WO2023088065A1 - Implant de polyéthylène de poids moléculaire très élevé et son procédé de préparation, et prothèse articulaire - Google Patents

Implant de polyéthylène de poids moléculaire très élevé et son procédé de préparation, et prothèse articulaire Download PDF

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WO2023088065A1
WO2023088065A1 PCT/CN2022/128130 CN2022128130W WO2023088065A1 WO 2023088065 A1 WO2023088065 A1 WO 2023088065A1 CN 2022128130 W CN2022128130 W CN 2022128130W WO 2023088065 A1 WO2023088065 A1 WO 2023088065A1
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weight polyethylene
ultra
molecular weight
high molecular
electron beam
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PCT/CN2022/128130
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Chinese (zh)
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俞天白
姚夏睿
潘忠诚
康伟琦
常兆华
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苏州微创关节医疗科技有限公司
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • the present application relates to the technical field of medical devices, in particular to an ultra-high molecular weight polyethylene implant, a preparation method thereof, and a joint prosthesis.
  • ultra-high molecular weight polyethylene Due to its excellent mechanical properties, self-lubrication and biocompatibility, ultra-high molecular weight polyethylene has been widely used in the field of artificial joint replacement to prepare implants for joint prostheses.
  • micron-sized ultra-high molecular weight polyethylene wear particles produced during long-term use of joint prosthesis are the primary cause of osteolysis. Osteolysis in turn leads to aseptic loosening of the joint prosthesis and eventual revision of the joint prosthesis. Therefore, the current research in the field of artificial joint replacement is mainly focused on how to reduce the wear rate of the ultra-high molecular weight polyethylene hip joint liner and knee joint liner when they are used in conjunction with the corresponding femoral head or femoral condyle.
  • ultra-high molecular weight polyethylene acetabular cup liners are often used.
  • the ultra-high molecular weight polyethylene is cross-linked by electron beam irradiation or ray irradiation, and the mobility of the conformational segment of the cross-linked polymer chain is reduced, thereby improving the friction resistance of the ultra-high molecular weight polyethylene acetabular cup lining;
  • cross-linking will reduce some mechanical properties of ultra-high molecular weight polyethylene, such as reducing the toughness and fatigue resistance of highly cross-linked ultra-high molecular weight polyethylene.
  • both the hip joint lining and the knee joint lining need to have good friction resistance and mechanical properties.
  • the present application provides a method for preparing an ultra-high molecular weight polyethylene implant, which includes the following steps:
  • the ultra-high molecular weight polyethylene molded parts are sequentially subjected to electron beam irradiation crosslinking treatment and annealing treatment;
  • the energy of the electron beam used is about 5 MeV to about 10 MeV
  • the irradiation dose is about 70 kGy to about 100 kGy
  • the metal plate is placed on the ultra-high molecular weight polyethylene molded part and the electron beam.
  • the friction surface of the ultra-high molecular weight polyethylene molded part is shielded between the beam sources, the friction surface is placed on the side close to the electron beam source, and the thickness of the metal plate is about 5 mm to about 12 mm.
  • the irradiation temperature of the electron beam irradiation cross-linking treatment is about 20°C to about 120°C.
  • the irradiation temperature of the electron beam irradiation crosslinking treatment is about 60°C to about 120°C.
  • the preparation method also includes the following steps:
  • the ultra-high molecular weight polyethylene molding is heated to about 60°C to about 120°C and kept for about 0.5h to about 1h.
  • the temperature of the annealing treatment is about 120° C. to about 150° C., and the treatment time is about 5 hours to about 10 hours.
  • the metal plate is an aluminum plate or a steel plate.
  • the energy of the electron beam used is about 9 MeV to about 10 MeV
  • the irradiation dose is about 73 kGy to about 77 kGy
  • the thickness of the metal plate is about 8 mm to about 10 mm.
  • the ultra-high molecular weight polyethylene molded part is selected from the molded parts whose thickness from the friction surface to the other side is the same as the thickness of the cross-linked layer of the ultra-high molecular weight polyethylene implant.
  • the present application also provides an ultra-high molecular weight polyethylene implant, which is prepared by the above-mentioned preparation method.
  • the thickness of the cross-linked layer of the ultra-high molecular weight polyethylene implant is about 10 mm to about 20 mm.
  • Another aspect of the present application further provides a joint prosthesis, characterized in that the joint prosthesis comprises a first support (110) and the ultra-high molecular weight polyethylene implant ( 120); the ultra-high molecular weight polyethylene implant (120) cooperates with the first support (110).
  • a second support (130) is also included, and the ultra-high molecular weight polyethylene implant (120) is arranged on the first support (110) and the second support (130). )between.
  • the frictional surface of the ultra-high molecular weight polyethylene implant (120) rubs against the surface of the first support (110) or the second support (130).
  • the joint prosthesis is selected from hip joints, knee joints, condyle joints, elbow joints, wrist joints, finger joints or shoulder joints.
  • FIG. 1 is a schematic structural view of an artificial joint according to an embodiment of the present application.
  • Fig. 2 is the structural representation of the knee joint liner product that embodiment 2 makes;
  • Fig. 3 is the trans vinylidene index inside the hip joint liner product that embodiment 1 and comparative example 1 make vary with the depth of the friction surface;
  • Fig. 4 is the trans vinylidene index inside the knee joint liner product that embodiment 2 and comparative example 2 make vary with the depth of the friction surface;
  • Fig. 5 is the trans-vinylene index inside the hip joint liner products prepared in Examples 3-8 as a function of the distance from the depth of the friction surface;
  • Fig. 6 is the trans-vinylene index inside the knee joint liner products prepared in Examples 9-14 as a function of the depth of the friction surface;
  • Fig. 7 is the trans vinylidene index inside the inner liner of the hip joint prepared in Example 1 and Example 15 along with the variation diagram of the penetration depth;
  • Fig. 8 is a diagram showing the variation of the trans-vinylene index inside the knee pads prepared in Example 2 and Example 16 with the penetration depth.
  • the first support body 120.
  • the ultra-high molecular weight polyethylene implant 130.
  • the second support body 130.
  • the traditional radiation cross-linking method is to control the cross-linking degree of ultra-high molecular weight polyethylene by controlling the irradiation dose of electron beam or gamma ray, but it cannot solve the problem of better wear resistance and good toughness and durability.
  • Mechanical properties such as fatigue properties.
  • ultra-high molecular weight polyethylene products there is no limit to the penetration of gamma ray irradiation, and all ultra-high molecular weight polyethylene products can be cross-linked.
  • the use of 50kGy gamma ray irradiation crosslinking can increase the friction resistance of ultra-high molecular weight polyethylene by nearly 50%, but further increasing the irradiation dose will reduce the mechanical properties of ultra-high molecular weight polyethylene.
  • One embodiment of the present application provides an ultra-high molecular weight polyethylene implant and a preparation method thereof.
  • the prepared ultra-high molecular weight polyethylene implant will be described in detail below in conjunction with the preparation method.
  • One embodiment of the present application provides a method for preparing an ultra-high molecular weight polyethylene implant, including the following step S20.
  • Step S20 Under a protective atmosphere, the ultra-high molecular weight polyethylene molding is subjected to electron beam irradiation crosslinking treatment and annealing treatment in sequence.
  • the energy of the electron beam used is about 5 MeV to about 10 MeV
  • the irradiation dose is about 70 kGy to about 100 kGy
  • the metal plate is placed on the ultra-high molecular weight polyethylene
  • the friction surface of the ultra-high molecular weight polyethylene molding is shielded between the molded part and the electron beam source, and the friction surface is placed on the side close to the electron beam source.
  • the thickness of the metal plate is about 5 mm to about 12 mm.
  • a thickness of about 10 mm to about 20 mm for the crosslinked layer can be achieved.
  • the penetration depth of electron beam irradiation depends on the energy of the electron beam, for example, the penetration depth of an electron beam of 10 MeV is about 3.2 cm.
  • This application controls the energy of the electron beam mainly to change the penetration depth of the electron beam to the sample of the UHMWPE molded part.
  • the metal plate is not used to shield, the radiation dose presents a nearly uniform distribution within the penetration depth range; and through The shielding method of the metal plate can shield the electron beam to a certain extent, so that the energy of the electron beam passing through the metal plate is attenuated to a certain extent.
  • This method is used to control the radiation dose received by the UHMWPE molding sample.
  • Gradient cross-linking is formed inside the ultra-high molecular weight polyethylene implant product, and a gradient cross-linked ultra-high molecular weight polyethylene implant product is prepared.
  • the preparation method of the ultra-high molecular weight polyethylene implant of the present application the ultra-high molecular weight polyethylene molded parts are subjected to electron beam irradiation crosslinking treatment and annealing treatment in sequence, and a metal plate is placed in the electron beam irradiation crosslinking treatment.
  • the friction surface of the ultra-high molecular weight polyethylene molding is blocked between the UHMWPE molded part and the electron beam source, and the friction surface is placed on the side close to the electron beam source; at the same time, by controlling the energy and radiation dose of the electron beam used and the thickness of the metal plate, so that the formed ultra-high molecular weight polyethylene implant product presents a gradient cross-linking within a certain thickness range, and the cross-linking degree of the ultra-high molecular weight polyethylene implant product gradually decreases from the friction surface to the other side , such ultra-high molecular weight polyethylene implant products present a higher degree of cross-linking on the friction surface, which improves the friction resistance of ultra-high molecular weight polyethylene implant products, while the ultra-high molecular weight polyethylene implant products are far away from The bulk of the friction surface achieves a low or no degree of crosslinking.
  • the cross-linking degree of UHMWPE implant products changes in a gradient manner, which also avoids the problem of product deformation caused by internal stress differences that may be caused by sharp changes in cross-link density, making UHMWPE implant products both With good mechanical properties, it can perform excellent in toughness and fatigue resistance, which can improve the safety of long-term use and prolong its service life in artificial hip replacement.
  • the friction surface is placed on the side close to the electron beam source, so that the metal plate is opposite to the friction surface to completely cover the friction surface, thereby realizing the shielding of the metal plate from the friction surface of the UHMWPE molding.
  • the shape and area of the metal plate are set to ensure complete shielding of the product to be irradiated, so as to control the radiation dose received by the UHMWPE molding.
  • the UHMWPE implant has a friction surface for mating.
  • acetabular cup liner blanks and knee joint liner blanks are typically made from ultra-high molecular weight polyethylene and have friction surfaces for mating.
  • the preparation method of the ultra-high molecular weight polyethylene implant of the present application simply realizes the gradient cross-linking of the ultra-high molecular weight polyethylene implant product without changing other processes by means of a metal plate, so that the ultra-high molecular weight polyethylene implant product is both It has better mechanical properties such as wear resistance, better toughness and fatigue resistance; thus, in the application of joint prosthesis, it reduces the generation of wear particles due to friction, thereby reducing the risk of osteolysis and reducing excessive
  • the revision rate of high molecular weight polyethylene implant replacement prolongs its service life in the human body, making it more suitable for artificial joint replacement technology.
  • the preparation method of the ultra-high molecular weight polyethylene implant of the present application does not have strict requirements on the morphology and structure of the ultra-high molecular weight polyethylene molding sample. Under the same conditions, the distance from the friction of the UHMWPE molding sample The radiation dose at the same depth of the surface is nearly equal. It can be understood that the shape and structure of the ultra-high molecular weight polyethylene molding sample can be controlled by the shape and structure of the mold.
  • the gradient cross-linked thickness of the ultra-high molecular weight polyethylene implant product produced by the above preparation method from the friction surface to the other side is about 10 mm to about 20 mm.
  • the gradient cross-linking thickness here refers to the thickness of the product exhibiting gradient cross-linking changes.
  • the ultra-high molecular weight polyethylene implant product forms a cross-linked layer from the friction surface to the other side, which is a gradient cross-linked layer, and the degree of cross-linking of the cross-linked layer gradually decreases from the friction surface to the other side;
  • the thickness of the layer is from about 10 mm to about 20 mm.
  • the other side can be the substrate opposite to the friction surface, that is, the ultra-high molecular weight polyethylene implant product includes a body, one side of the body is the friction surface, and the other side is the substrate.
  • the ultra-high molecular weight polyethylene molding produced by the above preparation method can be selected from the molding whose thickness from the friction surface to the other side is the same as the thickness of the gradient cross-linking (that is, the thickness of the cross-linking layer), so that the formation
  • the ultra-high molecular weight polyethylene implant products exhibit gradient crosslinking from the friction surface to the base.
  • the change rate of the cross-linking degree of the ultra-high molecular weight polyethylene implant product is represented by the change rate of the trans-vinylene index with the depth from the friction surface; The depth from a certain point inside the body product to the friction surface.
  • the relationship between the trans-vinylene index of the ultra-high molecular weight polyethylene implant product and the depth from the friction surface satisfies the following functional relationship:
  • TVI refers to the trans vinylene index (Trans Vinylene Index); D is the depth from the friction surface, which is the value in mm; A is a constant, which depends on the thickness of the metal plate. For example, when the thickness of the metal plate is 8mm, A is about 0.038.
  • the irradiation temperature of the electron beam irradiation crosslinking treatment is about 20°C to about 120°C.
  • the irradiation temperature of the electron beam irradiation crosslinking treatment is the temperature of the ultra-high molecular weight polyethylene molded part during the electron beam irradiation crosslinking treatment. It has been verified that the electron beam irradiation cross-linking treatment can be carried out at room temperature and under the heating conditions of the ultra-high molecular weight polyethylene molded parts, both of which can realize gradient cross-linking. Optionally, under heating.
  • the irradiation temperature of the electron beam irradiation crosslinking treatment is about 60°C to about 120°C.
  • the temperature of the ultra-high molecular weight polyethylene molded parts is subjected to electron beam irradiation crosslinking treatment at this irradiation temperature, and the crosslinking reaction is more likely to occur.
  • the preparation method further includes the following step S10: before the electron beam irradiation cross-linking treatment, heating the ultra-high molecular weight polyethylene molding to about 60° C. to about 120° C. for about 0.5 h to about 1 h.
  • the annealing condition is about 120° C. to about 150° C. for about 5 hours to about 10 hours.
  • the metal plate is aluminum plate or steel plate. It can be understood that the material selection of the metal plate is not limited thereto.
  • the energy of the electron beam used is about 9 MeV to about 10 MeV
  • the irradiation dose is about 73 kGy to about 77 kGy
  • the thickness of the metal plate is about 8 mm to about 10 mm.
  • the maximum cross-linking can be achieved on the friction surface, and the degree of cross-linking inside the product body gradually decreases as the distance from the friction surface gets deeper.
  • Another embodiment of the present application also provides an ultra-high molecular weight polyethylene implant, which is prepared by the above-mentioned preparation method.
  • Yet another embodiment of the present application also provides a joint prosthesis, including a first support body 110 and the above-mentioned ultra-high molecular weight polyethylene implant body 120 .
  • the ultra-high molecular weight polyethylene implant 120 fits with the first support 110 .
  • a second support body 130 is also included, wherein the ultra-high molecular weight polyethylene implant 120 is disposed between the first support body 110 and the second support body 130 .
  • the ultra-high molecular weight polyethylene implant 120 can also only cooperate with one support body (such as the first support body 110 or the second support body 130). At this time, the ultra-high molecular weight polyethylene implant body 120 The friction surface rubs against the surface of the support body.
  • the joint prosthesis 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 joint prostheses include, but are not limited to.
  • the ultra-high molecular weight polyethylene implant may be an acetabular cup liner.
  • the first supporting body 110 and the second supporting body 130 are respectively an acetabular prosthesis and a femoral head prosthesis; the friction surface of the ultra-high molecular weight polyethylene implant 120 is the side close to the femoral head prosthesis.
  • the UHMWPE implant 120 can be a knee joint liner.
  • the first supporting body 110 and the second supporting body 130 are the tibial tray and the femoral condyle prosthesis respectively, and the friction surface of the ultra-high molecular weight polyethylene implant 120 is the side close to the femoral condyle prosthesis.
  • a hip joint liner product is prepared, as shown by UHMWPE implant 120 in FIG. 1 .
  • the ultra-high molecular weight polyethylene acetabular cup liner molding was sealed in an aluminum foil bag in a nitrogen gas atmosphere by using a vacuum-filled inert gas sealing machine. During packaging, the aluminum foil bag is repeatedly evacuated and nitrogen-filled at least three times, and finally the high molecular weight polyethylene acetabular cup liner molding is heat-sealed in the aluminum foil bag in an atmosphere of nitrogen gas.
  • the ultra-high molecular weight polyethylene hip joint liner molded parts encapsulated in nitrogen are subjected to electron beam irradiation cross-linking at room temperature (25 ° C), and the metal plate is placed on the ultra-high molecular weight polyethylene during the electron beam irradiation cross-linking treatment.
  • the friction surface of the molded part of the ultra-high molecular weight polyethylene acetabular cup liner is shielded between the molded part and the electron beam source, and the friction surface is placed on the side close to the electron beam source.
  • the electron beam irradiation dose is 75kGy
  • the annealing temperature after irradiation is 120°C
  • the annealing time is 9h
  • the thickness of the aluminum plate used in the electron beam irradiation process is 8mm.
  • Example 2 It is basically the same as that of Example 1, except that no aluminum plate is used for shielding during electron beam irradiation.
  • Example 2 It is basically the same as that of Example 1, except that the molded part of the ultra-high molecular weight polyethylene acetabular cup liner is replaced by the molded part of the ultra-high molecular weight polyethylene knee joint liner.
  • Example 2 It is basically the same as that of Example 2, except that no aluminum plate is used for shielding during electron beam irradiation.
  • the hip joint liner and knee joint liner products prepared in Examples 1-2 and Comparative Examples 1-2 were tested for the change of internal trans-vinylene index with the depth from the friction surface, referring to the YY/T0814-2010 method, passing Infrared spectroscopy detects the trans-vinylene index (TVI) inside ultra-high molecular weight polyethylene, that is, the ratio of the absorption peak area at 965cm -1 to the total area of absorption peaks between 1330cm -1 and 1396cm -1 to determine Ultra-high molecular weight polyethylene products absorb the radiation dose level of electron beams, which in turn reflects the cross-linking degree of ultra-high molecular weight polyethylene. The results are shown in Figure 1 and Figure 3.
  • TVI trans-vinylene index
  • Fig. 3 shows the change of trans-vinylene index inside the hip joint lining products produced in Example 1 and Comparative Example 1 with and without aluminum plate shielding as a function of the depth from the friction surface.
  • the abscissa is the Depth into Sample, which is the depth from the friction surface, in mm; the ordinate is the Trans Vinylene Index (TVI), the same below.
  • TVI Trans Vinylene Index
  • Fig. 4 shows the changes of the trans-vinylene index inside the knee joint liner products produced in Example 2 and Comparative Example 2 with and without aluminum plate shielding as a function of the depth from the friction surface.
  • Examples 1-2 were shielded by an 8 mm thick aluminum plate, the trans-vinylene index (TVI) gradually decreased with the increase of the depth from the friction surface, showing a nearly linear change, indicating that the irradiated ultra-high molecular weight polyethylene product internally Gradient crosslinking.
  • the degree of cross-linking was higher at the hip and knee pads closer to the friction surface, and lower at the base of the hip and knee pads farther from the friction surface.
  • Example 3 Basically the same as Example 1, the difference is that steel plates are used to replace the aluminum plate in Example 1 during the irradiation process, and the thicknesses of the steel plates used in Examples 3-8 are 1mm, 3mm, 5mm, 8mm, 10mm and 12mm respectively.
  • the part key parameter of embodiment 3 ⁇ 8 is as shown in table 2 below:
  • Example 3 room temperature 10MeV 75kGy Steel plate, 1mm 120°C, 9h
  • Example 4 room temperature 10MeV 75kGy Steel plate, 3mm 120°C, 9h
  • Example 5 room temperature 10MeV 75kGy Steel plate, 5mm 120°C, 9h
  • Example 6 room temperature 10MeV 75kGy Steel plate, 8mm 120°C, 9h
  • Example 7 room temperature 10MeV 75kGy steel plate, 10mm 120°C, 9h
  • Example 8 room temperature 10MeV 75kGy Steel plate, 12mm 120°C, 9h
  • Example 2 It is basically the same as in Example 2, except that the aluminum plate in Example 2 is replaced by a steel plate in the irradiation process, and the thickness of the steel plates used in Examples 9 to 14 are 1mm, 3mm, 5mm, 8mm, 10mm and 12mm respectively.
  • Example 11 room temperature 10MeV 75kGy Steel plate, 5mm 120°C, 9h
  • Example 12 room temperature 10MeV 75kGy Steel plate, 8mm 120°C, 9h
  • Example 13 room temperature 10MeV 75kGy steel plate, 10mm 120°C, 9h
  • Example 14 room temperature 10MeV 75kGy Steel plate, 12mm 120°C, 9h
  • Fig. 5 shows the change of transvinylene index (TVI) with the penetration depth inside the hip joint lining products prepared in Examples 3-8 with different steel plate thicknesses.
  • Fig. 6 shows the change of transvinylene index (TVI) with the penetration depth inside the knee joint pad products prepared in Examples 9-14 with different steel plate thicknesses.
  • the trans vinylidene index (TVI) gradually decreased in the hip joint lining and knee joint lining, showing a nearly linear change, and in the hip joint lining and The degree of cross-linking was higher on the friction surface of the knee liner and lower on the hip liner and base of the knee liner, indicating a gradient of cross-linking within the irradiated product.
  • the transvinylene index (TVI) gradually decreases at the same thickness, indicating that the thicker steel plate has a greater shielding effect on electron beam irradiation.
  • the thickness of the steel plate exceeds 12 mm or more, the electron beam irradiation dose is greatly reduced, and the trans-vinylene index signal is so weak that it cannot be detected.
  • Example 2 It is basically the same as Example 1, except that: before the electron beam irradiation cross-linking step, the ultra-high molecular weight polyethylene hip joint lining molding is heated to 120° C. for 0.5 h, so that the electron beam irradiation cross-linking The coupling was carried out at 120°C.
  • Example 2 It is basically the same as Example 2, the difference is that before the step of electron beam irradiation crosslinking, the ultra-high molecular weight polyethylene knee joint liner molding is heated to 120 ° C for 1 hour to make electron beam irradiation crosslinking Carried out at 120°C.
  • Example 15 120°C for 0.5h 10MeV 75kGy Aluminum plate, 8mm 120°C, 9h
  • Example 16 120°C heat preservation for 1h 10MeV 75kGy Steel plate, 8mm 120°C, 9h
  • Fig. 7 is a diagram showing the variation of trans-vinylene index inside the hip joint linings prepared in Example 1 and Example 15 with the penetration depth under different irradiation temperatures.
  • RT represents normal temperature, corresponding to Example 1; 120°C corresponds to Example 15, and the following are similar.
  • Fig. 8 is a diagram showing the variation of trans-vinylene index inside the knee pads prepared in Example 2 and Example 16 with the penetration depth under different irradiation temperatures.
  • the trans vinylidene index (TVI) presents a gradient change in the hip joint lining and the knee joint lining no matter at room temperature or at 120 °C , the degree of cross-linking was higher on the friction surfaces of the hip liner and knee liner, but lower on the base of the hip liner and knee liner, indicating that gradient cross-linking occurred within the two products .
  • the relative content of transvinylene index (TVI) is higher, indicating that high temperature is more conducive to the crosslinking reaction of ultra-high molecular weight polyethylene.
  • the above examples and comparative examples show that in the process of electron beam irradiation, the irradiation temperature has little influence on the crosslinking degree of ultra-high molecular weight polyethylene, while the influence of the thickness of the metal plate is greater.
  • the thickness of the steel plate reaches more than 5mm, gradient cross-linking can be formed in the ultra-high molecular weight polyethylene hip joint lining and knee joint liner, and the gradient cross-linking density can also be adjusted by the thickness of the steel plate to directly form gradient cross-linking product.
  • Example 2 It is basically the same as Example 1, the difference is that the energy and irradiation dose of the electron beam are different, specifically the energy of the electron beam is 5 MeV, and the irradiation dose is 70kGy.
  • Example 2 It is basically the same as Example 1, except that the energy and radiation dose of the electron beam are different. Specifically, the energy of the electron beam is 8 MeV, the radiation dose is 100 kGy, and a steel plate with a thickness of 8 mm is used for shielding.
  • the energy of the electron beam is 8 MeV
  • the radiation dose is 100 kGy
  • a steel plate with a thickness of 8 mm is used for shielding.
  • Example 2 It is basically the same as in Example 1, except that: before the electron beam irradiation cross-linking step, the ultra-high molecular weight polyethylene hip joint lining molding is heated to 60° C. for 0.5 h, so that the electron beam irradiation cross-linking The association was performed at 60°C.
  • the ultra-high molecular weight polyethylene hip joint lining molded part was heated to 90° C. for 1 hour, so that the electron beam irradiation cross-linking was carried out at 90° C.
  • Example 2 It is basically the same as in Example 1, except that a steel plate with a thickness of 8 mm is used for shielding, and the annealing condition is 130° C. for 5 hours.
  • Example 2 It is basically the same as in Example 1, except that a steel plate with a thickness of 8 mm is used for shielding, and the annealing condition is 150° C. for 10 h.
  • Example 17 room temperature 5MeV 70kGy Aluminum plate, 8mm 120°C, 9h
  • Example 18 room temperature 8MeV 100kGy Steel plate, 8mm 120°C, 9h
  • Example 19 60 °C heat preservation 0.5h 10MeV 75kGy Aluminum plate, 8mm 120°C, 9h
  • Example 20 90°C for 1h 10MeV 75kGy Aluminum plate, 8mm 120°C, 9h
  • Example 21 room temperature 10MeV 75kGy Steel plate, 8mm 130°C, 5h
  • Example 22 room temperature 10MeV 75kGy Steel plate, 8mm 150°C, 10h
  • the friction and wear performance test conditions are cobalt chromium molybdenum ball head (32mm) vs molded acetabular liner, cobalt chromium molybdenum condyle (CR8) vs molded tibial liner, the friction and wear testing machine is displacement control, wear 5 million times, Weigh every 500,000 times.
  • Example 1 80.5 6.15 Comparative example 1 70.0 5.92 Comparative example 3 (not cross-linked) 142.8 12.89 Example 3 70.3 5.98 Example 4 70.2 5.96 Example 5 73.2 5.96 Example 6 80.5 6.17 Example 7 94.8 6.89 Example 8 101.8 7.34 Example 15 78.7 6.08 Example 17 82.5 7.11
  • Example 18 79.7 6.57
  • Example 19 79.6 6.01
  • Example 20 81.6 5.99
  • Example 21 81.5 6.11
  • Example 22 80.8 6.07
  • Example 2 81.0 25.48 Comparative example 2 71.3 20.37 Comparative example 4 (not cross-linked) 142.8 36.45 Example 9 70.8 20.12 Example 10 70.9 20.48 Example 11 73.9 20.56 Example 12 81.1 25.60 Example 13 95.2 30.25 Example 14 105.1 32.87 Example 16 80.5 25.36
  • Comparative Examples 1 and 2 did not use metal plates to shield, resulting in all cross-linked ultra-high molecular weight polyethylene, so although the products of Comparative Examples 1 and 2 have relatively high Low average wear rate, but its impact strength drops more, resulting in insufficient mechanical properties such as impact resistance.
  • Comparative examples 3-4 are uncrosslinked products, although their impact strength is relatively high, but their average wear rate is high and their wear resistance is insufficient.
  • the products of Examples 1-2 have good mechanical properties such as impact resistance and wear resistance.
  • Example 6 Compared with Example 1, in Examples 3 to 8, as the thickness of the metal plate increases, the crosslinking degree of the ultra-high molecular weight polyethylene decreases, so the mechanical properties such as impact resistance are improved, and the wear resistance is slightly decreased.
  • Example 6 except that the steel plate is used instead of the aluminum plate, other conditions are the same as in Example 1, and the performance test results are also similar, indicating that the steel plate and the aluminum plate have similar effects.
  • Examples 9 to 14 are the same, as the thickness of the metal plate increases, the crosslinking degree of ultra-high molecular weight polyethylene decreases, so the mechanical properties such as impact resistance are improved, and the wear resistance is slightly decreased.
  • Example 15 Compared with Example 1, Example 15, Example 19, and Example 20 increased the irradiation temperature, making the crosslinking of the surface easier, so the wear resistance performance was significantly improved, and the mechanical properties such as impact resistance did not decrease significantly.
  • the electron beam energy of embodiment 17, embodiment 18 all declines to some extent, and wherein the radiation dose of embodiment 17 is lower, so the degree of crosslinking reduces and causes mechanical properties such as impact resistance to improve, and wear resistance reduces, and embodiment
  • the irradiation dose of 18 was increased, so the degree of crosslinking did not change significantly, and the mechanical properties and wear properties did not change significantly; the annealing conditions were changed in Example 21 and Example 22, and the performance test results were similar to Example 1.
  • Example 16 increases the irradiation temperature, making the crosslinking of the surface easier, so the wear resistance performance is significantly improved, but the mechanical properties are not significantly reduced.

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

Abstract

La présente demande concerne un implant de polyéthylène de poids moléculaire très élevé et son procédé de préparation, et une prothèse articulaire. Le procédé de préparation comprend les étapes suivantes : la soumission séquentielle d'une pièce moulée en polyéthylène de masse moléculaire ultra-élevée à un traitement de réticulation par irradiation par faisceau d'électrons et un traitement de recuit dans une atmosphère protectrice, pendant le traitement de réticulation par irradiation par faisceau d'électrons, l'énergie d'un faisceau d'électrons utilisé dans celui-ci est d'environ 5 MeV à environ 10 MeV, et la dose d'irradiation de celui-ci est d'environ 70 kGy à environ 100 kGy ; et une plaque métallique est placée entre la pièce moulée en polyéthylène de poids moléculaire très élevé et une source de faisceau d'électrons pour protéger une surface de frottement de la pièce moulée en polyéthylène de poids moléculaire très élevé, la surface de frottement est disposée sur un côté proche de la source de faisceau d'électrons, et l'épaisseur de la plaque métallique est d'environ 5 mm à environ 12 mm.
PCT/CN2022/128130 2021-11-22 2022-10-28 Implant de polyéthylène de poids moléculaire très élevé et son procédé de préparation, et prothèse articulaire WO2023088065A1 (fr)

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CN114292431A (zh) * 2021-11-22 2022-04-08 苏州微创关节医疗科技有限公司 超高分子量聚乙烯植入体及其制备方法和关节假体
CN118165311A (zh) * 2024-03-25 2024-06-11 江苏毅松医疗科技有限公司 一种高交联超高分子量聚乙烯的制备方法、医用级超高分子量聚乙烯的制备方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU3562499A (en) * 1996-10-15 1999-11-01 Orthopaedic Hospital, The Wear resistant surface-gradient cross-linked polyethylene
US20040051213A1 (en) * 2000-12-12 2004-03-18 Muratoglu Orhun K. Selective controlled manipulation of polymers
US20100190882A1 (en) * 2007-01-25 2010-07-29 The General Hosital Corporation Methods for making oxidation-resistant cross-linked polymeric materials
CN101998974A (zh) * 2007-09-04 2011-03-30 史密夫和内修整形外科股份公司 用于支撑表面的超高分子量聚乙烯
US20120041094A1 (en) * 2009-02-20 2012-02-16 Ebru Oral High temperature melting
CN103006354A (zh) * 2012-11-29 2013-04-03 大连理工大学 一种梯度结构人工髋臼臼杯及其制备方法
US20150151866A1 (en) * 2012-05-11 2015-06-04 The General Hospital Corporation Antioxidant-stabilized joint implants
CN207262026U (zh) * 2017-12-13 2018-04-20 山东阳谷巨龙新型材料有限公司 一种新型钢塑复合板材
CN112770789A (zh) * 2020-06-25 2021-05-07 宽岳医疗器材（苏州）有限公司 超高分子量聚乙烯表面梯度交联方法及其应用
US20210237342A1 (en) * 2018-03-19 2021-08-05 Arevo, Inc. Cross-Linkable Thermoplastic Polymeric Materials for Use in Additive Manufacturing
CN114292431A (zh) * 2021-11-22 2022-04-08 苏州微创关节医疗科技有限公司 超高分子量聚乙烯植入体及其制备方法和关节假体

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU3562499A (en) * 1996-10-15 1999-11-01 Orthopaedic Hospital, The Wear resistant surface-gradient cross-linked polyethylene
US6165220A (en) * 1996-10-15 2000-12-26 The Orthopaedic Hospital Wear resistant surface-gradient crosslinked polyethylene
US20040051213A1 (en) * 2000-12-12 2004-03-18 Muratoglu Orhun K. Selective controlled manipulation of polymers
US20100190882A1 (en) * 2007-01-25 2010-07-29 The General Hosital Corporation Methods for making oxidation-resistant cross-linked polymeric materials
CN101998974A (zh) * 2007-09-04 2011-03-30 史密夫和内修整形外科股份公司 用于支撑表面的超高分子量聚乙烯
US20120041094A1 (en) * 2009-02-20 2012-02-16 Ebru Oral High temperature melting
US20150151866A1 (en) * 2012-05-11 2015-06-04 The General Hospital Corporation Antioxidant-stabilized joint implants
CN103006354A (zh) * 2012-11-29 2013-04-03 大连理工大学 一种梯度结构人工髋臼臼杯及其制备方法
CN207262026U (zh) * 2017-12-13 2018-04-20 山东阳谷巨龙新型材料有限公司 一种新型钢塑复合板材
US20210237342A1 (en) * 2018-03-19 2021-08-05 Arevo, Inc. Cross-Linkable Thermoplastic Polymeric Materials for Use in Additive Manufacturing
CN112770789A (zh) * 2020-06-25 2021-05-07 宽岳医疗器材（苏州）有限公司 超高分子量聚乙烯表面梯度交联方法及其应用
CN114292431A (zh) * 2021-11-22 2022-04-08 苏州微创关节医疗科技有限公司 超高分子量聚乙烯植入体及其制备方法和关节假体

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