CN107698792A - Fluorine richness polyether-ether-ketone/graphite nanometer composite material, its preparation method and artificial joint prosthesis - Google Patents

Fluorine richness polyether-ether-ketone/graphite nanometer composite material, its preparation method and artificial joint prosthesis Download PDF

Info

Publication number
CN107698792A
CN107698792A CN201710822801.XA CN201710822801A CN107698792A CN 107698792 A CN107698792 A CN 107698792A CN 201710822801 A CN201710822801 A CN 201710822801A CN 107698792 A CN107698792 A CN 107698792A
Authority
CN
China
Prior art keywords
graphite
ketone
ether
polyether
composite material
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.)
Granted
Application number
CN201710822801.XA
Other languages
Chinese (zh)
Other versions
CN107698792B (en
Inventor
马骏
庞博
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing AK Medical Co Ltd
Original Assignee
Beijing AK Medical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing AK Medical Co Ltd filed Critical Beijing AK Medical Co Ltd
Priority to CN201710822801.XA priority Critical patent/CN107698792B/en
Publication of CN107698792A publication Critical patent/CN107698792A/en
Application granted granted Critical
Publication of CN107698792B publication Critical patent/CN107698792B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/126—Halogenation
    • 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
    • A61L27/443—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with carbon 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • 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
    • A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols

Abstract

The invention provides fluorine richness polyether-ether-ketone/graphite nanometer composite material, its preparation method and artificial joint prosthesis.The preparation method includes：By the use of fluorinated organic compound as source ion implantation, using plasma injection technique carries out fluorine richness to polyether-ether-ketone/graphite nanometer composite material surface, in polyether-ether-ketone/graphite nanometer composite material area load fluorine atom.Surface fluorine richness is carried out to polyether-ether-ketone/graphite nanometer composite material using Plasma implantation techniques, improve the bioactivity of polyether-ether-ketone/graphite nanometer composite material, be advantageous to skeleton and grow into polyether-ether-ketone/graphite nanometer composite material surface, the fastness of the combination of polyether-ether-ketone/graphite nanometer composite material implant and skeleton is improved, so as to improve the stability and service life at a specified future date of implant.When Plasma inpouring technology is implemented, fluorinated organic compound is used as source ion implantation, will not form the impurity element to polyether-ether-ketone/graphite nanometer composite material pollution.

Description

Fluorine richness polyether-ether-ketone/graphite nanometer composite material, its preparation method and joint prosthesis Prosthese
Technical field
It is multiple in particular to a kind of fluorine richness polyether-ether-ketone/Nano graphite the present invention relates to artificial prosthesis Material Field Condensation material, its preparation method and artificial joint prosthesis.
Background technology
Since the sixties in last century, artificial joint replacement succeeded, the application of joint prosthesis is largely popularized, especially Be artificial, knee joint be countless patients solve motion problem.At present, artificial joint replacement has been considered as whole latter stage pass Save the effective treatment means of disease.It can not only release pain, improve range of motion and recover function of joint, prior It is to improve patients ' life quality.
Although the design and manufacture of joint prosthesis and clinical replacement operation level have increased significantly, lose in use The case of effect still constantly occurs.The classes such as the failure main forms of joint prosthesis are infection, dislocation, loosening, fracture, abrasion Type.Infection and dislocation mostly occur recent, and abrasion and bone dissolving are occurred in long term.Metal matches with ultra-high molecular weight polyethylene Joint prosthesis be the most frequently used combination at present, but polyethylene and bone dissolving caused by metal wear particles be failure at a specified future date most One of principal element.
Therefore, scholars constantly explore new combination, including：The application of high cross-linked polymer weight northylen, metal are to gold Category combination, ceramic-on-ceramic combination, ceramics have excellent friction and lubrication in vitro to polyethylene composition etc., these Combination novas Performance, but there is also respective shortcoming, and late result waits to observe.Metal-Metal interface, compared to metal to polyethylene interface Its coefficient of friction substantially reduces, and bone dissolution rate also decreases.But metal prostheses are worn release metal ions and particle, Potentially need further to be solved the problems such as the carcinogenic possibility of metal ion, metal allergy and renal toxicity, especially metal allergy May be closely related with Prothesis failure.Ceramics-ceramic interface, it is the minimum friction joint combination being currently known.Ceramics have pole High case hardness is advantageous to surface polishing, produces smaller surface roughness, can reduce friction.But ceramic-on-ceramic joint There is it is certain the shortcomings that, such as fragmentation of ceramic head and mortar cup, postoperative abnormal sound.
Therefore develop new materials for Joint Replacement has weight to extending joint prosthesis service life, improving minimal invasive treatment's quality Want meaning.Polyether-ether-ketone is a kind of new bio medical material with good biocompatibility, at present in plastic surgery, ridge The fields such as spinous process of the seventh cervical vertebra nail are applied.Polyether-ether-ketone has rigidity and flexibility, particularly to the fatigue resistance under alternate stress very It is prominent, it can be compared favourably with alloy material.Meanwhile its modulus of elasticity approaches with skeleton modulus of elasticity, avoids metal material Stress shielding problem caused by modulus of elasticity is excessive.
Although polyether-ether-ketone has preferable sliding properties, joint-friction pair is used as, its abrasion resistance properties still needs Improve.Conventional carbon fiber carries out fiber reinforcement processing to polyether-ether-ketone at present, but because polyether-ether-ketone surface is in nonpolar, its Bioactivity is poor, wearing no resistance seriously limits the application in artificial implantation material.In addition, there is also utilization for prior art Polyether-ether-ketone/graphite nanometer composite material that graphite modified polyether-ether-ketone is formed, the composite have good bio-compatible Property, mechanical property and anti-wear performance, modulus of elasticity match with skeleton, avoid that metal material modulus of elasticity is excessive to be caused Stress shielding problem；Its coefficient of friction very little simultaneously, as joint prosthesis plane materiel material, can significantly improve the wear-resistant of articular surface Performance is damaged, effectively reduces the abrasion of material, the bad biological respinse triggered by abrasive dust and aseptic loosening are reduced, so as to extend The life-span of artificial joint prosthesis.
However, polyether-ether-ketone/graphite nanometer composite material belongs to bio-inert material, without bioactivity, Integrated implant Poor-performing, it is unfavorable for the adhesion and growth of cell.Firm combination can not be formed with body bone tissue after implantation human body, so as to Influence at a specified future date stability of the implant in human body.Therefore, polyether-ether-ketone/graphite nanometer composite material is limited to be implanted into orthopaedics Widely apply in thing field.
The content of the invention
It is a primary object of the present invention to provide a kind of fluorine richness polyether-ether-ketone/graphite nanometer composite material, its preparation side Method and artificial joint prosthesis, to solve the problems, such as polyether-ether-ketone/graphite nanometer composite material osseointegration character difference in the prior art.
To achieve these goals, according to an aspect of the invention, there is provided a kind of fluorine richness polyether-ether-ketone/graphite is received The preparation method of nano composite material, the preparation method include：By the use of fluorinated organic compound as source ion implantation, using etc. from Daughter injection technique carries out fluorine richness to polyether-ether-ketone/graphite nanometer composite material surface, compound in polyether-ether-ketone/Nano graphite Material surface loads fluorine atom.
Further, above-mentioned fluorinated organic compound is carbon tetrafluoride, tetrafluoroethene and/or hexafluoropropene.
Further, the pressure of the plasma injection cavity of above-mentioned Plasma implantation techniques is 1.0 × 10-3Pa~ 0.1Pa, injecting voltage are 10~50kV, and preferably the injected pulse width of Plasma implantation techniques is 20~800 μ s, pulse weight Complex frequency is 5~100Hz；More preferably the discharge current of Plasma implantation techniques is 1~10A, preferably plasma injection skill The injection length of art is 0.5~10h.
Further, before stating Plasma implantation techniques on the implementation, above-mentioned preparation method also include to polyether-ether-ketone/ The process that graphite nanometer composite material is cleaned, preferred process are included successively using absolute ethyl alcohol and deionized water to polyethers ether Ketone/graphite nanometer composite material carries out 10~30min of ultrasonic cleaning.
Further, above-mentioned preparation method also includes the preparation process of polyether-ether-ketone/graphite nanometer composite material, the preparation Process includes：Step S1, graphite nanosheets solution is prepared by graphite raw material of expanded graphite, graphite nanosheets thickness is 1 ~100nm；Step S2, the liquid in graphite nanosheets solution is removed after graphite nanosheets solution and hydroquinones are mixed Material, obtain pre- intercalation raw material；Step S3, in the case where emulsifying stirring condition, by pre- intercalation raw material and 4,4 '-difluoro benzophenone, Solvent mixes, and forms the first reaction system；Step S4, the first reaction system is warming up in 150~180 DEG C of backward reaction systems Add alkali carbonate and form the second reaction system；And step S5, the second reaction system is entered between 200~325 DEG C Row reaction, obtains polyether-ether-ketone/graphite nanometer composite material, wherein, the dosages of graphite nanosheets is hydroquinones, 4,4 '- 0.1~2wt% of the gross mass of difluoro benzophenone and graphite nanosheets.
Further, above-mentioned steps S1 includes：After expanded graphite is put into alcohol, 4~8h of alcohol is ultrasonically treated, is obtained Graphite nanosheets solution, ethanol content is 60%~80% in preferably ethanol.
Further, above-mentioned steps S2 includes：In inert gas or nitrogen atmosphere, by graphite nanosheets solution and right Benzenediol mixes 6~10h under ultrasound condition, obtains the pre- intercalation solution of hydroquinones/graphite nanosheets；It is less than in pressure 4~12h is dried to the pre- intercalation solution of hydroquinones/graphite nanosheets under 133Pa vacuum condition, obtains pre- intercalation raw material.
Further, above-mentioned steps S3 includes：Pre- intercalation raw material and 4,4 '-difluoro benzophenone, solvent are added to band Have in emulsification mixer, inert gas or nitrogen are passed through into blender and open emulsification agitating function with 1000~ 3000r/min speed stirs 10~30min, the first reaction system is obtained, wherein it is preferred that hydroquinones and 4,4 '-difluorodiphenyl The mol ratio of ketone is 1:1~1:1.1, preferred solvent is diphenyl sulphone (DPS), further preferred diphenyl sulphone (DPS) and 4,4 '-difluoro benzophenone Volume ratio be 2:1~3:1.
Further, above-mentioned alkali carbonate is potassium carbonate and/or sodium carbonate, alkali carbonate and hydroquinones Mol ratio is 1.5:1~2.5:1.
Further, above-mentioned steps S5 includes：After the second reaction system is warming up to the first temperature and being incubated 2~5h, obtain To the 3rd reaction system, the first temperature is 200~240 DEG C；Make the 3rd reaction system be warming up to second temperature and be incubated 10~ After 30min, the 4th reaction system is obtained, second temperature is 250~270 DEG C；The 4th reaction system is set to be warming up to the 3rd temperature simultaneously The product system containing polyether-ether-ketone/graphite nanometer composite material is obtained after 2~3h of insulation, the 3rd temperature is 315~325 DEG C.
Further, above-mentioned steps S5 also includes extracting product system, and it is compound to obtain polyether-ether-ketone/Nano graphite Material, it is preferred to use acetone extracts to product system.
According to another aspect of the present invention, there is provided a kind of fluorine richness polyether-ether-ketone/graphite nanometer composite material, in use Any preparation method is stated to be prepared.
According to another aspect of the present invention, there is provided a kind of artificial joint prosthesis, artificial joint prosthesis includes being used for and people The contact site of body bone-contact, forming the material of contact site includes polyether-ether-ketone/graphite nanometer composite material, polyether-ether-ketone/stone Graphite nano composite material is above-mentioned fluorine richness polyether-ether-ketone/graphite nanometer composite material.
Apply the technical scheme of the present invention, using Plasma implantation techniques to polyether-ether-ketone/graphite nanometer composite material Carry out surface fluorine richness, improve the bioactivity of polyether-ether-ketone/graphite nanometer composite material, be advantageous to skeleton grow into it is poly- Ether ether ketone/graphite nanometer composite material surface, improve the knot of polyether-ether-ketone/graphite nanometer composite material implant and skeleton The fastness of conjunction, so as to improve the stability and service life at a specified future date of implant.When Plasma inpouring technology is implemented, in order to keep away Exempt from the impurity element introduced outside fluorine element, use fluorinated organic compound as source ion implantation, carbon therein, protium are poly- The element that ether ether ketone contains in itself, the impurity element to polyether-ether-ketone/graphite nanometer composite material pollution will not be formed.
Embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase Mutually combination.The present invention is described in detail below in conjunction with embodiment.
As the application background technology is analyzed, polyether-ether-ketone/graphite nanometer composite material belongs to bio-inert material, no With bioactivity, osseointegration character is poor, is unfavorable for the adhesion and growth of cell.Can not be with body bone tissue after implantation human body Firm combination is formed, so as to influence at a specified future date stability of the implant in human body.Therefore, polyether-ether-ketone/graphite is limited to receive Nano composite material is widely applied in orthopaedics implant field, multiple in order to solve above-mentioned existing polyether-ether-ketone/Nano graphite The problem of condensation material osseointegration character is poor, this application provides a kind of fluorine richness polyether-ether-ketone/graphite nanometer composite material Preparation method and artificial prosthesis.
In a kind of typical embodiment of the application, there is provided a kind of fluorine richness polyether-ether-ketone/Nano graphite composite wood The preparation method of material, the preparation method include：Source ion implantation, using plasma injection are used as by the use of fluorinated organic compound Technology carries out fluorine richness to polyether-ether-ketone/graphite nanometer composite material surface, on polyether-ether-ketone/graphite nanometer composite material surface Load fluorine atom.
Polyether-ether-ketone/graphite nanometer composite material has good biocompatibility and mechanical property, modulus of elasticity and people Body bone matches, avoid metal material modulus of elasticity it is excessive caused by stress shielding problem.Its coefficient of friction very little simultaneously, As implant articular surface material, the wear resistance of articular surface can be significantly improved, the abrasion of material is effectively reduced, reduces The bad biological respinse and aseptic loosening triggered by abrasive dust, so as to extend the life-span of implant.The application further utilizes Gas ions injection technique carries out surface fluorine richness to polyether-ether-ketone/graphite nanometer composite material, and obtained fluorine richness polyether-ether-ketone/ Graphite nanometer composite material includes polyether-ether-ketone/graphite nanometer composite material and for polyether-ether-ketone/Nano graphite composite wood Expect the fluorine atom that surface is modified, polyether-ether-ketone/graphite nanometer composite material surface is formed fluoride and fluorine-containing functional group, improve The bioactivity of polyether-ether-ketone/graphite nanometer composite material, being advantageous to skeleton, to grow into polyether-ether-ketone/Nano graphite compound Material surface, and then the fastness of the combination of polyether-ether-ketone/graphite nanometer composite material implant and skeleton is improved, from And improve the stability and service life at a specified future date of implant.When Plasma inpouring technology is implemented, in order to avoid introducing fluorine element Outside impurity element, use fluorinated organic compound as source ion implantation, carbon therein, protium are that polyether-ether-ketone contains in itself Some elements, the impurity element to polyether-ether-ketone/graphite nanometer composite material pollution will not be formed.
And fluorine is one of trace element necessary to human life activity, in the bone growth and development and maintenance bone of whole body Played a significant role in physiological structure function, fluoride and fluorine-containing functional group directly by stimulated osteoblastic proliferation and can add Strong basicity phosphatase activity, strengthen osteogenic action.On the other hand, gully shape can be formed in material surface after fluorine ion injection to receive Rice pattern, makes surface further be roughened.Therefore, the double effect based on its composition and structure has been obviously promoted Gegenbaur's cell and existed Sticking, sprawl and breeding for material surface, is greatly improved the bioactivity of polyether-ether-ketone/graphite nanometer composite material, has Polyether-ether-ketone/graphite nanometer composite material surface is grown into beneficial to skeleton, polyether-ether-ketone/graphite nanometer composite material is improved and plants Enter the fastness of the combination of thing and skeleton, so as to improve the stability and service life at a specified future date of implant.
In a kind of preferred embodiment of the application, above-mentioned fluorinated organic compound is carbon tetrafluoride (CF4), tetrafluoroethene (C2F4), hexafluoropropene (C3F6).Above-mentioned each fluorinated organic compound is easy to plasma, and does not contain impurity element.
Moreover it is preferred that the pressure of the plasma injection cavity of above-mentioned Plasma implantation techniques is 1.0 × 10-3Pa ~0.1Pa, injecting voltage are 10~50kV, and preferably the injected pulse width of Plasma implantation techniques is 20~800 μ s, pulse Repetition rate is 5~100Hz；More preferably the discharge current of Plasma implantation techniques is 1~10A；Preferably, above-mentioned plasma The injection length of body injection technique is 0.5~10h.By controlling above-mentioned condition so that the concentration and modified stable of fluorine atom Property it is more excellent, to control fluorine atom as the 0.1~10% of polyether-ether-ketone/graphite nanometer composite material surface atom sum.
In order to improve the adhesive force of Gegenbaur's cell and plasma injection efficiency, preferably implementing plasma injection skill Before art, above-mentioned preparation method also includes the mistake that polyether-ether-ketone/graphite nanometer composite material is roughened and cleaned Journey, the preferably process include carrying out blasting treatment to the surface of the polyether-ether-ketone/graphite nanometer composite material；Nothing is used successively Water-ethanol and deionized water carry out 10~30min of ultrasonic cleaning to polyether-ether-ketone/graphite nanometer composite material after blasting treatment. It is preferred that blasting treatment uses emergy of the powder diameter between 50~300 μm as abrasive material, in blasting treatment, preferred sandblasting distance For 3~10cm, more preferably compression pressure is 2~8bar, and further preferred injecting time is 5~60s.
Polyether-ether-ketone/graphite nanometer composite material for the application can be prepared using prior art, preferably above-mentioned Preparation method also includes the preparation process of polyether-ether-ketone/graphite nanometer composite material, and the preparation process includes：Step S1, with swollen Swollen graphite is that graphite raw material prepares graphite nanosheets solution, and graphite nanosheets thickness is 1~100nm；Step S2, by nanometer The liquid in graphite nanosheets solution is removed after graphite microchip solution and hydroquinones mixing, obtains pre- intercalation raw material； Step S3, in the case where emulsifying stirring condition, by pre- intercalation raw material and 4,4 '-difluoro benzophenone, solvent mixing, form the first reaction System；Step S4, the first reaction system is warming up to addition alkali carbonate in 150~180 DEG C of backward reaction systems and formed Second reaction system；And step S5, the second reaction system is reacted between 200~325 DEG C, obtain polyether-ether-ketone/ Graphite nanometer composite material, wherein, the dosages of graphite nanosheets is hydroquinones, 4,4 '-difluoro benzophenone and nanometer stone 0.1~2wt% of the gross mass of black microplate.
Graphite nanosheets are formed it into by carrying out processing to expanded graphite, and then improve its lubricant effect.Then will Graphite nanosheets first mix with hydroquinones, ensure that pre- intercalation raw material is formed in graphite nanosheets insertion hydroquinones Graphite nanosheets are dispersed in hydroquinones.Then under conditions of emulsification is stirred by pre- intercalation raw material and 4,4 '- Difluoro benzophenone, solvent mixing, ensure that the dispersed of each component.Further when carrying out home position polymerization reaction, protect It is dispersed in the polyether-ether-ketone formed to demonstrate,prove graphite nanosheets, and then ensure that the lubrication of graphite nanosheets Performance, and ensure that the original mechanical property of polyether-ether-ketone, and then the composite that above-mentioned preparation method is obtained is using extremely When in artificial joint prosthesis, as part or all of friction pair material, the abrasion resistance in joint prosthesis face can be significantly improved Can, the abrasion of material is effectively reduced, reduces the bad biological respinse triggered by abrasive dust and aseptic loosening, it is artificial so as to extend The life-span of articular prosthesis.Meanwhile by the thickness of graphite nanosheets and content control within the above range, be advantageous to it in polyethers It is dispersed in ether ketone, and then further improve the wearability of composite.
Further, it is preferable to above-mentioned steps S1 includes：After expanded graphite is put into alcohol, supersound process alcohol 4h~ 8h, obtain graphite nanosheets solution.Expanded graphite is disperseed into stripping in alcohol using ultrasound, it is molten to form graphite nanosheets Liquid, wherein alcohol are easy to be removed for the aqueous solution of ethanol in subsequent process, and not interfering with follow-up home position polymerization reaction is Scattered peeling effect is improved, ethanol content is 60%~80% in preferably ethanol.
In the application another kind preferred embodiment, above-mentioned steps S2 includes：, will in inert gas or nitrogen atmosphere Graphite nanosheets solution and hydroquinones mix 6~10h under ultrasound condition, and it is pre- to obtain hydroquinones/graphite nanosheets Intercalation solution；Pressure less than 133Pa vacuum condition under to the pre- intercalation solution of hydroquinones/graphite nanosheets dry 4~ 12h, obtain pre- intercalation raw material.Moisture removal is removed by ultrasonic removal ethanol and then with vacuum drying, is avoided in excessively harshness Under the conditions of remove alcohol caused by graphite nanosheets structure change and its intercalation dispersion effect in hydroquinones.
In the application another preferred embodiment, above-mentioned steps S3 includes：By pre- intercalation raw material and 4,4 '-difluoro two Benzophenone, solvent are added in the blender with emulsification agitating function, and inert gas or nitrogen are passed through into blender and is opened Open emulsification agitating function and 10~30min is stirred with 1000~3000r/min speed, obtain the first reaction system.Using with The pre- intercalation raw material of reactor and 4 of agitating function is emulsified, 4 '-difluoro benzophenone and solvent are stirred, emulsified, and make a nanometer stone Black microplate is dispersed wherein.In order to improve the conversion ratio of substrate, preferably hydroquinones and 4,4 '-difluoro benzophenone rubs You are than being 1:1~1:1.1.In addition, in order to improve pre- intercalation raw material and 4, the dispersibility of 4 '-difluoro benzophenone is preferably molten Agent is diphenyl sulphone (DPS), further preferred diphenyl sulphone (DPS) and 4, and the volume ratio of 4 '-difluoro benzophenone is 2:1~3:1.
In addition, in order to simplify post-reaction treatment flow, preferably above-mentioned alkali carbonate is potassium carbonate and/or sodium carbonate, The mol ratio of alkali carbonate and hydroquinones is 1.5:1~2.5:1.Above-mentioned alkali carbonate is in prepared by polyether-ether-ketone Conventional carbonate, therefore it is separable alkali metal to react complete rear last handling process to use existing follow-up processing flow Carbonate.
In the application another preferred embodiment, above-mentioned steps S5 includes：The second reaction system is set to be warming up to first Temperature and after being incubated 2~5h, obtains the 3rd reaction system, the first temperature is 200 DEG C~240 DEG C；The 3rd reaction system is set to heat up To second temperature and 10~30min of insulation, the 4th reaction system is obtained, second temperature is 250 DEG C~270 DEG C；Make the 4th anti- Answer system to be warming up to the 3rd temperature and obtain the product system containing polyether-ether-ketone/graphite nanometer composite material after being incubated 2~3h, 3rd temperature is 315~325 DEG C.Above-mentioned polymerisation is carried out at different temperatures stage by stage, is made during the course of the reaction, therein Azeotropy dehydrant is completely exhausted out.
In order to improve product purity, preferably above-mentioned steps S5 also includes extracting product system, obtain polyether-ether-ketone/ Graphite nanometer composite material, it is preferred to use acetone extracts to product system.Two gone out using acetone extract in product system Benzene sulfone, improve product purity.The multiple washed product system of deionized water and then re-dry can certainly be used also to realize and carry Pure effect.
In the application in another typical embodiment, there is provided a kind of fluorine richness polyether-ether-ketone/Nano graphite is compound Material, it is prepared using any of the above-described kind of preparation method.The application is using Plasma implantation techniques to polyether-ether-ketone/stone Graphite nano composite material carries out surface fluorine richness, improves the bioactivity of polyether-ether-ketone/graphite nanometer composite material, is advantageous to Skeleton grows into polyether-ether-ketone/graphite nanometer composite material surface, improves polyether-ether-ketone/graphite nanometer composite material implant And the fastness of the combination of skeleton, so as to improve the stability and service life at a specified future date of implant.
In the application in another typical embodiment, there is provided a kind of artificial joint prosthesis, artificial joint prosthesis bag The contact site for being contacted with skeleton is included, forming the material of contact site includes polyether-ether-ketone/graphite nanometer composite material, should Polyether-ether-ketone/graphite nanometer composite material is above-mentioned fluorine richness polyether-ether-ketone/graphite nanometer composite material.
Because the osseointegration character of fluorine richness polyether-ether-ketone/graphite nanometer composite material of the application is improved, because This, when using it for the contact site contacted with skeleton of manufacturing artificial articular prosthesis, can strengthen artificial joint prosthesis The fastness combined with body bone tissue, so that the artificial joint prosthesis has stability at a specified future date in human body.
Below with reference to embodiment and comparative example, the beneficial effect of the application is further illustrated.
Embodiment 1
The preparation of expanded graphite：Natural flake graphite is added into the concentrated sulfuric acid and concentrated nitric acid (volume ratio 4:1) in mixed liquor, often After temperature stirring 20h, cleaned repeatedly with distilled water to neutrality, dry more than 24h and remove moisture, graphite oxidation obtained above is inserted Stratification compound at high temperature (about 1000 DEG C or so) processing 15s after i.e. obtain expanded graphite.
The expanded graphite of the above-mentioned preparations of 12g is put into the alcoholic solution of ethanol content 70%, is ultrasonically treated 6h, is made and receives Rice graphite microchip solution.The thickness of graphite nanosheets is detected between 20~80nm by SEM.
110g hydroquinones is mixed with above-mentioned graphite nanosheets solution, under nitrogen protection, ultrasonic mixing 8h, The pre- intercalation solution of hydroquinones/graphite nanosheets is obtained, 6h is then dried under the conditions of vacuum (100Pa) and obtains pre- intercalation original Material.
By above-mentioned pre- intercalation raw material and 240g 4,4 '-difluoro benzophenone (4,4 '-difluoro benzophenone and hydroquinones Mol ratio be 1.1:1), (volume ratio of diphenyl sulphone (DPS) and 4,4 '-difluoro benzophenone is 2.1 to 400ml hexichol sulfoxide solvent:1) plus Enter into the stainless steel mixer with emulsification agitating function, be passed through nitrogen gas stirring and emulsify 10min (mixing speed 1500r/ Min), prevent graphite microchip from reuniting, form the first reaction system.Then under conditions of logical nitrogen, the first reaction system is heated It is allowed to warm to 180 DEG C, and thereto adds mixture (Anhydrous potassium carbonate, the sodium carbonate of 240g Anhydrous potassium carbonates, sodium carbonate Mol ratio is 1:1, the mol ratio of mixture and hydroquinones is 2:1) the second reaction system, is obtained；By the second reaction system liter Temperature is to 200 DEG C and reacts 3h and obtains the 3rd reaction system；3rd reaction system is warming up to 250 DEG C and is incubated 15min again and is obtained 4th reaction system；4th reaction system is warming up to 320 DEG C and reacted and terminates reaction after 2.5h, obtains product system.Will production After objects system crushes, extractor is sent into, with acetone extract 5 times, to remove diphenyl sulphone (DPS)；Product is in 120 DEG C, 100Pa after extraction After drying 12h under vacuum condition, polyether-ether-ketone/graphite nanometer composite material that graphite nanosheets content is 2wt% is obtained.
Above-mentioned polyether-ether-ketone/graphite nanometer composite material pellet is prepared into a diameter of 10mm by Shooting Technique, is highly 2mm exemplar, exemplar is carried out using absolute ethyl alcohol, deionized water being cleaned by ultrasonic each 20min successively, by the use of carbon tetrafluoride as etc. Source ion implantation, the implantation concentration of fluorine ion is 2.0 × 1019Individual/cm2, its injection technology parameter is：The pressure of working gas is 5.0×10-2Pa, injecting voltage 20kV, injected pulse width are 60 μ s, pulse recurrence frequency 15Hz, and discharge current is 1.5A, injection length 4h, obtain the sample of embodiment 1.
Embodiment 2
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 60 μ s, pulse recurrence frequency 15Hz, discharge current 1.5A, injection length 0.5h to press as 20kV, injected pulse width. Obtain the sample of embodiment 2.
Embodiment 3
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 60 μ s, pulse recurrence frequency 15Hz, discharge current 1.5A, injection length 10h to press as 20kV, injected pulse width. Obtain the sample of embodiment 3.
Embodiment 4
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 1.0 × 10-3Pa, injection electricity It is 60 μ s, pulse recurrence frequency 15Hz, discharge current 1.5A, injection length 4h to press as 20kV, injected pulse width. To the sample of embodiment 4.
Embodiment 5
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 0.1Pa, and injecting voltage is 20kV, injected pulse width are 60 μ s, pulse recurrence frequency 15Hz, discharge current 1.5A, injection length 4h.Obtain reality Apply the sample of example 5.
Embodiment 6
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 60 μ s, pulse recurrence frequency 15Hz, discharge current 1.5A, injection length 4h to press as 10kV, injected pulse width. To the sample of embodiment 6.
Embodiment 7
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 60 μ s, pulse recurrence frequency 15Hz, discharge current 1.5A, injection length 4h to press as 50kV, injected pulse width. To the sample of embodiment 7.
Embodiment 8
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 20 μ s, pulse recurrence frequency 15Hz, discharge current 1.5A, injection length 4h to press as 20kV, injected pulse width. To the sample of embodiment 8.
Embodiment 9
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 800 μ s, pulse recurrence frequency 15Hz, discharge current 1.5A, injection length 4h to press as 20kV, injected pulse width. Obtain the sample of embodiment 9.
Embodiment 10
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 60 μ s, pulse recurrence frequency 50Hz, discharge current 1.5A, injection length 4h to press as 20kV, injected pulse width. To the sample of embodiment 10.
Embodiment 11
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 60 μ s, pulse recurrence frequency 100Hz, discharge current 1.5A, injection length 4h to press as 20kV, injected pulse width. Obtain the sample of embodiment 11.
Embodiment 12
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 60 μ s, pulse recurrence frequency 15Hz, discharge current 5A, injection length 4h to press as 20kV, injected pulse width.Obtain The sample of embodiment 12.
Embodiment 13
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 60 μ s, pulse recurrence frequency 15Hz, discharge current 10A, injection length 4h to press as 20kV, injected pulse width. To the sample of embodiment 13.
Embodiment 14
Difference with embodiment 1 is, expanded graphite prepared by 12g embodiments 1 is put into the alcohol of ethanol content 70% In solution, 4h is ultrasonically treated, graphite nanosheets solution is made, the thickness that graphite nanosheets are detected by SEM is 60- Between 100nm.
Embodiment 15
Difference with embodiment 1 is, expanded graphite prepared by 12g embodiments 1 is put into the alcohol of ethanol content 70% In solution, 8h is ultrasonically treated, graphite nanosheets solution is made, the thickness that graphite nanosheets are detected by SEM is 1-60nm Between.
Embodiment 16
Difference with embodiment 1 is, expanded graphite prepared by 12g embodiments 1 is put into the alcohol of ethanol content 80% In solution, 6h is ultrasonically treated, graphite nanosheets solution is made, the thickness that graphite nanosheets are detected by SEM is 20- Between 100nm.
Embodiment 17
Difference with embodiment 1 is, expanded graphite prepared by 12g embodiments 1 is put into the alcohol of ethanol content 60% In solution, 6h is ultrasonically treated, graphite nanosheets solution is made, the thickness that graphite nanosheets are detected by SEM is 20- Between 100nm.
Embodiment 18
Difference with embodiment 1 is, 110g hydroquinones is mixed with above-mentioned graphite nanosheets solution, in nitrogen Under gas shielded, ultrasonic mixing 6h, the pre- intercalation solution of hydroquinones/graphite nanosheets is obtained, then under the conditions of vacuum (100Pa) Dry 6h and obtain pre- intercalation raw material.
Embodiment 19
Difference with embodiment 1 is, 110g hydroquinones is mixed with above-mentioned graphite nanosheets solution, in nitrogen Under gas shielded, ultrasonic mixing 10h, the pre- intercalation solution of hydroquinones/graphite nanosheets is obtained, then vacuum (100Pa) condition Lower dry 6h obtains pre- intercalation raw material.
Embodiment 20
Difference with embodiment 1 is, 110g hydroquinones is mixed with above-mentioned graphite nanosheets solution, in nitrogen Under gas shielded, ultrasonic mixing 8h, the pre- intercalation solution of hydroquinones/graphite nanosheets is obtained, then under the conditions of vacuum (100Pa) Dry 4h and obtain pre- intercalation raw material.
Embodiment 21
Difference with embodiment 1 is, 110g hydroquinones is mixed with above-mentioned graphite nanosheets solution, in nitrogen Under gas shielded, ultrasonic mixing 8h, the pre- intercalation solution of hydroquinones/graphite nanosheets is obtained, then under the conditions of vacuum (100Pa) Dry 12h and obtain pre- intercalation raw material.
Embodiment 22
Difference with embodiment 1 is, 110g hydroquinones is mixed with above-mentioned graphite nanosheets solution, in nitrogen Under gas shielded, ultrasonic mixing 5h, the pre- intercalation solution of hydroquinones/graphite nanosheets is obtained, then under the conditions of vacuum (100Pa) Dry 6h and obtain pre- intercalation raw material.
Embodiment 23
Difference with embodiment 1 is, by above-mentioned pre- intercalation raw material and 218g 4,4 '-difluoro benzophenone (4,4 '-two The mol ratio of fluorine benzophenone and hydroquinones is 1.0:1), 400ml hexichol sulfoxide solvent (diphenyl sulphone (DPS) and 4,4 '-difluorodiphenyl first The volume ratio of ketone is 2.1:1) it is added in the stainless steel mixer with emulsification agitating function, it is passed through nitrogen gas stirring and emulsifies 10min (mixing speed 1500r/min), prevents graphite microchip from reuniting, and forms the first reaction system.Then in the bar of logical nitrogen Under part, the first reaction system of heating is allowed to warm to 180 DEG C, and adds the mixing of 240g Anhydrous potassium carbonate, sodium carbonate thereto (Anhydrous potassium carbonate, the mol ratio of sodium carbonate are 1 to thing:1, the mol ratio of mixture and hydroquinones is 2:1) the second reaction, is obtained System；Second reaction system is warming up to 200 DEG C and reacts 3h and obtains the 3rd reaction system；3rd reaction system is warming up to again 250 DEG C and it is incubated 15min and obtains the 4th reaction system；By the 4th reaction system be warming up to 320 DEG C and react terminate after 2.5h it is anti- Should, obtain product system.After product system is crushed, extractor is sent into, with acetone extract 5 times, to remove diphenyl sulphone (DPS)；After extraction After product dries 12h under 120 DEG C, 100Pa vacuum condition, obtain polyether-ether-ketone that graphite nanosheets content is 2wt%/ Graphite nanometer composite material.
Embodiment 24
Difference with embodiment 1 is, by above-mentioned pre- intercalation raw material and 240g 4,4 '-difluoro benzophenone (4,4 '-two The mol ratio of fluorine benzophenone and hydroquinones is 1.1:1), 520ml hexichol sulfoxide solvent (diphenyl sulphone (DPS) and 4,4 '-difluorodiphenyl first The volume ratio of ketone is 3:1) it is added in the stainless steel mixer with emulsification agitating function, it is passed through nitrogen gas stirring and emulsifies 10min (mixing speed 1500r/min), prevents graphite microchip from reuniting, and forms the first reaction system.
Embodiment 25
Difference with embodiment 1 is, by above-mentioned pre- intercalation raw material and 240g 4,4 '-difluoro benzophenone (4,4 '-two The mol ratio of fluorine benzophenone and hydroquinones is 1.1:1), 400ml hexichol sulfoxide solvent (diphenyl sulphone (DPS) and 4,4 '-difluorodiphenyl first The volume ratio of ketone is 2.1:1) it is added in the stainless steel mixer with emulsification agitating function, it is passed through nitrogen gas stirring and emulsifies 30min (mixing speed 1500r/min), prevents graphite microchip from reuniting, and forms the first reaction system.
Embodiment 26
Difference with embodiment 1 is, by above-mentioned pre- intercalation raw material and 240g 4,4 '-difluoro benzophenone (4,4 '-two The mol ratio of fluorine benzophenone and hydroquinones is 1.1:1), 400ml hexichol sulfoxide solvent (diphenyl sulphone (DPS) and 4,4 '-difluorodiphenyl first The volume ratio of ketone is 2.1:1) it is added in the stainless steel mixer with emulsification agitating function, it is passed through nitrogen gas stirring and emulsifies 10min (mixing speed 1000r/min), prevents graphite microchip from reuniting, and forms the first reaction system.
Embodiment 27
Difference with embodiment 1 is, by above-mentioned pre- intercalation raw material and 240g 4,4 '-difluoro benzophenone (4,4 '-two The mol ratio of fluorine benzophenone and hydroquinones is 1.1:1), 400ml hexichol sulfoxide solvent (diphenyl sulphone (DPS) and 4,4 '-difluorodiphenyl first The volume ratio of ketone is 2.1:1) it is added in the stainless steel mixer with emulsification agitating function, it is passed through nitrogen gas stirring and emulsifies 10min (mixing speed 3000r/min), prevents graphite microchip from reuniting, and forms the first reaction system.
Embodiment 28
Difference with embodiment 1 is, under conditions of logical nitrogen, the first reaction system of heating is allowed to warm to 180 DEG C, And add 300g Anhydrous potassium carbonates thereto, (Anhydrous potassium carbonate, the mol ratio of sodium carbonate are 1 to the mixture of sodium carbonate:1, mixing The mol ratio of thing and hydroquinones is 2.5:1) the second reaction system, is obtained；Second reaction system is warming up to 200 DEG C and reacted 3h obtains the 3rd reaction system；3rd reaction system is warming up to 250 DEG C and is incubated 15min again and obtains the 4th reaction system；Will 4th reaction system is warming up to 320 DEG C and terminates reaction after reacting 2.5h, obtains product system.After product system is crushed, send Enter extractor, with acetone extract 5 times, to remove diphenyl sulphone (DPS)；Product is dried under 120 DEG C, 100Pa vacuum condition after extraction After 12h, polyether-ether-ketone/graphite nanometer composite material that graphite nanosheets content is 2wt% is obtained.
Embodiment 29
Difference with embodiment 1 is, under conditions of logical nitrogen, the first reaction system of heating is allowed to warm to 180 DEG C, And add 180g Anhydrous potassium carbonates thereto, (Anhydrous potassium carbonate, the mol ratio of sodium carbonate are 1 to the mixture of sodium carbonate:1, mixing The mol ratio of thing and hydroquinones is 1.5:1) the second reaction system, is obtained；Second reaction system is warming up to 200 DEG C and reacted 3h obtains the 3rd reaction system；3rd reaction system is warming up to 250 DEG C and is incubated 15min again and obtains the 4th reaction system；Will 4th reaction system is warming up to 320 DEG C and terminates reaction after reacting 2.5h, obtains product system.After product system is crushed, send Enter extractor, with acetone extract 5 times, to remove diphenyl sulphone (DPS)；Product is dried under 120 DEG C, 100Pa vacuum condition after extraction After 12h, polyether-ether-ketone/graphite nanometer composite material that graphite nanosheets content is 2wt% is obtained.
Embodiment 30
Difference with embodiment 1 is, under conditions of logical nitrogen, the first reaction system of heating is allowed to warm to 180 DEG C, And add 240g Anhydrous potassium carbonates thereto, (Anhydrous potassium carbonate, the mol ratio of sodium carbonate are 1 to the mixture of sodium carbonate:1, mixing The mol ratio of thing and hydroquinones is 2:1) the second reaction system, is obtained；Second reaction system is warming up to 240 DEG C and reacts 2h Obtain the 3rd reaction system；3rd reaction system is warming up to 270 DEG C and is incubated 10min again and obtains the 4th reaction system；By Four reaction systems are warming up to 325 DEG C and terminate reaction after reacting 2h, obtain product system.
Embodiment 31
Difference with embodiment 1 is, under conditions of logical nitrogen, the first reaction system of heating is allowed to warm to 180 DEG C, And add 240g Anhydrous potassium carbonates thereto, (Anhydrous potassium carbonate, the mol ratio of sodium carbonate are 1 to the mixture of sodium carbonate:1, mixing The mol ratio of thing and hydroquinones is 2:1) the second reaction system, is obtained；Second reaction system is warming up to 220 DEG C and reacts 5h Obtain the 3rd reaction system；3rd reaction system is warming up to 260 DEG C and is incubated 30min again and obtains the 4th reaction system；By Four reaction systems are warming up to 315 DEG C and terminate reaction after reacting 3h, obtain product system.
Embodiment 32
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 0.12Pa, and injecting voltage is 20kV, injected pulse width are 60 μ s, pulse recurrence frequency 15Hz, discharge current 10A, injection length 4h.Obtain reality Apply the sample of example 32.
Embodiment 33
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 60 μ s, pulse recurrence frequency 15Hz, discharge current 15A, injection length 4h to press as 20kV, injected pulse width. To the sample of embodiment 33.
Embodiment 34
Difference with embodiment 1 is that injection technology parameter is：The pressure of working gas is 5.0 × 10-2Pa, injection electricity It is 60 μ s, pulse recurrence frequency 15Hz, discharge current 10A, injection length 15h to press as 20kV, injected pulse width. To the sample of embodiment 34.
Embodiment 35
Difference with embodiment 1 is, above-mentioned polyether-ether-ketone/graphite nanometer composite material pellet is passed through into Shooting Technique system Standby a diameter of 10mm, it is highly 2mm exemplar, the use of emergy of the powder diameter between 50~300 μm is successively abrasive material pair Exemplar carries out blasting treatment, and wherein sandblasting distance is 8cm, compression pressure 6bar, injecting time 30s, is then utilized Absolute ethyl alcohol, deionized water are carried out being cleaned by ultrasonic each 20min to the exemplar after sandblasting, and Plasma inpouring is used as by the use of carbon tetrafluoride Source, the implantation concentration of fluorine ion is 2.0 × 1019Individual/cm2, its injection technology parameter is：The pressure of working gas is 5.0 × 10- 2Pa, injecting voltage 20kV, injected pulse width are 60 μ s, pulse recurrence frequency 15Hz, discharge current 1.5A, are injected Time is 4h, obtains the sample of embodiment 1.
Embodiment 36
Difference with embodiment 35 is that sandblasting procedures are as follows：Emergy of the powder diameter between 50~300 μm is mill Material carries out blasting treatment to exemplar, and wherein sandblasting distance is 3cm, compression pressure 2bar, injecting time 60s.
Embodiment 37
Difference with embodiment 35 is that sandblasting procedures are as follows：Emergy of the powder diameter between 50~300 μm is mill Material carries out blasting treatment to exemplar, and wherein sandblasting distance is 10cm, compression pressure 8bar, injecting time 5s.
Embodiment 38
Difference with embodiment 35 is that sandblasting procedures are as follows：Emergy of the powder diameter between 50~300 μm is mill Material carries out blasting treatment to exemplar, and wherein sandblasting distance is 12cm, compression pressure 5bar, injecting time 30s.
Analyzed using x-ray photoelectron spectroscopy (XPS) and calculate the specimen surface content of fluoride ion of each embodiment, as a result Such as table 1.
Cytology bioactivity is carried out to the sample of each embodiment using Human osteoblast-like cell system MG-63 Gegenbaur's cells model Experiment, unmodified polyether-ether-ketone/graphite nanometer composite material sample that embodiment 1 makes is as a control group (comparative example 1). High sugared cell culture medium recovery of the MG-63 Gegenbaur's cells containing 10% hyclone, be placed in 37 DEG C, humidity 95%, CO2Concentration Cultivated in 5% cell culture incubator, the next day change liquid, the form of optical microphotograph Microscopic observation cell, by exponential phase MG-63 Gegenbaur's cells are prepared into cell suspension.
By the standard specimen of experimental group and control group through gamma-ray irradiation sterilizing 2h, it is placed in 24 orifice plates.By what is prepared MG-63 cell suspension inoculations terminate cell culture after each group specimen surface, 24h.It is thin using acridine orange flourescent staining detection Born of the same parents adhere to and the quantity of propagation.With PBS (phosphate buffer, 1L PBS formulas:8g sodium chloride, 0.2g potassium chloride, 1.44g phosphorus Sour disodium hydrogen, 0.24g potassium dihydrogen phosphates) to rinse 3 times, concentration is that 95% ethanol fixes 5min, 0.05% Acridine orange 5min, PBS is rinsed 3 times；Fluorescence microscopy Microscopic observation, count, the cell quantity such as table 1 of material surface adhesion and propagation.
In addition, by obtained by each embodiment and comparative example sample add double screw extruder, high temperature (390 DEG C) melting, Through extrusion die extrusion molding bar, then through over mechanical processing, it is made in the artificial hip joint acetabular bone of each embodiment and comparative example Serve as a contrast prosthese.
By the artificial hip joint acetabular bone liner prosthese of the various embodiments described above and comparative example, with the artificial stock of medical vitallium Bone prosthese is matched, and is tested on artificial hip joint artificial wear-test machine, and standard ISO14242-2 is pressed in experiment：2000 《The abrasion part 2 of surgical implant full hip-joint prosthese：Measuring method》Carry out, test cycle number is 500000 times.Knot Fruit is as shown in table 1.
Table 1
Can be drawn by data in table, modified polyether-ether-ketone/graphite nanometer composite material (experimental group) surface adhesion and The cell quantity of propagation is substantially better than unmodified polyether-ether-ketone/graphite nanometer composite material.I.e. modified fluoro plasma injection Afterwards, the bioactivity of polyether-ether-ketone/graphite nanometer composite material is improved, and still, fluorine ion injection length is unsuitable long, Although the extension of injection length can increase the content of fluorine, the increase of the Oil repellent is bred for cell and the optimization of adhesion Act on unobvious.Meanwhile after graphite nanosheets are mixed in polyether-ether-ketone main body, the mill of polyether-ether-ketone can be greatly reduced Damage amount, illustrate that the wearability of composite has relative to pure polyether-ether-ketone and be obviously improved.
As can be seen from the above description, the above embodiments of the present invention realize following technique effect：
The application further carries out surface fluorine using Plasma implantation techniques to polyether-ether-ketone/graphite nanometer composite material It is modified, polyether-ether-ketone/graphite nanometer composite material surface is formed fluoride and fluorine-containing functional group, improve its bioactivity.And Fluorine is one of trace element necessary to human life activity, in the bone growth and development and maintenance skeleton physiology structure work(of whole body Played a significant role in energy, fluoride and fluorine-containing functional group directly by stimulated osteoblastic proliferation and can strengthen alkaline phosphatase Enzymatic activity, strengthen osteogenic action.On the other hand, gully shape nanotopography can be formed in material surface after fluorine ion injection, made Surface is further roughened.Therefore, the double effect based on its composition and structure has been obviously promoted Gegenbaur's cell in material surface Stick, sprawl and breed, the bioactivity of polyether-ether-ketone/graphite nanometer composite material is greatly improved, is advantageous to human body Bone grows into polyether-ether-ketone/graphite nanometer composite material surface, improves polyether-ether-ketone/graphite nanometer composite material implant and people The fastness of the combination of body bone, so as to improve the stability and service life at a specified future date of implant.
Graphite nanosheets are formed it into by carrying out processing to expanded graphite, and then improve its lubricant effect.Then will Graphite nanosheets first mix with hydroquinones, ensure that pre- intercalation raw material is formed in graphite nanosheets insertion hydroquinones Graphite nanosheets are dispersed in hydroquinones.Then under conditions of emulsification is stirred by pre- intercalation raw material and 4,4 '- Difluoro benzophenone, solvent mixing, ensure that the dispersed of each component.Further when carrying out home position polymerization reaction, protect It is dispersed in the polyether-ether-ketone formed to demonstrate,prove graphite nanosheets, and then ensure that the lubrication of graphite nanosheets Performance, and ensure that the original mechanical property of polyether-ether-ketone, and then the composite that above-mentioned preparation method is obtained is using extremely When in artificial joint prosthesis, as part or all of friction pair material, the abrasion resistance in joint prosthesis face can be significantly improved Can, the abrasion of material is effectively reduced, reduces the bad biological respinse triggered by abrasive dust and aseptic loosening, it is artificial so as to extend The life-span of articular prosthesis.Meanwhile by the thickness of graphite nanosheets and content control within the above range, be advantageous to it in polyethers It is dispersed in ether ketone, and then further improve the wearability of composite.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies Change, equivalent substitution, improvement etc., should be included in the scope of the protection.

Claims (13)

  1. A kind of 1. preparation method of fluorine richness polyether-ether-ketone/graphite nanometer composite material, it is characterised in that the preparation method bag Include：
    By the use of fluorinated organic compound as source ion implantation, using plasma injection technique is to polyether-ether-ketone/Nano graphite Composite material surface carries out fluorine richness, in the polyether-ether-ketone/graphite nanometer composite material area load fluorine atom.
  2. 2. preparation method according to claim 1, it is characterised in that the fluorinated organic compound is carbon tetrafluoride, four PVF and/or hexafluoropropene.
  3. 3. preparation method according to claim 1, it is characterised in that the plasma note of the Plasma implantation techniques The pressure for entering cavity is 1.0 × 10-3Pa~0.1Pa, injecting voltage are 10~50kV, preferably described Plasma implantation techniques Injected pulse width is 20~800 μ s, pulse recurrence frequency is 5~100Hz；More preferably described Plasma implantation techniques are put Electric current is 1~10A, and the injection length of preferably described Plasma implantation techniques is 0.5~10h.
  4. 4. preparation method according to claim 1, it is characterised in that before the Plasma implantation techniques are implemented, The preparation method also includes the process that the polyether-ether-ketone/graphite nanometer composite material is roughened and cleaned, It is preferred that the process includes：
    Blasting treatment is carried out to the surface of the polyether-ether-ketone/graphite nanometer composite material, preferably described blasting treatment uses powder Emergy of the last particle diameter between 50~300 μm is abrasive material, and in the blasting treatment, preferably sandblasting distance is 3~10cm, more excellent It is 2~8bar to select compression pressure, and further preferred injecting time is 5~60s；
    The polyether-ether-ketone after blasting treatment/graphite nanometer composite material is carried out using absolute ethyl alcohol and deionized water successively It is cleaned by ultrasonic 10~30min.
  5. 5. preparation method according to claim 1, it is characterised in that the preparation method also include the polyether-ether-ketone/ The preparation process of graphite nanometer composite material, the preparation process include：
    Step S1, graphite nanosheets solution being prepared using expanded graphite as graphite raw material, the graphite nanosheets thickness is 1~ 100nm；
    Step S2, removed after the graphite nanosheets solution and hydroquinones are mixed in the graphite nanosheets solution Liquid, obtain pre- intercalation raw material；
    Step S3, in the case where emulsifying stirring condition, the pre- intercalation raw material and 4, are formed 4 '-difluoro benzophenone, solvent mixing First reaction system；
    Step S4, first reaction system is warming up to addition alkali metal carbonic acid in 150~180 DEG C of backward reaction systems Salt forms the second reaction system；And
    Step S5, second reaction system is reacted between 200~325 DEG C, it is multiple to obtain polyether-ether-ketone/Nano graphite Condensation material, wherein, the dosages of the graphite nanosheets is the hydroquinones, described 4,4 '-difluoro benzophenone and described 0.1~2wt% of the gross mass of graphite nanosheets.
  6. 6. preparation method according to claim 5, it is characterised in that the step S1 includes：
    After the expanded graphite is put into alcohol, the 4~8h of alcohol is ultrasonically treated, it is molten to obtain the graphite nanosheets Liquid, ethanol content is 60%~80% in preferably described alcohol.
  7. 7. preparation method according to claim 5, it is characterised in that the step S2 includes：
    In inert gas or nitrogen atmosphere, the graphite nanosheets solution and hydroquinones are mixed 6 under ultrasound condition ~10h, obtain the pre- intercalation solution of hydroquinones/graphite nanosheets；
    Pressure less than 133Pa vacuum condition under to the pre- intercalation solution of the hydroquinones/graphite nanosheets dry 4~ 12h, obtain the pre- intercalation raw material.
  8. 8. preparation method according to claim 5, it is characterised in that the step S3 includes：
    By the pre- intercalation raw material and 4,4 '-difluoro benzophenone, solvent are added to in emulsification mixer, to described Inert gas or nitrogen are passed through in blender and open emulsification agitating function with 1000~3000r/min speed stirring 10~ 30min, first reaction system is obtained, wherein it is preferred that the hydroquinones and described 4, mole of 4 '-difluoro benzophenone Than for 1:1~1:1.1, preferably described solvent is diphenyl sulphone (DPS), the further preferred diphenyl sulphone (DPS) and described 4,4 '-difluorodiphenyl first The volume ratio of ketone is 2:1~3:1.
  9. 9. preparation method according to claim 5, it is characterised in that the alkali carbonate is potassium carbonate and/or carbon The mol ratio of sour sodium, the alkali carbonate and the hydroquinones is 1.5:1~2.5:1.
  10. 10. preparation method according to claim 5, it is characterised in that the step S5 includes：
    After second reaction system is warming up to the first temperature and being incubated 2~5h, the 3rd reaction system, first temperature are obtained Spend for 200~240 DEG C；
    After the 3rd reaction system is warming up to second temperature and being incubated 10~30min, the 4th reaction system is obtained, described the Two temperature are 250~270 DEG C；
    The 4th reaction system is set to be warming up to the 3rd temperature and obtain receiving containing the polyether-ether-ketone/graphite after being incubated 2~3h The product system of nano composite material, the 3rd temperature are 315~325 DEG C.
  11. 11. preparation method according to claim 10, it is characterised in that the step S5 also includes to the product system Extracted, obtain the polyether-ether-ketone/graphite nanometer composite material, it is preferred to use acetone extracts to the product system Take.
  12. 12. a kind of fluorine richness polyether-ether-ketone/graphite nanometer composite material, it is characterised in that using any in claim 1 to 11 Preparation method described in is prepared.
  13. 13. a kind of artificial joint prosthesis, the artificial joint prosthesis includes being used for the contact site contacted with skeleton, forms institute Stating the material of contact site includes polyether-ether-ketone/graphite nanometer composite material, it is characterised in that the polyether-ether-ketone/Nano graphite Composite is fluorine richness polyether-ether-ketone/graphite nanometer composite material described in claim 12.
CN201710822801.XA 2017-09-13 2017-09-13 Fluorine modified polyether-ether-ketone/graphite nano composite material, preparation method thereof and artificial joint prosthesis Active CN107698792B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710822801.XA CN107698792B (en) 2017-09-13 2017-09-13 Fluorine modified polyether-ether-ketone/graphite nano composite material, preparation method thereof and artificial joint prosthesis

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710822801.XA CN107698792B (en) 2017-09-13 2017-09-13 Fluorine modified polyether-ether-ketone/graphite nano composite material, preparation method thereof and artificial joint prosthesis

Publications (2)

Publication Number Publication Date
CN107698792A true CN107698792A (en) 2018-02-16
CN107698792B CN107698792B (en) 2020-10-20

Family

ID=61171638

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710822801.XA Active CN107698792B (en) 2017-09-13 2017-09-13 Fluorine modified polyether-ether-ketone/graphite nano composite material, preparation method thereof and artificial joint prosthesis

Country Status (1)

Country Link
CN (1) CN107698792B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117430855A (en) * 2023-10-16 2024-01-23 华中科技大学同济医学院附属同济医院 Modified polyether-ether-ketone material, preparation method thereof and application thereof in midwifery forceps

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009189948A (en) * 2008-02-14 2009-08-27 Gyoseiin Genshino Iinkai Kakuno Kenkyusho Plasma reactor for bimodal operation
CN105524410A (en) * 2015-11-03 2016-04-27 南京肯特复合材料有限公司 Calcium carbonate whisker reinforced PEEK/PTFE resin and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009189948A (en) * 2008-02-14 2009-08-27 Gyoseiin Genshino Iinkai Kakuno Kenkyusho Plasma reactor for bimodal operation
CN105524410A (en) * 2015-11-03 2016-04-27 南京肯特复合材料有限公司 Calcium carbonate whisker reinforced PEEK/PTFE resin and preparation method thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
刘秀菊等: "氮气等离子体注入改性对聚醚醚酮生物活性的影响", 《现代口腔医学杂志》 *
吴晓绵等: "聚醚醚酮种植材料TiO2颗粒喷砂处理的生物活性研究", 《现代医药卫生》 *
尹小龙等: "原位聚合法制备的聚醚醚酮/膨胀石墨复合材料及性能", 《高分子材料科学与工程》 *
王成焘: "《骨科植入物工程学 上》", 31 October 2016, 上海交通大学出版社 *
边炳鑫: "《石墨加工与石墨材料》", 31 May 2014, 中国矿业大学出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117430855A (en) * 2023-10-16 2024-01-23 华中科技大学同济医学院附属同济医院 Modified polyether-ether-ketone material, preparation method thereof and application thereof in midwifery forceps
CN117430855B (en) * 2023-10-16 2024-04-23 华中科技大学同济医学院附属同济医院 Modified polyether-ether-ketone material, preparation method thereof and application thereof in midwifery forceps

Also Published As

Publication number Publication date
CN107698792B (en) 2020-10-20

Similar Documents

Publication Publication Date Title
CN104212998B (en) Zn-Mg zinc alloy and preparation method and application thereof
JP3962715B2 (en) Use of autologous dermal fibroblasts to repair skin and soft tissue defects
CN104974467A (en) Nano-hydroxyapatite/polyether-ether-ketone composite material and bone repair body as well as preparation method and application thereof
CN106492285A (en) Injectable Acellular cartilaginous matrix particulate and its application in implant
CN1340080A (en) Hyaluronic acid gel composition, process for producing the same, and medical material containing the same
KR101121154B1 (en) A composition for transplant comprising adipose stem cells or adipocytes
CN100560641C (en) Mierocrystalline cellulose/soy protein composite sponge and preparation method thereof
CN107715182A (en) A kind of preparation method and applications of 3D printing composite magnetic metallic support
CN107556445B (en) Polyether-ether-ketone/graphite nano composite material, and preparation method and application thereof
CN112023120A (en) Injectable pre-filled bone repair particle and preparation method and application thereof
CN107158465B (en) Preparation method of bone scaffold composite material
CN108653814A (en) A kind of preparation method of Acellular cartilaginous matrix material
CN107698792A (en) Fluorine richness polyether-ether-ketone/graphite nanometer composite material, its preparation method and artificial joint prosthesis
CN111214702A (en) Injectable bionic repair material for defects of temporomandibular joint disc and preparation method and application thereof
CN107648672A (en) Fluorine richness polyether-ether-ketone/graphite nanometer composite material and artificial joint prosthesis
CN114366854B (en) Silica gel nose augmentation material of composite decalcified bone matrix
CN109106978A (en) A kind of human skin fibroblasts culture supernatant dressing and preparation method thereof
Li et al. Surface modification of nano-silica on the ligament advanced reinforcement system for accelerated bone formation: primary human osteoblasts testing in vitro and animal testing in vivo
CN213432005U (en) Titanium alloy artificial implant with micro-nano structure for enhancing surface cell adhesion
CN107261211A (en) A kind of people's bone alternate material and preparation method thereof
CN110507855B (en) Preparation method of heterogenous costal cartilage for local support effect
CN109880152B (en) Preparation method of oriented communicated porous biomedical stent, stent prepared by preparation method and application of stent in preparation of medical products
CN111888530A (en) Zinc oxide-polyether-ether-ketone composite material, preparation method and application thereof, and artificial joint formed by zinc oxide-polyether-ether-ketone composite material
CN111921014A (en) Rehmannia polysaccharide/heterogenous calcined bone composite bone repair material
CN100523082C (en) High-strength high-modulus absorbable calcium polyphosphate fibre/polylactide composition as intrabony fixing material and its preparing process

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
GR01 Patent grant
GR01 Patent grant