CN-122005945-A - Hydroxyapatite-nano calcium silicate-polyether-ether-ketone composite material and preparation method thereof

Abstract

The invention provides a hydroxyapatite-nano calcium silicate-polyether-ether-ketone composite material and a preparation method thereof, and relates to the technical field of bone implant materials. The composite material takes polyether-ether-ketone as a continuous matrix, hydroxyapatite and nano calcium silicate are uniformly dispersed in the matrix as bioactive phases, and the composite material comprises, by mass, 10-20% of hydroxyapatite, 1-10% of nano calcium silicate and 70-90% of polyether-ether-ketone, wherein the length-diameter ratio of the hydroxyapatite is 1.5-40. The invention takes polyether-ether-ketone as a matrix, and by cooperatively introducing hydroxyapatite and calcium silicate particles as a composite reinforcing phase, the mechanical strength and the modulus of the material are obviously improved, and meanwhile, the excellent bioactivity, the bone conductivity and the osseointegration capacity of the material are endowed, the crystallization performance and the biocompatibility of the material are further optimized, and the prepared composite material has excellent comprehensive performance and is suitable for an implant body for repairing bone defects of bearing parts.

Inventors

• SUN ZHENLONG
• ZHANG BIN
• LIU MINGXIA
• Chen Junnuo
• JIAN XIGAO
• WANG HAN
• PANG BO
• HE XIANGMING
• LIU CHENGDE
• XU SHIBO
• LU YAOPING

Assignees

• 大连理工大学
• 威高集团有限公司

Dates

Publication Date

20260512

Application Date

20260228

Claims (9)

1. 1. A composite material of hydroxyapatite-nano calcium silicate-polyether ether ketone is characterized in that polyether ether ketone is used as a continuous matrix, hydroxyapatite and nano calcium silicate are uniformly dispersed in the matrix as bioactive phases, the content of each component is 10-20% of the hydroxyapatite, 1-10% of the nano calcium silicate and 70-90% of the polyether ether ketone, and the length-diameter ratio of the hydroxyapatite is 1.5-40.
2. 2. The composite material of hydroxyapatite, nano calcium silicate and polyether ether ketone as set forth in claim 1, wherein the composite material consists of hydroxyapatite 12-20 wt%, nano calcium silicate 2-8 wt% and polyether ether ketone 75-85 wt%.
3. 3. The composite material of hydroxyapatite and nano calcium silicate and polyether ether ketone according to claim 2, wherein the composite material is 17-20% of hydroxyapatite.
4. 4. The composite material of hydroxyapatite and nano calcium silicate and polyether ether ketone as set forth in claim 1, wherein the needle-shaped hydroxyapatite is needle-shaped hydroxyapatite with length-diameter ratio of 10-40.
5. 5. The hydroxyapatite-nano calcium silicate-polyether ether ketone composite material according to claim 4, wherein the aspect ratio of the needle-shaped hydroxyapatite is 20-40.
6. 6. The hydroxyapatite-nano calcium silicate-polyether-ether-ketone composite material according to claim 1, wherein the average particle size of the hydroxyapatite is 4-5 mu m, the average particle size of the polyether-ether-ketone powder is 45-55 mu m, and the average particle size of the calcium silicate powder is 100-500nm.
7. 7. A method for preparing the hydroxyapatite-nano calcium silicate-polyether ether ketone composite material according to claim 1, which is characterized by comprising the following steps: Step one, raw material pretreatment and mixing, namely drying hydroxyapatite powder, nano calcium silicate powder and polyether-ether-ketone powder, and then placing the dried powder in mixing equipment to fully mix the dried powder for 0.5 to 2 hours to obtain uniform composite powder; step two, compression molding, namely loading the composite powder into a mold, and molding by adopting a compression molding process, wherein the maximum molding temperature is 360-400 ℃, and the pressure of the product is 0.1-0.5MPa; And thirdly, post-treatment, namely cooling and demolding the formed blank to obtain the hydroxyapatite-nano calcium silicate-polyether-ether-ketone composite material.
8. 8. The method of claim 7, wherein the molding process comprises a multi-stage heating and pressurizing process.
9. 9. The method of claim 8, wherein the compression molding process comprises a multi-stage heating process from room temperature to the maximum molding temperature, and different molding pressures are applied at different temperature stages.

Description

Hydroxyapatite-nano calcium silicate-polyether-ether-ketone composite material and preparation method thereof Technical Field The invention relates to the technical field of bone implant materials, in particular to a hydroxyapatite-nano calcium silicate-polyether-ether-ketone composite material and a preparation method thereof. Background In the fields of orthopaedics, plastic surgery, oral and maxillofacial surgery and the like, the implantation material is a key for repairing bone defects and reconstructing joint functions. At present, the clinically commonly used implant materials are mainly classified into metal, inorganic nonmetal, polymer and composite materials. The metal materials, such as stainless steel, titanium and titanium alloy, cobalt chromium molybdenum alloy, etc., have the advantages of high strength, good wear resistance, etc., but the elastic modulus is obviously higher than that of human bone tissue (such as titanium alloy elastic modulus is about 110-GPa, and human cortical bone elastic modulus is about 7-30 GPa), which is easy to cause a stress shielding effect to cause surrounding bone absorption and implantation loosening, and can cause local tissue reaction, allergy or systemic toxicity due to metal ion release (such as nickel, chromium, cobalt, aluminum, etc.) after long-term implantation, in addition, the metal implant has higher cost, and can interfere with medical images (such as CT and MRI to generate artifacts) to influence postoperative evaluation. Inorganic nonmetallic materials such as Hydroxyapatite (HA), bioglass, calcium phosphate ceramics and the like have good biocompatibility and bone conductivity, but have the common mechanical defects of large brittleness, poor toughness, insufficient fatigue resistance and the like, are difficult to bear physiological load of a load bearing part, and meanwhile, the elastic modulus is still higher, the degradation rate is difficult to match with the growth rate of new bone, and the implant is possibly broken prematurely or remained for a long time to prevent bone reconstruction. The polyether-ether-ketone (PEEK) is used as a semi-crystalline thermoplastic polymer material, has an elastic modulus (about 3-4 GPa) similar to that of human cortical bone, can effectively slow down stress shielding, has excellent ray permeability and magnetic resonance compatibility, does not influence postoperative imaging follow-up, and has good chemical resistance, fatigue resistance and relatively low processing and manufacturing cost. Has good application in the fields of spinal fusion device, joint prosthesis and the like. However, PEEK itself is a biologically inert material, lacks biological activity on the surface, is difficult to form firm chemical osseointegration with host bone tissue, and has limited long-term stability and osteoinductive capacity, which are major bottlenecks for its further wide application in orthopedics. To improve the bioactivity of PEEK, bioceramics are often introduced for compounding. At present, researches show that Calcium Silicate (CS) has good biodegradability and ion release activity (such as Si 4+、Ca2+) and can promote cell proliferation, angiogenesis and osteogenic differentiation, but the degradation rate is too fast and the mechanical strength is insufficient. Hydroxyapatite (HA) is a major inorganic component of human bone tissue, HAs excellent bone conductivity and chemical stability, and can directly form bonding with bone, but is brittle. Disclosure of Invention In order to solve the technical problems, the invention combines HA and CS together with PEEK, CS activates cellular biological response through controllable ion release, HA can provide a stable bone bonding interface, and PEEK is taken as a matrix to bear main mechanical support and structure maintenance. The three are cooperated, and a novel bone repair composite material with good mechanical matching property, bioactivity and long-term stability is hopeful to be constructed, so that the system solves multiple clinical challenges of stress shielding and ion release of metal materials, high brittleness of inorganic ceramic materials, biological inertia of pure PEEK and the like. The first aspect of the invention provides a hydroxyapatite-nano calcium silicate-polyether ether ketone composite material, which takes polyether ether ketone as a continuous matrix, and hydroxyapatite and nano calcium silicate as uniform dispersion in the matrix to serve as a bioactive phase, wherein the composite material comprises, by mass, 10-20% of hydroxyapatite, 1-10% of nano calcium silicate and 70-90% of polyether ether ketone, and the length-diameter ratio of the hydroxyapatite is 1.5-40. Preferably, the content of each component is 12-20% of hydroxyapatite, 2-8% of nano calcium silicate, 75-85% of polyether-ether-ketone, and further 17-20% of hydroxyapatite. Preferably, the hydroxyapatite is needle-shaped hydroxyapatite with an aspect ratio of 10-40, and furth