Polyether-ether-ketone bone repair material with multi-scale holes and preparation method thereof

Abstract

The invention discloses a polyether-ether-ketone bone repair material with multi-scale holes and a preparation method thereof, and belongs to the technical field of medical biological materials. The preparation method comprises the following steps: firstly, hot-pressing polyether-ether-ketone granules into a plate, after cleaning and drying, obtaining a partially foamed polyether-ether-ketone plate in a supercritical carbon dioxide foaming device, conducting sulfonation in a mixed acid solution of concentrated sulfuric acid and methane sulfonic acid, and conducting hydrothermal treatment and vacuum drying to obtain the polyether-ether-ketone bone repair material with multi-scale holes. Small-size micro-nano holes obtained through sulfonation are beneficial to adhesion of early osteoblasts, large-size micro holes obtained through supercritical carbon dioxide foaming are beneficial to ingrowth of bone tissues in a later period, the material has a multi-scale hole structure through simple two-step operation, and bone repair is promoted. Compared with a hole-making technology using a hole-making agent, a supercritical carbon dioxide foaming technology does not have a problem that the hole-making agent is not thoroughly removed and the possibility that the material is applied to the field of biomedicine is ensured.

Description

technical field

[0001] The invention belongs to the technical field of medical biomaterials, and in particular relates to a polyether ether ketone bone repair material with multi-scale pores and a preparation method thereof. Background technique

[0002] Polyetheretherketone (PEEK) is a semi-crystalline thermoplastic polymer that can be easily processed into various shapes to meet the needs of clinical implants. In addition, the elastic modulus (3-5GPa) and density of PEEK are close to those of human bones (about 18GPa), which are far lower than those of metal implants, which can effectively reduce stress shielding; at the same time, PEEK is non-toxic. , high temperature resistance, chemical corrosion resistance, ray penetrability and other excellent properties make it one of the most promising materials to replace metal implants. However, due to the hydrophobic surface and biological inertness of polyetheretherketone, the poor integration with osseointegration after implan...

Examples

Embodiment 1

[0023] PEEK pellets (melt index 22g / 10min, purchased from Changchun Jida Special Plastic Engineering Research Co., Ltd.) were placed in a vacuum hot press, and hot-pressed at 375°C and 2MPa to form a polyether ether with a thickness of 2mm. Then cut the polyether ether ketone plate into a disc with a diameter of 14mm, ultrasonically clean it three times with distilled water, ethanol, and acetone, each time for 10 minutes, and then vacuum-dry it at 80°C. The obtained sample is named PEEK. Then place the polyetheretherketone disc in a supercritical carbon dioxide foaming device, foam at 335°C and 10 MPa for 25 minutes, and release the pressure for 25 seconds, and obtain large particles with a size of 200-600 μm on the surface of the polyetheretherketone disc. hole and named it FPEEK. After that, immerse the polyetheretherketone disc and the foamed polyether ether ketone disc in the mixed acid solution for sulfonation (mixing concentrated sulfuric acid with a mass fraction of 98%...

Embodiment 2

[0026] The samples obtained in Example 1 before and after modification were sterilized in a high-temperature sterilizer. Then placed in a 24-well cell culture plate, the density of each well was 1×10 4 cell / mL of rat bone marrow mesenchymal stem cells (rBMSCs) suspension, then placed in a cell culture incubator at 37°C and 5% carbon dioxide saturated humidity, and the culture medium (containing 10% fetal bovine serum) was changed every 2 days low-sugar DMEM medium). After the cells have been cultured for 1, 4, and 7 days, take out the 24-well culture plate from the cell culture incubator, suck off the old culture medium, and add 200 μL of new culture medium containing 10% CCK-8 (CCK-8, Beyotime, Shanghai, China) Then put it in the cell culture incubator, take it out after 1h, take 100 μL of culture solution from each well and add it dropwise into a 96-well culture plate, use a microplate reader (iMark, Bio-Rad, USA) to measure the concentration of each well at a wavelength of...

Embodiment 3

[0029] The samples obtained in Example 1 before and after modification were sterilized in a high-temperature sterilizer. Then placed in a 24-well cell culture plate, the density of each well was 3×10 4 cell / mL bone marrow mesenchymal stem cells (rBMSCs) suspension, and then placed it in a cell culture incubator at 37°C and 5% carbon dioxide saturated humidity, and changed the culture medium (low glucose containing 10% fetal bovine serum) DMEM medium). After the cells have been cultured for 7 or 14 days, take out the 24-well culture plate from the cell culture incubator, suck off the old culture medium, and wash it with PBS for 3 times, 15 minutes each time, and then lyse it with 0.5% Triton-100 for 1 hour, and collect the lysed cells liquid. Then, the alkaline phosphatase (ALP) activity was obtained according to the instructions of the alkaline phosphatase kit (NanjingJiancheng, Nanjing, China) and the BCA protein concentration assay kit (BCA Protein Assay Kit, Shanghai, Chi...

technical field

[0001] The invention belongs to the technical field of medical biomaterials, and in particular relates to a polyether ether ketone bone repair material with multi-scale pores and a preparation method thereof. Background technique

[0002] Polyetheretherketone (PEEK) is a semi-crystalline thermoplastic polymer that can be easily processed into various shapes to meet the needs of clinical implants. In addition, the elastic modulus (3-5GPa) and density of PEEK are close to those of human bones (about 18GPa), which are far lower than those of metal implants, which can effectively reduce stress shielding; at the same time, PEEK is non-toxic. , high temperature resistance, chemical corrosion resistance, ray penetrability and other excellent properties make it one of the most promising materials to replace metal implants. However, due to the hydrophobic surface and biological inertness of polyetheretherketone, the poor integration with osseointegration after implan...

Examples

Embodiment 1

[0023] PEEK pellets (melt index 22g / 10min, purchased from Changchun Jida Special Plastic Engineering Research Co., Ltd.) were placed in a vacuum hot press, and hot-pressed at 375°C and 2MPa to form a polyether ether with a thickness of 2mm. Then cut the polyether ether ketone plate into a disc with a diameter of 14mm, ultrasonically clean it three times with distilled water, ethanol, and acetone, each time for 10 minutes, and then vacuum-dry it at 80°C. The obtained sample is named PEEK. Then place the polyetheretherketone disc in a supercritical carbon dioxide foaming device, foam at 335°C and 10 MPa for 25 minutes, and release the pressure for 25 seconds, and obtain large particles with a size of 200-600 μm on the surface of the polyetheretherketone disc. hole and named it FPEEK. After that, immerse the polyetheretherketone disc and the foamed polyether ether ketone disc in the mixed acid solution for sulfonation (mixing concentrated sulfuric acid with a mass fraction of 98%...

Embodiment 2

[0026] The samples obtained in Example 1 before and after modification were sterilized in a high-temperature sterilizer. Then placed in a 24-well cell culture plate, the density of each well was 1×10 4 cell / mL of rat bone marrow mesenchymal stem cells (rBMSCs) suspension, then placed in a cell culture incubator at 37°C and 5% carbon dioxide saturated humidity, and the culture medium (containing 10% fetal bovine serum) was changed every 2 days low-sugar DMEM medium). After the cells have been cultured for 1, 4, and 7 days, take out the 24-well culture plate from the cell culture incubator, suck off the old culture medium, and add 200 μL of new culture medium containing 10% CCK-8 (CCK-8, Beyotime, Shanghai, China) Then put it in the cell culture incubator, take it out after 1h, take 100 μL of culture solution from each well and add it dropwise into a 96-well culture plate, use a microplate reader (iMark, Bio-Rad, USA) to measure the concentration of each well at a wavelength of...

Embodiment 3

[0029] The samples obtained in Example 1 before and after modification were sterilized in a high-temperature sterilizer. Then placed in a 24-well cell culture plate, the density of each well was 3×10 4 cell / mL bone marrow mesenchymal stem cells (rBMSCs) suspension, and then placed it in a cell culture incubator at 37°C and 5% carbon dioxide saturated humidity, and changed the culture medium (low glucose containing 10% fetal bovine serum) DMEM medium). After the cells have been cultured for 7 or 14 days, take out the 24-well culture plate from the cell culture incubator, suck off the old culture medium, and wash it with PBS for 3 times, 15 minutes each time, and then lyse it with 0.5% Triton-100 for 1 hour, and collect the lysed cells liquid. Then, the alkaline phosphatase (ALP) activity was obtained according to the instructions of the alkaline phosphatase kit (NanjingJiancheng, Nanjing, China) and the BCA protein concentration assay kit (BCA Protein Assay Kit, Shanghai, Chi...

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