Mofs reinforced polyether ether ketone composites, methods of making and using the same

Abstract

This invention provides a MOFs-reinforced polyetheretherketone (PEEK) composite material, its preparation method, and its application, relating to the field of orthopedic implant materials technology. The MOFs-reinforced PEEK composite material of this invention is composed of MOF powder and PEEK. Based on the total mass of the composite material, the MOFs-reinforced PEEK composite material contains 0.1–15 wt% doped graphene or three-dimensional porous graphene powder, with the balance being PEEK. The purpose of this invention is to provide a novel MOFs-reinforced PEEK composite material to address the shortcomings of existing technologies. This invention features a simple process, low cost, and ease of industrial production, and can significantly improve the wear resistance of PEEK materials.

Description

Technical Field

[0001] This invention relates to the field of orthopedic implant materials technology, specifically to a MOF-reinforced polyetheretherketone composite material, its preparation method, and its application. Background Technology

[0002] Polyetheretherketone (PEEK), a high-performance specialty engineering plastic, is widely used in aerospace, automotive manufacturing, electronics, medical, and food processing fields due to its excellent high-temperature resistance, mechanical properties, self-lubricating properties, chemical corrosion resistance, flame retardancy, peel resistance, radiation resistance, stable insulation, and hydrolysis resistance. However, with the advancement of technology and industrial development, the performance requirements for materials are becoming increasingly stringent, and PEEK alone can no longer meet the demands in certain specific environments. Therefore, modifying and enhancing the properties of PEEK materials has become a research hotspot.

[0003] Metal-organic frameworks (MOFs), as a novel type of porous material, possess high specific surface area, tunable pore size, and unique physicochemical properties, making them promising for applications in gas storage, catalysis, sensing, and drug delivery. Combining MOFs with PEEK allows for the full utilization of the advantages of both, resulting in composite materials with superior performance. Based on this, this invention provides a MOF-reinforced polyetheretherketone composite material, its preparation method, and its applications. Summary of the Invention

[0004] The purpose of this invention is to provide a MOFs-reinforced polyether ether ketone composite material, its preparation method and application, which effectively improves the wear resistance of polyether ether ketone materials.

[0005] On one hand, the present invention provides a MOFs-reinforced polyetheretherketone composite material, the composite material being composed of MOFs powder and polyetheretherketone. Based on the total mass of the composite material, the MOFs-reinforced polyetheretherketone composite material contains 0.1 to 15 wt% doped graphene or three-dimensional porous graphene powder, with the remainder being polyetheretherketone.

[0006] Furthermore, the preparation method of the MOFs powder includes: dissolving 3-5 mmol of ferric chloride hexahydrate and 3-5 mmol of fumaric acid in 15-25 mL of water; heating at 90-110°C for 3-5 hours; cooling to room temperature, washing, and drying to obtain the product.

[0007] Furthermore, the specific surface area of ​​the MOF powder is 100–2000 m². 2 / g.

[0008] Furthermore, the particle size of the MOF powder is 5-200 nm.

[0009] On the other hand, the present invention also provides a method for preparing MOFs-reinforced polyether ether ketone composite material, the steps of which include mixing MOFs powder and polyether ether ketone and then hot pressing to obtain MOFs-reinforced polyether ether ketone composite material, wherein the MOFs-reinforced polyether ether ketone composite material contains 0.1 to 15 wt% doped graphene or three-dimensional porous graphene powder, and the balance is polyether ether ketone.

[0010] Furthermore, the mixing method is a high-speed shearing method, specifically, dispersion at 5000–25000 rpm for 30–60 min.

[0011] Furthermore, the hot pressing pressure is 20–100 MPa, the hot pressing temperature is 300–400 °C, and the pressure holding and heat holding time is 30–60 min.

[0012] The MOFs-reinforced polyether ether ketone composite material prepared in this invention is used in the preparation of artificial joint materials; the artificial joint is one or more of the hip joint, knee joint, and shoulder joint.

[0013] The beneficial effects of this invention are as follows:

[0014] (1) The special structure of MOF powder gives it a high specific surface area, elastic modulus and excellent heat transfer properties. MOF reinforced polyether ether ketone will produce a uniform and continuous transfer film on the wear surface, thereby reducing the friction coefficient and wear rate during the friction process.

[0015] (2) MOFs-enhanced polyether ether ketone can improve the biocompatibility of materials, reduce macrophage inflammatory response, and have a certain osteogenic effect, thereby improving the bonding strength between bone tissue and prosthesis materials.

[0016] (3) MOFs-reinforced polyether ether ketone also has certain antibacterial properties.

[0017] (4) This invention can be applied to orthopedic implants such as artificial hip joints, artificial knee joints, and artificial shoulder joints. Detailed Implementation

[0018] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] This invention provides a MOFs-reinforced polyetheretherketone composite material, which is composed of MOFs powder and polyetheretherketone. Based on the total mass of the composite material, the MOFs-reinforced polyetheretherketone composite material contains 0.1 to 15 wt% doped graphene or three-dimensional porous graphene powder, with the balance being polyetheretherketone.

[0020] The method for preparing the MOF powder includes:

[0021] (1) Dissolve 3-5 mmol of ferric chloride hexahydrate and 3-5 mmol of fumaric acid in 15-25 mL of water;

[0022] (2) Transfer the homogeneous solution to a stainless steel autoclave lined with polytetrafluoroethylene and heat it at 90-110℃ for 3-5 hours.

[0023] (3) After cooling to room temperature, the product is repeatedly washed with water and ethanol, and then dried in a vacuum oven at 60-70℃ for 7-9 hours. After grinding, MOF powder is obtained.

[0024] The specific surface area of ​​the MOF powder is 100–2000 m². 2 / g; the particle size of the MOFs powder is 5-200nm.

[0025] This invention also provides a method for preparing MOFs-reinforced polyetheretherketone composite materials, comprising the steps of mixing MOFs powder and polyetheretherketone and then hot-pressing to obtain MOFs-reinforced polyetheretherketone composite materials, wherein the MOFs-reinforced polyetheretherketone composite materials contain 0.1-15 wt% doped graphene or three-dimensional porous graphene powder, and the balance is polyetheretherketone; the mixing method is a high-speed shearing method, specifically dispersion at 5000-25000 rpm for 30-60 min; the hot-pressing pressure is 20-100 MPa, the hot-pressing temperature is 300-400℃, and the holding time is 30-60 min.

[0026] The following specific examples will provide further details.

[0027] Example 1

[0028] This embodiment provides a MOF-reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 50 μm; the reinforcing material is MOF powder with a specific surface area of ​​100 m². 2 / g.

[0029] The method for preparing the MOF powder includes:

[0030] (1) Dissolve 4 mmol of ferric chloride hexahydrate and 4 mmol of fumaric acid in 20 mL of water;

[0031] (2) Transfer the homogeneous solution to a stainless steel autoclave lined with polytetrafluoroethylene and heat it at 100°C for 4 hours.

[0032] (3) After cooling to room temperature, the product is repeatedly washed with water and ethanol, then dried in a vacuum oven at 65°C for 8 hours, and then ground to obtain MOF powder.

[0033] The MOF powder preparation methods in the following examples are the same as those in Example 1.

[0034] The composite material preparation process is as follows:

[0035] (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm;

[0036] (2) Based on a total weight of 1000g, weigh MOF powder and polyether ether ketone powder using an electronic balance at mass fractions of 0% / 100%, 1% / 99%, 3% / 97%, 5% / 95%, 8% / 92%, and 10% / 90%, respectively.

[0037] (3) Put MOF powder and polyether ether ketone powder into a high-speed shear disperser;

[0038] (4) The mixture is mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain mixed powder.

[0039] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain MOFs reinforced polyether ether ketone composite material.

[0040] (6) The friction properties of the composite material were tested by linear reciprocating motion under dry friction conditions without lubrication. The grinding pair was a Si3N3 ceramic ball with a load of 50N, a frequency of 2Hz, a grinding head sliding stroke of 5mm, and an experimental time of 30min.

[0041] Table 1 Properties of MOF-reinforced polyetheretherketone composites

[0042] MOF content / wt% Contact angle / θ° coefficient of friction / μ <![CDATA[Wear rate / mm 3 / (N·m)]]> 0 70 0.22 <![CDATA[2.15×10 -11 ]]> 1 69 0.16 <![CDATA[1.26×10 -11 ]]> 3 69 0.13 <![CDATA[1.17×10 -11 ]]> 5 68 0.08 <![CDATA[0.54×10 -11 ]]> 8 70 0.11 <![CDATA[0.89×10 -11 ]]> 10 69 0.12 <![CDATA[1.12×10 -11 ]]>

[0043] Example 2

[0044] This embodiment provides a MOF-reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is MOF powder with a specific surface area of ​​500 m². 2 / g.

[0045] The composite material preparation process is as follows:

[0046] (1) The polyether ether ketone powder was screened using a sieve with a pore size of 50 μm;

[0047] (2) Based on a total weight of 1000g, weigh MOF powder and polyether ether ketone powder using an electronic balance at mass fractions of 0% / 100%, 1% / 99%, 3% / 97%, 5% / 95%, 8% / 92%, and 10% / 90%, respectively.

[0048] (3) Place the MOFs polyether ether ketone powder into a high-speed shear disperser;

[0049] (4) The mixture was mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain a mixed powder;

[0050] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain MOFs reinforced polyether ether ketone composite material.

[0051] (6) Test the friction properties of composite materials: The test was conducted under dry friction conditions without lubrication, using linear reciprocating motion. The grinding pair was a Si3N3 ceramic ball, the load was 50N, the frequency was 2Hz, the grinding head sliding stroke was 5mm, and the test time was 30min.

[0052] Table 2 Properties of MOF-reinforced polyetheretherketone composites

[0053] MOF content / wt% Contact angle / θ° coefficient of friction / μ <![CDATA[Wear rate / mm 3 / (N·m)]]> 0 68 0.22 <![CDATA[2.15×10 -11 ]]> 1 70 0.13 <![CDATA[1.34×10 -11 ]]> 3 69 0.09 <![CDATA[0.93×10 -11 ]]> 5 70 0.03 <![CDATA[0.44×10 -11 ]]> 8 70 0.05 <![CDATA[0.79×10 -11 <!-- 3 -->]]> 10 69 0.08 <![CDATA[0.93×10 -11 ]]>

[0054] Example 3

[0055] This embodiment provides a MOF-reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is MOF powder with a specific surface area of ​​1000 m². 2 / g.

[0056] The composite material preparation process is as follows:

[0057] (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm;

[0058] (2) Based on a total weight of 1000g, weigh MOF powder and polyether ether ketone powder using an electronic balance at mass fractions of 0% / 100%, 1% / 99%, 3% / 97%, 5% / 95%, 8% / 92%, and 10% / 90%, respectively.

[0059] (3) Place MOFs and polyether ether ketone powder into a high-speed shear disperser;

[0060] (4) The mixture is mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain mixed powder.

[0061] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain MOFs reinforced polyether ether ketone composite material.

[0062] (6) Test the friction properties of composite materials: The test was conducted under dry friction conditions without lubrication, using linear reciprocating motion. The grinding pair was a Si3N3 ceramic ball, the load was 50N, the frequency was 2Hz, the grinding head sliding stroke was 5mm, and the test time was 30min.

[0063] Table 3 Properties of MOF-reinforced polyetheretherketone composites

[0064] MOF content / wt% Contact angle / θ° coefficient of friction / μ <![CDATA[Wear rate / mm 3 / (N·m)]]> 0 69 0.22 <![CDATA[2.15×10 -11 ]]> 1 69 0.19 <![CDATA[1.57×10 -11 ]]> 3 70 0.13 <![CDATA[1.31×10 -11 ]]> 5 70 0.09 <![CDATA[1.02×10 -11 ]]> 8 68 0.11 <![CDATA[1.13×10 -11 ]]> 10 68 0.14 <![CDATA[1.32×10 -11 ]]>

[0065] Example 4:

[0066] This embodiment provides a MOF-reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is MOF powder with a specific surface area of ​​1500 m². 2 / g.

[0067] The composite material preparation process is as follows:

[0068] (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm;

[0069] (2) Based on a total weight of 1000g, weigh MOF powder and polyether ether ketone powder using an electronic balance at mass fractions of 0% / 100%, 1% / 99%, 3% / 97%, 5% / 95%, 8% / 92%, and 10% / 90%, respectively.

[0070] (3) Place MOFs and polyether ether ketone powder into a high-speed shear disperser;

[0071] (4) The mixture was mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain a mixed powder;

[0072] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain MOFs reinforced polyether ether ketone composite material.

[0073] (6) Test the friction properties of composite materials: The test was conducted under dry friction conditions without lubrication, using linear reciprocating motion. The grinding pair was a Si3N3 ceramic ball, the load was 50N, the frequency was 2Hz, the grinding head sliding stroke was 5mm, and the test time was 30min.

[0074] Table 4 Properties of MOF-reinforced polyetheretherketone composites

[0075] MOF content / wt% Contact angle / θ° coefficient of friction / μ <![CDATA[Wear rate / mm 3 / (N·m) <!-- 4 -->]]> 0 68 0.22 <![CDATA[2.15×10 -11 ]]> 1 70 0.21 <![CDATA[2.04×10 -11 ]]> 3 69 0.19 <![CDATA[1.55×10 -11 ]]> 5 70 0.14 <![CDATA[1.33×10 -11 ]]> 8 70 0.16 <![CDATA[1.48×10 -11 ]]> 10 69 0.18 <![CDATA[1.51×10 -11 ]]>

[0076] Finally, it should be noted that the above embodiments and comparative examples are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention; those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention; and all technical solutions and improvements that do not depart from the spirit and scope of the present invention should be covered within the scope of the claims of the present invention.

Claims

1. A method for preparing MOFs-reinforced polyetheretherketone composite materials, characterized in that, The composite material is used in artificial joint materials. The composite material is composed of MOF powder and polyetheretherketone (PEEK). Based on the total mass of the composite material, the MOF-reinforced PEEK composite material contains 5 wt% MOFs, with the remainder being PEEK. The method includes: Dissolve 3-5 mmol of iron chloride hexahydrate and 3-5 mmol of fumaric acid in 15-25 mL of water; heat at 90-110 °C for 3-5 hours; after cooling to room temperature, wash, dry, and obtain; the specific surface area of the MOFs powder is 500 m 2 / g, and the particle size is 5-200 nm. The polyetheretherketone powder was screened using a sieve with a pore size of 50 μm, and the average particle size of the polyetheretherketone powder was 20 μm. Weigh out MOF powder and screened polyetheretherketone powder at 5% and 95% mass fractions respectively; MOF powder and screened polyetheretherketone powder are placed into a high-speed shear disperser; The mixture was prepared by mixing at a speed of 10,000 rpm using a high-speed shear disperser to obtain a mixed powder. The mixed powder was introduced into the mold cavity, and the hot pressing pressure was 30 MPa. The temperature was increased to 360°C at a heating rate of 10°C / min, and the pressure and temperature holding time was 45 min. Then, it was cooled to 100°C in the mold, demolded and sampled to obtain MOFs-reinforced polyether ether ketone composite material.