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WO2010057644A1 - Matières à base de polyéthylène - Google Patents

Matières à base de polyéthylène Download PDF

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Publication number
WO2010057644A1
WO2010057644A1 PCT/EP2009/008250 EP2009008250W WO2010057644A1 WO 2010057644 A1 WO2010057644 A1 WO 2010057644A1 EP 2009008250 W EP2009008250 W EP 2009008250W WO 2010057644 A1 WO2010057644 A1 WO 2010057644A1
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WO
WIPO (PCT)
Prior art keywords
cross
linked
molecular weight
composition
polymeric material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2009/008250
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English (en)
Inventor
Ming C. Shen
Werner Schneider
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.)
Zimmer GmbH
Original Assignee
Zimmer GmbH
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 Zimmer GmbH filed Critical Zimmer GmbH
Priority to EP09756680A priority Critical patent/EP2346941A1/fr
Priority to CN200980146547.XA priority patent/CN102307945B/zh
Publication of WO2010057644A1 publication Critical patent/WO2010057644A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

Definitions

  • compositions, articles and methods that include an ultra high molecular weight polyethylene in combination with another polymeric material.
  • certain embodiments are directed to compositions that include an ultrahigh molecular weight polyethylene material in combination with another different polyethylene material to provide a composition that is highly crystalline.
  • Ultra high molecular weight polyethylene is a widely accepted polymer for orthopedic uses such as acetabular liners, tibial inserts, patellae, glenoids, total disc inserts, etc.
  • UHMWPE typically has a molecular weight exceeding 10 6 Daltons.
  • e-beam electron beam
  • a composition comprising an ultra high molecular weight polyethylene material and a cross-linked polymeric material that has a different average molecular weight than an average molecular weight of the ultra high molecular weight polyethylene material.
  • the composition may also include an antioxidant.
  • the composition comprises crystalline and amorphous regions from each of a cross-linked form of the ultra high molecular weight polyethylene material and the cross-linked polymeric material, and wherein the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material is present in a lower amount by weight than the cross-linked form of the ultra high molecular weight polyethylene material.
  • the cross-linked form of ultra high molecular weight polyethylene material and the cross-linked polymeric material are each present in an effective amount to provide at least a bimodal molecular weight distribution in the composition.
  • the first antioxidant is a tocopherol and the cross-linked polymeric material is a different, cross-linked ultra high molecular weight polyethylene material.
  • the crystalline regions comprise first crystalline regions from the cross-linked ultra high molecular weight polyethylene material and second, different crystalline regions from the cross-linked polymeric material.
  • the second, different crystalline regions have a substantially homogenous distribution throughout the first crystalline regions of the composition.
  • the first crystalline regions and the second, different crystalline regions each have a substantially homogenous distribution throughout the composition.
  • the cross-linked polymeric material is present at an amount less than 20% by weight of the composition.
  • the composition further comprises a second antioxidant which is the same as or different than the first antioxidant.
  • the second antioxidant is a tocopherol or a tocotrienol.
  • the cross-linked polymeric material comprises a cross-linked ultra low molecular weight polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material comprises a cross-linked high density polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross- linked polymeric material comprises a cross-linked polyethylene, the first antioxidant comprises vitamin E and the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material comprises a cross-linked medium density polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material comprises a cross-linked low density polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material comprises a cross-linked linear low density polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material comprises a cross-linked very low density polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions comprise at least 62% by volume of the composition.
  • the compositions can further include an additive such as, for example, a biological agent..
  • the crystalline regions together comprise at least 80% by volume of the composition.
  • a cross-linked blend comprising a cross-linked ultra high molecular weight polyethylene material and a cross-linked polymeric material having a different average molecular weight than an average molecular weight of the cross-linked ultra high molecular weight polyethylene material.
  • the composition includes a first antioxidant.
  • the composition can include a mixture comprising the cross-linked polymeric material and a second antioxidant, in which the first antioxidant and the second antioxidant may be the same or different.
  • the composition comprises crystalline and amorphous regions from each of the cross-linked ultra high molecular weight polyethylene material and the cross-linked polymeric material, and wherein the crystalline regions together comprise at least 62% by volume of the cross-linked blend.
  • the cross-linked second polymeric material is present in a lower amount by weight than the cross-linked ultra high molecular weight polyethylene material.
  • the cross-linked ultra high molecular weight polyethylene material and the cross-linked polymeric material are each present in an effective amount to provide at least a bimodal molecular weight distribution in the composition.
  • the second antioxidant is a tocopherol and the polymer material of the cross- linked polymeric material is a different, cross-linked ultra high molecular weight polyethylene.
  • the crystalline regions comprise first crystalline regions from the cross-linked ultra high molecular weight polyethylene and second, different crystalline regions from the cross-linked polymeric material.
  • the second, different crystalline regions have a substantially homogenous distribution throughout the first crystalline regions of the composition.
  • the first crystalline regions and the second, different crystalline regions each have a substantially homogenous distribution throughout the composition.
  • the cross-linked polymeric material is present at an amount less than 20% by weight of the composition.
  • each of the first antioxidant and the second antioxidant is a tocopherol.
  • the first antioxidant and the second antioxidant is each a tocopherol or a tocotrienol with the first antioxidant being different than the second antioxidant.
  • the cross-linked polymeric material comprises a cross-linked ultra low molecular weight polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked high density polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked medium density polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked low density polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked linear low density polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked very low density polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the composition can include an additive such as, for example, a biological agent.
  • the cross-linked polymeric material is present in the composition in a lower amount by weight than the cross-linked ultra high molecular weight polyethylene material.
  • a composition comprising an ultra high molecular weight polyethylene material and a cross-linked polymeric material that has a different average particle size than an average particle size of the ultra high molecular weight polyethylene material.
  • the composition can include a first antioxidant.
  • the composition comprises crystalline and amorphous regions from each of a cross-linked form of the ultra high molecular weight polyethylene material and the cross- linked polymeric material, and wherein the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material is present in a lower amount by weight than the ultra high molecular weight polyethylene material.
  • the cross-linked form of ultra high molecular weight polyethylene material and the cross-linked polymeric material are each present in an effective amount to provide at least a bimodal molecular weight distribution in the composition.
  • the first antioxidant is a tocopherol and the cross-linked polymeric material is a different ultra high molecular weight polyethylene material.
  • the crystalline regions comprise first crystalline regions from ultra high molecular weight polyethylene material and second, different crystalline regions from the cross-linked polymeric material.
  • the second, different crystalline regions have a substantially homogenous distribution throughout the first crystalline regions of the composition.
  • the first crystalline regions and the second, different crystalline regions each have a substantially homogenous distribution throughout the composition.
  • the cross-linked polymeric material is present at an amount less than 20% by weight of the composition.
  • the composition further comprises a second antioxidant which is the same as or different than the first antioxidant.
  • the second antioxidant is a tocopherol or a tocotrienol.
  • the cross-linked polymeric material comprises a cross-linked ultra low molecular weight polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material comprises a cross-linked high density polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material comprises a cross-linked polyethylene, the first antioxidant comprises vitamin E and the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material comprises a cross- linked medium density polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material comprises a cross-linked low density polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material comprises a cross-linked linear low density polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linked polymeric material comprises a cross-linked very low density polyethylene, the first antioxidant comprises vitamin E, and the crystalline regions comprise at least 62% by volume of the composition.
  • the composition can include an additive such as, for example, a biological agent.
  • the crystalline regions of the composition together comprise at least 80% by volume of the composition.
  • a cross-linked blend comprising a cross-linked ultra high molecular weight polyethylene material and a cross-linked polymeric material.
  • the composition includes a first antioxidant and a mixture comprising a cross-linked polymeric material and a second antioxidant,
  • the cross- linked polymeric material has a different average particle size than an average particle size of the cross-linked ultra high molecular weight polyethylene material.
  • the first antioxidant and the second antioxidant may be the same or different.
  • the composition comprises crystalline and amorphous regions from each of the cross-linked ultra high molecular weight polyethylene material and the cross-linked polymeric material, and wherein the crystalline regions together comprise at least 62% by volume of the cross-linked blend.
  • the cross-linked second polymeric material is present in a lower amount by weight than the cross-linked ultra high molecular weight polyethylene material.
  • the cross-linked ultra high molecular weight polyethylene material and the cross-linked polymeric material are each present in an effective amount to provide at least a bimodal molecular weight distribution in the composition.
  • the second antioxidant is a tocopherol and the polymer material of the cross- linked polymeric material is a different, cross-linked ultra high molecular weight polyethylene.
  • the crystalline regions comprise first crystalline regions from the cross-linked ultra high molecular weight polyethylene and second, different crystalline regions from the cross-linked polymeric material.
  • the second, different crystalline regions have a substantially homogenous distribution throughout the first crystalline regions of the composition.
  • the first crystalline regions and the second, different crystalline regions each have a substantially homogenous distribution throughout the composition.
  • the cross- linked polymeric material is present at an amount less than 20% by weight of the composition.
  • each of the first antioxidant and the second antioxidant is a tocopherol.
  • the first antioxidant and the second antioxidant is each a tocopherol or a tocotrienol with the first antioxidant being different than the second antioxidant.
  • the cross-linked polymeric material comprises a cross-linked ultra low molecular weight polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked high density polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked medium density polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked low density polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked linear low density polyethylene, the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the cross-linked polymeric material comprises a cross-linked very low density polyethylene
  • the crystalline regions comprise at least 62% by volume of the composition and the first antioxidant and the second antioxidant each comprises vitamin E.
  • the composition can include at least one additive such as, for example, a biological agent.
  • the cross-linked polymeric material is present in the composition in a lower amount by weight than the cross-linked ultra high molecular weight polyethylene material.
  • a method comprising combining an ultra high molecular weight polyethylene material with an optional antioxidant and a cross-linked polymeric material that has a different average molecular weight than an average molecular weight of the ultra high molecular weight polyethylene material to provide a blend, and cross-linking the blend to provide a composition comprising crystalline and amorphous regions from each of cross-linked ultra high molecular weight polyethylene material and the cross-linked polymeric material, and wherein the crystalline regions together comprise at least 62% by volume of the composition is disclosed.
  • the cross-linking of the blend is performed by exposing the blend to electron beam radiation.
  • the method can include preparing the cross-linked polymeric material by exposing a polymeric material to electron beam radiation.
  • the method can include heating the polymeric material prior to exposure to the radiation.
  • the polymeric material is exposed to the electron beam radiation in the presence of another antioxidant which may be the same as or different than the antioxidant.
  • the method can include mixing the ultra high molecular weight polyethylene material, the antioxidant and the cross-linked polymeric material together until the cross-linked polymeric material is present in a substantially uniform distribution throughout the ultra high molecular weight polyethylene material.
  • the method can include mixing the ultra high molecular weight polyethylene material, the antioxidant and the cross-linked polymeric material together until the cross-linked polymeric material and the antioxidant are each present in a substantially uniform distribution throughout the ultra high molecular weight polyethylene material.
  • the method can include consolidating the blend prior to cross-linking the blend.
  • the method can include forming the consolidated, cross-linked blend into an implant.
  • the method can include sterilizing the formed implant.
  • the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross-linked ultra low molecular weight polyethylene. In other examples, the method can include selecting the polymeric material of the cross- linked polymeric material to be a cross-linked high density polyethylene. In additional examples, the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross-linked polyethylene. In further examples, the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross- linked medium density polyethylene. In certain examples, the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross-linked low density polyethylene.
  • the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross-linked linear low density polyethylene. In other examples, the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross-linked very low density polyethylene. In additional examples, the method can include selecting the antioxidant to be a tocopherol. In some examples, the method can include selecting the antioxidant to be a tocotrienol. In other examples, the method can include mixing the blend with an additive.
  • a method comprising combining an ultra high molecular weight polyethylene material with an optional antioxidant and a cross-linked polymeric material that has a different average particle size than an average particle size of the ultra high molecular weight polyethylene material to provide a blend, and cross-linking the blend to provide a composition comprising crystalline and amorphous regions from each of cross-linked ultra high molecular weight polyethylene material and the cross-linked polymeric material, and wherein the crystalline regions together comprise at least 62% by volume of the composition.
  • the cross-linking of the blend is performed by exposing the blend to electron beam radiation.
  • the method can include preparing the cross-linked polymeric material by exposing a polymeric material to electron beam radiation. In additional embodiments, the method can include heating the polymeric material prior to exposure to the radiation. In other embodiments, the polymeric material is exposed to the electron beam radiation in the presence of another antioxidant which may be the same as or different than the antioxidant. In some embodiments, the method can include mixing the ultra high molecular weight polyethylene material, the antioxidant and the cross-linked polymeric material together until the cross-linked polymeric material is present in a substantially uniform distribution throughout the ultra high molecular weight polyethylene material.
  • the method can include mixing the ultra high molecular weight polyethylene material, the antioxidant and the cross-linked polymeric material together until the cross-linked polymeric material and the antioxidant are each present in a substantially uniform distribution throughout the ultra high molecular weight polyethylene material.
  • the method can include consolidating the blend prior to cross-linking the blend.
  • the method can include forming the consolidated, cross-linked blend into an implant.
  • the method can include sterilizing the formed implant.
  • the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross-linked ultra low molecular weight polyethylene. In other examples, the method can include selecting the polymeric material of the cross- linked polymeric material to be a cross-linked high density polyethylene. In additional examples, the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross-linked polyethylene. In some examples, the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross- linked medium density polyethylene. In additional examples, the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross-linked low density polyethylene.
  • the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross-linked linear low density polyethylene. In other examples, the method can include selecting the polymeric material of the cross-linked polymeric material to be a cross-linked very low density polyethylene. In additional examples, the method can include selecting the antioxidant to be a tocopherol. In some examples, the method can include selecting the antioxidant to be a tocotrienol. In other examples, the method can include mixing the blend with an additive.
  • a method comprising combining a first ultra high molecular weight polyethylene material with a first antioxidant, cross-linking the combined first ultra high molecular weight polyethylene material, combining the cross-linked, first ultra high molecular weight polyethylene material with a second ultra high molecular weight polyethylene material to provide a blend, in which the second ultra high molecular weight polyethylene material has a different average molecular weight than an average molecular weight of the cross-linked, first ultra high molecular weight polyethylene material, combining the blend with a second antioxidant, and cross-linking the combined blend and second antioxidant to provide a composition comprising crystalline and amorphous regions and wherein the crystalline regions together comprise at least 62% by volume of the composition is described.
  • the cross-linking of the combined blend is performed by exposing the blend to electron beam radiation.
  • the method can include cross-linking the combined, first ultra high molecular weight polyethylene material using electron beam radiation.
  • the method can include heating the combined, first ultra high molecular weight polyethylene material prior to exposure to the electron beam radiation.
  • the method can include mixing the blend and the second antioxidant until the cross-linked, first ultra high molecular weight polyethylene material is present in a substantially uniform distribution throughout the second ultra high molecular weight polyethylene material.
  • the method can include mixing the blend and the second antioxidant together until the cross-linked, first ultra high molecular weight polyethylene material and the second antioxidant are each present in a substantially uniform distribution throughout the second ultra high molecular weight polyethylene material.
  • the method can include selecting the first antioxidant and the second antioxidant to be a tocopherol.
  • the method can include consolidating the combined blend and second antioxidant prior to cross- linking the combined blend and second antioxidant.
  • the method can include forming the consolidated, combined blend into an implant.
  • the method can include mixing the cross-linked, combined blend with an additive.
  • a method comprising combining a first ultra high molecular weight polyethylene material with a first antioxidant, cross-linking the combined first ultra high molecular weight polyethylene material, combining the cross-linked, first ultra high molecular weight polyethylene material with a second ultra high molecular weight polyethylene material to provide a blend, in which the second ultra high molecular weight polyethylene material has a different average particle size than an average particle size of the first ultra high molecular weight polyethylene material, combining the blend with a second antioxidant, and cross-linking the combined blend and second antioxidant to provide a composition comprising crystalline and amorphous regions and wherein the crystalline regions together comprise at least 62% by volume of the composition is disclosed.
  • the cross-linking of the combined blend is performed by exposing the blend to electron beam radiation.
  • the method can include cross-linking the combined, first ultra high molecular weight polyethylene material using electron beam radiation.
  • the method can include heating the combined, first ultra high molecular weight polyethylene material prior to exposure to the electron beam radiation.
  • the method can include mixing the blend and the second antioxidant until the cross-linked, first ultra high molecular weight polyethylene material is present in a substantially uniform distribution throughout the second ultra high molecular weight polyethylene material.
  • the method can include mixing the blend and the second antioxidant together until the cross-linked, first ultra high molecular weight polyethylene material and the second antioxidant are each present in a substantially uniform distribution throughout the second ultra high molecular weight polyethylene material.
  • the method can include selecting the first antioxidant and the second antioxidant to be a tocopherol.
  • the method can include consolidating the combined blend and second antioxidant prior to cross-linking the combined blend and second antioxidant.
  • the method can include forming the consolidated, combined blend into an implant.
  • the method can include mixing the cross-linked, combined blend with an additive.
  • a method of facilitating production of an implant comprising providing an ultra high molecular weight polyethylene material, providing a polymeric material having a different average molecular weight than an average molecular weight of the ultra high molecular weight polyethylene, and providing instructions to use the ultra high molecular weight polyethylene material and the polymeric material to produce a composition comprising crystalline and amorphous regions in which crystalline regions together comprise at least 62% by volume of the composition is provided.
  • the method can include providing instructions for using the composition to produce an implant. In other embodiments, the method can include providing instructions for sterilizing the implant. In additional embodiments, the polymeric material having the different average molecular weight is a polyethylene.
  • a method of facilitating production of an implant comprising providing an ultra high molecular weight polyethylene material, providing a polymeric material having a different average particle size than an average particle size of the ultra high molecular weight polyethylene, and providing instructions to use the ultra high molecular weight polyethylene material and the polymeric material to produce a composition comprising crystalline and amorphous regions in which crystalline regions together comprise at least 55% by volume of the composition is disclosed.
  • the method can include instructions for using the composition to produce an implant.
  • the method can include providing instructions for sterilizing the implant.
  • the polymeric material having the different average particle size is a polyethylene.
  • a method of facilitating production of an implant comprising providing a composition comprising a cross-linked ultra high molecular weight polyethylene material and a cross-linked polymeric material having a different average molecular weight than an average molecular weight of the cross-linked ultra high molecular weight polyethylene, in which the composition comprises crystalline and amorphous regions from each of the materials, and in which crystalline regions together comprise at least 62% by volume of the composition is described.
  • a method of facilitating production of an implant comprising providing a composition comprising a cross-linked ultra high molecular weight polyethylene material and a cross-linked polymeric material having a different average particle size than an average particle size of the cross-linked ultra high molecular weight polyethylene, in which the composition comprises crystalline and amorphous regions from each of the materials, and in which crystalline regions together comprise at least 62% by volume of the composition is disclosed.
  • FIG. 1 is an illustration showing a bimodal molecular weight distribution of a composition, in accordance with certain examples
  • FIG. 2 is an illustration showing crystalline regions of a composition, in accordance with certain examples
  • FIG. 3 is a flow chart showing one method of producing the compositions described herein, in accordance with certain examples
  • FIG. 4 is another a flow chart showing a method of producing the compositions described herein, in accordance with certain examples
  • FIG. 5 is a differential scanning calorimetry scan of a mixture of
  • GUR 1020/GUR 1050 using a first heating cycle, a cooling cycle and a second heating cycle, in accordance with certain examples
  • FIG. 6 is a differential scanning calorimetry scan of a mixture of
  • GUR1020/GHR8020 using a first heating cycle, a cooling cycle and a second heating cycle, in accordance with certain examples
  • FIG. 7 is a differential scanning calorimetry scan of a mixture of
  • GUR1050/GHR8020 using a first heating cycle, a cooling cycle and a second heating cycle, in accordance with certain examples
  • FIG. 8 is a differential scanning calorimetry scan of a mixture of
  • GUR1020/GUR4050-3 using a first heating cycle, a cooling cycle and a second heating cycle, in accordance with certain examples.
  • FTG. 9 is a differential scanning calorimetry scan of a mixture of
  • GUR1050/GUR4050-3 using a first heating cycle, a cooling cycle and a second heating cycle, in accordance with certain examples;
  • compositions described herein include a base material, a secondary material present in a lower amount than the base material and optionally an antioxidant.
  • the composition includes crystalline regions and amorphous regions and is characterized by having crystalline regions of 55%, 6O ⁇ 0, 62%, 65%, 70%, 75%, 80%, 85% or more by volume of the composition, with the crystalline regions comprising crystalline regions from each of the base material and the secondary material.
  • Such high crystallinity provides desirable physical and mechanical properties so that the compositions are suitable for use in medical implants.
  • compositions described herein are directed to an ultra high molecular weight polyethylene (UHMWPE) based composition having increased mechanical properties, such as for example wear resistance, oxidation resistance and tribological properties.
  • UHMWPE ultra high molecular weight polyethylene
  • Embodiments of the compositions include two or more different crystalline structures or regions in the composition to provide high crystallinities and improved properties.
  • crystalline regions from one of the materials may have a substantially uniform distribution in crystalline regions from the other material to permit tighter packing of the materials, which can increase the overall mechanical strength of implants including the composition.
  • Certain embodiments described below include mixtures of a UHMWPE, which is referred to in certain instances as the base material, and another polymeric material, which may be a different UHMWPE or may be a non-UHMWPE material and which is referred to in certain instances as a secondary material.
  • the exact difference in the two materials can vary, and, in certain embodiments, the two materials have a different average molecular weight, a different average particle size or both.
  • the combination of the two materials can provide a bimodal molecular weight distribution.
  • the composition can be cross-linked and still possess a crystallinity higher than that observed in cross-linked UHMWPE alone while not being so brittle to be subject to premature cracking or fatigue.
  • the combination of two different crystalline regions can provide high crystallinity while still providing a composition that is not as brittle as compositions having high crystallinities but only a single type of crystal.
  • the compositions described herein can include two polyethylene materials having a different average molecular weight, a different average particle size or both.
  • the compositions can include a first polyethylene, which may or may not be cross-linked, having a first average particle size, and a second polyethylene, which may or may not be cross-linked, having a second average particle size that is different than the first average particle size.
  • the compositions can include a first polyethylene, which may or may not be cross-linked, having a first average molecular weight, and a second polyethylene, which may or may not be cross-linked, having a second average molecular weight that is different than the first average molecular weight.
  • a first polyethylene which may or may not be cross-linked, having a first average molecular weight
  • a second polyethylene which may or may not be cross-linked, having a second average molecular weight that is different than the first average molecular weight.
  • the compositions described herein can include one or more UHMWPE base materials.
  • UHMWPE is a semi crystalline, linear homopolymer of ethylene, which may be produced by stereospecific polymerization with a Ziegler-Natta catalyst at low pressure (6-8 bar) and low temperature (66-80 0 C). The synthesis of nascent UHMWPE results in a fine granular powder. The molecular weight and its distribution can be controlled by process parameters such as temperature, time and pressure.
  • UHMWPE generally has a molecular weight of at least about 2,000,000 g/mol. Suitable UHMWPE materials for use as raw materials may be in the form of a powder or mixture of powders.
  • the UHMWPE material may be prepared almost entirely from UHMWPE powder, or may be formed by combining UHMWPE powder with other suitable materials, solvents, diluents or the like.
  • suitable UHMWPE materials include, but are not limited to, GUR 1020 and GUR 1050 available from Ticona Engineering Polymers.
  • the UHMWPE material may be present in a major amount in the composition.
  • Major amount refers to at least 50% by weight.
  • the UHMWPE base material can be combined with a secondary material that can be a different type of UHMWPE material or a non-UHMWPE material.
  • a secondary material that can be a different type of UHMWPE material or a non-UHMWPE material.
  • FIG. 1 an illustration is shown where a UHMWPE material is mixed with a different polymeric material to provide the shown bimodal molecular weight distribution.
  • the distribution can include, for example, a first maxima 110, which can represent the average molecular weight of the secondary material, and a second maxima 120, which can represent the average molecular weight of the base material.
  • FIG. 1 shows a composition where the secondary material has a lower average molecular weight than the base material
  • the secondary material can have a higher average molecular weight than the base material.
  • different crystalline regions are present in the final composition, with certain crystalline regions from the base material and other crystalline regions from the secondary material.
  • the total volume of the composition attributed to the crystalline regions can be at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or more with the balance of the volume representing amorphous regions.
  • a typical crystallinity value of known polyethylene materials in the presence of an antioxidant is less than 60%.
  • the degree of crystallinity present in the composition may be determined, for example, using differential scanning calorimetry.
  • the crystalline regions of the secondary material can be substantially uniformly distributed within the crystalline regions from the base material.
  • the crystalline regions of the secondary material can be present in a substantially non-uniform distribution throughout the crystalline regions of the base material.
  • FIG. 2 is an illustration showing crystalline and amorphous regions in a composition. The crystalline regions are represented in FIG. 2 as a bar 210.
  • the composition can be used to provide an implant having a cyclic stress intensity of at least 0.75 MPa-m l/2 , 0.9 MPa-m 1/2 or higher. Cyclic stress intensity can be measured, for example, using compact tension (CT) specimens.
  • CT compact tension
  • CT specimens are cuboids with a square side view, having a defined crack in the middle and a hole in the portions above and below the crack to apply the cyclic forces.
  • Cyclic deformation and plasticity mechanisms have been linked to wear processes in hip and knee UHMWPE components. Such components are, specifically in tibial inserts, subjected to high cyclic contact stresses resulting in pitting and delamination associated with fatigue and fracture processes. As reported in literature, these fatigue mechanisms have been related to a yield stress associated with the plastic flow of polymers. Clinical performance of UHMWPE implants has been associated with deformation and plasticity induced damage below the articulation surface due to sliding and high contact stresses.
  • the cyclic stress intensity factor ⁇ K is the characteristic driving parameter for fatigue crack propagation. In diagrams, this is normally plotted against the crack propagation.
  • a suitable measuring method is standardized for example in ASTM E647 - 08 Standard Test Method for Measurement of Fatigue Crack Growth Rates.
  • Expressing fatigue crack propagation as a function of stress intensity factor ⁇ K provides results that are independent of planar geometry, thus enabling exchange and comparison of data obtained from a variety of specimen configurations and loading conditions. Moreover, this feature enables fatigue crack propagation versus stress intensity factor ⁇ K data to be utilized in the design and evaluation of engineering structures.
  • the composition includes two different UHMWPE materials
  • the first UHMWPE material can be GUR1050 and the second UHMWPE material can be GUR 1020, either in native form or in a cross-linked form.
  • the first UHMWPE material can be GUR 1050 and the second UHMWPE material can be cross-linked GUR1050 having an average molecular weight that is different than the GUR1050 of the first material.
  • the first UHMWPE material can be GUR1020 and the second UHMWPE material can be cross-linked GUR1050.
  • the first UHMWPE material can be GUR 1020 and the second UHMWPE material can be cross-linked GUR 1020 having a molecular weight that is different than the GUR 1020 of the first material.
  • Other combinations and UHMWPE materials for use as the base and secondary materials will be readily selected by the person of ordinary skill in the art, given the benefit of this disclosure.
  • the compositions described herein can include a UHMWPE base material and a non-UHMWPE secondary material.
  • the UHMWPE material may be any one or more of the UHMWPE materials described herein or other suitable UHMWPE materials.
  • the non-UHMWPE material is typically a polymeric material and may be based, for example, on ethylene, propylene or other olefinic polymers.
  • Illustrative non-UHMWPE materials that can be used with the UHMWPE base materials include, but are not limited to, non-UHMWPE polyethylenes, polypropylene, thermoplastics, thermosets and other materials.
  • the non-UHMWPE material can be any one or more of an acrylonitrile butadiene styrene polymer, an acrylic polymer, a celluloid polymer, a cellulose acetate polymer, a cycloolefin copolymer, an ethylene-vinyl acetate polymer, an ethylene vinyl alcohol polymer, a fluoroplastic, an ionomer, an acrylic/PVC alloy, a liquid crystal polymer, a polyacetal polymer, a polyacrylate polymer, a polyacrylonitrile polymer, a polyamide polymer, a polyamide-imide polymer, a polyaryletherketone polymer, a polybutadiene polymer, a polybutylene polymer, a polybutylene terephthalate polymer, a polycaprolactone polymer, a polychlorotrifluoroethylene polymer, a polyethylene terephthalate polymer, a polycyclohexylene
  • the average molecular weight or the average particle size, or both is desirably different than the selected UHMWPE material used as the base material.
  • the non-UHMWPE polyethylene material can be any one or more of an ultra low molecular weight polyethylene (ULMWPE), a high molecular weight polyethylene (HMWPE), a high density polyethylene (HDPE), a high density cross-linked polyethylene (HDXLPE), a cross-linked polyethylene (PEX or XLPE), a medium density polyethylene (MDPE), a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE) and a very low density polyethylene (VLDPE).
  • the non-UHMWPE polyethylene material can be cross-linked prior to combining with the UHMWPE material
  • the secondary material that is combined with the base material can be combined with an antioxidant prior to mixing with the base material.
  • the antioxidant can be mixed or blended until a substantially uniform distribution of the antioxidant is present throughout the secondary material.
  • the antioxidant can be doped into, added to or otherwise combined with the secondary material such that a non-uniform distribution of the antioxidant is present in the secondary material.
  • the antioxidant selected for use can be any suitable antioxidant including, but not limited to, a tocopherol such as vitamin E, a tocotrienol, a carotene, a flavinoid, a vitamin, a co-factor or other suitable antioxidants that will be selected by the person of ordinary skill in the art, given the benefit of this disclosure.
  • the amount of antioxidant present can vary and desirably the antioxidant is not present in such a large amount that it would interfere with any processing steps that the secondary material undergoes.
  • the antioxidant can be present from about 0.1-2 weight percent, e.g., 0.2, 0.3, 0.4 or 0.5 weight percent.
  • mixing or blending of the material can be performed using suitable mixing techniques, blending apparatus and the like. For example, physical mixing, mixing with the aid of a solvent, mixing with the aid of a solvent (e.g. CO 2 ) under supercritical temperature and pressure conditions, and ultrasonic mixing are illustrative techniques that can be used. Suitable mixing processes of these types are also described, for example, in U.S. Pat. Nos. 6,448,315 and 6,277,390, the disclosures of which are hereby incorporated by reference.
  • the combined secondary material and antioxidant can be subjected to one or more steps prior to combining with the base material.
  • the combined secondary material and antioxidant can be exposed to radiation or a chemical cross-linking agent to promote cross-linking of the secondary material.
  • the exact form, absorbed dose and dose rate of the radiation can vary, and the radiation used may be, for example, visible light radiation, infrared radiation, ultraviolet radiation, electron beam radiation, gamma radiation, or X-ray radiation.
  • the radiation can be obtained from any suitable source such as an atomic pile, a resonant transformer accelerator, a Van de Graaff electron accelerator, a Linac electron accelerator, a Rhodotron accelerator, a betatron, a synchrotron, a cyclotron, or the like.
  • Illustrative cross-linking dosages may provide a total dose of about 50 kGy to about 200 kGy.
  • the secondary material can be exposed to a series of radiation doses which provide the total dose, whereas in other examples a single radiation dose can be used.
  • exposure of the secondary material to radiation can be performed at room temperature and atmospheric pressure. In other examples, exposure of the secondary material to radiation can be performed at an elevated temperature and atmospheric pressure. For example, it can be desirable to heat the secondary material to a desired temperature prior to cross-linking.
  • Such heating can be performed at atmospheric pressure or can be performed at a pressure greater than or less than atmospheric pressure. Increased temperature and pressures other than atmospheric pressure can assist in the formation of more or fewer crystalline regions within the cross-linked secondary material.
  • a solvent or plasticizer can be present during cross-linking of the secondary material, whereas in other examples, the secondary material can be cross-linked in the absence of a solvent and/or a plasticizer. Depending on the particular material selected for use as the secondary material, it may be desirable to suspend or dissolve the material in a suitable solvent to facilitate cross-linking and any other treatment steps. Once the secondary material is cross-linked, the solvent can be removed or can be included when the cross-linked secondary material is combined with the base material.
  • the cross-linked secondary material can be combined with the base material.
  • the exact amount of each of the materials used can vary and desirably the base material is present in a major amount.
  • the percent ratio of base material:secondary material can vary from about 95:5, 90: 10, 85: 15, 80:20, 75:25, 70:30, 65:45, 60:40, 55:45: 54:46: 53:47: 52:48, 51:49 or any ratio in between these illustrative ratios.
  • the base material can be present in a minor amount with the secondary material being present in a major amount.
  • the base and secondary materials can be blended until a substantially uniform distribution of the cross- linked polymer of the secondary material is present throughout the base material. In other embodiments, the base and secondary materials can be blended until a substantially uniform distribution of each of the cross-linked polymer and the antioxidant of the secondary material is present throughout the base material. In some examples, it can be desirable to mix the base and secondary materials such that a non-uniform distribution of the secondary material in the base material is present.
  • the combined base material and the secondary material can be mixed or blended with an antioxidant, which can be the same or a different antioxidant used with the secondary material.
  • the antioxidant can be any one or more of those antioxidants listed herein including, but not limited to, a tocopherol such as vitamin E, a tocotrienol, a carotene, a flavinoid, a vitamin, a co-factor or other suitable antioxidants that will be selected by the person of ordinary skill in the art, given the benefit of this disclosure.
  • the antioxidant added to the combined base and secondary materials is added in an amount that is substantially the same as the amount added to the secondary material, whereas in other examples, the antioxidant can be added to the combined base and secondary materials in a lower or higher amount. It can be desirable, for example, to add the antioxidant at a higher amount where the resulting composition is intended for use as an implant having a high fatigue strength, e.g., a hip or a knee.
  • the antioxidant added to the combined blend can be added, for example, in an amount equal to, 1.5 times, two times or three times greater than the amount added to the secondary material.
  • about 0.2-5 weight percent antioxidant can be added to the combined blend, e.g., about 0.5, 0.75 or 1.0 weight percent of the antioxidant can be added to the combined blend.
  • the blend of base material, cross-linked secondary material and antioxidant can be exposed to radiation to cross-link the blend.
  • the blend by cross-linking the blend, crystalline regions from the base material and the secondary material are present.
  • the cross-linked base material and the cross- linked secondary material each contribute to the crystalline regions of the cross-linked blend.
  • the crystalline regions of the blend may together comprise at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or more of the total volume of the blend. In certain embodiments, about 10%, 15% or 20% of the crystalline regions are from the secondary material and the balance of the crystalline regions are from the base material.
  • the radiation used to cross-link the blend can vary and in certain instances visible light radiation, infrared radiation, ultraviolet radiation, electron beam radiation, gamma radiation, or X-ray radiation can be used.
  • the radiation can be obtained from any suitable source such as an atomic pile, a resonant transformer accelerator, a Van de Graaff electron accelerator, a Linac electron accelerator, a Rhodotron accelerator, a betatron, a synchrotron, a cyclotron, or the like. Radiation from these sources will produce ionizing radiation such as electrons, protons, neutrons, deuterons, gamma rays, X rays, alpha particles, and beta particles.
  • Illustrative cross-linking dosages may provide a total dose of about 50 kGy to about 200 kGy.
  • the blend can be exposed to radiation administered in a single dose or in multiple doses.
  • each of the secondary material and the blend can be cross- linked using electron beam radiation.
  • the use of electron beam radiation may be particularly desirable to provide a composition having desired physical properties.
  • Electron beam radiation exposure may be performed using conventionally available electron beam accelerators.
  • One commercial source for such an accelerator is IBA Technologies Group, Belgium. Suitable accelerators may produce an electron beam energy between about 2 and about 50 MeV, more particularly about 10 MeV, and are generally capable of accomplishing a selected radiation dose and/or dosage rate.
  • Electron beam exposure may be carried out in a generally inert atmosphere, including for example, an argon, nitrogen, vacuum, or oxygen scavenger atmosphere. Exposure may also be carried out in air under ambient conditions as described herein.
  • the blend of base material, cross-linked secondary material and antioxidant can be exposed to a chemical cross-linking agent to cross-link the blend.
  • the cross-linking agent can be used either alone or in combination with radiation to cross-link the blend.
  • Illustrative cross-linking agents include but are not limited to peroxides such as, for example, dicumyl peroxide or other suitable chemical cross-linking agents that will be selected by the person of ordinary skill in the art, given the benefit of this disclosure.
  • the blend can be formed into bar stock or preforms prior to cross-linking or after cross-linking. For example, it can be desirable to form the blend into a desired shape prior to cross-linking.
  • Such shapes may be produced using molding, compression molding or other suitable techniques that can provide a desired form.
  • post-shaping treatment steps can be performed such that the shaped material is further shaped or machined into a desired final shape, e.g., into a desired implant such as acetabular liners, tibial inserts, glenoids, artificial hips and knees, cups or liners for artificial hips and knees, spinal replacement disks, intraspinous devices, artificial shoulder, elbow, feet, ankle and finger joints, mandibles, and bearings of artificial hearts and the like.
  • the compositions described herein can be used in implants where weight bearing and sliding is desired. Such processing may take place in a low humidity and low oxygen environment to prevent premature oxidation of the part.
  • the material may be used as part of a composite material or may be layered or coated onto another substrate. In other examples, the material may be used as the core of an implant with additional materials layered or coated onto the core.
  • the shaped material can be sterilized according to known protocols such as exposure to gamma sterilization, electron beam sterilization and/or ethylene-oxide gas sterilization.
  • the radiation dose level used to sterilize is typically less than the dose used to cross-link the blend, though any suitable radiation level that can provide sterilization may be used.
  • compositions disclosed herein can be used with one or more additives.
  • the properties and form of the additives can vary and additives may be used to impart a desired color, texture, shape, radioopacity, viscosity or other physical properties to the composition.
  • an additive that can promote or deter cross-linking, depending on the desired level of cross-linking in the final composition can be used.
  • Illustrative cross-linking promoters include, but are not limited to, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate.
  • an antioxidant can be present to reduce the degree of cross-linking.
  • other reagents that can scavenge free radicals can be present to reduce the degree of cross-linking in the composition.
  • the additive may be another polymer, such as the illustrative polymers described herein.
  • the additive used with the compositions described herein may be a biological agent.
  • a biological agent include, but are not limited to, an antibiotic, a steroid, a drug, a growth factor such as bone morphogenic protein, an osteocyte, an osteoclast or other cells, a vitamin, a chondroitin, a glucosamine, a glycosoaminglycan or other biological materials commonly used to in methods to regrow, repair and/or restore bone and/or cartilage injuries.
  • tribological components such as metal and/or ceramic articulating components and/or preassembled bipolar components may be joined with the composition.
  • metal backing e.g. plates or shields
  • surface components such as a trabecular metal, fiber metal, Sulmesh® coatings, meshes, cancellous titanium, and/or metal or polymer coatings may be added to or joined with the composition.
  • radiomarkers or radiopacifiers such as tantalum, steel and/or titanium balls, wires, bolts or pegs may be added.
  • locking features such as rings, bolts, pegs, snaps and/or cements/adhesives may be added.
  • additional components may be used to form sandwich implant designs, radiomarked implants, metal-backed implants to prevent direct bone contact, functional growth surfaces, and/or implants with locking features.
  • Additional suitable components for combining with the compositions described herein to provide an implant having a desired physical structure and/or desired physical features will be readily selected by the person of ordinary skill in the art, given the benefit of this disclosure.
  • the methods described herein can be used to produce a composition without subjecting the composition to post-cross-linking melt annealing. In particular, desirable properties can be achieved in the absence of post-cross-linking melt annealing.
  • melt-annealing can alter the desired level of crystallinity in a non-desired manner.
  • the compositions described herein may be referred to as non-annealed compositions.
  • the compositions described herein can be produced in many different ways. Referring to FIG. 3, a secondary material 302 can be mixed with an antioxidant 304 to provide a mixture or blend 310. The mixture or blend 310 can be exposed to radiation to provide a cross-linked secondary material 320. The cross-linked secondary material 320 is mixed with a UHMWPE material 325 to provide a blend 330.
  • An antioxidant 335 can be mixed with the blend 330 to provide a blend having an antioxidant 340.
  • the blend with antioxidant 340 can then be exposed to radiation to provide a cross-linked blend 345 and provide a resulting composition having at least 55% by volume crystalline regions.
  • the cross-linked blend 345 can then be shaped or formed into an implant 350.
  • the secondary material 402 can be mixed with an antioxidant 404 to provide a mixture or blend 410.
  • the mixture or blend 410 can be exposed to radiation to provide a cross-linked secondary material 420.
  • the cross- linked secondary material 420 is mixed with a UHMWPE material 425 to provide a blend 430.
  • An antioxidant 435 can be mixed with the blend 430 to provide a blend having an antioxidant 440.
  • the blend with antioxidant can then be consolidated to provide a consolidated blend 445.
  • the consolidated blend 445 can be exposed to radiation to provide a cross-linked blend 450 and to provide a resulting composition having at least 55% by volume crystalline regions.
  • the cross-linked blend can then be shaped or formed into an implant at a step 460.
  • the method can include combining a UHMWPE material and a cross-linked polymeric material that is a different material than the UHMWPE material to provide a blend.
  • the cross-linked polymeric material may have a different average molecular weight or a different average particle size than the UHMWPE material, in either a cross-linked or non cross-linked form.
  • an antioxidant can be included in the combination.
  • the method can also include cross-linking the blend to provide a composition comprising crystalline and amorphous regions from each of the UHMWPE material and the cross-linked polymeric material, and wherein the crystalline regions together comprise at least 55% by volume of the composition.
  • the crystalline regions together comprises at least 60%, 65%, 70%, 75%, 80%, 85% by volume or more of the composition.
  • each of the cross-linking steps can be performed using electron beam radiation or one of the cross-linking steps can be performed using gamma radiation or other cross-linking means.
  • the polymeric material can be heated prior to exposure to the radiation to cross-link the polymeric material.
  • the polymeric material can be exposed to the gamma radiation in the presence of another antioxidant which may be the same as or different than the antioxidant.
  • the UHMWPE material, the antioxidant and the cross- linked polymeric material are mixed together until the cross-linked polymeric material is present in a substantially uniform distribution throughout the UHMWPE material.
  • the UHMWPE material, the antioxidant and the cross-linked polymeric material are mixed together until the cross-linked polymeric material and the antioxidant are each present in a substantially uniform distribution throughout the UHMWPE material.
  • the method can include consolidating the blend prior to cross-linking the blend.
  • the method can include forming the consolidated, cross-linked blend into an implant.
  • the method can include sterilizing the formed implant.
  • the method can include selecting the polymeric material of the cross-linked polymeric material to be one or more of a cross-linked ultra high or low molecular weight polyethylene, a cross-linked high density polyethylene, a cross-linked polyethylene, a cross- linked medium density polyethylene, a cross-linked low density polyethylene, a cross-linked linear low density polyethylene, or a cross-linked very low density polyethylene,
  • the antioxidant can be a tocopherol, a tocotrienol or combinations thereof.
  • the method can include mixing the blend with an additive.
  • the compositions described herein can be produced using a method that includes cross-linking a first UHMWPE material optionally in the presence of a first antioxidant.
  • the cross-linked, first UHMWPE material can be combined with a second UHMWPE material that is different than the cross-linked, first UHMWPE material to provide a blend.
  • the second UHMWPE material has a different average molecular weight or a different average particle size than the cross-linked, first UHMWPE material.
  • the blend can be combined with a second antioxidant.
  • the combination can then be cross-linked to provide a composition comprising crystalline and amorphous regions from each of the first and second UHMWPE materials.
  • the crystalline regions together comprise at least 55% by volume of the composition.
  • the crystalline regions together comprises at least 60%, 65%, 70%, 75%, 80%, 85% by volume or more of the composition.
  • each of the cross-linking steps can be performed using electron beam radiation or one of the cross-linking steps can be performed using gamma radiation or other cross-linking means.
  • the method can include heating the combined first UHMWPE material prior to exposure to the radiation.
  • the method can include mixing the blend and the second antioxidant until the cross-linked, first UHMWPE material is present in a substantially uniform distribution throughout the second UHMWPE material.
  • the method can include mixing the blend and the second antioxidant together until the cross-linked, first UHMWPE material and the second antioxidant are each present in a substantially uniform distribution throughout the second UHMWPE material.
  • each of the first antioxidant and the second antioxidant can be a tocopherol, a tocotrienol or combinations thereof.
  • the method can include the combined blend prior to cross-linking. In other examples, the method can include forming the consolidated, combined blend into an implant. In some examples, the method can include mixing the cross-linked, combined blend with an additive.
  • a method of facilitating production of an implant comprises providing a UHMWPE, providing a polymeric material different from the UHMWPE and providing instructions to use the UHMWPE material and the polymeric material to produce a composition comprising crystalline and amorphous regions from each of the UHMWPE material and the polymeric material, and wherein the crystalline regions together comprise at least 55% by volume of the composition.
  • the polymeric material that is different than the UHMWPE can have a different average particle size or a different average molecular weight.
  • the method can include instructions for using the composition in an implant. In other examples, the method can include instructions for sterilizing the implant.
  • the method can include instructions for including one or more additives in the composition. Additional steps to facilitate production of an implant including the compositions disclosed herein will be recognized by the person of ordinary skill in art, given the benefit of this disclosure.
  • a method of facilitating production of an implant comprising providing a composition comprising a cross-linked ultra high molecular weight polyethylene material and a cross-linked polymeric material having a different average molecular weight than an average molecular weight of the cross-linked ultra high molecular weight polyethylene can be performed.
  • the composition comprises crystalline and amorphous regions from each of the materials, and in which crystalline regions together comprise at least 62% by volume of the composition.
  • a method of facilitating production of an implant comprising providing a composition comprising a cross-linked ultra high molecular weight polyethylene material and a cross-linked polymeric material having a different average particle size than an average particle size of the cross-linked ultra high molecular weight polyethylene can be performed.
  • the composition comprises crystalline and amorphous regions from each of the materials, and in which crystalline regions together comprise at least 62% by volume of the composition.
  • Blended polyethylenes were mixed in batch quantities to provide homogenous powder blends. Subsequent powder was direct compression molded to pucks. From each trial series, some of the pucks were subjected to an irradiation process for cross-linking of the material. Cross-linking took place at elevated temperature of 120 0 C with an electron beam dose of 95 kGy. Since the materials were prepared without addition of vitamin E, the materials were melt annealed for saturation of free radicals. All materials were evaluated by tensile testing, impact testing and differential scanning calorimetry in non-cross-linked and cross-linked conditions. The resulting data is listed below in Table 3.
  • FIG. 5 is a DSC scan of a mixture of GUR 1020/GUR 1050 using a first heating cycle, a cooling cycle and a second heating cycle.
  • the crystallinity was measured to be 46.86% during the first heating cycle, and the peak temperatures was measured to be 139.7 0 C.
  • the crystallinity was 44.94% and the peak temperature for a first peak was 120.5 0 C and was 138.5 0 C for a second peak.
  • FIG. 6 is a DSC scan of a mixture of GUR1020/GHR8020 using a first heating cycle, a cooling cycle and a second heating cycle.
  • the crystallinity was measured to be 50.18% during the first heating cycle, and the peak temperature was 134.6 0 C for a first peak and 138.5 0 C for a second peak.
  • the crystallinity was 47.64% and the peak temperature was 131.5 0 C for a first peak and 137.5 0 C for a second peak.
  • FIG. 7 is a DSC scan of a mixture of GUR1050/GHR8020 using a first heating cycle, a cooling cycle and a second heating cycle.
  • the crystallinity was measured to be 52.11% during the first heating cycle, and the peak temperature was 134.4 0 C for a first peak.
  • the crystallinity was 49.40% and the peak temperature was 131.7 0 C for a first peak and 138.2 0 C for a second peak.
  • HG. 8 is a DSC scan of a mixture of GUR1020/GUR4050-3 using a first heating cycle, a cooling cycle and a second heating cycle.
  • the crystallinity was measured to be 47.94% during the first heating cycle, and the peak temperature was 129.5 0 C for a first peak and 139.5 0 C for a second peak.
  • the crystallinity was 45.91% and the peak temperature was 124.9 0 C for a first peak and 138.2 0 C for a second peak.
  • FIG. 9 is a DSC scan of a mixture of GUR1050/GUR4050-3 using a first heating cycle, a cooling cycle and a second heating cycle.
  • the crystallinity was measured to be 47.14% during the first heating cycle, and the peak temperature was 139.7 0 C for a first peak.
  • the crystallinity was 44.86% and the peak temperature was 120.3 0 C for a first peak and 139.2 0 C for a second peak.
  • a composition is produced using a UHMWPE as a base material, a polyethylene powder as a secondary material and vitamin E as an antioxidant.
  • a blend of a polyethylene powder is produced by combining the polyethylene powder with about 0.2 weight percent vitamin E.
  • the combined blend is heated up to about 100 0 C.
  • the heated, combined blend is irradiated four times with electron beam radiation to provide a total dose of 50 kGy to 200 kGy.
  • the resulting cross-linked material is blended with a UHMWPE, e.g., GUR 1020 or other material that is different than the cross-linked polyethylene material, in a ratio of about 20% by weight cross-linked material and 80% by weight UHMWPE.
  • About 0.2 weight percent vitamin E is then added.
  • This blend is then formed into bar or preforms.
  • the formed bars or performs are irradiated with electron beam radiation at a total dose of about 200 kGy.
  • the cross-linked bars or preforms are then machined or shaped into a desired implant, e.g., a hip implant.
  • the implant is optionally sterilized using gamma-sterilization, ethylene oxide gas or other sterilization means.
  • a composition is produced using a UHMWPE as a base material, a polyethylene powder as a secondary material and vitamin E as an antioxidant.
  • a blend of the polyethylene powder is produced by combining the polyethylene powder with about 0.2 weight percent vitamin E.
  • the combined blend is heated up to about 100 0 C.
  • the heated, combined blend is irradiated four times with electron beam radiation to provide a total dose of 50 kGy to 200 kGy.
  • the resulting cross-linked material is blended with a UHMWPE, e.g., GUR1020 or other material that is different than the cross-linked polyethylene, in a ratio of about 20% by weight cross-linked material and 80% by weight UHMWPE.
  • About 0.5 weight percent vitamin E is then added.
  • This blend is then formed into bar or preforms.
  • the formed bars or performs are irradiated with electron beam radiation at a total dose of about 150 kGy.
  • the cross-linked bars or preforms are then machined or shaped into a desired implant, e.g., a knee implant.
  • the implant is optionally sterilized using gamma-sterilization, ethylene oxide gas or other sterilization means.
  • a composition is produced using UHMWPE as a base material, an ultra low molecular weight polyethylene as a secondary material and vitamin E as an antioxidant.
  • a blend of an ultra low molecular weight polyethylene is produced by combining the polyethylene with about 0.1-0.2 weight percent vitamin E. The blend is irradiated one-four times with electron beam radiation to provide a total dose of 50 kGy to 200 kGy.
  • the resulting cross-linked material is blended with a UHMWPE, e.g., GUR1020 or other material that is different than the cross-linked ultra low molecular weight polyethylene, in a ratio of about 10-20% by weight cross-linked ultra low molecular weight polyethylene and 80-90% by weight UHMWPE.
  • a composition is produced using UHMWPE as a base material, a cross-linked high density polyethylene as a secondary material and vitamin E as an antioxidant.
  • a blend of the cross-linked high density polyethylene is produced by combining the polyethylene with about 0.1-0.2 weight percent vitamin E.
  • the resulting blend is blended with a UHMWPE, e.g., GUR 1020 or other material that is different than the cross-linked high density polyethylene, in a ratio of about 10-20% by weight cross-linked high density polyethylene and 80-90% by weight UHMWPE.
  • About 0.2-0.5 weight percent vitamin E is then added. This blend is then formed into bar or preforms.
  • the formed bars or preforms are irradiated with electron beam radiation one to four times at a total dose of about 50-200 kGy.
  • the cross-linked bars or preforms are then machined or shaped into a desired implant.
  • the implant is optionally sterilized using gamma-sterilization, ethylene oxide gas or other sterilization means.
  • a composition is produced using UHMWPE as a base material, a high density polyethylene as a secondary material and vitamin E as an antioxidant.
  • a blend of the high density polyethylene is produced by combining the polyethylene with about 0.1-0.2 weight percent vitamin E. The blend is irradiated one-four times with electron beam radiation to provide a total dose of 50 kGy to 200 kGy.
  • the resulting cross-linked material is blended with a UHMWPE, e.g., GUR1020 or other material that is different than the cross-linked high density polyethylene, in a ratio of about 10-20% by weight cross-linked high density polyethylene and 80-90% by weight UHMWPE. About 0.2-0.5 weight percent vitamin E is then added.
  • This blend is then formed into bar or preforms.
  • the formed bars or preforms are irradiated with electron beam radiation one-four times at a total dose of about 50-200 kGy.
  • the cross-linked bars or preforms are then machined or shaped into a desired implant.
  • the implant is optionally sterilized using gamma-sterilization, ethylene oxide gas or other sterilization means.
  • a composition is produced using UHMWPE as a base material, a medium density polyethylene as a secondary material and vitamin E as an antioxidant.
  • a blend of the medium density polyethylene is produced by combining the polyethylene with about 0.1-0.2 weight percent vitamin E.
  • the blend is irradiated one to four times with electron beam radiation to provide a total dose of 50 kGy to 200 kGy.
  • the resulting cross-linked material is blended with a UHMWPE, e.g., GUR1020 or other material that is different than the cross- linked medium density polyethylene, in a ratio of about 10-20% by weight cross-linked medium density polyethylene and 80-90% by weight UHMWPE.
  • About 0.2-0.5 weight percent vitamin E is then added.
  • This blend is then formed into bar or preforms.
  • the formed bars or preforms are irradiated with electron beam radiation one to four times at a total dose of about 50-200 kGy.
  • the cross-linked bars or preforms are then machined or shaped into a desired implant.
  • the implant is optionally sterilized using gamma-sterilization, ethylene oxide gas or other sterilization means.
  • a composition is produced using UHMWPE as a base material, a low density polyethylene as a secondary material and vitamin E as an antioxidant.
  • a blend of the low density polyethylene is produced by combining the polyethylene with about 0.1-0.2 weight percent vitamin E.
  • the blend is irradiated one to four times with electron beam radiation to provide a total dose of 50 kGy to 200 kGy.
  • the resulting cross-linked material is blended with a UHMWPE, e.g., GUR 1020 or other material that is different than the cross-linked low density polyethylene, in a ratio of about 20% by weight cross-linked low density polyethylene and 80% by weight UHMWPE.
  • About 0.2-0.5 weight percent vitamin E is then added.
  • This blend is then formed into bar or preforms.
  • the formed bars or preforms are i ⁇ -adiated with electron beam radiation one to four times at a total dose of about 50-200 kGy.
  • the cross-linked bars or preforms are then machined or shaped into a desired implant.
  • the implant is optionally sterilized using gamma-sterilization, ethylene oxide gas or other sterilization means.
  • a composition is produced using UHMWPE as a base material, a linear low density polyethylene as a secondary material and vitamin E as an antioxidant.
  • a blend of the linear low density polyethylene is produced by combining the polyethylene with about 0.1-0.2 weight percent vitamin E. The blend is irradiated one to four times with electron beam radiation to provide a total dose of 50 kGy to 200 kGy.
  • the resulting cross-linked material is blended with a UHMWPE, e.g., GUR1020 or other material that is different than the cross- linked linear low density polyethylene, in a ratio of about 10-20% by weight cross-linked linear low density polyethylene and 80-90% by weight UHMWPE. About 0.2-0.5 weight percent vitamin E is then added.
  • This blend is then formed into bar or preforms.
  • the formed bars or preforms are irradiated with electron beam radiation one to four times at a total dose of about 50-200 kGy.
  • the cross-linked bars or preforms are then machined or shaped into a desired implant.
  • the implant is optionally sterilized using gamma-sterilization, ethylene oxide gas or other sterilization means.
  • a composition is produced using UHMWPE as a base material, a very low density polyethylene as a secondary material and vitamin E as an antioxidant.
  • a blend of the very low density polyethylene is produced by combining the polyethylene with about 0.1-0.2 weight percent vitamin E. The blend is irradiated one to four times with electron beam radiation to provide a total dose of 50 kGy to 200 kGy.
  • the resulting cross-linked material is blended with a UHMWPE, e.g., GUR1020 or other material that is different than the cross- linked very low density polyethylene, in a ratio of about 10-20% by weight cross-linked very low density polyethylene and 80-90% by weight UHMWPE. About 0.2-0.5 weight percent vitamin E is then added.
  • This blend is then formed into bar or preforms.
  • the formed bars or preforms are irradiated with electron beam radiation one to four times at a total dose of about 50-200 kGy.
  • the cross-linked bars or preforms are then machined or shaped into a desired implant.
  • the implant is optionally sterilized using gamma-sterilization, ethylene oxide gas or other sterilization means.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne, selon des modes de réalisation, des compositions de polymère comprenant une matière de base, une matière secondaire et un antioxydant. La composition comprend également des régions cristallines et des régions amorphes, les régions cristallines constituant au moins 62 % en volume de la composition. Dans certains modes de réalisation, la matière de base est une matière en polyéthylène de masse moléculaire très élevée et la matière secondaire est une matière en polyéthylène qui est différente de la matière de base.
PCT/EP2009/008250 2008-11-20 2009-11-19 Matières à base de polyéthylène Ceased WO2010057644A1 (fr)

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EP09756680A EP2346941A1 (fr) 2008-11-20 2009-11-19 Matières à base de polyéthylène
CN200980146547.XA CN102307945B (zh) 2008-11-20 2009-11-19 聚乙烯材料

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ITMI20121315A1 (it) * 2012-07-27 2014-01-28 Versalis Spa Composizione stabilizzata comprendente omopolimeri o copolimeri dell'etilene ed antiossidanti naturali
WO2014016336A1 (fr) * 2012-07-27 2014-01-30 Versalis S.P.A Composition stabilisée comprenant des homopolymères ou des copolymères de l'éthylène et des antioxydants naturels
US9534105B2 (en) 2012-07-27 2017-01-03 Versalis S.P.A. Stabilized composition comprising homopolymers or copolymers of ethylene and natural antioxidants

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CN102307945A (zh) 2012-01-04
US9745462B2 (en) 2017-08-29
EP2346941A1 (fr) 2011-07-27
US20100137481A1 (en) 2010-06-03

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