CN110330683A - The preparation method of bionical polyether-ether-ketone joint prosthesis mortar with soft or hard composite construction - Google Patents

The preparation method of bionical polyether-ether-ketone joint prosthesis mortar with soft or hard composite construction Download PDF

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CN110330683A
CN110330683A CN201910501851.7A CN201910501851A CN110330683A CN 110330683 A CN110330683 A CN 110330683A CN 201910501851 A CN201910501851 A CN 201910501851A CN 110330683 A CN110330683 A CN 110330683A
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ether
polyether
ketone
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joint prosthesis
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CN110330683B (en
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刘昀彤
赵晓铎
熊党生
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Nanjing Tech University
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Nanjing Tech University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/16Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/18Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/52Hydrogels or hydrocolloids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36After-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36After-treatment
    • C08J9/40Impregnation
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/452Lubricants
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606Coatings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/24Materials or treatment for tissue regeneration for joint reconstruction
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/16Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24Homopolymers or copolymers of amides or imides
    • C08J2433/26Homopolymers or copolymers of acrylamide or methacrylamide

Abstract

The preparation method of the invention discloses a kind of bionical polyether-ether-ketone joint prosthesis mortar with soft or hard composite construction.The method is using rigid polyether ether ketone or derivatives thereof joint prosthesis mortar cup as matrix, using the method for laser boring in its surface construction hole configurations, later in conjunction with ultraviolet light irradiation graft polymerization technique, one layer of soft hydrogel layer is prepared in the polyether-ether-ketone joint prosthesis mortar cup surface with hole configurations, finally hydrogel-polyether-ether-ketone composite material is immersed in ferric ion solutions, strengthen hydrogel layer, obtains bionical low friction polyether-ether-ketone joint prosthesis mortar cup.Polyether-ether-ketone joint mortar cup surface of the invention has one layer of soft hydrogel layer; on the basis of retaining polyether-ether-ketone or derivatives thereof bulk properties; significantly improve polyether-ether-ketone mortar cup surface wetability and coefficient of friction; coefficient of friction and abrasion loss is effectively reduced; surface soft hydrogel layer can protect matrix, from the Bionic Design structurally and functionally realized to natural joint lubricating system.

Description

The preparation method of bionical polyether-ether-ketone joint prosthesis mortar with soft or hard composite construction
Technical field
The present invention relates to a kind of biomimetic material technology fields, are related to a kind of bionical polyether-ether-ketone with soft or hard composite construction The preparation method of joint prosthesis mortar.
Background technique
Polyether-ether-ketone (PEEK) is a kind of material nontoxic, with good chemical stability and biocompatibility, wide at present It is general to be applied to joint prosthesis manufacturing field.However, the surface PEEK is in hydrophobicity and chemical inertness, the coefficient of friction of pure PEEK material It is relatively high, seriously limit its application in clinic.
Chinese patent application 201510797209.X is using plasma immersion ion implantation technique to polyetheretherketonematerials materials It is modified to carry out zirconium-ion implantation, while introducing micro-nano structure on the surface of the material, bioactive ingredients zirconium oxide is also introduced into, to mention Mechanical performance, bioactivity and the bone formation performance of high polyether-ether-ketone, while also assigning material certain antibiotic property.But this method The Tribological Properties of PEEK can not be improved.In order to improve the tribological property of PEEK material, Chinese patent 201510629322.7 using carbon fiber reinforced polyetheretherketonecomposite composite material as bearing substrate, prepares by with good wettability and life The multiple dimensioned carrying surface layer that the nano grade polymer brush layer and micro-scale surface texture layer of object compatibility are combined.Though this method The coefficient of friction of joint prosthesis mortar cup is so reduced to 0.099, but coefficient of friction and wear-resisting property also need further to improve.
In natural joint lubricating system, one layer of soft cartilage with spongelike structure is integrated to firmly by calcified layer On the subchondral bone of matter, a kind of layered structure with " soft or hard compound " is formd.Wherein, soft cartilage surface can play suction It receives, storage knuckle synovia, reduces the lubricating action of friction during exercise;Hard subchondral bone is cancellous bone, absorbable when stress Stress, maintains joint shape at buffering concussion, plays an important role to protection cartilage.
Summary of the invention
The system of the purpose of the present invention is to provide a kind of bionical polyether-ether-ketone joint prosthesis mortar with soft or hard composite construction Preparation Method.This method simulates its structure and function according to articular cartilage-subchondral bone composite construction, with hard PEEK (or its Derivative) joint prosthesis mortar cup be base material, its surface construct soft hydrogel layer, realize " soft or hard compound " layered structure Building, significantly improve the tribological property and service life of PEEK joint prosthesis.
Technical scheme is as follows:
The preparation method of bionical polyether-ether-ketone joint prosthesis mortar with soft or hard composite construction, the joint prosthesis mortar cup It is made of polyether-ether-ketone substrate and soft hydrogel layer, it is porous in the building of polyether-ether-ketone surface using laser surface texturing techniques Structure recycles ultraviolet light irradiation graft polymerization technique to construct soft hydrogel layer in polyether-ether-ketone articular surface, finally by water Gel-polyether-ether-ketone composite material immerses in ferric ion solutions, strengthens hydrogel layer, it is artificial to obtain bionical low friction polyether-ether-ketone Cotyla cup, the specific steps are as follows:
Step 1, it is constructed using laser surface texturing techniques on polyether-ether-ketone or derivatives thereof surface regularly arranged more Pore structure;
Step 2, by acrylamide, acrylic acid, crosslinking agent N, N'- methylene-bisacrylamide and photoinitiator α -one penta 2 Acid is soluble in water, stirs evenly, obtains hydrogel pre-gathering solutions, and wherein the ratio of the amount of the substance of acrylic acid and acrylamide is 1: 3~1:5, N, N'- methylene-bisacrylamide are the 0.1%~0.5% of the amount summation of acrylamide and acrylic substance;
Step 3, hydrogel pre-gathering solutions are added dropwise in the polyether-ether-ketone obtained in step 1 or derivatives thereof surface, are put into ultraviolet It is irradiated under lamp, obtains hydrogel-polyether-ether-ketone composite material;
Step 4, hydrogel-polyether-ether-ketone composite material is immersed into ferric ion solutions, enhances hydrogel layer, obtains having soft The bionical polyether-ether-ketone joint prosthesis mortar of hard composite construction.
In a specific embodiment of the present invention, in step 1, the porous structure is 100 μm of radius, adjacent two micropores circle At a distance of 400 μm of round microwell array between the heart.
In a specific embodiment of the present invention, in step 2, in the hydrogel pre-gathering solutions, the concentration of acrylamide For 3mol/L.
In a specific embodiment of the present invention, in step 2, the α-ketoglutaric acid is acrylamide and acrylic substance Amount summation 0.1%.
In a specific embodiment of the present invention, in step 3, the condition of the radiation grafting copolymerization is spoke under 500w mercury lamp It is 0.5~1h according to the time.
Preferably, in step 4, the ferric ion solutions are ferric nitrate or ferric chloride solution, concentration 0.25mol/L.
Preferably, in step 4, the soaking time be for 24 hours more than.
Compared with prior art, the invention has the following advantages that
(1) polyether-ether-ketone joint mortar cup surface of the invention has one layer of soft hydrogel layer, surface soft polypropylene acid- Polyacrylamide-iron ion hydrogel layer can protect matrix, have " soft or hard compound " layered structure, from structurally and functionally realizing To the Bionic Design of natural joint lubricating system.
(2) bionical polyether-ether-ketone joint prosthesis mortar prepared by the present invention friction testing condition under the same conditions, and it is pure Polyether-ether-ketone (0.32) is compared, and coefficient of friction reduces by 91%, down to 0.03 or so.In addition, hydrogel layer can play storage, release The effect of lubricant is put, the tribological property of joint prosthesis load bearing interface can be effectively improved;And hard PEEK substrate provides The bearing capacity of color, effective protection hydrogel layer extend joint prosthesis load bearing interface service life.
(3) method of the invention is low in cost, low to equipment requirement degree, efficient quick easy to operate, without to polyethers ether Ketone (or derivatives thereof) surface progress high-precision surface grinding process, it is suitable for industrialized mass production.
Detailed description of the invention
Fig. 1 is the preparation flow schematic diagram of the bionical polyether-ether-ketone joint prosthesis mortar with soft or hard composite construction.
Fig. 2 is that pure PEEK is measured under the load of 8N with the bionical polyether-ether-ketone joint prosthesis mortar with soft or hard composite construction Coefficient of friction contrast schematic diagram.
Load of bionical polyether-ether-ketone joint prosthesis mortar (b) of the Fig. 3 for pure PEEK (a) and with soft or hard composite construction in 8N Lower friction 15min rear surface polishing scratch figure is (c) the bionical polyether-ether-ketone joint prosthesis mortar with soft or hard composite construction in 8N load Lower friction 15min, polishing scratch figure after impregnating 15 days in deionized water.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
In following embodiments, frictional behaviour test condition is as follows:
It is tested and is commented using frictional behaviour of the UMT friction wear testing machine to bionical polyether-ether-ketone joint prosthesis mortar cup Valence.Friction is stainless steel ball (R=60mm) with pair, and friction mode is the mode that reciprocatingly slides, and lubricant medium is deionized water, is applied Load is 5N~8N, sliding length 2mm, sliding speed 2mm/s, when friction testing a length of 15min.With pure PEEK material phase Than the coefficient of friction of the bionical polyether-ether-ketone joint prosthesis mortar with soft or hard composite construction of the invention reduces by 91%, and polishing scratch is aobvious Work shoals, and can restore substantially after impregnating 15d in deionized water.Bionical polyethers ether with soft or hard composite construction of the invention The comparison of the coefficient of friction and polishing scratch of ketone joint prosthesis mortar and pure PEEK material is as shown in Figures 2 and 3 respectively.
Embodiment 1
By polyether-ether-ketone (or derivatives thereof) joint prosthesis mortar cup is placed under laser marking machine, use the method for laser boring Preparing porous structure in mortar cup surface, (porous structure is 100 μm of radius, at a distance of 400 μm of circle between the adjacent two micropore center of circle Shape microwell array).2.1324g acrylamide (3mol/L) is added into 10ml deionized water, 0.7206g acrylic acid is (with propylene The ratio between amount of amide material is 1:3), 0.0062g N, N'- methylene-bisacrylamide (accounts for acrylamide, acrylic substance The 0.1% of the sum of amount), 0.0058g α-ketoglutaric acid (account for acrylamide, acrylic substance the sum of amount 0.1%), stirring is equal It is even to obtain hydrogel pre-gathering solutions.1ml hydrogel pre-gathering solutions are added dropwise on polyether-ether-ketone surface, glass slide is covered on polyethers ether Ketone surface is put under ultraviolet lamp (500w mercury lamp) and irradiates 0.5h.The iron nitrate solution for preparing 0.25mol/L, by gained water-setting Glue-polyether-ether-ketone composite material immerses iron nitrate solution for 24 hours, enhances hydrogel layer, then immerse 3d in deionized water, and it is extra to remove Iron ion obtains bionical low friction polyether-ether-ketone joint prosthesis mortar cup.It is 0.07 that coefficient of friction is measured under the load of 5N.
Embodiment 2
By polyether-ether-ketone (or derivatives thereof) joint prosthesis mortar cup is placed under laser marking machine, use the method for laser boring Preparing porous structure in mortar cup surface, (porous structure is 100 μm of radius, at a distance of 400 μm of circle between the adjacent two micropore center of circle Shape microwell array).2.1324g acrylamide (3mol/L) is added into 10ml deionized water, 0.5405g acrylic acid is (with propylene The ratio between amount of amide material is 1:4), 0.0173g N, N'- methylene-bisacrylamide (accounts for acrylamide, acrylic substance The 0.3% of the sum of amount), 0.0055g α-ketoglutaric acid (account for acrylamide, acrylic substance the sum of amount 0.1%), stirring is equal It is even to obtain hydrogel pre-gathering solutions.1ml hydrogel pre-gathering solutions are added dropwise on polyether-ether-ketone surface, glass slide is covered on polyethers ether Ketone surface is put under ultraviolet lamp (500w mercury lamp) and irradiates 1h.The iron nitrate solution for preparing 0.25mol/L, by gained hydrogel- Polyether-ether-ketone composite material immerses iron nitrate solution for 24 hours, enhances hydrogel layer, then immerse 3d in deionized water, removes extra iron Ion obtains bionical low friction polyether-ether-ketone joint prosthesis mortar cup.It is 0.05 that coefficient of friction is measured under the load of 8N.
Embodiment 3
By polyether-ether-ketone (or derivatives thereof) joint prosthesis mortar cup is placed under laser marking machine, use the method for laser boring Preparing porous structure in mortar cup surface, (porous structure is 100 μm of radius, at a distance of 400 μm of circle between the adjacent two micropore center of circle Shape microwell array).2.1324g acrylamide (3mol/L) is added into 10ml deionized water, 0.4324g acrylic acid is (with propylene The ratio between amount of amide material is 1:5), 0.0278g N, N'- methylene-bisacrylamide (accounts for acrylamide, acrylic substance The 0.5% of the sum of amount), 0.0053g α-ketoglutaric acid (account for acrylamide, acrylic substance the sum of amount 0.1%), stirring is equal It is even to obtain hydrogel pre-gathering solutions.1ml hydrogel pre-gathering solutions are added dropwise on polyether-ether-ketone surface, glass slide is covered on polyethers ether Ketone surface is put under ultraviolet lamp (500w mercury lamp) and irradiates 0.5h.The iron nitrate solution for preparing 0.25mol/L, by gained water-setting Glue-polyether-ether-ketone composite material immerses iron nitrate solution for 24 hours, enhances hydrogel layer, then immerse 3d in deionized water, and it is extra to remove Iron ion obtains bionical low friction polyether-ether-ketone joint prosthesis mortar cup.It is 0.03 that coefficient of friction is measured under the load of 5N.
Comparative example 1
By polyether-ether-ketone (or derivatives thereof) joint prosthesis mortar cup is placed under laser marking machine, use the method for laser boring Preparing porous structure in mortar cup surface, (porous structure is 100 μm of radius, at a distance of 400 μm of circle between the adjacent two micropore center of circle Shape microwell array).2.1324g acrylamide (3mol/L) is added into 10ml deionized water, 0.3603g acrylic acid is (with propylene The ratio between amount of amide material is 1:6), 0.0027g N, N'- methylene-bisacrylamide (accounts for acrylamide, acrylic substance The 0.05% of the sum of amount), 0.0051g α-ketoglutaric acid (account for acrylamide, acrylic substance the sum of amount 0.1%), stirring Uniformly obtain hydrogel pre-gathering solutions.1ml hydrogel pre-gathering solutions are added dropwise on polyether-ether-ketone surface, glass slide is covered on polyethers Ether ketone surface is put under ultraviolet lamp (500w mercury lamp) and irradiates 0.5h.The iron nitrate solution for preparing 0.25mol/L, by gained water Gel-polyether-ether-ketone composite material immerses iron nitrate solution for 24 hours, enhances hydrogel layer, then immerse 3d in deionized water, removes more Remaining iron ion obtains bionical low friction polyether-ether-ketone joint prosthesis mortar cup.It is 0.15 that coefficient of friction is measured under the load of 2N, and Friction posterior surface gel layer is worn, and wearability is bad.
Comparative example 2
By polyether-ether-ketone (or derivatives thereof) joint prosthesis mortar cup is placed under laser marking machine, use the method for laser boring Preparing porous structure in mortar cup surface, (porous structure is 100 μm of radius, at a distance of 400 μm of circle between the adjacent two micropore center of circle Shape microwell array).2.1324g acrylamide (3mol/L) is added into 10ml deionized water, 1.0809g acrylic acid is (with propylene The ratio between amount of amide material is 1:2), 0.0694g N, N'- methylene-bisacrylamide (accounts for acrylamide, acrylic substance The 1% of the sum of amount), 0.0066g α-ketoglutaric acid (account for acrylamide, acrylic substance the sum of amount 0.1%), stir evenly Obtain hydrogel pre-gathering solutions.1ml hydrogel pre-gathering solutions are added dropwise on polyether-ether-ketone surface, glass slide is covered on polyether-ether-ketone Surface is put under ultraviolet lamp (500w mercury lamp) and irradiates 1h.The iron nitrate solution for preparing 0.25mol/L, gained hydrogel-is poly- Polyetherether ketone composite immerses iron nitrate solution for 24 hours, enhances hydrogel layer, then immerses 3d in deionized water, remove extra iron from Son obtains bionical low friction polyether-ether-ketone joint prosthesis mortar cup.It is 0.2 that coefficient of friction is measured under the load of 10N.
Comparative example 3
By polyether-ether-ketone (or derivatives thereof) joint prosthesis mortar cup is placed under laser marking machine, use the method for laser boring Preparing porous structure in mortar cup surface, (porous structure is 100 μm of radius, at a distance of 400 μm of circle between the adjacent two micropore center of circle Shape microwell array).2.1324g acrylamide (3mol/L) is added into 10ml deionized water, 1.0809g acrylic acid is (with propylene The ratio between amount of amide material is 1:2), 0.0347g N, N'- methylene-bisacrylamide (accounts for acrylamide, acrylic substance The 0.5% of the sum of amount), 0.0066g α-ketoglutaric acid (account for acrylamide, acrylic substance the sum of amount 0.1%), stirring is equal It is even to obtain hydrogel pre-gathering solutions.1ml hydrogel pre-gathering solutions are added dropwise on polyether-ether-ketone surface, glass slide is covered on polyethers ether Ketone surface is put under ultraviolet lamp (500w mercury lamp) and irradiates 1.5h.The iron nitrate solution for preparing 0.25mol/L, by gained water-setting Glue-polyether-ether-ketone composite material immerses iron nitrate solution for 24 hours, enhances hydrogel layer, then immerse 3d in deionized water, and it is extra to remove Iron ion obtains bionical low friction polyether-ether-ketone joint prosthesis mortar cup.It is 0.17 that coefficient of friction is measured under the load of 10N.

Claims (8)

1. the preparation method of the bionical polyether-ether-ketone joint prosthesis mortar with soft or hard composite construction, which is characterized in that specific steps It is as follows:
Step 1, regularly arranged porous knot is constructed on polyether-ether-ketone or derivatives thereof surface using laser surface texturing techniques Structure;
Step 2, acrylamide, acrylic acid, crosslinking agent N, N'- methylene-bisacrylamide and photoinitiator α-ketoglutaric acid is molten Yu Shuizhong is stirred evenly, and obtains hydrogel pre-gathering solutions, wherein the ratio of the amount of the substance of acrylic acid and acrylamide be 1:3~ 1:5, N, N'- methylene-bisacrylamide are the 0.1%~0.5% of the amount summation of acrylamide and acrylic substance;
Step 3, hydrogel pre-gathering solutions are added dropwise in the polyether-ether-ketone obtained in step 1 or derivatives thereof surface, are put under ultraviolet lamp Irradiation, obtains hydrogel-polyether-ether-ketone composite material;
Step 4, hydrogel-polyether-ether-ketone composite material is immersed into ferric ion solutions, enhances hydrogel layer, obtains having soft or hard multiple Close the bionical polyether-ether-ketone joint prosthesis mortar of structure.
2. preparation method according to claim 1, which is characterized in that in step 1, the porous structure is 100 μ of radius M, at a distance of 400 μm of round microwell array between the adjacent two micropore center of circle.
3. preparation method according to claim 1, which is characterized in that in step 2, in the hydrogel pre-gathering solutions, The concentration of acrylamide is 3mol/L.
4. preparation method according to claim 1, which is characterized in that in step 2, the α-ketoglutaric acid is acryloyl The 0.1% of the amount summation of amine and acrylic substance.
5. preparation method according to claim 1, which is characterized in that in step 3, the condition of the radiation grafting copolymerization It is 0.5~1h for irradiation time under 500w mercury lamp.
6. preparation method according to claim 1, which is characterized in that in step 4, the ferric ion solutions are ferric nitrate Or ferric chloride solution.
7. preparation method according to claim 1, which is characterized in that in step 4, the ferric ion solutions concentration is 0.25mol/L。
8. preparation method according to claim 1, which is characterized in that in step 4, the soaking time be for 24 hours more than.
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CN111437076A (en) * 2020-04-02 2020-07-24 青岛大学附属医院 Multi-piece combined artificial joint mortar cup structure
CN113350570A (en) * 2021-06-17 2021-09-07 湘潭大学 Artificial joint with self-repairing textured composite film structure and preparation method thereof
CN113350570B (en) * 2021-06-17 2022-03-08 湘潭大学 Artificial joint with self-repairing textured composite film structure and preparation method thereof
CN115382017A (en) * 2022-08-16 2022-11-25 兰州大学 Novel 3D printing polyether-ether-ketone implant capable of carrying medicine and preparation method thereof
CN117736566A (en) * 2024-02-19 2024-03-22 上海珀利医用材料有限公司 Carbon fiber reinforced polyaryletherketone medical composite material and preparation method and application thereof

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