阅读说明：本技术 一种高生物活性peek复合材料人工关节假体及其制备方法 (High-bioactivity PEEK composite material artificial joint prosthesis and preparation method thereof ) 是由 高崇勇 王逸杰 于 2019-12-03 设计创作，主要内容包括：本发明属于新材料领域。本发明涉及一种高生物活性PEEK复合材料人工关节假体及其制备方法,该方法以苯胺封端的醚酮结构物A、4-溴苯甲酸乙酯作为原料,经过Buchwald–Hartwig偶联反应、水解反应得到了一种双羧基封端的醚酮结构物,与羟基磷灰石、PEEK共混挤出后得到高生物活性PEEK复合材料,经注塑成型得到高生物活性PEEK复合材料人工关节假体,在提高PEEK的生物活性并提供PEEK与羟基磷灰石间的牢度的同时,兼具利于细胞黏附和增殖的作用,保证该材料足够的强度和良好的生物相容性,具有较高的临床使用价值和广阔的市场前景。(The invention belongs to the field of new materials. The invention relates to a high biological activity PEEK composite material artificial joint prosthesis and a preparation method thereof, the method takes an aniline-terminated ether ketone structure A and 4-ethyl bromobenzoate as raw materials, a double-carboxyl-terminated ether ketone structure is obtained through Buchwald-Hartwig coupling reaction and hydrolysis reaction, the high biological activity PEEK composite material is obtained after blending and extrusion with hydroxyapatite and PEEK, and the high biological activity PEEK composite material artificial joint prosthesis is obtained through injection molding.)

1. A preparation method of a high-bioactivity PEEK composite material is characterized by comprising the following steps: comprises the following steps:

(1) Buchwald-Hartwig coupling reaction to obtain benzoate-terminated ether ketone structure, which is marked as B;

(2) performing hydrolysis reaction to obtain a carboxyl-terminated ether ketone structure, and marking as C;

(3) c modifying hydroxyapatite;

(4) and (4) blending and extruding to obtain the PEEK composite material granules.

2. The preparation method of the PEEK composite material with high biological activity as claimed in claim 1, wherein the PEEK composite material comprises: the step (1) is specifically as follows:

dissolving 1mol of aniline-terminated ether ketone structure A and 1-1.2mol of 4-ethyl bromobenzoate in 30mol of organic solvent, adding 0.001-0.1 mol of palladium catalyst and 1mol of sodium tert-butoxide, and stirring at 80-100 ℃ for 36-48h to obtain benzoate-terminated ether ketone structure B.

3. The preparation method of the PEEK composite material with high biological activity as claimed in claim 1, wherein the PEEK composite material comprises: the step (2) is specifically as follows:

dissolving 1mol of B in 30mol of organic solvent, adding 1-5 mol% of sodium hydroxide aqueous solution, stirring for 10-20h, filtering, distilling under reduced pressure, adding 1-5 mol% of acetic acid, stirring for 1-4h, distilling under reduced pressure and drying to obtain a carboxyl-terminated ether ketone structure, which is marked as C.

4. The preparation method of the PEEK composite material with high biological activity as claimed in claim 1, wherein the PEEK composite material comprises: the step (3) is specifically as follows:

dispersing 100 parts by weight of hydroxyapatite raw material with the particle size of 0.1-5 mu m in an organic solvent, ultrasonically dispersing for 0.5-2h, adding 50-150 parts by weight of C, heating and stirring at the temperature of 110-120 ℃ for reaction, and filtering, washing and drying after the reaction is completed to obtain C modified hydroxyapatite;

the dosage ratio of the hydroxyapatite to the organic solvent is as follows: 10-20g/100 mL.

5. The preparation method of the PEEK composite material with high biological activity as claimed in claim 1, wherein the PEEK composite material comprises: the step (4) is specifically as follows:

respectively placing 50-70 parts by weight of medical grade PEEK resin and 30-50 parts by weight of C modified hydroxyapatite in a drying oven at 160 ℃ for drying for 0.5-2h, mixing, stirring at the stirring speed of 1000-1500r/min for 10-20min, adding into a double-screw extruder for extrusion, and setting the temperature of each zone as follows: the temperature of the first zone is 370-minus 380 ℃, the temperature of the second zone is 385-minus 395 ℃, the temperature of the third zone is 400-minus 410 ℃, the rotating speed of the screw is 100-minus 500r/min, and the PEEK composite material granules are obtained through traction, wire drawing and granulation.

6. The preparation method of the PEEK composite material with high biological activity as claimed in claim 2, wherein the PEEK composite material comprises: the palladium catalyst is Pd (OAc)₂、Pd₂(dba)₃、(CyPFtBu)PbCl₂And one or more of XPhos.

7. The method for preparing PEEK composite material with high bioactivity according to any one of claims 2, 3 or 4, wherein the PEEK composite material comprises the following steps: the organic solvent is DMF, THF, dioxane or DME.

8. A high-bioactivity PEEK composite material artificial joint prosthesis is prepared from the following raw materials in parts by weight: 55-80 parts of medical PEEK resin and 20-45 parts of PEEK composite material granules.

9. The high bioactivity PEEK composite material artificial joint prosthesis according to claim 8, the preparation method comprises: mixing medical grade PEEK resin and PEEK composite material granules, feeding the mixture to the double-screw extruder for linkage injection molding after the time is 10-20min at the speed of 1500r/min for 1000-.

Technical Field

The invention relates to a high-bioactivity PEEK composite material artificial joint prosthesis and a preparation method thereof. The invention belongs to the field of new materials.

Background

In order to improve the bioactivity of PEEK, inorganic fillers with bioactivity, such as Hydroxyapatite (HA), Bioactive Glass (BG), tricalcium phosphate (β -TCP) and the like are often mixed in the PEEK, the HA HAs good human tissue compatibility, bioactivity, bone conduction activity and bone inductivity and is widely applied to orthopedics clinic at present.

PEEK and HA are continuously modified to meet the increasingly urgent needs of human life. The current method is to coat HA on the surface of PEEK, and the excellent mechanical properties of the PEEK structure and the bioactivity of HA are utilized, but the poor interface compatibility of HA and PEEK leads to the limited use of the method. Therefore, the research on a medium with high compatibility and good dispersibility between HA and PEEK is particularly important, and the processing and injection molding are effective means for increasing the PEEK composite material with high compatibility and good dispersibility between PEEK and HA.

Disclosure of Invention

The invention aims to provide a high-bioactivity PEEK composite material and a preparation method thereof aiming at the defects of poor compatibility of PEEK and HA interface and low bioactivity of a PEEK composite material in the prior art.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a preparation method of a high-bioactivity PEEK composite material is characterized by comprising the following steps: comprises the following steps:

(1) Buchwald-Hartwig coupling reaction to obtain benzoate-terminated ether ketone structure, which is marked as B;

(2) hydrolysis reaction to obtain a carboxyl-terminated ether ketone structure, which is marked as C

(3) C modifying hydroxyapatite;

(4) and (4) blending and extruding to obtain the PEEK composite material granules.

Further, the step (1) is specifically as follows:

dissolving 1mol of aniline-terminated ether ketone structure A and 1-1.2mol of 4-ethyl bromobenzoate in 30mol of organic solvent, adding 0.001-0.1 mol of palladium catalyst and 1mol of sodium tert-butoxide, and stirring at 80-100 ℃ for 36-48h to obtain benzoate-terminated ether ketone structure B.

Further, the step (2) is specifically as follows:

dissolving 1mol of B in 30mol of organic solvent, adding 1-5 mol% of sodium hydroxide aqueous solution, stirring for 10-20h, filtering, distilling under reduced pressure, adding 1-5 mol% of acetic acid, stirring for 1-4h, distilling under reduced pressure and drying to obtain a carboxyl-terminated ether ketone structure, which is marked as C.

Further, the step (3) is specifically:

dispersing 100 parts by weight of hydroxyapatite raw material with the particle size of 0.1-5 mu m in an organic solvent, ultrasonically dispersing for 0.5-2h, adding 50-150 parts by weight of C, heating and stirring at the temperature of 110-120 ℃ for reaction, and filtering, washing and drying after the reaction is completed to obtain C modified hydroxyapatite;

the dosage ratio of the hydroxyapatite to the organic solvent is as follows: 10-20g/100 mL.

Further, the step (4) is specifically as follows:

respectively placing 50-70 parts by weight of medical grade PEEK resin and 30-50 parts by weight of C modified hydroxyapatite in a drying oven at 160 ℃ for drying for 0.5-2h, mixing, stirring at the stirring speed of 1000-1500r/min for 10-20min, adding into a double-screw extruder for extrusion, and setting the temperature of each zone as follows: the temperature of the first zone is 370-minus 380 ℃, the temperature of the second zone is 385-minus 395 ℃, the temperature of the third zone is 400-minus 410 ℃, the rotating speed of the screw is 100-minus 500r/min, and the PEEK composite material granules are obtained through traction, wire drawing and granulation.

Further, the palladium catalyst is Pd (OAc)₂、Pd₂(dba)₃、(CyPFtBu)PbCl₂And one or more of XPhos.

Further, the organic solvent is DMF, THF, dioxane or DME.

A high-bioactivity PEEK composite material artificial joint prosthesis is prepared from the following raw materials in parts by weight: 55-80 parts of medical PEEK resin and 20-45 parts of PEEK composite material granules.

Further, the preparation method of the high-bioactivity PEEK composite material artificial joint prosthesis comprises the following steps: mixing medical grade PEEK resin and PEEK composite material granules, feeding the mixture to the double-screw extruder for linkage injection molding after the time is 10-20min at the speed of 1500r/min for 1000-.

The preparation process of the carboxyl-terminated ether ketone structure (C) provided by the invention is as follows:

the invention has the beneficial effects that:

(1) the invention provides a high-bioactivity PEEK composite material and a preparation method thereof. Adopts the process of firstly modifying, then dispersing at high speed and then mixing and granulating. Through chemical reaction modified hydroxyapatite, homodisperse modified hydroxyapatite and PEEK obtain the blend, dry back rethread high speed mixer misce bene, can extrude processing, obtain novel PEEK composite material granule.

(2) According to the high-bioactivity PEEK composite material artificial joint prosthesis provided by the invention, a carboxyl-terminated ether ketone structure (C) is synthesized by adopting Buchwald-Hartwig coupling reaction and hydrolysis reaction of modified hydroxyapatite which is one of raw materials, so that the advantage of high yield and high efficiency of the Buchwald-Hartwig coupling reaction is combined on one hand; on the other hand, the existence of the secondary amino group increases the hydrophilicity of the material, is beneficial to the adhesion and proliferation of cells and improves the biocompatibility.

(3) The high-bioactivity PEEK composite artificial joint prosthesis provided by the invention reduces ion release of metal pairs and generation of metal abrasive dust, HAs excellent mechanical properties (good compatibility of the composite PEEK and HA) and biological properties, and can be applied to the fields related to bioengineering materials.

(4) The high-bioactivity PEEK composite material artificial joint prosthesis provided by the invention has good biocompatibility and bioactivity, has the properties of strength, modulus and the like of a bone prosthesis matched with human bones, has good corrosion resistance and long service life, and can completely meet the clinical requirements on bone repair.

The specific implementation mode is as follows:

the present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.