CN112587732A - Preparation method of nano-hydroxyapatite and sulfonated polyether ether ketone composite material - Google Patents
Preparation method of nano-hydroxyapatite and sulfonated polyether ether ketone composite material Download PDFInfo
- Publication number
- CN112587732A CN112587732A CN202011212350.6A CN202011212350A CN112587732A CN 112587732 A CN112587732 A CN 112587732A CN 202011212350 A CN202011212350 A CN 202011212350A CN 112587732 A CN112587732 A CN 112587732A
- Authority
- CN
- China
- Prior art keywords
- sulfonated polyether
- hydroxyapatite
- ether ketone
- polyether ether
- sol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/425—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of phosphorus containing material, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Public Health (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Dermatology (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a preparation method of a nano hydroxyapatite and sulfonated polyether ether ketone composite material, wherein the preparation of the composite material comprises the preparation of sol, hydroxyapatite gel and a sulfonated polyether ether ketone matrix, and the preparation of a coating; the sol is prepared by adding a certain amount of absolute ethyl alcohol and pure water into triethyl phosphite for dilution, and stirring to obtain sol; the preparation of the gel is that calcium nitrate is dissolved in absolute ethyl alcohol, then the sol is added, and the hydroxyapatite gel solution is obtained after stirring and aging; the preparation of the coating is that the sulfonated polyether ether ketone matrix is put into hydroxyapatite gel solution, and is calcined after being dipped and coated with gel, so as to obtain the composite material. The sulfonated polyether ether ketone and the hydroxyapatite are organically combined together, and the preparation method provides more abundant functionalized modification sites, combines fine crystal grains of the hydroxyapatite, can obviously improve the bioactivity, and ensures that the material has enough strength.
Description
Technical Field
The invention belongs to the technical field of treating orthopedic diseases and beautifying and reshaping, and particularly relates to a preparation method of a nano hydroxyapatite composite material.
Background
When a human bone is damaged, the bone needs to be repaired. Natural autologous bone is the most ideal donor in terms of osteoconductive, osteoinductive and osteogenic capacity, but due to limited availability, it is not possible to provide sufficient bone source when the defect site is large. At present, aiming at bone defects in clinic, the used repair materials are various, and mainly comprise artificially synthesized hydroxyapatite, organic bone cement, allogeneic bone, alpha-tricalcium phosphate, beta-tricalcium phosphate and orthopedic products added with active factors such as collagen, BMP-2 and the like.
Due to the limited number of clinical applications of autologous bone graft, hydroxyapatite is the main inorganic component of human skeleton, and has bioactivity and bone conduction capability.
Hydroxyapatite (HA) is the main inorganic component of human skeleton and tooth, HAs good biological activity and biocompatibility, and can be actively connected with bone formation after being implanted into human body to induce the growth and formation of new bone. The nano HA can be widely applied to the repair and replacement of biological hard tissues and is an ideal substitute material for human bones. However, pure hydroxyapatite is hard, brittle, low in strength, poor in toughness, not easy to carve, not well inosculated with surrounding tissues, and lower in fracture strength and fracture toughness indexes than those of artificial compact bones, so that the application of the pure hydroxyapatite to weight bearing parts of human bodies is limited. In order to overcome the defects and improve the mechanical property, a hydroxyapatite coating can be prepared on a substrate by adopting a sol-gel method, the advantages of various materials are integrated, and the composite biological material with good biological property and mechanical property is obtained.
Polyether-ether-ketone (PEEK) is a wholly aromatic semi-crystalline polymer, is thermoplastic special engineering plastic with excellent comprehensive performance, and resists high temperature; resistance to many organic or inorganic chemicals; in the aspect of mechanical property, the strength, the elastic modulus and the fracture toughness are high, the strength loss at high temperature is small, and the dimensional stability is good; in the aspect of friction performance, the high-temperature wear resistance is more outstanding; in the aspect of molding processing, all processing methods of thermoplastic resins can be used for processing, including extrusion, injection molding, melt spinning, and the like. PEEK has good mechanical properties, excellent radiation resistance, insulativity and other characteristics, and is more and more widely applied to spinal surgeries, traumas and orthopedic medical products in clinic. Has better biocompatibility and adjustable mechanical property. However, PEEK lacks biological activity, so that its use in the medical field is limited.
The preparation method of the hydroxyapatite and PEEK composite material mainly comprises a mechanical mixing method, an extrusion-cryogenic grinding method, a solvent mixing method, a solvent precipitation method and the like.
The mechanical mixing method mixes the two powders using a mechanical mixing device, and the method has a simple process, but cannot uniformly disperse the nano-filler in the matrix in a nano-scale. The double-screw extrusion-cryogenic pulverization method is used for melting and blending the two materials, extruding and granulating the two materials, and then carrying out cryogenic pulverization, so that small-particle-size powder cannot be prepared, the particle shape of the powder is extremely irregular, and the flowability is poor. Solvent mixing methods generally require the use of some organic solvent, and residual solvent can reduce the biocompatibility of the composite. Polyetheretherketone has very strong solvent resistance, and a solvent precipitation method is generally not suitable for preparing the polyetheretherketone composite material.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a preparation method of a nano-hydroxyapatite and sulfonated polyether ether ketone composite material, which can effectively compound the nano-hydroxyapatite and the sulfonated polyether ether ketone together, can obviously improve the bioactivity, and can ensure enough strength.
The invention also aims to provide a preparation method of the nano-hydroxyapatite and sulfonated polyether ether ketone composite material, which can keep the good performance of polyether ether ketone, simultaneously provide more abundant functional modification sites and is suitable for the fields of bearing bone replacement and bone repair.
The inventor researches and discovers that: sulfonated polyether ether ketone (SPEEK) and hydroxyapatite have respective advantages, and a key point is how to organically combine the sulfonated polyether ether ketone and the hydroxyapatite to fully exert the functions of the sulfonated polyether ether ketone and the hydroxyapatite. The good performance of the polyether-ether-ketone is maintained, meanwhile, richer functional modification sites are provided, and the composite biological material with more excellent performance can be prepared; furthermore, the higher the bioactivity is, in combination with the fine grains of hydroxyapatite.
Based on this, the invention is realized as follows:
a preparation method of a nano-hydroxyapatite and sulfonated polyether ether ketone composite material comprises the steps of preparing sol, hydroxyapatite gel and a sulfonated polyether ether ketone matrix, and preparing a coating;
preparing sol: adding anhydrous ethanol into triethyl phosphite to prepare a solution with the concentration of 0.040mol/L-0.060mol/L, adding 25-50% pure water by volume for dilution, and stirring to obtain sol;
further, anhydrous ethanol is added into triethyl phosphite (the content is not less than 99.5 percent) for dissolution, and a solution with the concentration of 0.040mol/L-0.060mol/L is prepared. Adding 25-50% pure water into the solution, sealing the bottle cap, and stirring vigorously on a magnetic stirrer for more than 10 hours to obtain clear sol with certain viscosity.
Preparation of hydroxyapatite gel: dissolving calcium nitrate in absolute ethyl alcohol to prepare a solution with the concentration of 0.025mol/L-0.050mol/L, then adding the sol, stirring after mixing, and aging to obtain a hydroxyapatite gel solution;
further, calcium nitrate (content not less than 99.5%) is dissolved in anhydrous ethanol, and during the dissolving process, heating and stirring are continuously carried out. Then dropping into the completely hydrolyzed phosphorus sol, preparing according to the atomic ratio of Ca to P of 1.67, sealing the bottle cap after mixing, stirring vigorously for more than 2 hours, and aging the stirred sol at room temperature for 36-72 hours.
Preparation of sulfonated polyether ether ketone: drying 10 g of polyetheretherketone granular material at 100 ℃ for 10 hours under vacuum, dissolving the dried material in 500ml of concentrated sulfuric acid (95% -98%) at 25 ℃, stirring vigorously for 2 hours, pouring the reaction solution into ice water with the volume of 5-8 times of that of the ice water, stirring continuously for 1 hour, standing for 24 hours, and filtering and washing precipitates with pure water for multiple times until the pH value is 7. Finally, the product is dried in vacuum for 24 hours at the temperature of 60 ℃ to obtain the sulfonated polyether-ether-ketone. Sulfonated polyether ether ketone (SPEEK) is sulfonated on an aromatic ring structure of polyether ether ketone (PEEK), so that the good performance of the polyether ether ketone can be maintained, and meanwhile, more abundant functional modification sites are provided. And further preparing the sulfonated polyether-ether-ketone into a sulfonated polyether-ether-ketone matrix.
Preparing a coating: and putting the sulfonated polyether-ether-ketone matrix into a hydroxyapatite gel solution, fully dipping the sulfonated polyether-ether-ketone matrix into the hydroxyapatite gel solution, and calcining the sulfonated polyether-ether-ketone matrix after the hydroxyapatite gel solution is fully dipped into the gel to obtain the composite material.
Further, the sulfonated polyether ether ketone matrix is placed in a sol-gel solution of hydroxyapatite for dip coating, then is placed in an ultrasonic cleaning machine for 2-20 minutes, then is placed in a drying box, is dried for more than 30 minutes at 80 ℃, is placed in a sintering furnace, and is calcined for 30-60 minutes at a determined temperature. The calcining temperature is 600-800 ℃. And (3) sequentially carrying out dip coating, drying and calcining on the calcined substrate, and repeating for multiple times (more than one time) until a film with enough thickness is formed.
According to the invention, through the preparation of sol and gel, sulfonated polyether ether ketone and hydroxyapatite are organically combined together, and through the preparation method, the aromatic ring structure of polyether ether ketone is sulfonated to obtain sulfonated polyether ether ketone, so that the good performance of polyether ether ketone can be maintained, meanwhile, more abundant functionalized modification sites are provided, and the fine crystal grains of hydroxyapatite are combined, so that the bioactivity can be obviously improved, and the material has enough strength.
The preparation method of the composite material has the advantages of simple process, low cost and wide application, and is suitable for preparing coatings of sulfonated polyether ether ketone substrates with various scales and sizes.
Moreover, the composite material can realize controllable shape, good biocompatibility, good bioactivity and enough strength required by bearing bones, and has higher clinical use value and wide market prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The inventor researches and discovers that: sulfonated polyether ether ketone (SPEEK) and hydroxyapatite have respective advantages, and a key point is how to organically combine the sulfonated polyether ether ketone and the hydroxyapatite to fully exert the functions of the sulfonated polyether ether ketone and the hydroxyapatite. Sulfonated polyether ether ketone (SPEEK) is sulfonated on an aromatic ring structure of polyether ether ketone (PEEK), so that the good performance of the polyether ether ketone can be maintained, meanwhile, more abundant functionalized modification sites are provided, and the composite biological material with more excellent performance can be prepared. The finer the crystal grain of the hydroxyapatite, the higher the bioactivity thereof. The nano-hydroxyapatite is compounded with the sulfonated polyether ether ketone, so that the biological activity can be obviously improved, the sufficient strength is ensured, and the composite material is suitable for the fields of load-bearing bone replacement and bone repair.
Therefore, the preparation method of the nano-hydroxyapatite and sulfonated polyether ether ketone composite material, which is realized by the invention, mainly comprises the following steps of preparing hydroxyapatite gel and a sulfonated polyether ether ketone matrix, and preparing a coating:
preparing sol: adding anhydrous ethanol into triethyl phosphite to prepare a solution with the concentration of 0.040mol/L-0.060mol/L, adding 25-50% pure water by volume for dilution, sealing a bottle cap, and stirring vigorously on a magnetic stirrer for more than 10 hours to obtain clear sol with certain viscosity.
Preparation of hydroxyapatite gel: dissolving calcium nitrate in absolute ethyl alcohol to prepare a solution with the concentration of 0.025mol/L-0.050mol/L, and continuously heating and stirring in the dissolving process. Then adding the sol, preparing according to the proportion that the atomic ratio of Ca and P is 1.67, sealing a bottle cap after the preparation is finished, stirring vigorously for more than 2 hours, and aging the stirred sol at room temperature for 36-72 hours to obtain the hydroxyapatite gel solution.
Preparation of sulfonated polyether ether ketone (sulfonated polyether ether ketone is prepared according to the proportion): drying 10 g of polyether-ether-ketone granular material at 100 ℃ for 10 hours in vacuum, dissolving the dried material in 500ml of concentrated sulfuric acid (95% -98%) at 25 ℃, after vigorously stirring for 2 hours, pouring the reaction solution into ice water with the volume 5-8 times that of the reaction solution, continuously stirring for 1 hour, standing for 24 hours, and repeatedly filtering and washing precipitates with pure water until the pH value is 7; finally, the product is dried in vacuum for 24 hours at the temperature of 60 ℃ to obtain the sulfonated polyether-ether-ketone. The sulfonated polyether-ether-ketone is sulfonated on an aromatic ring structure of the polyether-ether-ketone, so that the good performance of the polyether-ether-ketone can be kept, and meanwhile, more abundant functional modification sites are provided. And preparing the sulfonated polyether-ether-ketone into a sulfonated polyether-ether-ketone matrix.
Preparing a coating: and putting the sulfonated polyether ether ketone matrix into a hydroxyapatite gel solution, fully dipping the sulfonated polyether ether ketone matrix into the hydroxyapatite gel solution, and calcining the sulfonated polyether ether ketone matrix to obtain the nano hydroxyapatite and sulfonated polyether ether ketone composite material.
Wherein, the content of the triethyl phosphite is not less than 99.5 percent, and the content of the calcium nitrate is not less than 99.5 percent.
The sulfonated polyether ether ketone material can be used for preparing sulfonated polyether ether ketone matrixes with various shapes and sizes according to requirements.
The sulfonated polyether ether ketone matrix is placed in a sol-gel solution of hydroxyapatite for dip coating, then is placed in an ultrasonic cleaning machine for 2-20 minutes, then is placed in a drying box, is dried for more than 30 minutes at 80 ℃, is placed in a sintering furnace, and is calcined for 30-60 minutes at a determined temperature. The calcining temperature is 600-800 ℃. And sequentially carrying out dip coating, drying, calcining and repeating for multiple times on the calcined sulfonated polyether-ether-ketone matrix until a film with enough thickness is formed. By the method, the sulfonated polyether ether ketone and the hydroxyapatite can be organically combined together, the structure is stable, the sulfonated polyether ether ketone keeps good performance of the polyether ether ketone, meanwhile, more abundant functional modification sites are provided, the sulfonated polyether ether ketone lies in fine grains of the combined hydroxyapatite, the bioactivity can be obviously improved, and meanwhile, the stable structure formed by sintering enables the prepared composite material to have enough strength and meet the requirements of operations and other materials.
The preparation method provided by the invention can realize the controllable shape, good biocompatibility, good bioactivity and enough strength required by bearing bones, has higher clinical use value and wide market prospect, and can be widely applied to various aspects such as bone repair, beauty treatment and the like.
Example 1.
Preparing sol: adding a certain amount of absolute ethyl alcohol into triethyl phosphite with the content of not less than 99.5 percent to prepare a solution with the concentration of 0.040mol/L, then adding pure water with the volume of 25 percent for dilution, sealing a bottle cap, and stirring vigorously on a magnetic stirrer for 10 hours to obtain clear sol with certain viscosity.
Preparation of hydroxyapatite gel: dissolving calcium nitrate in absolute ethyl alcohol to prepare a solution with the concentration of 0.025mol/L, and continuously heating and stirring the solution in the dissolving process. Then adding the sol, preparing according to the proportion that the atomic ratio of Ca and P is 1.67, sealing a bottle cap after the preparation is finished, stirring vigorously for more than 2.5 hours, and aging the stirred sol at room temperature for 36 hours to obtain the hydroxyapatite gel solution.
Preparation of sulfonated polyether ether ketone: after 10 g of a polyetheretherketone granulate mass were dried at 100 ℃ under vacuum for 10 hours, dissolved in 500ml of concentrated sulfuric acid (95%) at 25 ℃ and stirred vigorously for 2 hours, the reaction solution was poured into 5 times the volume of ice water, stirred continuously for 1 hour, left to stand for 24 hours, and the precipitate was filtered and washed several times with water until the pH was 7. Finally, the product is dried in vacuum at 60 ℃ for 24 hours to obtain the sulfonated polyether ether ketone. And then the sulfonated polyether-ether-ketone material is prepared into a sulfonated polyether-ether-ketone matrix with the required shape, scale and size.
Preparing a coating: placing a sulfonated polyether ether ketone matrix in a hydroxyapatite sol-gel solution, placing the sulfonated polyether ether ketone matrix in an ultrasonic cleaning machine for 10 minutes, then placing the sulfonated polyether ether ketone matrix in a drying box, drying the sulfonated polyether ether ketone matrix for 30 minutes at 80 ℃, then placing the sulfonated polyether ether ketone matrix in a sintering furnace, and calcining the sulfonated polyether ether ketone matrix for 30 minutes at 800 ℃; and sequentially carrying out dip coating, drying, calcining and repeating for multiple times on the calcined sulfonated polyether-ether-ketone matrix until a film with enough thickness is formed, thus obtaining the composite material.
Example 2.
Preparing sol: adding a certain amount of absolute ethyl alcohol into triethyl phosphite with the content of not less than 99.5 percent to prepare a solution with the concentration of 0.060mol/L, adding 50 percent of pure water by volume for dilution, sealing a bottle cap, and violently stirring on a magnetic stirrer for 12 hours to obtain clear sol with certain viscosity.
Preparation of hydroxyapatite gel: dissolving calcium nitrate with the content of not less than 99.5% in absolute ethyl alcohol to prepare a solution with the concentration of 0.050mol/L, and continuously heating and stirring in the dissolving process. And adding the sol, preparing according to the atomic ratio of Ca to P of 1.67, sealing a bottle cap after the preparation is finished, stirring vigorously for 3 hours, and aging the stirred sol at room temperature for 72 hours to obtain a hydroxyapatite gel solution.
Preparation of sulfonated polyether ether ketone: after 10 g of a polyetheretherketone granulate mass were dried at 100 ℃ under vacuum for 10 hours, dissolved in 500ml of concentrated sulfuric acid (98%) at 25 ℃ and stirred vigorously for 2 hours, the reaction solution was poured into 8 times the volume of ice water, stirred continuously for 1 hour, left to stand for 24 hours, and the precipitate was filtered and washed several times with water until the pH was 7. Finally, the product is dried in vacuum at 60 ℃ for 24 hours to obtain the sulfonated polyether ether ketone. And then the sulfonated polyether-ether-ketone material is made into a sulfonated polyether-ether-ketone matrix with the required shape, scale and size.
Preparing a coating: placing a sulfonated polyether ether ketone matrix in a hydroxyapatite sol-gel solution, placing the sulfonated polyether ether ketone matrix in an ultrasonic cleaning machine for 6 minutes, then placing the sulfonated polyether ether ketone matrix in a drying box, drying the sulfonated polyether ether ketone matrix for 35 minutes at the temperature of 80 ℃, then placing the sulfonated polyether ether ketone matrix in a sintering furnace, and calcining the sulfonated polyether ether ketone matrix for 40 minutes at the calcining temperature of 800 ℃; and sequentially carrying out dip coating, drying, calcining and repeating for multiple times on the calcined sulfonated polyether-ether-ketone matrix until a film with enough thickness is formed, thus obtaining the composite material.
Example 3.
Preparing sol: adding a certain amount of absolute ethyl alcohol into triethyl phosphite with the content of not less than 99.5 percent to prepare a solution with the concentration of 0.050mol/L, and adding 35 percent of pure water by volume for dilution. Adding pure water into the solution, sealing the bottle cap, and stirring vigorously on a magnetic stirrer for 11 hours to obtain clear sol with certain viscosity.
Preparation of hydroxyapatite gel: dissolving calcium nitrate with the content of not less than 99.5% in absolute ethyl alcohol, dissolving the calcium nitrate in the absolute ethyl alcohol to prepare a solution with the concentration of 0.035mol/L, and continuously heating and stirring in the dissolving process. And adding the sol, preparing according to the proportion that the atomic ratio of Ca to P is 1.67, sealing a bottle cap after the preparation is finished, stirring vigorously for more than 2 hours, and aging the stirred sol at room temperature for 56 hours to obtain the hydroxyapatite gel solution. .
Preparation of sulfonated polyether ether ketone: after 10 g of a polyetheretherketone granulate mass were dried at 100 ℃ under vacuum for 10 hours, dissolved in 500ml of concentrated sulfuric acid (96%) at 25 ℃ and stirred vigorously for 2 hours, the reaction solution was poured into 6 times the volume of ice water, stirred continuously for 1 hour, left to stand for 24 hours, and the precipitate was filtered and washed several times with water until the pH was 7. Finally, the product is dried in vacuum at 60 ℃ for 24 hours to obtain the sulfonated polyether ether ketone. And then the sulfonated polyether-ether-ketone material is made into a sulfonated polyether-ether-ketone matrix with the required shape, scale and size.
Preparing a coating: placing a sulfonated polyether ether ketone matrix in a hydroxyapatite sol-gel solution, placing the sulfonated polyether ether ketone matrix in an ultrasonic cleaning machine for 15 minutes, then placing the sulfonated polyether ether ketone matrix in a drying box, drying the sulfonated polyether ether ketone matrix for 40 minutes at 80 ℃, then placing the sulfonated polyether ether ketone matrix in a sintering furnace, and calcining the sulfonated polyether ether ketone matrix for 50 minutes at 700 ℃; and sequentially carrying out dip coating, drying, calcining and repeating for multiple times on the calcined sulfonated polyether-ether-ketone matrix until a film with enough thickness is formed, thus obtaining the composite material.
Example 4.
Preparing sol: adding a certain amount of absolute ethyl alcohol into triethyl phosphite with the content of not less than 99.5 percent to prepare a solution with the concentration of 0.045mol/L, adding 45 percent volume of pure water for dilution, sealing a bottle cap, and stirring vigorously on a magnetic stirrer for 13 hours to obtain clear sol with certain viscosity.
Preparation of hydroxyapatite gel: dissolving calcium nitrate with the content of not less than 99.5% in absolute ethyl alcohol, dissolving the calcium nitrate in the absolute ethyl alcohol to prepare a solution with the concentration of 0.045mol/L, and continuously heating and stirring in the dissolving process. Then adding the sol, preparing according to the proportion that the atomic ratio of Ca and P is 1.67, sealing a bottle cap after the preparation is finished, stirring vigorously for 3.5 hours, and aging the stirred sol at room temperature for 62 hours to obtain the hydroxyapatite gel solution. .
Preparation of sulfonated polyether ether ketone: after 10 g of a polyetheretherketone granulate mass were dried at 100 ℃ under vacuum for 10 hours, dissolved in 500ml of concentrated sulfuric acid (97%) at 25 ℃ and stirred vigorously for 2 hours, the reaction solution was poured into 7 times the volume of ice water, stirred continuously for 1 hour, left to stand for 24 hours, and the precipitate was filtered and washed several times with water until the pH was 7. Finally, the product is dried in vacuum at 60 ℃ for 24 hours to obtain the sulfonated polyether ether ketone. And then the sulfonated polyether-ether-ketone material is made into a sulfonated polyether-ether-ketone matrix with the required shape, scale and size.
Preparing a coating: placing a sulfonated polyether ether ketone matrix in a hydroxyapatite sol-gel solution, placing the sulfonated polyether ether ketone matrix in an ultrasonic cleaning machine for 2 minutes, then placing the sulfonated polyether ether ketone matrix in a drying box, drying the sulfonated polyether ether ketone matrix for 45 minutes at the temperature of 80 ℃, then placing the sulfonated polyether ether ketone matrix in a sintering furnace, and calcining the sulfonated polyether ether ketone matrix for 60 minutes at the calcining temperature of 600 ℃; and sequentially carrying out dip coating, drying, calcining and repeating for multiple times on the calcined sulfonated polyether-ether-ketone matrix until a film with enough thickness is formed, thus obtaining the composite material.
Example 5.
Preparing sol: adding a certain amount of absolute ethyl alcohol into triethyl phosphite with the content of not less than 99.5 percent to prepare a solution with the concentration of 0.055mol/L, adding pure water with the volume of 40 percent to dilute, sealing a bottle cap, and stirring vigorously on a magnetic stirrer for 15 hours to obtain clear sol with certain viscosity.
Preparation of hydroxyapatite gel: dissolving calcium nitrate with the content of not less than 99.5% in absolute ethyl alcohol, dissolving the calcium nitrate in the absolute ethyl alcohol to prepare a solution with the concentration of 0.040mol/L, and continuously heating and stirring in the dissolving process. And adding the sol, preparing according to the atomic ratio of Ca to P of 1.67, sealing a bottle cap after the preparation is finished, stirring vigorously for 4 hours, and aging the stirred sol at room temperature for 42 hours to obtain a hydroxyapatite gel solution.
Preparation of sulfonated polyether ether ketone: after 10 g of a polyetheretherketone granulate mass were dried at 100 ℃ under vacuum for 10 hours, dissolved in 500ml of concentrated sulfuric acid (95%) at 25 ℃ and stirred vigorously for 2 hours, the reaction solution was poured into 5.5 times the volume of ice water, stirring was continued for 1 hour, and left to stand for 24 hours, and the precipitate was filtered and washed with water several times until the pH was 7. Finally, the product is dried in vacuum at 60 ℃ for 24 hours to obtain the sulfonated polyether ether ketone. And then the sulfonated polyether-ether-ketone material is made into a sulfonated polyether-ether-ketone matrix with the required shape, scale and size.
Preparing a coating: placing a sulfonated polyether ether ketone matrix in a hydroxyapatite sol-gel solution, placing the sulfonated polyether ether ketone matrix in an ultrasonic cleaning machine for 18 minutes, then placing the sulfonated polyether ether ketone matrix in a drying box, drying the sulfonated polyether ether ketone matrix for 50 minutes at the temperature of 80 ℃, then placing the sulfonated polyether ether ketone matrix in a sintering furnace, and calcining the sulfonated polyether ether ketone matrix for 55 minutes at the calcining temperature of 650 ℃; and sequentially carrying out dip coating, drying, calcining and repeating for multiple times on the calcined sulfonated polyether-ether-ketone matrix until a film with enough thickness is formed, thus obtaining the composite material.
Example 6.
Preparing sol: adding a certain amount of absolute ethyl alcohol into triethyl phosphite with the content of not less than 99.5 percent to prepare the solution with the concentration of 0.040mol/L, adding 30 percent volume of pure water for dilution, sealing a bottle cap, and stirring vigorously on a magnetic stirrer for 16 hours to obtain clear sol with certain viscosity.
Preparation of hydroxyapatite gel: dissolving calcium nitrate with the content of not less than 99.5% in absolute ethyl alcohol, dissolving the calcium nitrate in the absolute ethyl alcohol to prepare a solution with the concentration of 0.030mol/L, and continuously heating and stirring the solution in the dissolving process. Then adding the sol, preparing according to the proportion that the atomic ratio of Ca and P is 1.67, sealing a bottle cap after the preparation is finished, stirring vigorously for more than 2 hours, and aging the stirred sol at room temperature for 48 hours to obtain the hydroxyapatite gel solution. .
Preparation of sulfonated polyether ether ketone: after 10 g of a polyetheretherketone granulate mass were dried at 100 ℃ under vacuum for 10 hours, dissolved in 500ml of concentrated sulfuric acid (98%) at 25 ℃ and stirred vigorously for 2 hours, the reaction solution was poured into 6 times the volume of ice water, stirred continuously for 1 hour, left to stand for 24 hours, and the precipitate was filtered and washed several times with water until the pH was 7. Finally, the product is dried in vacuum at 60 ℃ for 24 hours to obtain the sulfonated polyether ether ketone. And then the sulfonated polyether-ether-ketone material is made into a sulfonated polyether-ether-ketone matrix with the required shape, scale and size.
Preparing a coating: placing a sulfonated polyether ether ketone matrix in a hydroxyapatite sol-gel solution, placing the sulfonated polyether ether ketone matrix in an ultrasonic cleaning machine for 4 minutes, then placing the sulfonated polyether ether ketone matrix in a drying box, drying the sulfonated polyether ether ketone matrix for 55 minutes at the temperature of 80 ℃, then placing the sulfonated polyether ether ketone matrix in a sintering furnace, and calcining the sulfonated polyether ether ketone matrix for 35 minutes at the calcining temperature of 750 ℃; and sequentially carrying out dip coating, drying, calcining and repeating for multiple times on the calcined sulfonated polyether-ether-ketone matrix until a film with enough thickness is formed, thus obtaining the composite material.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a nano-hydroxyapatite and sulfonated polyether ether ketone composite material comprises the steps of preparing sol, hydroxyapatite gel and a sulfonated polyether ether ketone matrix, and preparing a coating;
preparing sol: adding absolute ethyl alcohol into triethyl phosphite to prepare a solution, adding pure water for dilution, and stirring to obtain sol;
preparation of hydroxyapatite gel: dissolving calcium nitrate in absolute ethyl alcohol, then adding the sol, stirring and ageing to obtain a hydroxyapatite gel solution;
preparation of sulfonated polyether ether ketone: drying 10 g of polyether-ether-ketone granular material at 100 ℃ for 10 hours in vacuum, dissolving the dried material in 500ml of concentrated sulfuric acid at 25 ℃, after vigorously stirring for 2 hours, pouring the reaction solution into ice water with the volume of 5-8 times of that of the ice water, continuously stirring for 1 hour, standing for 24 hours, and repeatedly filtering and washing precipitates with pure water until the pH value is 7; finally, vacuum drying the product at 60 ℃ for 24 hours to obtain sulfonated polyether-ether-ketone, and further preparing the sulfonated polyether-ether-ketone into a sulfonated polyether-ether-ketone matrix;
preparing a coating: and putting the sulfonated polyether-ether-ketone matrix into a hydroxyapatite gel solution, fully dipping the sulfonated polyether-ether-ketone matrix into the hydroxyapatite gel solution, and calcining the sulfonated polyether-ether-ketone matrix after the hydroxyapatite gel solution is fully dipped into the gel to obtain the composite material.
2. The method for preparing nano hydroxyapatite and sulfonated polyether ether ketone composite material according to claim 1, wherein in the step of preparing the sol, the content of triethyl phosphite is not less than 99.5%, anhydrous ethanol is added to the triethyl phosphite to prepare a solution with a concentration of 0.040mol/L-0.060mol/L, and 25% -50% by volume of pure water is added for dilution.
3. The method for preparing nano hydroxyapatite and sulfonated polyether ether ketone composite material according to claim 2, wherein after dilution, the mixture is vigorously stirred for more than 10 hours on a magnetic stirrer to obtain clear sol with certain viscosity.
4. The method for preparing nano hydroxyapatite and sulfonated polyether ether ketone composite material according to claim 1, wherein in the step of preparing hydroxyapatite gel, calcium nitrate with the content not less than 99.5 percent is dissolved in absolute ethyl alcohol, and the calcium nitrate is continuously heated and stirred in the dissolving process; calcium nitrate is dissolved in absolute ethyl alcohol to prepare a solution with the concentration of 0.025mol/L-0.050 mol/L.
5. The method for preparing nano hydroxyapatite and sulfonated polyether ether ketone composite material according to claim 4, wherein the solution is added into the sol, the ratio of the solution to the sol is prepared according to the atomic ratio of Ca to P being 1.67, after the mixing, the bottle cap is sealed, the stirring is vigorously carried out for more than 2 hours, and the stirred sol is placed at room temperature and aged for 36-72 hours.
6. The method for preparing nano hydroxyapatite and sulfonated polyether ether ketone composite material according to claim 1, wherein the coating is prepared by the steps of dipping the sulfonated polyether ether ketone matrix in a hydroxyapatite sol-gel solution, putting the coated sulfonated polyether ether ketone matrix in an ultrasonic cleaning machine for 2-20 minutes, drying the coated sulfonated polyether ether ketone matrix in a drying oven, and calcining the dried coated sulfonated polyether ether ketone matrix.
7. The method for preparing nano hydroxyapatite and sulfonated polyether ether ketone composite material according to claim 6, wherein the nano hydroxyapatite and sulfonated polyether ether ketone composite material is dried in a drying oven at 80 ℃ for more than 30 minutes, and then is placed in a sintering furnace to be calcined at a determined temperature for 30-60 minutes.
8. The method for preparing nano hydroxyapatite and sulfonated polyether ether ketone composite material according to claim 7, wherein the calcination temperature is 600 ℃ to 800 ℃.
9. The method for preparing nano-hydroxyapatite and sulfonated polyether ether ketone composite material according to claim 8, wherein the steps of dip coating, drying, calcining and repeating are sequentially carried out on the calcined substrate at least once until a film with enough thickness is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011212350.6A CN112587732A (en) | 2020-11-03 | 2020-11-03 | Preparation method of nano-hydroxyapatite and sulfonated polyether ether ketone composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011212350.6A CN112587732A (en) | 2020-11-03 | 2020-11-03 | Preparation method of nano-hydroxyapatite and sulfonated polyether ether ketone composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112587732A true CN112587732A (en) | 2021-04-02 |
Family
ID=75180535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011212350.6A Pending CN112587732A (en) | 2020-11-03 | 2020-11-03 | Preparation method of nano-hydroxyapatite and sulfonated polyether ether ketone composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112587732A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113201163A (en) * | 2021-04-20 | 2021-08-03 | 上海交通大学医学院附属仁济医院 | Modified polyether-ether-ketone and preparation method and application thereof |
| CN115282335A (en) * | 2022-08-05 | 2022-11-04 | 河北医科大学口腔医院 | Preparation method of bone repair scaffold |
| CN116874976A (en) * | 2023-07-20 | 2023-10-13 | 成都美益博雅材料科技有限公司 | Bioglass-polyether-ether-ketone composite material and preparation method thereof |
| CN117731832A (en) * | 2024-02-19 | 2024-03-22 | 上海珀利医用材料有限公司 | Medical polyether-ether-ketone composite material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060134160A1 (en) * | 2002-09-13 | 2006-06-22 | The University Of British Columbia | Calcium phosphate coated implantable medical devices and processes for making same |
| KR100890935B1 (en) * | 2008-04-30 | 2009-04-02 | 한국지질자원연구원 | Bioactive composition using peek and cao-sio2 for artificial bone and method for manufacture thereof |
| US20100040668A1 (en) * | 2006-01-12 | 2010-02-18 | Rutgers, The State University Of New Jersey | Biomimetic Hydroxyapatite Composite Materials and Methods for the Preparation Thereof |
| CN103191468A (en) * | 2013-04-19 | 2013-07-10 | 深圳大学 | Human bone substitute material and preparation method thereof |
| CN104497344A (en) * | 2014-12-29 | 2015-04-08 | 中国科学院上海硅酸盐研究所 | Method for modifying polyether-ether-ketone surface |
| CN107198698A (en) * | 2017-06-12 | 2017-09-26 | 深圳大学 | Sulfonated polyether-ether-ketone is being prepared for treating purposes and people's bone alternate material in the medicine of osteoma |
-
2020
- 2020-11-03 CN CN202011212350.6A patent/CN112587732A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060134160A1 (en) * | 2002-09-13 | 2006-06-22 | The University Of British Columbia | Calcium phosphate coated implantable medical devices and processes for making same |
| US20100040668A1 (en) * | 2006-01-12 | 2010-02-18 | Rutgers, The State University Of New Jersey | Biomimetic Hydroxyapatite Composite Materials and Methods for the Preparation Thereof |
| KR100890935B1 (en) * | 2008-04-30 | 2009-04-02 | 한국지질자원연구원 | Bioactive composition using peek and cao-sio2 for artificial bone and method for manufacture thereof |
| CN103191468A (en) * | 2013-04-19 | 2013-07-10 | 深圳大学 | Human bone substitute material and preparation method thereof |
| CN104497344A (en) * | 2014-12-29 | 2015-04-08 | 中国科学院上海硅酸盐研究所 | Method for modifying polyether-ether-ketone surface |
| CN107198698A (en) * | 2017-06-12 | 2017-09-26 | 深圳大学 | Sulfonated polyether-ether-ketone is being prepared for treating purposes and people's bone alternate material in the medicine of osteoma |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113201163A (en) * | 2021-04-20 | 2021-08-03 | 上海交通大学医学院附属仁济医院 | Modified polyether-ether-ketone and preparation method and application thereof |
| CN115282335A (en) * | 2022-08-05 | 2022-11-04 | 河北医科大学口腔医院 | Preparation method of bone repair scaffold |
| CN115282335B (en) * | 2022-08-05 | 2023-08-29 | 河北医科大学口腔医院 | Preparation method of bone repair stent |
| CN116874976A (en) * | 2023-07-20 | 2023-10-13 | 成都美益博雅材料科技有限公司 | Bioglass-polyether-ether-ketone composite material and preparation method thereof |
| CN116874976B (en) * | 2023-07-20 | 2024-04-26 | 成都美益博雅材料科技有限公司 | Bioglass-polyether-ether-ketone composite material and preparation method thereof |
| CN117731832A (en) * | 2024-02-19 | 2024-03-22 | 上海珀利医用材料有限公司 | Medical polyether-ether-ketone composite material and preparation method and application thereof |
| CN117731832B (en) * | 2024-02-19 | 2024-05-10 | 上海珀利医用材料有限公司 | Medical polyether-ether-ketone composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112587732A (en) | Preparation method of nano-hydroxyapatite and sulfonated polyether ether ketone composite material | |
| Nie et al. | Physicochemical characterization and biocompatibility in vitro of biphasic calcium phosphate/polyvinyl alcohol scaffolds prepared by freeze-drying method for bone tissue engineering applications | |
| Gomes et al. | A brief review on hydroxyapatite production and use in biomedicine | |
| Zhang et al. | 3D printing of calcium phosphate bioceramic with tailored biodegradation rate for skull bone tissue reconstruction | |
| WO2018072679A1 (en) | Biomimetic biomineralized artificial bone repair material and preparation method therefor and use thereof | |
| Cui et al. | An injectable borate bioactive glass cement for bone repair: preparation, bioactivity and setting mechanism | |
| Zhou et al. | Biomimetic fabrication of a three-level hierarchical calcium phosphate/collagen/hydroxyapatite scaffold for bone tissue engineering | |
| CN101157045B (en) | Complex self-curing material, method and application of bioactivity calcium phosphate/tricalcium silicate | |
| Li et al. | Preparation and characterization of homogeneous hydroxyapatite/chitosan composite scaffolds via in-situ hydration | |
| JP2004511320A (en) | Biocompatible cement containing reactive calcium phosphate nanoparticles and methods of making and using said cement | |
| CN105536070A (en) | Composite bone cement and preparation method thereof | |
| WO2022166408A1 (en) | Bioactive composite material for bone and preparation method therefor and use thereof | |
| CN104446432A (en) | Magnetic hydroxyapatite bioceramic and preparation method thereof | |
| Raucci et al. | Poly (Epsilon-lysine) dendrons tethered with phosphoserine increase mesenchymal stem cell differentiation potential of calcium phosphate gels | |
| CN110180030B (en) | Collagen-compounded calcium phosphate bioceramic and preparation and use methods thereof | |
| Guo et al. | Osteogenic effects of magnesium substitution in nano-structured β-tricalcium phosphate produced by microwave synthesis | |
| Alshemary et al. | Biomechanical evaluation of an injectable alginate/dicalcium phosphate cement composites for bone tissue engineering | |
| Zhao et al. | Improvement of interfacial properties and bioactivity of CF/PEEK composites by rapid biomineralization of hydroxyapatite | |
| CN109432494B (en) | PEEK microsphere with special topological appearance on surface, and preparation method and application thereof | |
| Farag et al. | New nano-bioactive glass/magnesium phosphate composites by sol-gel route for bone defect treatment | |
| Oyedeji et al. | Fabrication and characterization of hydroxyapatite-strontium/polylactic acid composite for potential applications in bone regeneration | |
| Abdel-Fattah et al. | Tailoring the properties and functions of phosphate/silk/Ag/chitosan scaffolds | |
| KR100787526B1 (en) | Synthesis of spherical shaped hydroxyapatite, alpha-tricalcium phosphate and beta-tricalcium phosphate nano powders depending on the ph by microwave assisted process | |
| CN106620843A (en) | Composite bone cement with bioactivity and antibacterial activity as well as preparation method and application | |
| Anandan et al. | Synthesis methods of hydroxyapatite and biomedical applications: an updated review |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210402 |
|
| RJ01 | Rejection of invention patent application after publication |