Classifications

• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/12—Chemical modification
  • C08J7/123—Treatment by wave energy or particle radiation
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
  • A61L2/0005—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts
  • A61L2/0011—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts using physical methods
  • A61L2/0029—Radiation
  • A61L2/0035—Gamma radiation
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
  • A61L2/0005—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts
  • A61L2/0011—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts using physical methods
  • A61L2/0029—Radiation
  • A61L2/0041—X-rays
• • 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
  • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
  • A61L2/0005—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts
  • A61L2/0011—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts using physical methods
  • A61L2/0029—Radiation
  • A61L2/007—Particle radiation, e.g. electron-beam, alpha or beta radiation
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
  • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
  • A61L2/08—Radiation
  • A61L2/081—Gamma radiation
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
  • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
  • A61L2/08—Radiation
  • A61L2/082—X-rays
• • 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
  • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
  • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
  • A61L2/08—Radiation
  • A61L2/087—Particle radiation, e.g. electron-beam, alpha or beta radiation
• • 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
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08J2300/102—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen 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
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2296—Oxides; Hydroxides of metals of zinc
• • 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
  • C08K5/0058—Biocides

Definitions

• the invention relates to fluoropolymer articles that have been irradiated with at least 5 KiloGray of radiation, where the resulting articles have low levels of leachable or extractable fluoride ion.
• the low fluoride ion leaching from the irradiated article is related to the presence of low levels of metalic salts or oxides in the fluoropolymer composition.
• the invention is especially useful for fluoropolymer articles in which the fluoropolymer layer contacts a biological or pharmaceutical fluid, and where the article is subjected to sterilization by irradiation.
• PVDF polyvinylidene fluoride
• Additives are often added to fiuorpolymers to improve their properties. For example: flame retardancy (US 7,642,313), and whiteness after heat processing (adding sodium acetate as described in US 7,045,584 and US 7,012,122). White pigments, such a Ti0 2 and ZnO have been added to improve the fluoropolymer whiteness, the whiteness can be diminished during heat processing.
• Us 7,192,646 describes the use of 5 to 15 percent of acid acceptors in a fluroelastomer used in fuel hose.
• the acid acceptors include magnesium oxide, calcium hydroxide, litharge, dibasic lead phosphte, calcium oxide, and zinc oxide.
• Irradiation of fiuropolymers may be done for several reasons, such grafting of functional groups (such as the grafting of maleic anhydride onto a fluorpolymer as described in US 7,241 ,817), to create branching and enhance properties (US 7,241 ,817), to create branching and enhance properties (US 7,241 ,817), to create branching and enhance properties (US 7,241 ,817), to create branching and enhance properties (US
• Fluoropolymers are known for their stability, and fluoride ion is very difficult to leach or extract from a fluoropolymer.
• fluoropolymers exposed to irradiatoin and other high energy radiation can undergo scission of some polymer bonds, or can create carbon-carbon double bonds (which can cause decoloration), with the release of small amounts of fluoride ions and small fluoride-containing moleculres.
• Other fluorinated compounds used in the polymeriztion of a fluoropolymer, residual monomer, and oligomers can also release fluoride ions and small fluroride-containing molecules.
• other leachable fluorine-containing small molecules include, but are not limited to: HF, fluorine-containing monomers and oligomers, and fluorinated surfactants. The fluoride ion is extremely reactive.
• An added advantage of the invention is that the reduction of the fluoride ion concentration tends to reduce discoloration of the fluoropolymer, leading to a whiter article.
• the invention relates to an irradiated fluoropolymer article comprising at least one fluoropolymer composition layer that will contact a fluid, wherein said fluoropolymer composition comprises at least one fluoropolymer and from 50 to
• the invention further relates to a sterile fluoropolymer article and wherein said fluoropolymer composition comprises from 50 to 50,000 ppm of at least one metal salt or a metal oxide, and the fluoropolymer has been exposed to at least 20 KGray of radiation; wherein said article, when formed into a 2 mil thick bag, and irradiated with 25-50 KGray of gamma radiation, and filled with a 80% strill water for injection/20% ethanol solution, with a suface to liquid volume ratio of 2.2 1 /cm for 14 days at 40°C results in less than 10 ppm of extracted fluoride ion.
• the invention further relates to a process of forming a sterile fluoropolymer article invloving the step of adding from 500 to 50,000 ppm of a metal salt or oxide to a fluoropolymer to form a fluoropolymer composition, followed by irradiation of the flouropolymer composition either before, or preferably after the fluoropolymer composition is formed into and article.
• the invention relates to a fluoropolymer composition containing at least one fluoropolymer and low levels of at least one metal salt or oxide. These compositions have been found to have very low leachable fluoride ions following irradiation.
• the fluoropolymers useful in the invention are those containing at least 50 weight percent of one or more fluoromonomers, preferably at least 75 weight percent of fluoromonomers and more preferably from 80 to 100 weight percent of
• fluoromonomer as used according to the invention means a fluorinated and olefmically unsaturated monomer capable of undergoing free radical polymerization reaction.
• Suitable exemplary fluoromonomers for use according to the invention include, but are not limited to, vinylidene fluoride, vinyl fluoride, trifluoroethylene, tetrafluoro ethylene (TFE), ethylene tetrafluoro ethylene, hexafluoropropylene (HFP), 2,3,3,3 -tetrafluoropropene, and their respective copolymers.
• Preferred fluoropolymers are polyvinylidene fluoride homopolymer
• PVDF polyvinylidene fluoride
• ETFE polyethylene trifluoroethylene
• CTFE chlorothrifluoroethylene
• fluoro-terpolymers are also contemplated, including terpolymers such as those having tetrafluoroethylene, hexafluoropropene and vinylidene fluoride monomer units.
• the fluoropolymer is a polyvinylidene fluoride.
• Polyvinylidene fluoride polymers of the invention include the homopolymer made by polymerizing vinylidene fluoride (VDF), and copolymers, terpolymers and higher polymers of vinylidene fluoride, (referred to herein as a group as "copolymers), where the vinylidene fluoride units comprise greater than 70 percent of the total weight of all the monomer units in the polymer, and more preferably, comprise greater than 75, more preferably greater than 80 weight percent of the total weight of the monomer units.
• VDF vinylidene fluoride
• copolymers terpolymers and higher polymers of vinylidene fluoride
• Copolymers, terpolymers and higher polymers of vinylidene fluoride may be made by reacting vinylidene fluoride with one or more monomers from the group consisting of vinyl fluoride, trifluoroethene, tetrafluoroethene, one or more of partly or fully fluorinated alpha-olefins such as 3,3,3-trifluoro-1-propene, 1,2,3,3,3- pentafluoropropene, 3,3,3,4,4-pentafluoro-1-butene, and hexafluoropropene, 2,3,3,3- tetrafluoropropene (1234yf), the partly fluorinated olefin hexafluoroisobutylene, perfluorinated vinyl ethers, such as perfiuoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoro-n-propyl vinyl ether, and perfluoro-2-prop
• Preferred copolymers include those comprising from about 71 to about 99 weight percent VDF, and correspondingly from about 1 to about 29 percent TFE; from about 71 to 99 weight percent VDF, and correspondingly from about 1 to 29 percent HFP, and from about 71 to 99 weight percent VDF, and correspondingly from about 1 to 29 weight percent chlorotrifluoroethylene (CTFE).
• CTFE chlorotrifluoroethylene
• Most preferred PVDF copolymers include are those having 2 to 30 weight percent of HFP, such as KYNAR FLEX 2850, 2750 and 2500 resins (Arkema Inc.).
• ZnO zinc oxide
• an article formed from this fluoropolymer composition and exposed to radiation is found to have dramatically decreased levels of leachable fluoride ion, with only a small increase in leachable cation.
• the amount of leached Zn cation is proportional to the amount of the addition of the ZnO to the PVDF.
• the salts should be free flowing for handling and processing during extrusion. This also means that their particles would not stick to each other upon exposure to atmospheric moisture. This is important because, in some cases, primary particles are very fine but upon exposure to moisture they would stick to each other and their surface to weight ratio would substancially reduce. Moreover, water soluble salts tend to leach into the water based fluids easily.
• the salts should not be toxic to, and preferrably very compatible with living organisms. If the fluoropolymer composition is used to form the surface of an article in contact with, or containing a fluid that will come in contact with, a biological system, the level of cations must be below levels that are toxic to the living organism. It is known that the leached ions (both anions and cations) could prevent cell growth or have other harmful effects.
• the level of leached fluoride ion should be less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm, even more preferably less than 500 ppb, and most preferably less than 100 ppb following irradiation. It is noted that a level of sodium fluoride of about 1 ppm or less is added by many municipalities to the drinking water supply.
• This level of leachable ions is based on the leachable ions from a 2 mil thick PVDF bag radiated with 25-50 KGray, preferaly 40-50 KGray of gamma radiation with surface to liguid volume ratio of 2.2 1/cm containing a mixture of 80% sterile water for injection (SWFI) and 20% ethanol stored for 14 days at 40°C.
• SWFI sterile water for injection
• leachable fluoride ion While reducing the level of leachable fluoride ion, the level of leachable cations also needs to be minimized below toxic levels for those cations.
• Some anions and cations are known to be present in living organisms, and are required for cell metabolism. These include, with average normal concentrations in human serum; sodium (3200 ppm), calcium (100 ppm), potassium (170 ppm), magnesium (20 ppm) and zinc (1 ppm) cations, as well as sulfate, phosphate, chloride, carbonate, and bicarbonate anions.
• the metal salts most useful in the invention are selected to include cations and anions compatible with living organisms - those having relatively high concentrations in in human serum.
• Preferred anions are magnesium, calcium, potassium, sodium and zinc, while preferred anions include, but are not limited to, phosphate, sulfate, chloride, oxide, acetate, and formate.
• Sodium salts are preferred since the human body can tolerate high levels of sodium ions - though sodium salts also tend to be more water soluble than many other salts - increasing the leachability and also absorbing large amounts of water.
• Calcium and potasium salts both have similar molecular weights, however, calcium has two valence electrons which means that it should be twice as efficient as potassium at similar weight additions.
• Magnesium has the advantage of being almost 40% lighter than sodium and calcium and also has two electron valences however, the concentartion of this ion in the blood is almost 1/5 of calcium.
• Zinc is also a preferred cation, having two valence electrons, though it is almost 60% heavier than calcium.
• nitrate anions are also useful.
• Oxides are a preferred anion since they are not toxic to the human body and are light.
• Acetate, formate, sterate, oxylate and other organic anions are also preferred, since they contain only carbon, hydrogen and oxygen and are generally bio-compatible.
• Zinc oxide is especially preferred since it is a stable, non-hygroscopic, and has a low water solubility.
• Useful salts and oxide of the invention include, but are not limited to: Sodium Salts:
• Magnesium Salts Magnes
• the level of metal salts added to the PVDF ranges from 50 to 50,000 ppm, preferably 100 to 10,000 ppm, and more preferably 500 to 5,000 ppm.
• the lower limit represents the effective level of salt needed to provide a significant decrease in the level of leachable fluoride ion, and other small fluorine-containing molecules, following radiation.
• the upper limit is open-ended, providing a reduction in leachable fluoride ion, however the excess cations may negatively effect other properties of the fluoropolymer composition.
• the fluoropolymer composition of the invention is formed by blending the fluoropolymer with one or more metal salts or oxides.
• the blending can occur in any known manner. Generally the addition of the salt or oxide to the fluoropolymer will occur after polymerization and following any water-washing - especially for water soluble salts.
• the metal salt or oxide could be added into the polymer latex at any point.
• the polymer latex and a salt or oxide solution/suspension could be co-spray dried to form the fluoropolymer composition.
• the metal salt could be added as the sole coagulant, or as a mixture with other coagulants in the coagulation stage of the process.
• the dry fluoropolymer powder could be dry blended with the metal salt or oxide, or the fluropolymer and metal salt or oxide could even be added seperately into a processing unit (such as an extruder) and be melt-blended just prior to pelletization or forming into a final article.
• a processing unit such as an extruder
• the polymer composition could also contain one or more typical additives including, but not limited to, pigments, dyes, fillers, surfactants, flame retardants, antioxidants, heat stabilizers, and other polymers miscible with PVDF, at low levels, generally below 5 wt percent in total, and preferably lower for high-purity applications.
• typical additives including, but not limited to, pigments, dyes, fillers, surfactants, flame retardants, antioxidants, heat stabilizers, and other polymers miscible with PVDF, at low levels, generally below 5 wt percent in total, and preferably lower for high-purity applications.
• the fluoropolymer composition of the invention is formed into articles by known means, such as by extrusion or co-extrusion, coating, injection molding, roto- molding, powder coating, fluidized bed coating and blow molding.
• fluoropolymer composition of the invention is on the side of the article that will be in contact with a fluid - generally the inside surface for a tube, container, bag or vessel; though it could also be on both sides of an article such as a catheter that contacts fluids on both sides.
• An implant would have the fluoropolymer on the outside of the implant.
• the article can be a mono -layer or a multi-layer article.
• the fluoropolymer layer of the article is at least 1 mil in thickness.
• Fluoropolymer articles of the invention include, but are not limited to: containers (including for foods, milk, water, media, blood, solutions for intervenous delivery (IV) and pharmaceuticals), fittings, filters, tubing, bags, capilary tubes, pipettes, syringes, vessels, disposable reactors or reactor liners, connectors, stirrers, pipe, injection-molded articles, and packaging - including food packaging.
• a bag is formed by forming a multilayer film that is then bonded along the edges to another film by heat sealing or radio frequency radiation.
• the fluoropolymer composition is formed into a article by laser sintering, including an article such as a bone or joint replacement.
• Irradiation is generally performed on the article after it is formed, though in some cases, as in polymer grafting, or irradiation for property improvement, the radiation can occur on the polymer powder prior to final fabrication into an article.
• the article is exposed to radiation energy for the purpose of sterilization.
• sterilization or “sterilization”, as used herein is meant that all forms of microbial life are destroyed.
• the exposure to radiation can be prior to contact of the fluropolymer compositoin with a fluid - though it is anticipated that in some cases a bag containing an inner layer of the fluoropolymer composiiton can be formed, and filled with a fluid (such as a serum, saline solution, pharmaceutical or other fluid), and the irradiation of the bag and its contents could be done in a single step.
• Sterilization of the polymer composition of the invention can also include heat sterilization (autoclave).
• Heat energy for a time and intensity to achieve sterilization would generally result in an increase in fluoride ions - yet the composition of the invention would result in the levels of extractable fluoride ion to be below 10 ppm, preferably below 1 ppm, more preferably below 500 ppb, and most preferably below 100 ppb.
• irradiation used in the invention would include, but not be limited to, alpha, beta, and gamma radiation, laser energy, electron beam, x-rays,
• Electron beam (e-beam) and gamma radiation are especially preferred for
• the level of radiation exposure would be greater than 5 KGray, preferably greater than 10 KGray, more preferably from 20-70 KGray for

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• 2012
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