阅读说明：本技术 一种高生物活性聚醚醚酮复合材料人工假体及其制备方法 (High-bioactivity polyether-ether-ketone composite material artificial 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聚醚醚酮复合材料人工假体及其制备方法,该方法以4,4`-二[2-(1-丙烯基)苯氧基]二苯甲酮、3-(巯基甲基)苯甲酸作为原料,经过加成反应得到了一种双羧基封端的醚酮结构物,与羟基磷灰石、聚醚醚酮共混挤出后得到高生物活性聚醚醚酮复合材料,经注塑成型得到高生物活性聚醚醚酮复合材料人工假体,在提高聚醚醚酮的生物活性并提供聚醚醚酮与羟基磷灰石间的牢度,同时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 polyether-ether-ketone composite material artificial prosthesis and a preparation method thereof, the method takes 4, 4' -bis [2- (1-propenyl) phenoxy ] benzophenone and 3- (mercaptomethyl) benzoic acid as raw materials, a dicarboxyl end-capped ether ketone structure is obtained through addition reaction, the high biological activity polyether-ether-ketone composite material is obtained after blending and extrusion with hydroxyapatite and polyether-ether-ketone, the high biological activity polyether-ether-ketone composite material artificial prosthesis is obtained through injection molding, the biological activity of the polyether-ether-ketone is improved, the fastness between the polyether-ether-ketone and the hydroxyapatite is provided, meanwhile, the sufficient strength and the good biological compatibility of the material are ensured, and the high biological activity polyether-ether-ketone composite material artificial prosthesis has high clinical use value and wide market prospect.)

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

(1) click reaction to obtain a double-carboxyl-terminated ether ketone structure marked as A;

(2) a modifying hydroxyapatite;

(3) and (3) blending and extruding to obtain the polyether-ether-ketone composite material granules.

2. The preparation method of the polyether-ether-ketone composite material with high biological activity according to claim 1, wherein the preparation method comprises the following steps: the step (1) is specifically as follows:

dissolving 1mol of 4, 4' -bis [2- (1-propenyl) phenoxy ] benzophenone and 1-1.2mol of 3- (mercaptomethyl) benzoic acid in 30mol of organic solvent, uniformly stirring, placing under a UV lamp, and illuminating for 0-5min to obtain a dicarboxyl terminated ether ketone structure, which is marked as A.

3. The preparation method of the polyether-ether-ketone composite material with high biological activity according to claim 1, wherein the preparation method comprises the following steps: the step (2) 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 A, heating and stirring at the temperature of 110-120 ℃ for reaction, filtering, washing and drying after the reaction is completed to obtain modified hydroxyapatite A;

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

4. The preparation method of the polyether-ether-ketone composite material with high biological activity according to claim 1, wherein the preparation method comprises the following steps: the step (3) is specifically as follows:

respectively placing 50-70 parts by weight of medical grade polyether-ether-ketone resin and 30-50 parts by weight of modified hydroxyapatite in a drying oven at 160 ℃ for drying for 0.5-2h, mixing, stirring at the stirring speed of 800-: the temperature of the first zone is 370-375 ℃, the temperature of the second zone is 380-385 ℃, the temperature of the third zone is 390-395 ℃, the temperature of the fourth zone is 400-405 ℃, the screw rotation speed is 100-500r/min, and the polyether-ether-ketone composite material granules are obtained through traction, wire drawing and granulation.

5. The method for preparing the high bioactivity polyetheretherketone composite material according to claim 2 or 3, wherein the method comprises the following steps: the organic solvent is N, N-dimethylformamide or dimethylacetamide.

6. An artificial prosthesis made of a polyether-ether-ketone composite material with high biological activity is prepared from the following raw materials in parts by weight: 50-70 parts of medical grade polyether-ether-ketone resin and 30-50 parts of polyether-ether-ketone composite material granules.

7. The high bioactivity polyetheretherketone composite material artificial prosthesis according to claim 6, which is prepared by the following steps: mixing medical grade polyetheretherketone resin and polyetheretherketone composite material granules, feeding the mixture into the double-screw extruder for linkage injection molding at the speed of 800-1500r/min for 5-20min, wherein the temperature of an injection mold for injection molding is 175-4 MPa, the injection back pressure is 2-4MPa, and the injection pressure is 170-180MPa, and performing injection molding to obtain the artificial prosthesis.

Technical Field

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

Background

Bone plays an important role in supporting, hematopoiesis, and maintaining the blood calcium balance in the human body, and bone damage seriously affects the human health and the quality of life of patients. According to statistics, the number of patients with bone defects or bone injuries caused by various traffic, production accidents, orthopedic diseases and other factors in China is as many as tens of millions of people every year, and about 200 tens of thousands of patients need to be subjected to joint replacement surgery. Bone damage seriously affects the quality of life of patients and becomes a serious social problem.

The currently used artificial bone replacement materials are still mainly metals: stainless steel and cobalt-based alloy are used as biomedical metal implant materials applied earlier, and have the defects of insufficient biocompatibility, poor osteogenesis inducing capability, easy generation of stress shielding effect and the like; although the biocompatibility of titanium and titanium alloy metal materials is improved, the titanium alloy reacts with body fluid to easily release toxic ions such as aluminum, vanadium and the like, and the strength of the pure titanium implant is insufficient and is difficult to meet the requirements of the orthopedic implant.

Polyetheretherketone (PEEK) has the advantages of excellent mechanical property, wear resistance, heat resistance, chemical stability and the like, has elastic modulus close to that of natural bones, and is a bone substitute material suitable for being implanted into a human body for a long time. However, PEEK is an inert material, and lacks affinity with human tissues, so that biologic connection between the implant and adjacent bone tissues and soft tissues cannot be realized, osteoinductivity is poor, and bone ingrowth is not facilitated.

Hydroxyapatite (HA) is a common biological tissue material which is non-toxic and non-antigenic, HAs good biological activity, biocompatibility and osteoinductivity, and is a promising bone tissue substitute material. Pure HA HAs relatively poor mechanical properties, which greatly limits its application in bone joint replacements that need to withstand greater loads. The single HA is not high in bonding strength with the matrix, and is easy to fall off under the action of body fluid after being implanted into a human body. Therefore, the PEEK composite material which is formed by processing and injection molding and HAs strong compatibility and good dispersibility between the PEEK and HA is more significant.

Disclosure of Invention

The invention aims to overcome the defect of poor medical bioactivity of polyether-ether-ketone in the prior art, and provides high-bioactivity polyether-ether-ketone and a preparation method thereof, wherein 4, 4' -bis [2- (1-propenyl) phenoxy ] benzophenone and 3- (mercaptomethyl) benzoic acid are used as raw materials, a dicarboxyl end-capped ether-ketone structure is obtained through an addition reaction, and is blended and extruded with hydroxyapatite and polyether-ether-ketone to obtain a high-bioactivity polyether-ether-ketone composite material, and the high-bioactivity polyether-ether-ketone composite material artificial prosthesis is obtained through injection molding.

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

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

(1) click reaction to obtain a double-carboxyl-terminated ether ketone structure marked as A;

(2) a modifying hydroxyapatite;

(3) and (3) blending and extruding to obtain the polyether-ether-ketone composite material granules.

Preferably, the step (1) is specifically:

dissolving 1mol of 4, 4' -bis [2- (1-propenyl) phenoxy ] benzophenone and 1-1.2mol of 3- (mercaptomethyl) benzoic acid in 30mol of organic solvent, uniformly stirring, placing under a UV lamp, and illuminating for 0-5min to obtain a dicarboxyl terminated ether ketone structure, which is marked as A.

Preferably, the step (2) 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 A, heating and stirring at the temperature of 110-120 ℃ for reaction, filtering, washing and drying after the reaction is completed to obtain modified hydroxyapatite A;

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

preferably, the step (3) is specifically:

respectively placing 50-70 parts by weight of medical grade polyether-ether-ketone resin and 30-50 parts by weight of modified hydroxyapatite in a drying oven at 160 ℃ for drying for 0.5-2h, mixing, stirring at the stirring speed of 800-: the temperature of the first zone is 370-375 ℃, the temperature of the second zone is 380-385 ℃, the temperature of the third zone is 390-395 ℃, the temperature of the fourth zone is 400-405 ℃, the screw rotation speed is 100-500r/min, and the polyether-ether-ketone composite material granules are obtained through traction, wire drawing and granulation;

preferably, the organic solvent is N, N-dimethylformamide or dimethylacetamide.

An artificial prosthesis made of a polyether-ether-ketone composite material with high biological activity is prepared from the following raw materials in parts by weight: 50-70 parts of medical grade polyether-ether-ketone resin and 30-50 parts of polyether-ether-ketone composite material granules.

Preferably, the preparation method of the high-bioactivity artificial prosthesis made of the polyether-ether-ketone composite material comprises the following steps: mixing medical grade polyetheretherketone resin and polyetheretherketone composite material granules, feeding the mixture into the double-screw extruder for linkage injection molding at the speed of 800-1500r/min for 5-20min, wherein the temperature of an injection mold for injection molding is 175-4 MPa, the injection back pressure is 2-4MPa, and the injection pressure is 170-180MPa, and performing injection molding to obtain the artificial prosthesis.

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

the invention has the beneficial effects that:

(1) the invention provides a polyether-ether-ketone composite material with high biological activity and a preparation method thereof. Adopts the process of firstly modifying, then dispersing at high speed and then mixing and granulating. The preparation method comprises the steps of modifying hydroxyapatite through chemical reaction, uniformly dispersing the modified hydroxyapatite and polyether-ether-ketone to obtain a blend, drying the blend, uniformly mixing the dried blend through a high-speed stirrer, and carrying out extrusion processing to obtain the novel polyether-ether-ketone composite particles.

(2) According to the artificial prosthesis made of the high-bioactivity polyether-ether-ketone composite material, the modified hydroxyapatite which is one of the raw materials is synthesized into the carboxyl-terminated ether-ketone structure (A) by adopting the UV technology and click reaction, and on one hand, the advantages of high yield and rapid reaction of UV photocuring and click reaction are combined; on the other hand, the reaction is simple and easy to operate.

(3) The high-bioactivity artificial prosthesis made of the polyether-ether-ketone composite material provided by the invention reduces ion release of metal pairs and generation of metal abrasive dust, has excellent mechanical property and biological property, and can be applied to the fields related to aerospace materials and bioengineering materials.

(4) The high-bioactivity polyether-ether-ketone composite material artificial 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.