapatite and polyetheretherketone is limited, and excessive hydroxyapatite particles tend to agglomerate in the matrix, leading to stress concentration, thereby reducing the overall mechanical properties of the material and making it difficult to meet the mechanical strength requirements of artificial skull prostheses in practical applications. On the other hand, the existing polyetheretherketone / hydroxyapatite composite materials have poor flexibility and are prone to brittle fracture when subjected to external forces. They cannot adapt well to the complex movements and physiological deformations of the human skull, limiting their widespread application in the field of artificial skull prostheses. Summary of the Invention

[0005] To solve the above problems, embodiments of the present invention provide a polyetheretherketone composite material, a preparation method thereof, and an application thereof in 3D printing of an artificial skull prosthesis.

[0006] In a first aspect, an embodiment of the present invention provides a polyetheretherketone composite material, which comprises the following raw materials in parts by weight:

[0007] 50-60 parts of polyetheretherketone, 40-50 parts of modified hydroxyapatite and 4-9 parts of chitosan;

[0008] The modified hydroxyapatite is obtained by modifying hydroxyapatite with a cage-type polysilsesquioxane containing a carboxyl group;

[0009] The deacetylation degree of the chitosan is 70-85%.

[0010] Furthermore, the preparation method of the carboxyl-containing cage-type polysilsesquioxane comprises the following steps:

[0011] γ-aminopropyltriethoxysilane, a first solvent, and a basic catalyst are mixed and stirred at a temperature of 45-55° C. for 23-25 ​​hours; after the reaction, a second solvent is added for precipitation, and the mixture is filtered and vacuum dried to obtain an amino-containing cage-type polysilsesquioxane;

[0012] dissolving the amino-containing cage-type polysilsesquioxane in a third solvent, adding an acid anhydride compound, controlling the molar ratio of the amino-containing cage-type polysilsesquioxane to the acid anhydride compound to be 1:(2-4), and stirring the mixture at 55-65° C. for 7-9 hours; after the reaction is completed, removing the solvent by reduced pressure distillation to obtain the carboxyl-containing cage-type polysilsesquioxane;

[0013] The first solvent includes at least one of water, acetonitrile and propanol, the second solvent includes tetrahydrofuran, the alkaline catalyst includes tetraethylammonium hydroxide, the third solvent includes at least one of N,N-dimethylformamide and dimethyl sulfoxide, and the acid anhydride compound includes maleic anhydride.

[0014] Furthermore, the preparation method of the modified hydroxyapatite comprises the following steps:

[0015] The carboxyl-containing cage-type polysilsesquioxane and the hydroxyapatite are added to an ethanol aqueous solution and subjected to ultrasonic heating and stirring, followed by filtering and drying to obtain the modified hydroxyapatite.

[0016] Furthermore, the weight ratio of the carboxyl-containing cage-type polysilsesquioxane, the hydroxyapatite and the ethanol aqueous solution is (1-3): (9-14): (25-30), and the volume fraction of the ethanol aqueous solution is 60-70%.

[0017] Furthermore, the working condition parameters of the ultrasonic heating and stirring include: ultrasonic power of 400-500W, temperature of 50-60°C, time of 45-60min, and stirring speed of 200-300rpm.

[0018] Furthermore, the deacetylation degree of the chitosan is 80%.

[0019] In a second aspect, based on the same inventive concept, an embodiment of the present invention provides a method for preparing the polyetheretherketone composite material according to any one of the first aspects, the method for preparing the polyetheretherketone composite material comprising the following steps:

[0020] The polyetheretherketone and modified hydroxyapatite are mixed, and then added into a twin-screw extruder for melt extrusion to obtain a polyetheretherketone intermediate;

[0021] The polyetheretherketone intermediate is immersed in a chitosan acetic acid solution, and then the solvent is removed, dried and hot-pressed to obtain the polyetheretherketone composite material.

[0022] Furthermore, the working condition parameters of the twin-screw extruder include: feeding section temperature of 330~340℃, compression section temperature of 345~355℃, mixing section temperature of 360~370℃, exhaust section temperature of 355~365℃, homogenization section temperature of 370~375℃, head temperature of 370~375℃, and screw speed of 100~150rpm.

[0023] Furthermore, the working condition parameters of the hot pressing treatment include: temperature of 175-185° C., pressure of 10-15 MPa, and time of 20-40 min.

[0024] In the third aspect, based on the same inventive concept, an embodiment of the present invention provides the use of the polyetheretherketone composite material described in any one of the first aspects or the polyetheretherketone composite material obtained by the preparation method of the polyetheretherketone composite material described in any one of the second aspects in 3D printing artificial skull prostheses.

[0025] The above technical solution provided by the embodiment of the present invention has at least the following advantages compared with the prior art:

[0026] Embodiments of the present invention provide a polyetheretherketone composite material, a preparation method thereof, and an application in 3D-printed artificial skull prostheses. Based on the existing polyetheretherketone / hydroxyapatite system, the present invention effectively solves the problem of decreased tensile strength caused by excessive addition of hydroxyapatite by using a carboxyl-containing cage-type polysilsesquioxane and introducing chitosan with an appropriate degree of deacetylation, thereby improving the flexibility of the material. The result is a polyetheretherketone composite material with high hydroxyapatite content, excellent tensile strength, and good flexibility, which can fully meet the application requirements of bone implants such as artificial skull prostheses. DETAILED DESCRIPTION

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts are within the scope of protection of the present invention.

[0028] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0029] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present invention only and are not intended to limit the scope of the invention. The experimental methods in the following examples where specific conditions are not specified are generally measured in accordance with national standards. If there are no corresponding national standards, then the methods are carried out in accordance with general international standards, conventional conditions, or the conditions recommended by the manufacturer.

[0030] The main raw materials involved in the following examples and comparative examples are as follows:

[0031] Polyetheretherketone: brand or product model is 380G.

[0032] Hydroxyapatite: brand or product model is H861730, particle size is 60-80nm.

[0033] Chitosan 1: brand or product model is C915936, and the degree of deacetylation is 70%.

[0034] Chitosan 2: brand or product model is C915934, and the degree of deacetylation is 80%.

[0035] Chitosan 3: brand or product model is S24914-100g, and the degree of deacetylation is 85%.

[0036] Chitosan 4: brand or product model is S22208, and the degree of deacetylation is 95%.

[0037] Carboxyl-containing cage-type polysilsesquioxane 1: the brand or product model is Q-0153526, and the specific name is CA0298-OctaMaleamic Acid POSS (cage-type polysilsesquioxane-octacarboxyl).

[0038] Carboxyl-containing cage-type polysilsesquioxane 2: It is prepared according to the method disclosed in the prior art, specifically comprising the following process: 332 ml of γ-aminopropyltriethoxysilane, 135 ml of deionized water, 15 ml of acetonitrile, 60 ml of propanol and 7.5 ml of tetraethylammonium hydroxide are mixed, and the mixture is stirred and reacted at a constant temperature of 50°C for 24 hours; after the reaction is completed, 650 ml of tetrahydrofuran is added and low-temperature precipitation is carried out at a temperature of 5°C, and the mixture is filtered and vacuum dried to obtain an amino-containing cage-type polysilsesquioxane; the amino-containing cage-type polysilsesquioxane is dissolved in N,N-dimethylformamide, maleic anhydride is added, and the molar ratio of the amino-containing cage-type polysilsesquioxane to the acid anhydride compound is controlled to be 1:3, and the mixture is stirred and reacted at 60°C for 8 hours; after the reaction is completed, the solvent is removed by reduced pressure distillation to obtain the carboxyl-containing cage-type polysilsesquioxane.

[0039] Example 1

[0040] This example provides a polyetheretherketone composite material, which comprises the following raw materials in parts by weight:

[0041] 55.5 parts of polyetheretherketone, 45 parts of modified hydroxyapatite and 6.5 parts of chitosan (specifically chitosan 2);

[0042] The modified hydroxyapatite is obtained by modifying hydroxyapatite with a carboxyl-containing cage-type polysilsesquioxane (specifically, carboxyl-containing cage-type polysilsesquioxane 2), and specifically includes the following process:

[0043] The carboxyl-containing cage-type polysilsesquioxane and the hydroxyapatite are added to an ethanol aqueous solution and ultrasonically heated and stirred, followed by filtration and drying to obtain the modified hydroxyapatite; wherein the weight ratio of the carboxyl-containing cage-type polysilsesquioxane, the hydroxyapatite and the ethanol aqueous solution is 2:11:28, and the volume fraction of the ethanol aqueous solution is 65%; the working condition parameters of the ultrasonic heating and stirring include: ultrasonic power of 450 W, temperature of 55° C., time of 50 min, and stirring speed of 260 rpm.

[0044] The preparation method of the polyetheretherketone composite material comprises the following steps:

[0045] The polyetheretherketone and modified hydroxyapatite were pre-dried and mechanically stirred at 600 rpm, and then added into a twin-screw extruder for melt extrusion to obtain a polyetheretherketone intermediate;

[0046] Chitosan was added to a 4.5% by mass acetic acid aqueous solution and stirred to obtain a chitosan acetic acid solution;

[0047] adding the polyetheretherketone intermediate into the chitosan acetic acid solution and immersing for 2 hours, then removing the solvent, drying and hot pressing to obtain the polyetheretherketone composite material;

[0048] Among them, the working condition parameters of the twin-screw extruder include: feeding section temperature of 335°C, compression section temperature of 350°C, mixing section temperature of 365°C, exhaust section temperature of 360°C, homogenization section temperature of 372°C, head temperature of 372°C, and screw speed of 120rpm; the working condition parameters of the hot pressing treatment include: temperature of 180°C, pressure of 12Mpa, and time of 30min.

[0049] Example 2

[0050] This example provides a polyetheretherketone composite material, which comprises the following raw materials in parts by weight:

[0051] 50 parts of polyetheretherketone, 40 parts of modified hydroxyapatite and 4 parts of chitosan (specifically chitosan 1);

[0052] The modified hydroxyapatite is obtained by modifying hydroxyapatite with a carboxyl-containing cage-type polysilsesquioxane (specifically, carboxyl-containing cage-type polysilsesquioxane 1), and specifically includes the following process:

[0053] The carboxyl-containing cage-type polysilsesquioxane and the hydroxyapatite are added to an ethanol aqueous solution and ultrasonically heated and stirred, followed by filtration and drying to obtain the modified hydroxyapatite; wherein the weight ratio of the carboxyl-containing cage-type polysilsesquioxane, the hydroxyapatite and the ethanol aqueous solution is 1:9:25, and the volume fraction of the ethanol aqueous solution is 60%; the working condition parameters of the ultrasonic heating and stirring include: ultrasonic power of 400 W, temperature of 50° C., time of 60 min, and stirring speed of 300 rpm.

[0054] The preparation method of the polyetheretherketone composite material comprises the following steps:

[0055] The polyetheretherketone and modified hydroxyapatite were pre-dried and mechanically stirred at 600 rpm, and then added into a twin-screw extruder for melt extrusion to obtain a polyetheretherketone intermediate;

[0056] Chitosan was added to a 4.5% by mass acetic acid aqueous solution and stirred to obtain a chitosan acetic acid solution;

[0057] adding the polyetheretherketone intermediate into the chitosan acetic acid solution and immersing for 2 hours, then removing the solvent, drying and hot pressing to obtain the polyetheretherketone composite material;

[0058] Among them, the working condition parameters of the twin-screw extruder include: feeding section temperature of 330°C, compression section temperature of 345°C, mixing section temperature of 360°C, exhaust section temperature of 355°C, homogenization section temperature of 370°C, head temperature of 370°C, and screw speed of 150rpm; the working condition parameters of the hot pressing treatment include: temperature of 185°C, pressure of 10Mpa, and time of 20min.

[0059] Example 3

[0060] This example provides a polyetheretherketone composite material, which comprises the following raw materials in parts by weight:

[0061] 60 parts of polyetheretherketone, 50 parts of modified hydroxyapatite and 9 parts of chitosan (specifically chitosan 3);

[0062] The modified hydroxyapatite is obtained by modifying hydroxyapatite with a carboxyl-containing cage-type polysilsesquioxane (specifically, carboxyl-containing cage-type polysilsesquioxane 2), and specifically includes the following process:

[0063] The carboxyl-containing cage-type polysilsesquioxane and the hydroxyapatite are added to an ethanol aqueous solution and ultrasonically heated and stirred, followed by filtration and drying to obtain the modified hydroxyapatite; wherein the weight ratio of the carboxyl-containing cage-type polysilsesquioxane, the hydroxyapatite and the ethanol aqueous solution is 3:14:30, and the volume fraction of the ethanol aqueous solution is 70%; the working condition parameters of the ultrasonic heating and stirring include: ultrasonic power of 500 W, temperature of 60° C., time of 45 min, and stirring speed of 200 rpm.

[0064] The preparation method of the polyetheretherketone composite material comprises the following steps:

[0065] The polyetheretherketone and modified hydroxyapatite were pre-dried and mechanically stirred at 600 rpm, and then added into a twin-screw extruder for melt extrusion to obtain a polyetheretherketone intermediate;

[0066] Chitosan was added to a 4.5% by mass acetic acid aqueous solution and stirred to obtain a chitosan acetic acid solution;

[0067] adding the polyetheretherketone intermediate into the chitosan acetic acid solution and immersing for 2 hours, then removing the solvent, drying and hot pressing to obtain the polyetheretherketone composite material;

[0068] Among them, the working condition parameters of the twin-screw extruder include: feeding section temperature of 340°C, compression section temperature of 355°C, mixing section temperature of 370°C, exhaust section temperature of 365°C, homogenization section temperature of 375°C, head temperature of 375°C, and screw speed of 100rpm; the working condition parameters of the hot pressing treatment include: temperature of 175°C, pressure of 15Mpa, and time of 40min.

[0069] Comparative Example 1

[0070] This example provides a polyetheretherketone composite material and a preparation method thereof, which differs from Example 1 only in that:

[0071] (1) The modified hydroxyapatite was replaced by unmodified hydroxyapatite (i.e., the hydroxyapatite raw material in Example 1).

[0072] Comparative Example 2

[0073] This example provides a polyetheretherketone composite material and a preparation method thereof, which differs from Example 1 only in that:

[0074] (1) Chitosan 2 was replaced by chitosan 4 (i.e., the deacetylation degree of chitosan was too high).

[0075] Test Case

[0076] In this example, mechanical properties of the polyetheretherketone composite materials obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were tested. The test results are shown in Table 1.

[0077] Table 1

[0078]

[0079] From Table 1 we can see that:

[0080] 1) When a high amount of hydroxyapatite is added, the polyetheretherketone composite materials provided in Examples 1 to 3 of the present invention still maintain excellent tensile strength and good elastic modulus, indicating that they have the characteristics of high hydroxyapatite content, excellent tensile strength and good flexibility.

[0081] 2) When the amount of hydroxyapatite added is high, in Comparative Example 1, since the hydroxyapatite is not modified with the carboxyl-containing cage-type polysilsesquioxane, the compatibility of hydroxyapatite in the system is poor, resulting in a significant decrease in the mechanical properties of the polyetheretherketone composite material.

[0082] 3) When the amount of hydroxyapatite added is high, the rigidity of chitosan 4 is too high in Comparative Example 2, resulting in a significant increase in the elastic modulus of the polyetheretherketone composite material and a decrease in the tensile strength to a certain extent.

[0083] Various embodiments of the present invention may be presented in the form of a range; it should be understood that the description in a range format is only for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; therefore, the range description should be considered to have specifically disclosed all possible subranges and single numerical values ​​within the range. For example, the description of a range from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated herein, it is intended to include any cited numeral (fractional or integer) within the indicated range.

[0084] The foregoing description is intended only to provide specific embodiments of the present invention, which will enable those skilled in the art to understand and implement the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not intended to be limited to the embodiments shown herein, but is intended to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A polyetheretherketone composite material, characterized in that The polyetheretherketone composite material comprises the following raw materials in parts by weight: 50-60 parts of polyetheretherketone, 40-50 parts of modified hydroxyapatite and 4-9 parts of chitosan; The modified hydroxyapatite is obtained by modifying hydroxyapatite with a cage-type polysilsesquioxane containing a carboxyl group; The deacetylation degree of the chitosan is 70-85%.

2. The polyetheretherketone composite material according to claim 1, characterized in that The preparation method of the carboxyl-containing cage-type polysilsesquioxane comprises the following steps: γ-aminopropyltriethoxysilane, a first solvent, and a basic catalyst are mixed and stirred at a temperature of 45-55° C. for 23-25 ​​hours; after the reaction, a second solvent is added for precipitation, and the mixture is filtered and vacuum dried to obtain an amino-containing cage-type polysilsesquioxane; dissolving the amino-containing cage-type polysilsesquioxane in a third solvent, adding an acid anhydride compound, controlling the molar ratio of the amino-containing cage-type polysilsesquioxane to the acid anhydride compound to be 1:(2-4), and stirring the mixture at 55-65° C. for 7-9 hours; after the reaction is completed, removing the solvent by reduced pressure distillation to obtain the carboxyl-containing cage-type polysilsesquioxane; The first solvent includes at least one of water, acetonitrile and propanol, the second solvent includes tetrahydrofuran, the alkaline catalyst includes tetraethylammonium hydroxide, the third solvent includes at least one of N,N-dimethylformamide and dimethyl sulfoxide, and the acid anhydride compound includes maleic anhydride.

3. The polyetheretherketone composite material according to claim 1, characterized in that The preparation method of the modified hydroxyapatite comprises the following steps: The carboxyl-containing cage-type polysilsesquioxane and the hydroxyapatite are added to an ethanol aqueous solution and subjected to ultrasonic heating and stirring, followed by filtering and drying to obtain the modified hydroxyapatite.

4. The polyetheretherketone composite material according to claim 3, characterized in that The weight ratio of the carboxyl-containing cage-type polysilsesquioxane, the hydroxyapatite and the ethanol aqueous solution is (1-3):(9-14):(25-30), and the volume fraction of the ethanol aqueous solution is 60-70%.

5. The polyetheretherketone composite material according to claim 3, characterized in that The working condition parameters of the ultrasonic heating and stirring include: ultrasonic power of 400-500W, temperature of 50-60°C, time of 45-60min, and stirring speed of 200-300rpm.

6. The polyetheretherketone composite material according to claim 1, characterized in that The deacetylation degree of the chitosan is 80%.

7. A method for preparing the polyetheretherketone composite material according to any one of claims 1 to 6, characterized in that: The preparation method of the polyetheretherketone composite material comprises the following steps: The polyetheretherketone and modified hydroxyapatite are mixed, and then added into a twin-screw extruder for melt extrusion to obtain a polyetheretherketone intermediate; The polyetheretherketone intermediate is immersed in a chitosan acetic acid solution, and then the solvent is removed, dried and hot-pressed to obtain the polyetheretherketone composite material.

8. The method for preparing the polyetheretherketone composite material according to claim 7, characterized in that: The working condition parameters of the twin-screw extruder include: feeding section temperature of 330~340℃, compression section temperature of 345~355℃, mixing section temperature of 360~370℃, exhaust section temperature of 355~365℃, homogenization section temperature of 370~375℃, die head temperature of 370~375℃, and screw speed of 100~150rpm.

9. The method for preparing the polyetheretherketone composite material according to claim 7, characterized in that: The working condition parameters of the hot pressing treatment include: temperature of 175-185° C., pressure of 10-15 MPa, and time of 20-40 min.

10. Use of the polyetheretherketone composite material according to any one of claims 1 to 6 or the polyetheretherketone composite material obtained by the preparation method of the polyetheretherketone composite material according to any one of claims 7 to 9 in 3D printing of a human skull prosthesis.

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