CN113980324A - Ultra-high molecular weight polyethylene implant, preparation method thereof and artificial joint - Google Patents

Ultra-high molecular weight polyethylene implant, preparation method thereof and artificial joint Download PDF

Info

Publication number
CN113980324A
CN113980324A CN202111290659.1A CN202111290659A CN113980324A CN 113980324 A CN113980324 A CN 113980324A CN 202111290659 A CN202111290659 A CN 202111290659A CN 113980324 A CN113980324 A CN 113980324A
Authority
CN
China
Prior art keywords
molecular weight
weight polyethylene
treatment
hydrophilic
ultra
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111290659.1A
Other languages
Chinese (zh)
Inventor
俞天白
姚夏睿
梁柱
潘忠诚
常兆华
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.)
Suzhou Microport Orthorecon Co Ltd
Original Assignee
Suzhou Microport Orthorecon 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 Suzhou Microport Orthorecon Co Ltd filed Critical Suzhou Microport Orthorecon Co Ltd
Priority to CN202111290659.1A priority Critical patent/CN113980324A/en
Publication of CN113980324A publication Critical patent/CN113980324A/en
Priority to PCT/CN2022/128111 priority patent/WO2023078165A1/en
Pending legal-status Critical Current

Links

Images

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
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dermatology (AREA)
  • General Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Veterinary Medicine (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Public Health (AREA)
  • Toxicology (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention relates to an ultrahigh molecular weight polyethylene implant, a preparation method thereof and an artificial joint. The preparation method comprises the following steps: under the protective atmosphere, carrying out electron beam irradiation treatment on the ultra-high molecular weight polyethylene molded part, wherein the total irradiation dose of the irradiation treatment is 20 KGy-200 KGy; under the protective atmosphere, placing the formed piece subjected to the irradiation treatment in a hydrophilic monomer solution to perform grafting reaction under the initiation of free radicals generated by the irradiation treatment, wherein the grafting reaction temperature is 50-80 ℃, the grafting reaction time is 30-200 min, and the total concentration of hydrophilic monomers in the hydrophilic monomer solution is 0.1-1.0 mol/L; and annealing the grafted product; the temperature of the annealing treatment is 110-160 ℃, and the time is 1-10 h. The ultrahigh molecular weight polyethylene implant prepared by the preparation method has better wear resistance.

Description

Ultra-high molecular weight polyethylene implant, preparation method thereof and artificial joint
Technical Field
The invention relates to the technical field of medical instruments, in particular to an ultrahigh molecular weight polyethylene implant, a preparation method thereof and an artificial joint.
Background
Ultra-high molecular weight polyethylene (UHMWPE) is gaining market favor for its excellent impact properties, friction resistance, and self-lubricity, particularly in the surgical implant context, UHMWPE has been used as an artificial joint material for over 50 years.
Although the ultra-high molecular weight polyethylene has excellent comprehensive performance, the UHMWPE in the artificial joint friction pair can rub with the metal or ceramic hard end in vivo for a long time along with the increase of the service life of the artificial joint. The fine friction debris produced by UHMWPE can cause adverse biological reactions leading to osteolysis and aseptic loosening. The bad influence of the abrasive dust on the artificial joint prompts people to modify the material so as to achieve the aim of improving the wear resistance of the material.
Disclosure of Invention
Based on this, there is a need for an ultrahigh molecular weight polyethylene implant with better wear resistance, a preparation method thereof and an artificial joint.
A preparation method of an ultra-high molecular weight polyethylene implant comprises the following steps:
under the protective atmosphere, carrying out electron beam irradiation treatment on the ultra-high molecular weight polyethylene molded part, wherein the total irradiation dose of the irradiation treatment is 20 KGy-200 KGy;
under the protective atmosphere, placing the formed piece subjected to the irradiation treatment in a hydrophilic monomer solution to perform grafting reaction under the initiation of free radicals generated by the irradiation treatment, wherein the grafting reaction temperature is 50-80 ℃, the grafting reaction time is 30-200 min, and the total concentration of hydrophilic monomers in the hydrophilic monomer solution is 0.1-1.0 mol/L; and
annealing treatment is carried out on the grafted reaction; the temperature of the annealing treatment is 110-160 ℃, and the time is 1-10 h.
In some embodiments, the irradiation treatment has an irradiation dose rate of 1KGy/s to 4 KGy/s.
In some embodiments, the total irradiation dose of the irradiation treatment is 110KGy to 200 KGy.
In some of these embodiments, the hydrophilic monomer is selected from at least one of hydroxyethyl acrylate, methacrylic acid, acrylic acid, and 2-methacryloyloxyethyl phosphorylcholine.
In some of these embodiments, the hydrophilic monomer is selected from one or a mixture of 2-methacryloyloxyethyl phosphorylcholine and hydroxyethyl acrylate.
In some embodiments, the total concentration of hydrophilic monomers in the hydrophilic monomer solution is 0.6mol/L to 1.0 mol/L.
In some embodiments, the temperature of the grafting reaction is 60-80 ℃ and the time is 40-180 min.
In some embodiments, the annealing treatment temperature is 140-150 ℃ and the time is 4-10 h; and/or
The annealing treatment is carried out under vacuum condition or protective atmosphere.
An ultra-high molecular weight polyethylene implant prepared by the preparation method.
An artificial joint comprising a first support, a second support and an ultra high molecular weight polyethylene implant as described above; the ultra-high molecular weight polyethylene implant is arranged between the first supporting body and the second supporting body.
According to the preparation method of the ultrahigh molecular weight polyethylene implant, the ultrahigh molecular weight polyethylene molded part is subjected to electron beam irradiation treatment under a specific condition, then a grafting reaction is initiated to react for a specific time at a specific temperature by using free radicals generated by the irradiation treatment, the irradiation treatment and the grafting reaction are controlled to be carried out in sequence, and then the residual free radicals are crosslinked under a specific annealing treatment condition, so that a hydrophilic surface is formed on the surface of the ultrahigh molecular weight polyethylene molded part, UHMWPE molecules form a three-dimensional network crosslinking structure, the crosslinking degree of the surface of a product is further improved, the surface hydrophilicity of the prepared ultrahigh molecular weight polyethylene implant is improved, the friction coefficient is reduced, and the wear resistance of the ultrahigh molecular weight polyethylene implant is remarkably improved.
According to the preparation method of the ultrahigh molecular weight polyethylene implant, the hydrophilic grafting modification and crosslinking process is completed by optimizing the process and adopting a one-step electron beam irradiation mode, the grafting reaction process is simple, a photoinitiator, an acetone solvent and the like are not required to be additionally used, the harm of chemical residues to a human body is effectively avoided, and the hydrophilic grafting is effectively realized; the advantages of electron beam irradiation crosslinking and hydrophilic grafting are combined, and the surface lubrication property and the wear resistance of the ultrahigh molecular weight polyethylene implant are synergistically improved.
Drawings
Fig. 1 is a schematic structural view of an artificial joint according to an embodiment of the present invention.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It is to be understood that these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
An embodiment of the present invention provides an ultra-high molecular weight polyethylene implant and a method for preparing the same. The ultra-high molecular weight polyethylene implant obtained will be described in detail below with reference to the preparation method.
An embodiment of the present invention provides a method for preparing an ultra-high molecular weight polyethylene implant, including the following steps S10 to S30.
Step S10: and (3) carrying out electron beam irradiation treatment on the ultra-high molecular weight polyethylene molded part in a protective atmosphere, wherein the total irradiation dose of the irradiation treatment is 20 KGy-200 Kgy.
According to the analysis of the crosslinking principle, the chemical crosslinking generates active centers from free radicals generated by peroxide decomposition and unsaturated points in molecules, and the active centers are connected through monomers to form the chemically crosslinked UHMWPE. In the accelerated aging process of UHMWPE formed by chemical crosslinking, the base material is easy to oxidize and can not meet the use requirement. Compared with the traditional chemical crosslinking, the electron beam irradiation crosslinking can effectively avoid the oxidation risk brought by a peroxide crosslinking agent introduced in the chemical crosslinking process.
In addition, compared with chemical crosslinking, the radiation crosslinking in a physical mode has higher uniformity, the crosslinking degree can be controlled by the radiation dose, and a crosslinking agent does not need to be added, so the method is more favorably suitable for the field of artificial joint materials.
If the total irradiation dose is less than 20KGy, the generated radicals are insufficient, which may affect the grafting ratio in step S20 and the progress of the crosslinking reaction in step S30. If the total irradiation dose is higher than 200KGy, on one hand, excessive free radicals are generated, such as incomplete annealing, and the residual free radicals may cause accelerated aging of the product, and on the other hand, molecular chain breakage of the ultra-high molecular weight polyethylene may be caused, and the molecular weight is reduced.
Step S20: under the protective atmosphere, placing the formed piece subjected to irradiation treatment in a hydrophilic monomer solution to perform grafting reaction under the initiation of free radicals generated by irradiation treatment, wherein the temperature of the grafting reaction is 50-80 ℃, the time is 30-200 min, and the total concentration of hydrophilic monomers in the hydrophilic monomer solution is 0.1-1.0 mol/L.
The hydrophilic monomer is grafted on the ultra-high molecular weight polyethylene, the skeleton structure of the ultra-high molecular weight polyethylene is hardly changed, and simultaneously, the polar monomer with various functions is grafted on the main chain of the ultra-high molecular weight polyethylene, so that the original characteristics are maintained, and new functions are added. When the hydrophilic monomer is grafted to the surface of the ultra-high molecular weight polyethylene polymer to form a hydrophilic surface, the hydrophilic monomer is connected with the surface of the polymer through a chemical bond instead of being attached to the surface of the ultra-high molecular weight polyethylene polymer, so that the hydrophilic monomer on the surface of the ultra-high molecular weight polyethylene polymer is combined more firmly and is not easy to break along with friction.
Step S30: annealing treatment is carried out on the grafted reaction; the temperature of the annealing treatment is 110-160 ℃, and the time is 1-10 h.
According to the preparation method of the ultrahigh molecular weight polyethylene implant, the ultrahigh molecular weight polyethylene molded part is subjected to electron beam irradiation treatment under a specific condition, then a grafting reaction is initiated to react for a specific time at a specific temperature by using free radicals generated by the irradiation treatment, the irradiation treatment and the grafting reaction are controlled to be carried out in sequence, and then the residual free radicals are crosslinked under a specific annealing treatment condition, so that a hydrophilic surface is formed on the surface of the ultrahigh molecular weight polyethylene molded part, UHMWPE molecules form a three-dimensional network crosslinking structure, the crosslinking degree of the surface of a product is further improved, the surface hydrophilicity of the prepared ultrahigh molecular weight polyethylene implant is improved, the friction coefficient is reduced, and the wear resistance of the ultrahigh molecular weight polyethylene implant is remarkably improved.
According to the preparation method of the ultrahigh molecular weight polyethylene implant, the hydrophilic grafting modification and crosslinking process is completed by optimizing the process and adopting a one-step electron beam irradiation mode, the grafting reaction process is simple, a photoinitiator, an acetone solvent and the like are not required to be additionally used, the harm of chemical residues to a human body is effectively avoided, and the hydrophilic grafting is effectively realized; the advantages of electron beam irradiation crosslinking and hydrophilic grafting are combined, and the surface lubrication property and the wear resistance of the ultrahigh molecular weight polyethylene implant are synergistically improved.
The ultra-high molecular weight polyethylene implant is applied to the artificial joint friction pair, reduces the wear rate of the artificial joint in the using process, further reduces the possibility of osteolysis and aseptic loosening, and prolongs the service life of the artificial joint.
The preparation method of the ultra-high molecular weight polyethylene implant adopts an electron beam irradiation technology, is a safe and efficient method, and does not bring secondary chemical reagent pollution to products. Compared with a chemical crosslinking mode, the preparation method of the ultrahigh molecular weight polyethylene implant avoids the problem of crosslinking degree difference caused by uneven dispersion existing in the crosslinking modification by using crosslinking agents such as peroxide and the like, and also avoids the problem that the application of the crosslinking agent molecules in the field of artificial joints is limited due to the biological performance of the crosslinking agent molecules.
In some embodiments, the irradiation treatment has an irradiation dose rate of 1KGy/s to 4 KGy/s.
Further preferably, the total irradiation dose of the irradiation treatment is 110KGy to 200 Kgy. The total irradiation dose is controlled within the range, so that the crosslinking degree of the prepared ultrahigh molecular weight polyethylene implant can be further improved.
In some of these embodiments, the hydrophilic monomer is at least one selected from the group consisting of hydroxyethyl acrylate, methacrylic acid, acrylic acid, and 2-Methacryloyloxyethyl Phosphorylcholine (MPC).
Further, the hydrophilic monomer is selected from one or a mixture of two of 2-methacryloyloxyethyl phosphorylcholine and hydroxyethyl acrylate.
Further preferably, the total concentration of the hydrophilic monomers in the hydrophilic monomer solution is 0.6mol/L to 1.0 mol/L. The total concentration of the hydrophilic monomer is controlled within the range, so that the surface hydrophilic property of the prepared ultrahigh molecular weight polyethylene implant can be further improved, and the surface lubricating property of the implant can be further improved.
Further preferably, the temperature of the grafting reaction is 60-80 ℃ and the time is 40-180 min. The temperature and the duration of the grafting reaction are controlled within the range, so that the surface hydrophilic property of the prepared ultrahigh molecular weight polyethylene implant can be further improved, and the surface lubricating property of the implant can be further improved.
Further preferably, the temperature of the annealing treatment is 140 ℃ to 150 ℃ and the time is 4h to 10 h. If the heat treatment temperature is too low, residual free radicals are bound by molecular chains, the movement capability is poor, the free radicals cannot be recombined, and the purpose of effectively eliminating the residual free radicals cannot be achieved. The temperature and the duration of the annealing treatment are controlled within the range, so that the crosslinking degree of the prepared ultrahigh molecular weight polyethylene implant can be further improved, residual free radicals can be eliminated, the residual free radicals can be prevented from contacting oxygen, and the aging of products is accelerated.
In some of these embodiments, the annealing process is performed under vacuum conditions or a protective atmosphere.
It is understood that the above-mentioned protective atmosphere includes, but is not limited to, nitrogen, inert gas which does not participate in the reaction.
Referring to fig. 1, another embodiment of the present invention further provides an artificial joint, including a first supporting body 110 and the ultra-high molecular weight polyethylene implant 120, wherein the first supporting body 110 and the ultra-high molecular weight polyethylene implant 120 are in contact with each other and slide relatively; or comprises a first support body 110, a second support body 130 and the ultra-high molecular weight polyethylene implant 120, wherein the first support body 110 and the second support body 130 respectively contact with the ultra-high molecular weight polyethylene implant 120 and slide relatively. Wherein the ultra-high molecular weight polyethylene implant 120 is disposed between the first support 110 and the second support 130.
In some of these embodiments, the artificial joint is a hip joint, a knee joint, a condyle joint, an elbow joint, a wrist joint, a finger joint, or a shoulder joint. It is understood that prosthetic joints include, but are not limited to, such.
Specifically, in the particular example shown in fig. 1, the prosthetic joint is a hip joint and the ultra-high molecular weight polyethylene implant 120 is an acetabular liner. The first support 110 and the second support 120 are an acetabular cup prosthesis and a femoral head prosthesis, respectively. It is understood that the surfaces of the ultra-high molecular weight polyethylene implant 120, which contact the first support 110 and the second support 130, are hydrophilic surfaces.
In other examples, for example, the prosthetic joint may be a knee joint and the ultra-high molecular weight polyethylene implant 120 may be a knee joint spacer. Further, the first support body 110 and the second support body 130 are a femoral condyle prosthesis and a tibial tray prosthesis, respectively. Others are not to be taken as an example.
In order to make the objects, technical solutions and advantages of the present invention more concise and clear, the present invention is described with the following specific embodiments, but the present invention is by no means limited to these embodiments. The following described examples are only preferred embodiments of the present invention, which can be used to describe the present invention and should not be construed as limiting the scope of the present invention. It should be understood that any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
In order to better illustrate the invention, the following examples are given to further illustrate the invention. The following are specific examples.
Example 1
(1) UHMWPE having a molecular mass of 500 tens of thousands is produced as a sample of an artificial joint spacer having a surface roughness of 0.39 μm, which is then subjected to a cleaning and drying process. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 1.5KGy/s, and the total irradiation dose is 20 KGy.
(4) The irradiated sample was quickly placed in the grafting monomer solution and the grafting reaction was carried out at 60 ℃ under nitrogen protection (the purpose of the quick placement was to allow the grafting reaction to proceed under initiation of free radicals generated by the irradiation treatment) for 180 min. Wherein, the hydrophilic monomer is a mixed monomer of hydroxyethyl acrylate and 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and the molar ratio of the two monomers is 1: 3, the total concentration of the monomers is 0.80 mol/L.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 120 ℃, and the annealing time is 5 h.
(6) And cleaning and vacuum drying the annealed sample.
Example 2
(1) UHMWPE having a molecular mass of 350 ten thousand is produced into an artificial joint spacer sample having a surface roughness of 0.55 μm, which is then subjected to a cleaning and drying process. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 4.0KGy/s, and the total irradiation dose is 200 KGy.
(4) And (3) quickly putting the irradiated sample into a grafting monomer solution, and carrying out grafting reaction at the temperature of 70 ℃ under the protection of nitrogen for 120 min. Wherein the hydrophilic monomer is 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and the total concentration of the monomers is 0.60 mol/L.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 140 ℃, and the annealing time is 10 h.
(6) And cleaning and vacuum drying the annealed sample.
Example 3
(1) UHMWPE having a molecular mass of 500 tens of thousands is produced as an artificial joint spacer sample having a surface roughness of 0.90 μm, which is then subjected to a cleaning and drying process. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 1KGy/s, and the total irradiation dose is 90 KGy.
(4) And (3) quickly putting the irradiated sample into a grafting monomer solution, and carrying out grafting reaction at the temperature of 50 ℃ under the protection of nitrogen for 30 min. Wherein, the hydrophilic monomer is a mixed monomer of hydroxyethyl acrylate, methacrylic acid and acrylic acid, and the molar ratio of the three monomers is 1: 1.5: 2, the total concentration of the monomers is 0.1 mol/L.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 110 ℃, and the annealing time is 6 h.
(6) And cleaning and vacuum drying the annealed sample.
Example 4
(1) UHMWPE having a molecular mass of 500 tens of thousands is produced as an artificial joint spacer sample having a surface roughness of 0.30 μm, which is then subjected to a cleaning and drying process. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 2.7KGy/s, and the total irradiation dose is 85 KGy.
(4) And (3) quickly putting the irradiated sample into a grafting monomer solution, and carrying out grafting reaction at the temperature of 80 ℃ under the protection of nitrogen for 40 min. The hydrophilic monomer is a mixed monomer of methacrylic acid and 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and the molar ratio of the two monomers is 1: 1, the total concentration of the monomers is 1.0 mol/L.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 160 ℃, and the annealing time is 1 h.
(6) And cleaning and vacuum drying the annealed sample.
Example 5
(1) UHMWPE having a molecular mass of 500 ten thousand was fabricated into an artificial joint spacer sample having a surface roughness of 0.66 μm, which was then subjected to a cleaning and drying process. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 3KGy/s, and the total irradiation dose is 110 KGy.
(4) And (3) quickly putting the irradiated sample into a grafting monomer solution, and carrying out grafting reaction at the temperature of 50 ℃ under the protection of nitrogen for 200 min. Wherein the hydrophilic monomer is hydroxyethyl acrylate, and the total concentration of the monomers is 0.40 mol/L.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 150 ℃, and the annealing time is 4 h.
(6) And cleaning and vacuum drying the annealed sample.
Example 6
Compared with example 2, the method is basically the same, except that the hydrophilic monomer is a mixed monomer of hydroxyethyl acrylate and 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and the molar ratio of the two monomers is 1: 2, the total concentration of the monomers is 0.60 mol/L.
Comparative example 1
UHMWPE having a molecular mass of 500 ten thousand was prepared into an artificial joint spacer sample having a surface roughness of 0.45 μm, which was then subjected to a cleaning and drying process.
Comparative example 2
(1) UHMWPE having a molecular mass of 500 ten thousand was prepared into an artificial joint spacer sample having a surface roughness of 0.57 μm, which was then subjected to a cleaning and drying process. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 2.5KGy/s, and the total irradiation dose is 95 KGy.
(3) And placing the sample subjected to irradiation in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 150 ℃, and the annealing time is 6 h.
(4) And cleaning and vacuum drying the annealed sample.
Comparative example 3
(1) UHMWPE having a molecular mass of 500 tens of thousands was produced as an artificial joint spacer sample having a surface roughness of 0.41 μm, which was then subjected to a cleaning and drying treatment. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 3.1KGy/s, and the total irradiation dose is 10 KGy.
(4) And (3) quickly putting the irradiated sample into a grafting monomer solution, and carrying out grafting reaction at the temperature of 80 ℃ under the protection of nitrogen for 40 min. Wherein, the hydrophilic monomer is a mixed monomer of hydroxyethyl acrylate and 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and the molar ratio of the two monomers is 1: 2, the total concentration of the monomers is 1.0 mol/L.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 150 ℃, and the annealing time is 1 h.
(6) And cleaning and vacuum drying the annealed sample.
Comparative example 4
(1) UHMWPE having a molecular mass of 500 tens of thousands was produced as an artificial joint spacer sample having a surface roughness of 0.46 μm, which was then subjected to a cleaning and drying treatment. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 2.9KGy/s, and the total irradiation dose is 50 KGy.
(4) And (3) quickly putting the irradiated sample into a grafting monomer solution, and carrying out grafting reaction at room temperature under the protection of nitrogen for 60 min. Wherein, the hydrophilic monomer is a mixed monomer of methacrylic acid and 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and the molar ratio of the two monomers is 1: 2, the total concentration of the monomers is 0.8 mol/L.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 150 ℃, and the annealing time is 2 h.
(6) And cleaning and vacuum drying the annealed sample.
Comparative example 5
(1) UHMWPE having a molecular mass of 500 tens of thousands was produced as an artificial joint spacer sample having a surface roughness of 0.53 μm, which was then subjected to a cleaning and drying treatment. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 1.9KGy/s, and the total irradiation dose is 90 KGy.
(4) And (3) quickly putting the irradiated sample into a grafting monomer solution, and carrying out grafting reaction at the temperature of 60 ℃ under the protection of nitrogen for 10 min. Wherein, the hydrophilic monomer is a mixed monomer of hydroxyethyl acrylate, methacrylic acid and 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and the molar ratio of the two monomers is 1: 1: 2, the total concentration of the monomers is 0.8 mol/L.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 150 ℃, and the annealing time is 2.5 h.
(6) And cleaning and vacuum drying the annealed sample.
Comparative example 6
(1) UHMWPE having a molecular mass of 500 tens of thousands is produced as a sample of an artificial joint spacer having a surface roughness of 0.55 μm, which is then subjected to a cleaning and drying process. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 2.4KGy/s, and the total irradiation dose is 80 KGy.
(4) And (3) quickly putting the irradiated sample into a grafting monomer solution, and carrying out grafting reaction at the temperature of 60 ℃ under the protection of nitrogen for 60 min. The hydrophilic monomer is a mixed monomer of hydroxyethyl acrylate and 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and the molar ratio of the two monomers is 1: 1, the total concentration of the monomers is 0.05 mol/L.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 140 ℃, and the annealing time is 4 h.
(6) And cleaning and vacuum drying the annealed sample.
Comparative example 7
(1) UHMWPE having a molecular mass of 500 tens of thousands is produced as an artificial joint spacer sample having a surface roughness of 0.50 μm, which is then subjected to a cleaning and drying process. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 2.5KGy/s, and the total irradiation dose is 100 KGy.
(4) And (3) quickly putting the irradiated sample into a grafting monomer solution, and carrying out grafting reaction at the temperature of 65 ℃ under the protection of nitrogen for 50 min. The hydrophilic monomer is a mixed monomer of methacrylic acid and 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and the molar ratio of the two monomers is 1: 1, the total concentration of the monomers is 0.7 mol/L.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 90 ℃, and the annealing time is 3 h.
(6) And cleaning and vacuum drying the annealed sample.
Comparative example 8
(1) UHMWPE having a molecular mass of 500 tens of thousands is produced as an artificial joint spacer sample having a surface roughness of 0.44 μm, which is then subjected to a cleaning and drying process. After the treatment, the mixture is placed in an aluminum foil bag for filling nitrogen and isolating oxygen for packaging.
(2) And (3) carrying out electron beam irradiation on the oxygen-isolated packaged sample, wherein the irradiation dose rate is 2.2KGy/s, and the total irradiation dose is 120 KGy.
(4) And (3) quickly putting the irradiated sample into a grafting monomer solution, and carrying out grafting reaction at the temperature of 60 ℃ under the protection of nitrogen for 70 min. The hydrophilic monomer is a mixed monomer of hydroxyethyl acrylate and 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and the molar ratio of the two monomers is 1: 2, the total concentration of the monomers is 0.6 mol/L.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment to generate a three-dimensional crosslinking structure. The annealing temperature is 150 ℃, and the annealing time is 0.5 h.
(6) And cleaning and vacuum drying the annealed sample.
Comparative example 9
(direct irradiation method)
(1) UHMWPE with the molecular mass of 350 ten thousand is selected to prepare an artificial joint gasket sample, the surface roughness result is 0.50 mu m, then ultrasonic cleaning is carried out for many times, and vacuum drying is carried out after the cleaning is finished.
(2) And (3) putting the cleaned and dried sample into a grafting monomer solution, and filling nitrogen and sealing. The hydrophilic monomer is 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and the monomer concentration is 0.6 mol/L.
(3) The encapsulated samples were irradiated with an electron beam at a dose rate of 4.0KGy/s for a total dose of 200 KGy.
(4) And (3) heating and post-treating the irradiated sample, wherein the temperature is controlled at 70 ℃ and the time is 120 min.
(5) And (3) placing the sample subjected to hydrophilic grafting in a vacuum drying oven for annealing treatment, eliminating residual free radicals and generating a three-dimensional crosslinking structure. The annealing temperature is 140 ℃, and the annealing time is 10 h.
(6) And cleaning and vacuum drying the annealed sample.
Some of the parameters of the examples and comparative examples are shown in table 1 below:
TABLE 1
Figure BDA0003334584530000131
(I) surface hydrophilicity test
A drop of pure water (2. mu.L) was dropped onto the surface of the samples of each example and comparative example after the graft modification step, and the water contact angle size was directly measured after each drop (60s) using a Guangdong Beidou precision instruments Co., Ltd. PT-705A water contact angle meter. The test was repeated 10 times for each sample, and the measured water contact angle values were averaged, and the results are shown in table 2 below. Taking example 1 as an example, the surface hydrophilicity test object is a sample subjected to the hydrophilic grafting reaction of step (4) but not subjected to the annealing treatment of step (5).
TABLE 2
Figure BDA0003334584530000132
Figure BDA0003334584530000141
The hydrophilic grafting reaction conditions of examples 1 to 6 and comparative examples 7 to 8 are controlled in the above range, and good hydrophilic grafting can be obtained, so that the sample has a small water contact angle after the graft modification step. Among them, the sample after the graft modification step of example 6 has the smallest water contact angle and the surface hydrophilicity is better.
In comparative example 1 and comparative example 2, since the hydrophilic grafting reaction was not performed, the water contact angle was large and the surface had no hydrophilic property. Comparative example 3 has insufficient graft initiating ability due to small irradiation dose, resulting in poor hydrophilic property. Comparative example 4 since the reaction was carried out at normal temperature, it was difficult to form effective graft. Comparative example 5 controls the hydrophilic grafting reaction time to be too short, resulting in non-ideal hydrophilic grafting effect. The hydrophilic grafting reaction of comparative example 6 has a graft monomer concentration too low to form an effective hydrophilic layer. Comparative example 9 adopts a direct irradiation method, and more monomers are directly irradiated for monomer homopolymerization, so that the grafting rate is reduced, and the hydrophilic modification effect is not good enough.
(II) measurement of swelling degree of Cross-linking
After the UHMWPE is irradiated by electron beams, chemical bonds of molecular chains are broken to form free radicals, and the free radicals are recombined to form a crosslinking structure. The crosslinked UHMWPE can only swell in a corresponding good solvent and can not be dissolved. Thus, the degree of crosslinking of the UHMWPE can be characterized by measuring the volume change before and after swelling. The samples prepared in each example and comparative example were tested for swelling degree using a swelling degree tester POM-HDH8 made by Suzhou minimally invasive osteology (group) Co., Ltd., reference YY/T0813-2010 Standard method for in situ determination of parameters of molecular network of crosslinked ultra-high molecular weight polyethylene (UHMWPE), and the results are shown in Table 3.
TABLE 3
Figure BDA0003334584530000142
Figure BDA0003334584530000151
Comparative example 1 did not undergo irradiation crosslinking, did not produce a crosslinked structure, and had a large swelling value. Comparative examples 2-6 have irradiation and annealing processes, produce effective cross-linked structures, and have small swelling degrees. Comparative example 3 has a smaller irradiation dose and a lower overall degree of crosslinking after annealing. Comparative examples 7 and 8 although effective irradiation was also performed to generate a crosslinked structure, the annealing temperature of comparative example 7 was too low, the annealing time of comparative example 8 was too short, the residual radicals were bound by the molecular chain, the mobility was poor, the radicals could not be recombined, and it was not favorable to eliminate the residual radicals, and thus the degree of crosslinking was not high. Comparative example 9 a cross-linked structure was produced by effective irradiation.
Examples 1 to 6 all produced effective crosslinked structures with a small degree of swelling.
By combining the results of the surface hydrophilicity test and the crosslinking swelling degree test, the surface hydrophilicity and the crosslinking swelling degree of the film can be shown that the film in the embodiments 1 to 6 of the invention has a smaller water contact angle and a smaller swelling degree at the same time, which indicates that the film has better surface hydrophilicity and higher crosslinking degree; while comparative examples 1 to 9 cannot simultaneously achieve both a small water contact angle and a small swelling property.
(III) Friction Performance test
The method is characterized in that an Antopa TRB pin disc friction experiment device is used for testing the friction coefficient and the wear rate, the CoCrMo is adopted as a friction pin and the UHMWPE is adopted as a friction disc according to the reference standard ASTM G99-17, calf serum is added as lubricating liquid for testing under the room temperature condition, the positive pressure is 70N, and the testing frequency is 1 Hz. The friction disks were made of the materials of the examples and comparative examples, respectively, and the friction coefficient and wear rate of the samples of the examples and comparative examples were measured, and the results are shown in table 4.
TABLE 4
Coefficient of friction Wear Rate (mg/MC)
Example 1 0.049 3.8
Example 2 0.041 1.8
Example 3 0.055 3.4
Example 4 0.047 3.2
Example 5 0.051 3.9
Example 6 0.036 1.3
Comparative example 1 0.093 10.3
Comparative example 2 0.083 7.1
Comparative example 3 0.079 6.5
Comparative example 4 0.075 6.6
Comparative example 5 0.077 6.1
Comparative example 6 0.073 6.3
Comparative example 7 0.048 6.9
Comparative example 8 0.050 6.8
Comparative example 9 0.075 6.2
The surfaces of the comparative example 1 and the comparative example 2 have no hydrophilic lubricating property, and the friction coefficient is larger; and comparative example 1 did not undergo a crosslinking reaction and the wear rate was high. Comparative examples 3 to 6 had poor hydrophilic grafting effect and higher friction coefficient. Comparative examples 2, 3, 4, 5 and 6 have improved wear resistance due to irradiation crosslinking, but all have higher wear rates than samples with an effective hydrophilic lubricating layer. Comparative examples 7 and 8 are effectively hydrophilic grafted to reduce the surface friction coefficient and form a certain cross-linked structure, but are not effectively annealed, and a large amount of residual free radicals accelerate oxidation in the abrasion process, so that the abrasion rate is increased. The comparative example 9 adopts a direct irradiation method, most of hydrophilic monomers carry out monomer homopolymerization, the actual grafting rate is low, an effective hydrophilic lubricating layer is difficult to form, and the friction coefficient and the wear rate are high.
The samples prepared in examples 1-6 have a low friction coefficient and a low wear rate. In conclusion, the sample prepared by the method has better surface hydrophilicity and higher crosslinking degree, and further the wear resistance of the sample is improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the patent of the invention is subject to the appended claims, and the description can be used for explaining the contents of the claims.

Claims (10)

1. A preparation method of an ultrahigh molecular weight polyethylene implant is characterized by comprising the following steps:
under the protective atmosphere, carrying out electron beam irradiation treatment on the ultra-high molecular weight polyethylene molded part, wherein the total irradiation dose of the irradiation treatment is 20 KGy-200 KGy;
under the protective atmosphere, placing the formed piece subjected to the irradiation treatment in a hydrophilic monomer solution to perform grafting reaction under the initiation of free radicals generated by the irradiation treatment, wherein the grafting reaction temperature is 50-80 ℃, the grafting reaction time is 30-200 min, and the total concentration of hydrophilic monomers in the hydrophilic monomer solution is 0.1-1.0 mol/L; and
annealing treatment is carried out on the grafted reaction; the temperature of the annealing treatment is 110-160 ℃, and the time is 1-10 h.
2. The method according to claim 1, wherein the irradiation treatment is carried out at an irradiation dose rate of 1KGy/s to 4 KGy/s.
3. The method according to claim 1, wherein the total irradiation dose of the irradiation treatment is 110KGy to 200 KGy.
4. The method according to claim 1, wherein the hydrophilic monomer is at least one selected from the group consisting of hydroxyethyl acrylate, methacrylic acid, acrylic acid and 2-methacryloyloxyethyl phosphorylcholine.
5. The method of claim 4, wherein the hydrophilic monomer is selected from the group consisting of 2-methacryloyloxyethyl phosphorylcholine and hydroxyethyl acrylate, or a mixture thereof.
6. The method according to claim 1, wherein the total concentration of the hydrophilic monomers in the hydrophilic monomer solution is 0.6mol/L to 1.0 mol/L.
7. The process according to any one of claims 1 to 6, wherein the temperature of the grafting reaction is 60 ℃ to 80 ℃ for 40min to 180 min.
8. The method according to any one of claims 1 to 6, wherein the annealing treatment is carried out at a temperature of 140 ℃ to 150 ℃ for 4 hours to 10 hours; and/or
The annealing treatment is carried out under vacuum condition or protective atmosphere.
9. An ultra-high molecular weight polyethylene implant, produced by the method of any one of claims 1 to 8.
10. An artificial joint comprising a first support, a second support, and the ultra high molecular weight polyethylene implant of claim 9; the ultra-high molecular weight polyethylene implant is arranged between the first supporting body and the second supporting body.
CN202111290659.1A 2021-11-02 2021-11-02 Ultra-high molecular weight polyethylene implant, preparation method thereof and artificial joint Pending CN113980324A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202111290659.1A CN113980324A (en) 2021-11-02 2021-11-02 Ultra-high molecular weight polyethylene implant, preparation method thereof and artificial joint
PCT/CN2022/128111 WO2023078165A1 (en) 2021-11-02 2022-10-28 Ultrahigh molecular weight polyethylene implant and preparation method therefor, and artificial joint

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111290659.1A CN113980324A (en) 2021-11-02 2021-11-02 Ultra-high molecular weight polyethylene implant, preparation method thereof and artificial joint

Publications (1)

Publication Number Publication Date
CN113980324A true CN113980324A (en) 2022-01-28

Family

ID=79745910

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111290659.1A Pending CN113980324A (en) 2021-11-02 2021-11-02 Ultra-high molecular weight polyethylene implant, preparation method thereof and artificial joint

Country Status (2)

Country Link
CN (1) CN113980324A (en)
WO (1) WO2023078165A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023078165A1 (en) * 2021-11-02 2023-05-11 苏州微创关节医疗科技有限公司 Ultrahigh molecular weight polyethylene implant and preparation method therefor, and artificial joint

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020107300A1 (en) * 1996-10-02 2002-08-08 Saum Kenneth Ashley Process for medical implant of cross-linked ultrahigh molecular weight polyethylene having improved balance of wear properties and oxidation resistance
CN1503682A (en) * 2001-02-23 2004-06-09 ʷ Cross-linked ultra-high molecular weight polyethylene for use as medical implant
CN102443109A (en) * 2011-09-23 2012-05-09 长春工业大学 Functionalized ultrahigh-molecular-weight polyethylene resin and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2429930C (en) * 2002-06-06 2008-10-14 Howmedica Osteonics Corp. Sequentially cross-linked polyethylene
CN102078227A (en) * 2010-11-24 2011-06-01 南京理工大学 Polyethylene artificial joint capable of improving biocompatibility and tribological property and preparation method thereof
CN102505474B (en) * 2011-11-29 2013-12-18 中国科学院上海应用物理研究所 Modified ultrahigh molecular weight polyethylene fiber and preparation method thereof
CN102604188B (en) * 2012-03-02 2014-02-05 中国科学院宁波材料技术与工程研究所 Antioxidant cross-linked polymer and preparation method thereof
CN103007353B (en) * 2012-12-24 2014-08-20 南京理工大学 Ultrahigh-molecular weight polyethylene composite material for artificial joint and preparation method of ultrahigh-molecular weight polyethylene composite material
CN113980324A (en) * 2021-11-02 2022-01-28 苏州微创关节医疗科技有限公司 Ultra-high molecular weight polyethylene implant, preparation method thereof and artificial joint

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020107300A1 (en) * 1996-10-02 2002-08-08 Saum Kenneth Ashley Process for medical implant of cross-linked ultrahigh molecular weight polyethylene having improved balance of wear properties and oxidation resistance
CN1503682A (en) * 2001-02-23 2004-06-09 ʷ Cross-linked ultra-high molecular weight polyethylene for use as medical implant
CN102443109A (en) * 2011-09-23 2012-05-09 长春工业大学 Functionalized ultrahigh-molecular-weight polyethylene resin and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
顾其胜等: "《透明质酸与临床医学》", 30 November 2003, 第二军医大学出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023078165A1 (en) * 2021-11-02 2023-05-11 苏州微创关节医疗科技有限公司 Ultrahigh molecular weight polyethylene implant and preparation method therefor, and artificial joint

Also Published As

Publication number Publication date
WO2023078165A1 (en) 2023-05-11

Similar Documents

Publication Publication Date Title
JP4963838B2 (en) Low wear sliding member and artificial joint using the same
Ratner et al. Plasma deposition and treatment for biomaterial applications
CA2439270C (en) Cross-linked ultra-high molecular weight polyethylene for use as medical implant
JP5918924B2 (en) Method for manufacturing biocompatible and low wear sliding member
Luan et al. Surface modification of poly (styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via UV-induced graft polymerization of N-vinyl pyrrolidone
JP5028080B2 (en) Low wear sliding member and artificial joint using the same
US20030040807A1 (en) Plasma-assisted surface modification of polymers for medical device applications
US8927616B2 (en) Modified polymeric materials and methods of modifying polymeric materials
CN113980324A (en) Ultra-high molecular weight polyethylene implant, preparation method thereof and artificial joint
WO2007116690A1 (en) Biomaterial, artificial joint using the same and method of producing the same
EP0238508B1 (en) Polymeric intraocular lens material having improved surface properties
JP2002541916A (en) Selective cross-linked polyethylene shaping device
CN115093509B (en) Ultrahigh molecular weight polyethylene material with self-lubricating and antibacterial properties, and preparation method and application thereof
Wang et al. Ceramic femoral heads prevent runaway wear for highly crosslinked polyethylene acetabular cups by third-body bone cement particles
WO2023088085A1 (en) Joint friction pair and joint prosthesis
CN115403814A (en) Ultra-high molecular weight polyethylene with long-acting lubricating articular cartilage-imitating coating and preparation method and application thereof
Morejón et al. Synthesis and characterization of poly (methyl methacrylate-styrene) copolymeric beads for bone cements
WO2022054743A1 (en) Method for forming graft layer, method for producing composite, and treatment liquid for forming graft layer
JP2015073786A (en) Antioxidant and artificial prosthesis member
CN114174392A (en) Method for coating a prosthesis with heat
KR100280352B1 (en) Surface Modifying Method of Ultra High Molecular Weight Polyethylene for Use in Artificial Articular Joint
Kennedy New biomaterials by carbocationic processes
JP7501859B2 (en) Manufacturing method for medical devices
Avilov et al. Composite materials formation for orthopaedic implants
CN118252973A (en) PAEK joint prosthesis with high bonding strength with bone cement and treatment method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20220128

RJ01 Rejection of invention patent application after publication