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
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
  • C08K5/3417—Five-membered rings condensed with carbocyclic rings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/02—Making granules by dividing preformed material
  • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/12—Making granules characterised by structure or composition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/16—Auxiliary treatment of granules
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
  • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
  • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
  • B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
• • 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
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/203—Solid polymers with solid and/or liquid additives
• • 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
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
  • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
• • 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
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • 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
  • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • 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
  • C08K3/02—Elements
  • C08K3/08—Metals
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

• Oxygen scavengers are believed to react with oxygen that is trapped in the package or that permeates from outside of the package, thus extending to life of package contents.
• packages include films, bottles, containers, and the like.
• Food, beverages (such as beer and fruit juices), cosmetics, medicines, and the like are particularly sensitive to oxygen exposure and require high barrier properties to oxygen to preserve the freshness of the package contents and avoid changes in flavor, texture and color.
• transition metal catalysts such as cobalt II neodecanoate (“CoNDA”) or octoate (U.S. Pat. No. 6,083,585; U.S. Pat. No. 7,097,890; Devlieghere F., Vermeiren L., Debevere J. (2004) International Dairy Journal, 14: 273-285), in order to accelerate the scavenging rate.
• CoNDA cobalt II neodecanoate
• octoate U.S. Pat. No. 6,083,585; U.S. Pat. No. 7,097,890; Devlieghere F., Vermeiren L., Debevere J. (2004) International Dairy Journal, 14: 273-285
• oxygen scavenging compositions that can be manufactured in a form that is easier to handle, amenable to milling, and can be combined with a powdered oxygen scavenger composition for use as a single component in the manufacturing process of packaging materials and other articles.
• the invention in one aspect, relates to oxygen scavenging polymer compositions, methods of making the compositions, articles prepared from the compositions, and methods of making the articles.
• transition metal master batch compositions comprising: (a) a polymer carrier; and (b) a transition metal composition dispersed in the solid polymer carrier; wherein the transition metal composition is present in an amount greater than about 30,000 ppm (by metal) based on the weight of the transition metal master batch composition.
• transition metal compact compositions comprising: (a) an oxygen scavenger composition; and (b) a transition metal master batch composition dispersed in the oxygen scavenger composition; wherein the oxygen scavenger composition is present in an amount greater than about 85 weigh percent; wherein the transition metal master batch composition comprises: (i) a polymer carrier; and (ii) a transition metal composition dispersed in the solid polymer carrier; wherein the transition metal composition is present in an amount greater than about 30,000 ppm (by metal) based on the weight of the transition metal master batch composition.
• a transition metal master batch composition comprising the step of extruding a transition metal master batch composition, the composition comprising: (a) a polymer carrier; and (b) a transition metal composition; wherein the transition metal composition is present in an amount greater than about 30,000 ppm (by metal) based on the weight of the transition metal master batch composition.
• transition metal compacted pellets comprising the steps of (1) extruding a transition metal master batch composition, the composition comprising: (a) a solid polymer carrier; and (b) a transition metal composition; wherein the transition metal composition is present in an amount greater than about 30,000 ppm (by metal) based on the weight of the transition metal master batch composition; (2) processing the extrudate comprising the transition metal master batch composition to particulate form by milling or pulverization, wherein the particle size is less than about 5.0 mm screen size; (3) preparing a homogeneous mixture comprising the particulate transition metal master batch composition and a powdered oxygen scavenger composition, wherein the powdered oxygen scavenger composition is present in an amount greater than about 85 weigh percent based on the combined weight of the particulate transition metal master batch composition and the powdered oxygen scavenger composition; and (4) forming compacted single pellets from the homogeneous mixture comprising the particulate transition metal master batch composition
• Also disclosed are methods for the manufacture of an article comprising the steps of (1) combining polyester pellets with transition metal compacted pellets in a melt processing zone; wherein the transition metal compacted pellets comprise an oxygen scavenger composition present in an amount greater than about 85 weight percent and a transition metal master batch composition present in an amount greater than about 10 weight percent; wherein the let down ratio of the transition metal compacted pellets is greater than about 1%; (2) forming a melt; and (3) extruding the melt, thereby forming the article.
• compositions of the invention Disclosed are the components to be used to prepare the compositions of the invention as well as the compositions themselves to be used within the methods disclosed herein.
• these and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds can not be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary.
• a “polymer” when referred to in the specification and the claims, the term should be construed to include not just the reaction product of a single polymerization, but also to blends or physical mixtures of more than one polymer, since the thermoplastic polymers described herein may be satisfactorily blended with one another so that it may be difficult to afterward identify the source.
• a “PET homopolymer or copolymer” (sometimes hereinafter described simply as a “PET polymer”) should be construed, for example, to include both the product of a single polymerization as well as mixtures of more than one PET homopolymer or copolymer.
• a “polyolefin polymer” or a “polybutadiene homopolymer or copolymer” should be construed, for example, to include both the reaction product of a single polymerization as well as mixtures of more than one polybutadiene homopolymer or copolymer.
• references to a composition or a polymer blend containing “an” ingredient or “a” polymer is intended to include other ingredients or other polymers, respectively, in addition to the one named.
• the oxygen-scavenging polymer may either be added neat or as a concentrate, unless the context indicates otherwise.
• the oxygen-scavenging polymer may be added as a copolycondensate.
• Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
• the terms “optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
• the term “substantially” means that the subsequently described event or circumstance completely occurs or that the subsequently described event or circumstance generally, typically, or approximately occurs.
• the agent need not be completely released. Rather, this term conveys to a person skilled in the relevant art that the agent need only be released to an extent that an effective amount is no longer unreleased.
• polymer refers to a relatively high molecular weight organic compound, natural or synthetic, whose structure can be represented by a repeated small unit, the monomer (e.g., polyethylene, rubber, cellulose). Synthetic polymers are typically formed by addition or condensation polymerization of monomers. The number of monomers/constitutional units within a given polymer may vary widely, ranging, for example, from 5 to 10 to 25 to 50 to 100 to 1000 to 10,000 or more monomer units.
• the term “monomers” may refer to the free monomers and those that are incorporated into polymers, with the distinction being clear from the context in which the term is used.
• homopolymer refers to a polymer formed from a single type of monomer are called homopolymers
• copolymer refers to a polymer formed from two or more different repeating units (monomer residues).
• the two or more types of monomers within a given copolymer may be present in any of a variety of distributions including random, statistical, gradient and periodic (e.g., alternating) distributions, among others.
• One particular type of copolymer is a “block copolymer,” which as used herein is a copolymer that contains two or more polymer chains of different composition, which chains may be selected from homopolymer chains and copolymer chains (e.g., random, statistical, gradient or periodic copolymer chains).
• a polymer “chain” is a linear assembly of monomers and may correspond to an entire polymer or to a portion of a polymer.
• a copolymer can be an alternating copolymer, a random copolymer, a block copolymer, or a graft copolymer. It is also contemplated that, in certain aspects, various block segments of a block copolymer can themselves comprise copolymers.
• polyester polymer refers to a condensation polymer in which more than 50 percent of the groups connecting repeat units are ester groups.
• polyesters may include polyesters, poly(ester-amides) and poly(ester-imides), so long as more than half of the connecting groups are ester groups.
• suitable polyester polymers can have at least 70% of the connecting groups as esters.
• suitable polyester polymers can have at least 90% of the connecting groups as ester.
• polyester polymers can have essentially all of the connecting groups as esters. The proportion of ester connecting groups can be estimated to a first approximation by the molar ratios of monomers used to make the polyester.
• polyethylene terephthalate and “PET” refer to a polyester polymer in which the diol repeat units are from ethylene glycol and the dicarboxylic acid repeat units are from terephthalic acid. These terms are meant to include PET no matter how prepared.
• a monomer used in the preparation of PET can be synthesized by the esterification reaction between terephthalic acid and ethylene glycol with water as a byproduct.
• a monomer used in the preparation of PET can be prepared by the transesterification reaction between ethylene glycol and dimethyl terephthalate with methanol as a byproduct. Polymerization can be through a polycondensation reaction of the monomers with ethylene glycol as the byproduct.
• PET or polyethylene terephthalate are meant to include polyethylene terephthalate polymers which are reacted with minor, e.g., less than about 20 percent by weight of the polymer, amounts of modifying agents.
• modifying agents include various diols such as 1,4 butane diol, cyclohexane dimethanol and 1,3 propane diol.
• Other modifying agents include various diacids such as isophthalic acid, adipic acid, 2,6 naphthalene dicarboxylic acid and p-hydroxy benzoic acid. Minor amounts of chain branching agents and/or chain terminating agents may also be used.
• chain branching agents include, for example, polyfunctional acids and/or polyfunctional alcohols such as trimethylol propane and pentaerythritol.
• Chain terminating agents include monofunctional alcohols and/or monofunctional carboxylic acids such as stearic acid and benzoic acid. Mixtures of the chain branching and chain terminating agents may also be used.
• PET which contains such chain branching agents and chain terminating agents is described in U.S. Ser. No. 894,674 filed Apr. 10, 1978 (now U.S. Pat. No. 4,161,579) by Edelman et al and entitled “Extrusion Grade Polyethylene Terephthalate”. The disclosure of this patent application is hereby incorporated by reference.
• polyethylene terephthalate and “PET” are meant to include polyethylene terephthalate polymers containing minor amounts of modifying agents or chain branching agents, the remainder of this specification, for purposes of illustration, is generally directed to PET which does not contain these modifying agents or chain branching agents.
• PET polyethylene terephthalate
• PET refers to a thermoplastic polyester resin that can exist both as an amorphous (transparent) and as a semi-crystalline (opaque and white) material.
• PET can also exist as a semicrystalline transparent material, as used in the side walls of PET bottles. In such aspects, the crystals are smaller than the wavelength of visible light and thus do not make the material opaque and white.
• PET polyethylene terephthalate
• PET can be provided as a copolymer having, in addition to terephthalic acid residues and ethylene glycol residues, additional isophthalic acid residues and/or cycloheanedimethanol residues. It is also understood that PET polymer and/or copolymer can be provided as part of a polymer blend.
• ppm is parts per million by weight.
• a residue of a chemical species refers to the moiety that is the resulting product of the chemical species in a particular reaction scheme or subsequent formulation or chemical product, regardless of whether the moiety is actually obtained from the chemical species.
• an ethylene glycol residue in a polyester refers to one or more —OCH 2 CH 2 O— units in the polyester, regardless of whether ethylene glycol was used to prepare the polyester.
• a sebacic acid residue in a polyester refers to one or more —CO(CH 2 ) 8 CO— moieties in the polyester, regardless of whether the residue is obtained by reacting sebacic acid or an ester thereof to obtain the polyester.
• a very close synonym of the term “residue” is the term “radical,” which as used in the specification and concluding claims, refers to a fragment, group, or substructure of a molecule described herein, regardless of how the molecule is prepared.
• radical refers to a fragment, group, or substructure of a molecule described herein, regardless of how the molecule is prepared.
• a 2,4-thiazolidinedione radical in a particular compound has the structure
• radical for example an alkyl
• substituted alkyl can be further modified (i.e., substituted alkyl) by having bonded thereto one or more “substituent radicals.”
• the number of atoms in a given radical is not critical to the present invention unless it is indicated to the contrary elsewhere herein.
• a structure of a compound can be represented by a formula:
• n is typically an integer. That is, R n is understood to represent five independent substituents, R n(a) , R n(b) , R n(c) , R n(d) , R n(e) .
• independent substituents it is meant that each R substituent can be independently defined. For example, if in one instance R n(a) is halogen, then R n(b) is not necessarily halogen in that instance.
• the term “substituted” is contemplated to include all permissible substituents of organic compounds.
• the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds.
• Illustrative substituents include, for example, those described below.
• the permissible substituents can be one or more and the same or different for appropriate organic compounds.
• the heteroatoms, such as nitrogen can have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms.
• substitution or “substituted with” include the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc.
• the invention relates to transition metal master batch compositions comprising (a) a polymer carrier; and (b) a transition metal composition dispersed in the solid polymer carrier; wherein the transition metal composition is present in an amount greater than about 30,000 ppm (by metal) based on the weight of the transition metal master batch composition.
• the transition metal master batch composition advantageously achieves a high load level of a transition metal composition dispersed in a carrier polymer.
• the transition metal master batch compositions provide a transition metal oxygen scavenging catalyst in an easy to handle solid that can be processed to a form with desired solid handling characterists.
• the transition metal master batch composition can be milled, pelletized, pulverized, or powdered to appropriate size and solid handling characteristics.
• the transition metal composition can be readily milled to a size suitable for blending, e.g. less than about 1.0 mm, with another material, e.g. a powdered oxygen scavenger, for use in co-compaction and other applications.
• another material e.g. a powdered oxygen scavenger
• the transition metal master batch compositions of the invention make feasible co-compaction of a transition metal compostion with a powdered oxygen scavenger.
• the invention also relates to compositions comprising a transition metal compact composition
• a transition metal compact composition comprising: (a) an oxygen scavenger composition; and (b) a transition metal master batch composition dispersed in the oxygen scavenger composition; wherein the oxygen scavenger composition is present in an amount greater than about 85 weigh percent; wherein the transition metal master batch composition comprises: (i) a polymer carrier; and (ii) a transition metal composition dispersed in the solid polymer carrier; wherein the transition metal composition is present in an amount greater than about 30,000 ppm (by metal) based on the weight of the transition metal master batch composition.
• the transition metal compact composition can be readily compacted into pellets or granules, which advantageously can be used as a single component oxygen scavenger/catalyst system for use in packaging applications.
• the carrier polymer can be used as the carrier polymer.
• the disclosed compositions enable oxygen scavenging, and thus the carrier polymer generally includes those polymers that can be subject to oxidation.
• polymers that exhibit at least some oxygen permeability are useful with the disclosed compositions, at least inasmuch as the disclosed compositions can reduce the oxidative damage to the polymer.
• the polymer carrier comprises a polyester polymer.
• the polyester polymer is a polyalkyl terephthalate, or a copolymer thereof.
• the polyester polymer is polyethylene terephthalate, or a copolymer thereof.
• the polyester polymer is a polymer comprising repeating aromatic units selected from terephthalic acid residues, isophthalic acid residues, and naphthalenic acid residues.
• the polyester polymer is selected from polyethylene terephthalate, poly(dimethyl cyclohexane terephthalate), polytrimethylene terephthalate, polynaphthalate, or a copolymer thereof.
• the carrier polymer can be a polymer commonly used in packaging materials including polyethylene, such as low density polyethylene, very low density polyethylene, ultra-low density polyethylene, high density polyethylene, and linear low density polyethylene; polyesters such as (PET), (PEN) and their copolymers such as PET/IP; polyvinyl chloride (PVC); polyvinylidene chloride (PVDC); and ethylene copolymers such as ethylene/vinyl acetate copolymer, ethylene/alkyl (meth)acrylate copolymers, ethylene/(meth)acrylic acid copolymers, and ionomers. Blends of different base polymers also can be used.
• polyethylene such as low density polyethylene, very low density polyethylene, ultra-low density polyethylene, high density polyethylene, and linear low density polyethylene
• polyesters such as (PET), (PEN) and their copolymers such as PET/IP
• PVC polyvinyl chloride
• PVDC polyvinylidene chloride
• the carrier polymer can include one or more polymers approved by the U.S. Food and Drug Administration (FDA). Examples include polyethylene terephthalate, polypropylene, and polyethylene.
• FDA U.S. Food and Drug Administration
• the carrier polymer comprises a polyester polymer or copolymer.
• polyesters include polymers of phthalic acids, such as polyethylene terephthalate (PET), or a copolymer thereof.
• PET for example, can be made from terephthalic acid and ethylene glycol. PET can also be made using dimethyl terephthalate and ethylene glycol.
• Preferred copolymers of phthalic acids include copolymers of a phthalic acid and one or more hydroxylated organic compounds.
• Suitable hydroxylated organic compounds include 1,4-cyclohexandedimethanol, 1,2-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol (2 MPDO), 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and diols containing one or more oxygen atoms in the chain, e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, or mixtures of these, and the like.
• the carrier polymer includes a polyethylene terephthalate homopolymer and copolymer modified with one or more polycarboxylic acid modifiers in a cumulative amount of less than about 15 mole %, or about 10 mole % or less, or about 8 mole % or less, or one or more hydroxyl compound modifiers in an amount of less than about 60 mol %, or less than about 50 mole %, or less than about 40 mole %, or less than about 15 mole %, or about 10 mole % or less, or about 8 mole % or less and polyethylene naphthalate homopolymers and copolymers modified with a cumulative amount of less than about 15 mole %, or about 10 mole % or less, or about 8 mole % or less, of one or more polycarboxylic acid modifiers or modified with less than about 60 mol %, or less than about 50 mole %, or less than about 40 mole %, or less than about 15 mole
• Polyesters such as PET can be prepared by polymerization procedures known in the art sufficient to effect esterification and polycondensation.
• Polyester melt phase manufacturing processes include direct condensation of a dicarboxylic acid with a diol, optionally in the presence of one or more esterification catalysts, in the esterification zone, followed by polycondensation in the prepolymer and finishing zones in the presence of a polycondensation catalyst; or ester exchange usually in the presence of a transesterification catalyst in the ester exchange zone, followed by prepolymerization and polymerization in the presence of a polycondensation catalyst.
• the polymer carrier of the invention relates to a polyester polymer.
• the polyester polymer is any thermoplastic polyester polymer, e.g. partially aromatic polyester polymers or polyester polymers mainly derived from an aromatic diacid and an aliphatic diol.
• the polyester polymer is polyethylene terephthalate.
• the polyethylene terephthalate polymer has ethylene terephthalate units in an amount of at least 60 mole %, in an amount of at least 85 mole %, in an amount at least 90 mole %, and in an amount at least 92 mole %, as measured by the mole % of ingredients added to the reaction mixture.
• a polyethylene terephthalate polymer may comprise a copolyester of ethylene terephthalate units and other units derived from an alkylene glycol or aryl glycol with a aliphatic or aryl dicarboxylic acid.
• Polyethylene terephthalate polymers can be manufactured by reacting a diacid or diester component comprising at least 60 mole % terephthalic acid or C 1-C 4 dialkylterephthalate, preferably at least 70 mole %, more preferably at least 85 mole %, even more preferably, at least 90 mole %, and for many applications will be at least 95 mole %, and a diol component comprising at least 60 mole % ethylene glycol, preferably at least 70 mole %, more preferably at least 85 mole %, even more preferably at least 90 mole %, and for many applications, will be at least 95 mole %.
• the diacid component is terephthalic acid and the diol component is ethylene glycol.
• the mole percentage for all of the diacid component totals 100 mole %, and the mole percentage for all of the diol component totals 100 mole %.
• the polyester pellet composition may be formed by admixing polyester polymers with other thermoplastic polymers, such as polycarbonate (PC) and polyamides.
• the polyester pellet composition can comprise a majority of a polyester polymer, e.g. a polyester polymer present in an amount of at least 80 wt. %, present in an amount at least 95 wt. %, and an in an amount at least 98 wt. %, based on the weight of polymers (excluding fillers, fibers, impact modifiers, or other polymers which may form a discontinuous phase).
• the polyester polymer can comprise at least 60 wt. % of a polyethylene terephthalate, at least 90 wt.
• a polyethylene terephthalate polymer can contain at least 60 mole % of ethylene terephthalate units.
• the polyethylene terephthalate can be made from at least 90 mole % terephthalic acid and at least 90 mole % of ethylene glycol.
• polyesters such as polyethylene terephthalate polymer are made by reacting a glycol with a dicarboxylic acid as the free acid or its dimethyl ester to produce a prepolymer compound which is then polycondensed to produce the polyester. If required, the molecular weight of the polyester can then be increased further by solid state polymerization. In one aspect, after melt phase and/or solid state polycondensation the polyesters have an intrinsic viscosity (It. V.) of at least 0.60 dL/g, and at least 0.70 dL/g measured at 25° C. in a 60/40 ratio by weight of phenol/tetrachloroethane.
• It. V. intrinsic viscosity
• the acid component of the polyester polymer can be modified with units derived from one or more additional dicarboxylic acids.
• additional dicarboxylic acids include aromatic dicarboxylic acids preferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, or cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms.
• dicarboxylic acid units useful for modifying the acid component are units from phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4′-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and the like, with isophthalic acid, naphthalene-2,6-dicarboxylic acid, and cyclohexanedicarboxylic acid being most preferable. It should be understood that use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is included in the term “dicarboxylic acid”.
• the diol component of the present polyester can be modified with units from additional diols including cycloaliphatic diols preferably having 6 to 20 carbon atoms and aliphatic diols preferably having 3 to 20 carbon atoms.
• diols examples include diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentanediol-(2,4), 2-methylpentanediol-(1,4), 2,2,4-trimethylpentane-diol-(1,3), 2,5-ethylhexanediol-(1,3), 2,2-diethyl propane-diol-(1,3), hexanediol-(1,3), 1,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl
• Polyesters can be prepared by conventional polymerization procedures well-known in the art sufficient to effect esterification and polycondensation.
• Polyester polycondensation processes include direct condensation of dicarboxylic acid with the diol, ester interchange, and solid state polymerization methods.
• Typical polyesterification catalysts which can be used include titanium alkoxides, dibutyl tin dilaruate, and antimony oxide or antimony triacetate, used separately or in combination, optionally with zinc, manganese, or magnesium acetates or benzoates and/or other such catalyst materials as are well known to those skilled in the art.
• Phosphorus and cobalt compounds may also optionally be present.
• a mixture of one or more dicarboxylic acids, preferably aromatic dicarboxylic acids, or ester forming derivatives thereof, and one or more diols may be heated in the presence of esterification and/or transesterification catalysts in an esterification zone, optionally with a polycondensation catalyst, at temperatures in the range of about 150° C. to about 300° C., or alternatively, about 200° C. to about 300° C., and in conventional reactions, typically between about 260° C. to about 300° C., and pressures ranging from atmospheric to about 0.2 mmHg Normally, the dicarboxylic acid is esterified with the diol(s) at elevated pressure and at a temperature of about 240° C.
• Polycondensation reactions are initiated and continued in the melt phase in a prepolymerization zone and finished in the melt phase in a finishing zone, after which polycondensation reactions are continued in the solid state in a solid stating zone.
• molecular weight build up is effected by increasing the temperature from about 260° C. up to about 280° C. and lowering the pressure while excess diol is removed from the mixture.
• Polycondensation can be continued in a finishing zone in a series of finishing vessels ramped up to higher temperatures until an ItV of about 0.70 dL/g or less is achieved.
• the catalyst material such as antimony oxide or triacetate may be added to the prepolymerization zone along with phosphorus, cobalt compounds, and colorants, which may optionally be added to the finishing zone.
• phosphorus, cobalt compounds, and colorants may optionally be added to the finishing zone.
• crystallization aids such as elemental antimony or reduced antimony, carbon black, graphite, black iron oxide, red iron oxide and the like, sticky bottle additives such as talc, and fillers and the like can be included.
• the resin may also contain small amounts of branching agents such as trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylol propane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art. All of these additives and many others and their use are well known in the art and do not require extensive discussion.
• branching agents such as trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylol propane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art. All of these additives and many others and their use are well known in the art and do not require extensive discussion.
• compositions of the present invention relate to a transition metal composition, wherein the transition metal is in a positive oxidation state.
• the transition metal composition in the presence of a suitable oxygen scavenger composition is believed to catalyze the oxygen scavenging properties of the oxygen scavenger composition.
• the transition metal composition enhances the oxygen scavenging properties of the oxygen scavenger composition.
• the transition metal can be a transition metal from the first, second, or third transition series of the Periodic Table.
• the metal can be Rh, Ru, Pd, Os, Ir, Pt, or one of the elements in the series of Sc to Zn (e.g., Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn).
• the transition metal is cobalt. Cobalt can be used in +2 or +3 oxidation states. In some aspects, it is preferred to use cobalt in the +2 oxidation state.
• the transition metal is rhodium. For example, rhodium in the +2, +3, or +4 oxidation state can be used.
• the transition metal is manganese.
• manganese in the +2 or +3 oxidation state can be used.
• the transition metal is iron.
• iron in the +2 or +3 oxidation state can be used.
• the transition metal is nickel.
• the transition metal is copper.
• copper in the +1 or +2 oxidation state can be used.
• the transition metal can also be a positive oxidation form of zinc.
• the transition metal can be ruthenium.
• the transition metal composition may also be an ionomer, in which case a polymeric counter-ion is employed.
• the transition metal can be present as a salt.
• the cation of the salt can be the transition metal in a positive oxidation state.
• a variety of anions can stabilize the positively charged transition metal.
• Suitable anions for the salts include, but are not limited to, halides, such as chloride; carboxylates, such as neodecanoate, octanoate, acetate, butyrate, lactate, naphthalate, malate, stearate, acetate, acetylacetonate, linoleate, oleate, palmitate, 2-ethylhexanoate, tallate, resinate, 3,5,5-trimethylhexoate, valerate, cyclohexanebutyrate, acetylacetonate, benzaylacetonate, dodecylacetylacetonate, benzoate, oxalate, citrate, tartrate or ethylene glycolate; or as their oxides,
• the transition metal is selected from cobalt 2-ethylhexanoate, cobalt oleate, cobalt neodecanoate, cobalt 2-ethylhexanoate, cobalt acetate, cobalt stearate, and cobalt benzoate.
• the transition is cobalt neodecanoate.
• the transition metal composition is in the form of a concentrated solid, semi-solid, gel or paste. In a still further aspect, the transition metal composition is in the form of a pastille.
• the transition metal is present in the pastille in a weight percent amount of about 15% to about 30% (by metal). In a yet further aspect, the transition metal is present in the pastille in an weight percent amount of about 17% to about 25% (by metal). In a still further aspect, the transition metal is present in the pastille in an weight percent amount of about 19% to about 22% (by metal).
• the transition metal comprises cobalt, copper, rhodium, platinum, rhenium, ruthenium, palladium, tungsten, osmium, cadmium, silver, tantalum, hafnium, vanadium, titanium, chromium, nickel, zinc, or manganese. In a still further aspect, the transition metal comprises cobalt.
• the transition metal in the transition metal composition comprises cobalt.
• the source of cobalt in the transition metal composition comprises a cobalt carboxylate or cobalt neodecanoate, or mixtures thereof.
• the source of cobalt in the transition metal composition comprises cobalt neodecanoate.
• At least a portion of the cobalt in the transition metal composition is present in the +2 or +3 oxidation state. In a still further aspect, at least a portion of the cobalt in the transition metal composition is present in the +2 oxidation state.
• the transition metal in the transition metal composition comprises zinc.
• the source of cobalt in the transition metal composition comprises a zinc carboxylate or zinc neodecanoate, or mixtures thereof.
• the source of zinc in the transition metal composition comprises zinc neodecanoate.
• the compositions of the present invention relate to oxygen scavenger compositions.
• the oxygen scavenger compositions comprise various materials which are selected by one skilled in the art based on their material handling characteristics, end-use, and specifications of the finished articles. The materials may be single or multi-component which can be further mixed, compounded, or blended with additional materials as required.
• Oxygen scavenger compositions can comprise organic molecules, including monomers or polymers, and/or transition metal compositions. When included in the manufacture of packaging materials, such oxygen scavenger compositions are believed to react with oxygen that is trapped in the package or that permeates from outside of the package, thus extending to life of package contents.
• packages include films, bottles, containers, and the like. Food, beverages (such as beer and fruit juices), cosmetics, medicines, and the like are particularly sensitive to oxygen exposure and require high barrier properties to oxygen to preserve the freshness of the package contents and avoid changes in flavor, texture and color.
• oxygen scavenging material Use of certain polyamides in combination with a transition metal is known to be useful as the oxygen scavenging material.
• One particularly useful polyamide is MXD6 which contains meta-xylene residues in the polymer chain. See, for example, U.S. Pat. Nos. 5,639,815; 5,049,624; and 5,021,515.
• Other oxygen scavenger compostions include potassium sulfite (U.S. Pat. No. 4,536,409), unsaturated hydrocarbons (U.S. Pat. No. 5,211,875), and ascorbic acid derivatives (U.S. Pat. No. 5,075,362).
• the oxygen scavenger compositions useful in the present comprise: (a) a base polymer; (b) at least one compound of Formula I or II:
• the oxygen scavenger composition of the transition metal compact composition comprises the material DC-100.
• the oxygen scavenger composition of the transition metal compact composition comprises the material DC-300.
• the material DC-100 and DC-300 are manufactured by and are commercially available from Constar International. Preparation of these materials and other material useful as oxygen scavenger compostions of the present invention are described in U.S. Pat. No. 7,691,290 and U.S. Pat. No. 7,994,245; and in U.S. Ser. No. 12/945,351 (Publ. No. US 2011/0172335) and U.S. Ser. No. 12/945,355 (Publ. No. US 2011/0117301), which are herein incorporated by reference.
• the oxygen scavenger compositions comprises a compound represented by the formula:
• n and p are independently 0 or an integer from 1 to 5; each R 1 and R 2 is independently selected from H, C 1 -C 12 alkyl, C 1 -C 6 alkoxy, C 6 -C 20 aryloxy, hydroxy, C 2 -C 6 alkenyl, NR 19 R 20 , acetyl, nitro, glyceryl, carbohydrate, —C( ⁇ O)H, L, or two R 1 or two R 2 groups can form a group of the formula —O—R 18 —O; R 3 and R 4 are each H; R 5 to R 10 are independently selected from H or C 1 -C 3 alkyl; and R 18 is C 2 -C 6 alkyl.
• n and p are each 0, 1, or 2.
• R 1 and R 2 are independently selected from H, C 1 -C 4 alkyl, hydroxy, C 1 -C 3 alkoxy, or carbohydrate.
• R 1 and R 2 are independently selected from H, methyl, ethyl, hydroxy, methoxy, ethoxy, or glucose.
• each of R 5 to R 10 are H.
• R 1 and R 2 are each H.
• the oxygen scavenger compositions comprises a compound represented by the formula:
• L is a linking group of the formula —(O—R 21 ) z —O—, —(NH—R 21 ) z —NH—, —(NH—C( ⁇ O)R 22 ) t —NH, —NH—R 25 —NH(C( ⁇ O)R 26 NHR 25 NH) u —, —(O—R 23 —O—R 24 —C( ⁇ O) s —O— where L is attached to a carbon atom of Ar (for example, replaces a H atom of the Ar) in structure (I) or where R 12 or R 13 of structure (II) is L; R 11 is selected from H, C 1 -C 12 alkyl, C 1 -C 6 alkoxy, C 6 -C 20 aryloxy, hydroxy, C 2 -C 6 alkenyl, NR 19 R 20 , acetyl, nitro, glyceryl, carbohydrate
• R 16 and R 17 are each H.
• each R 11 is independently selected from H, C 1 -C 4 alkyl, hydroxy, or C 1 -C 3 alkoxy, or carbohydrate.
• each R 11 is independently selected from H, methyl, ethyl, hydroxy, methoxy, or ethoxy.
• the oxygen scavenger composition comprises a compound represented by a formula:
• the oxygen scavenger composition comprises a compound represented by a formula:
• the oxygen scavenger composition comprises a compound represented by a formula:
• the oxygen scavenger composition comprises a compound represented by a formula:
• the oxygen scavenger composition comprises a compound represented by a formula:
• the oxygen scavenger composition comprises a compound represented by a formula:
• the oxygen scavenger composition comprises a compound represented by a formula:
• the oxygen scavenger composition comprises a compound represented by a formula:
• the oxygen scavenger composition comprises a compound represented by a formula:
• the oxygen scavenger composition comprises a compound represented by a formula:
• the invention relates to a transition metal master batch composition
• a transition metal master batch composition comprising: (a) a polymer carrier; and (b) a transition metal composition dispersed in the solid polymer carrier; wherein the transition metal composition is present in an amount greater than about 30,000 ppm (by metal) based on the weight of the transition metal master batch composition.
• the polymer carrier of the transition master batch composition comprises a polyester polymer.
• the polyester polymer is a polyalkyl terephthalate, or a copolymer thereof.
• the polyester polymer is polyethylene terephthalate, or a copolymer thereof.
• the polyester polymer is a polymer comprising repeating aromatic units selected from terephthalic acid residues, isophthalic acid residues, and naphthalenic acid residues.
• the polyester polymer is selected from polyethylene terephthalate, poly(dimethyl cyclohexane terephthalate), polytrimethylene terephthalate, polynaphthalate, or a copolymer thereof.
• the amount of the polymer carrier present in the transition metal master batch composition is at least about 75 weight percent. In a still further aspect, the amount of the polymer carrier present in the transition metal master batch composition is from about 70 weight percent to about 90 weight percent. In a yet further aspect, the amount of the polymer carrier present in the transition metal master batch composition is from about 75 weight percent to about 85 weight percent. In an even further aspect, the amount of the polymer carrier present in the solid concentrate composition is from about 77 weight percent to about 82 weight percent.
• the polymer carrier present in the transition metal master batch compostion is a polyester polymer and is present in an amount that is at least about 75 weight percent. In a still further aspect, the polymer carrier present in the transition metal master batch compostion is a polyester polymer and is present in an amount that is from about 70 weight percent to about 90 weight percent. In a further aspect, the polymer carrier present in the transition metal master batch compostion is a polyester polymer and is present in an amount that is from about 75 weight percent to about 85 weight percent. In a further aspect, the polymer carrier present in the transition metal master batch compostion is a polyester polymer and is present in an amount that is from about 77 weight percent to about 82 weight percent.
• the polymer carrier present in the transition metal master batch compostion is PET and is present in an amount that is at least about 75 weight percent. In a still further aspect, the polymer carrier present in the transition metal master batch compostion is PET and is present in an amount that is from about 70 weight percent to about 90 weight percent. In a further aspect, the polymer carrier present in the transition metal master batch compostion is PET and is present in an amount that is from about 75 weight percent to about 85 weight percent. In a further aspect, the polymer carrier present in the transition metal master batch compostion is PET and is present in an amount that is from about 77 weight percent to about 82 weight percent.
• the transition metal composition is present in the transition metal master composition in an amount greater than about 35,000 ppm (by metal) based on the weight of the transition metal master batch composition. In a still further aspect, the transition metal composition is present in the transition metal master composition in an amount greater than about 40,000 ppm (by metal) based on the weight of the transition metal master batch composition. In a yet further aspect, the transition metal composition is present in the transition metal master composition in an amount from about 30,000 ppm to about 60,000 pm (by metal) based on the weight of the transition metal master batch composition.
• the transition metal composition is present in the transition metal master composition in an amount from about 35,000 ppm to about 55,000 pm (by metal) based on the weight of the transition metal master batch composition. In a still further aspect, the transition metal composition is present in the transition metal master composition in an amount from about 37,500 ppm to about 52,500 pm (by metal) based on the weight of the transition metal master batch composition. In a yet further aspect, the transition metal composition is present in the transition metal master composition in an amount from about 37,500 ppm to about 47,500 pm (by metal) based on the weight of the transition metal master batch composition.
• the transition metal composition is present in the transition metal master composition in an amount from about 38,950 ppm to about 47,500 pm (by metal) based on the weight of the transition metal master batch composition. In a still further aspect, the transition metal composition is present in the transition metal master composition in an amount from about 40,000 ppm to about 60,000 pm (by metal) based on the weight of the transition metal master batch composition. In a yet further aspect, the transition metal composition is present in the transition metal master composition in an amount from about 40,000 ppm to about 50,000 pm (by metal) based on the weight of the transition metal master batch composition. In an even further aspect, the transition metal composition is present in the transition metal master composition in an amount from about 30,000 ppm to about 47,500 pm (by metal) based on the weight of the transition metal master batch composition.
• the transition metal composition is in the form of a concentrated solid, semi-solid, gel or paste. In a still further aspect, the transition metal composition is in the form of a pastille. In a yet further aspect, the let down ratio of the pastille into the solid polymer carrier is about 10% to about 30%. In an even further aspect, the let down ratio of the pastille into the solid polymer carrier is about 15% to about 25%. In a still further aspect, the let down ratio of the pastille into the solid polymer carrier is about 17% to about 22%. In a yet further aspect, the let down ratio of the pastille into the solid polymer carrier is about 19% to about 22%.
• the invention relates to a transition metal compact composition
• a transition metal compact composition comprising: (a) an oxygen scavenger composition; and (b) a transition metal master batch composition dispersed in the oxygen scavenger composition; wherein the oxygen scavenger composition is present in an amount greater than about 85 weigh percent; wherein the transition metal master batch composition comprises: (i) a polymer carrier; and (ii) a transition metal composition dispersed in the solid polymer carrier; wherein the transition metal composition is present in an amount greater than about 30,000 ppm (by metal) based on the weight of the transition metal master batch composition.
• the oxygen scavenger composition of the transition metal compact composition is present in a weight percent amount of about 70% to about 90% based on the weight of the transition metal compact composition. In a still further aspect, the oxygen scavenger composition of the transition metal compact composition is present in a weight percent amount of about 80% to about 90% based on the weight of the transition metal compact composition. In a yet further aspect, the oxygen scavenger composition of the transition metal compact composition is present in a weight percent amount of from about 85% to about 89% based on the weight of the transition metal compact composition. In an even further aspect, the oxygen scavenger composition of the transition metal compact composition is present in a weight percent amount of from about 70% to about 90% based on the weight of the transition metal compact composition.
• the oxygen scavenger composition of the transition metal compact composition is present in a weight percent amount of from about 80% to about 90% based on the weight of the transition metal compact composition. In a still further aspect, the oxygen scavenger composition of the transition metal compact composition is present in a weight percent amount of from about 85% to about 89% based on the weight of the transition metal compact composition.
• the transition metal master batch composition of the transition metal compact composition is present in a weight percent amount of from about 10% to about 20% based on the weight of the transition metal compact composition. In a still further aspect, the transition metal master batch composition of the transition metal compact composition is present in a weight percent amount of from about 10% to about 15% based on the weight of the transition metal compact composition. In a yet further aspect, the transition metal master batch composition of the transition metal compact composition is present in a weight percent amount of from about 10% to about 13% based on the weight of the transition metal compact composition.
• the transition metal of the transition metal compact composition is present in an amount greater than about 4,000 ppm (by metal) based on the weight of the transition metal compact composition. In a still further aspect, the transition metal of the transition metal compact composition is present in an amount greater than about 5,000 ppm (by metal) based on the weight of the transition metal compact composition. In a yet further aspect, the transition metal of the transition metal compact composition is present in an amount of from about 4,000 ppm to about 6,000 ppm (by metal) based on the weight of the transition metal compact composition. In an even further aspect, the transition metal of the transition metal compact composition is present in an amount of about from 5,000 ppm to about 6,000 ppm (by metal) based on the weight of the transition metal compact composition. In a still further aspect, the transition metal of the transition metal compact composition is present in an amount of about from 5,000 ppm to about 5,500 ppm (by metal) based on the weight of the transition metal compact composition.
• the invention relates to methods of making transition metal master batch compositions. In a further aspect, the invention relates to methods of making transition metal compacted pellets. In a yet further aspect, the invention relates to making an article.
• compositions of this invention can be prepared by employing the methods as described in the following, in addition to other standard manipulations that are known in the literature, exemplified in the experimental sections or clear to one skilled in the art.
• the invention relates to methods of making a transition metal master batch composition
• a transition metal master batch composition comprising the step of extruding a transition metal master batch composition, the composition comprising: (a) a polymer carrier; and (b) a transition metal composition; wherein the transition metal composition is present in an amount greater than about 30,000 ppm (by metal) based on the weight of the transition metal master batch composition.
• the method further comprises the step of milling the transition metal master batch composition following the step of extrusion.
• the transition metal master batch composition is milled to a size less than about 5.0 mm screen size.
• the transition metal master batch composition is milled to a size less than about 4.0 mm screen size.
• the transition metal master batch composition is milled to a size less than about 3.0 mm screen size.
• the transition metal master batch composition is milled to a size less than about 2.0 mm screen size.
• the transition metal master batch composition is milled to a size less than about 1.0 mm screen size.
• the method further comprises the step of drying the transition metal master batch composition following the step of milling.
• the milled transition metal master batch composition can be dried in an atmosphere of dried air or other inert gas, such as nitrogen, and if desired, under sub-atmospheric pressure.
• the method further comprises the step of pulverizing the transition metal master batch composition following the step of extrusion.
• the transition metal master batch composition is pulverized to a size less than about 5.0 mm screen size.
• the transition metal master batch composition is pulverized to a size less than about 4.0 mm screen size.
• the transition metal master batch composition is pulverized to a size less than about 3.0 mm screen size.
• the transition metal master batch composition is pulverized to a size less than about 2.0 mm screen size.
• the transition metal master batch composition is pulverized to a size less than about 1.0 mm screen size.
• the method further comprises the step of drying the transition metal master batch composition following the step of pulverizing.
• the pulverized transition metal master batch composition can be dried in an atmosphere of dried air or other inert gas, such as nitrogen, and if desired, under sub-atmospheric pressure.
• the method further comprises the step of drying the transition metal master batch composition following the step of extrusion.
• the transition metal master batch composition can be dried in an atmosphere of dried air or other inert gas, such as nitrogen, and if desired, under sub-atmospheric pressure.
• transition metal master batch compositions of the present invention may be prepared by a variety of extrusion or melt compounding methods known in the art. Any suitable equipment designed to melt the carrier polymer pellets, to combine the components of the concentrate, and mix them may be used. Alternatively, the functions may be performed in more than one piece of equipment. This may be in continuous or batch processes.
• Example of equipment that may be used include, but are not limited to, two-roll mills, two rotor mixers with open mixing chambers, internal mixers with a single rotor, internal mixers with multiple counterrotating rotors, internal mixers with multiple corotating rotors, internal mixers with multiple mixing chambers, single screw extruders, planetary screw extruders, corotating twin screw extruders, counterrotating twin screw extruders conical extruders, and the like.
• These mixing devices are well known in the art and described in many references, such as W. Michaeli, “Plastics Processing: An Introduction”, Carl Hanser Verlag, Kunststoff, 1995; “Polymer Mixing: Technology and Engineering”, J. L. White, A. Y. Coran and A. Moet, Eds., Carl Hanser Verlag, Kunststoff, 2001; and “Plastics Compounding: Equipment and Processing”, D. B. Todd, Ed., Carl Hanser Verlag, Kunststoff, 1998.
• the components may also be mixed using static mixers in which the mixing elements are stationary and the mixing is accomplished by multiple reorientations of a melt stream containing the molten carrier polymer and the transition metal composition as it flows through the static elements, or molten polymer may be mixed with the cobalt salt in stirred vessels.
• manufacture of a transition metal master batch composition is accomplished by either dry feeding a separate stream or streams of carrier polymer pellet base resin(s) and a separate stream of transition metal composition or by dry blending the polyester with the cobalt additive which may then be fed together to the melt processing zone of a twin-screw compounder for melt mixing at an appropriate temperature (i.e. that melts the carrier polymer) and dispersing of the transition metal compostion into the carrier polymer matrix.
• the carrier polymer/transition metal composition melt mixture is then quenched in water and cut into cylindrical pellets for further use in downstream application.
• the solidified pellets or concentrate can be used either in its amorphous form or it can be crystallized by agitating and heating at an appropriate temperature for an extended time, e.g. greater than about 300° F. for a polyester carrier polymer such as PET.
• any conventional process used to add concentrates to a bulk stream of polymer in a melt processing zone for making the article is suitable.
• pellets of carrier polymer e.g. a polyester polymer such as PET
• a transition metal composition e.g. cobalt neodecanoate in pastilles comprising about 20.5% cobalt
• the pellets may be fed to the melt processing zone as individual streams, or in a combination of streams with one or more of the streams being a combination of two or more types of pellets.
• the invention relates to methods of making transition metal compacted pellets comprising the steps of: (1) extruding a transition metal master batch composition, the composition comprising: (a) a solid polymer carrier; and (b) a transition metal composition; wherein the transition metal composition is present in an amount greater than about 30,000 ppm (by metal) based on the weight of the transition metal master batch composition; (2) processing the extrudate comprising the transition metal master batch composition to particulate form by milling or pulverization, wherein the particle size is less than about 5.0 mm screen size; (3) preparing a homogeneous mixture comprising the particulate transition metal master batch composition and a powdered oxygen scavenger composition, wherein the powdered oxygen scavenger composition is present in an amount greater than about 85 weigh percent based on the combined weight of the particulate transition metal master batch composition and the powdered oxygen scavenger composition; and (4) forming compacted single pellets from the homogeneous mixture comprising the particulate
• Manufacture of the compacted pellets of the invention can be by methods known to one skilled in the art involving various compactors and sifters to obtain compacted pellets of a desired size distribution.
• compaction can be accomplished using a roller compactor such as a Bepex or Fitzpatrick Chilsonator roller compactor.
• a 7 ⁇ 10 chilosonator roller compactor is commonly found in industrial use, but a chilsonator of this particular configuration is not required.
• a non-limiting example of manufacture of the compacted can comprise the following steps: a) the homogenous mixture as described in the foregoing paragraph can be feed in a chilsonator roller compactor, which initially generates a somewhat continuous stick; b) the somewhat continuous stick generated by the chilsonator roller compactor is fed into a mill with about a 3 ⁇ 8 inch screen, thereby producing smaller granules; c) the granules from the preceding step can then pass through a separator, e.g. a screen sifter such as a 48 inch Sweco or similar screen sifter with a ring cleaner option; and d) then the material can then be discharged through a rare earth station into drums.
• a separator e.g. a screen sifter such as a 48 inch Sweco or similar screen sifter with a ring cleaner option
• the screen sifter can equipped with a #4 and/or #12 mesh sizes.
• the exact nature of the screen meshes in each deck of the sifter can be adjusted to optimize production efficiency and quality standards required of the compacted pellets.
• attrition testing can be carried out on random drums to monitor the effectiveness of the compaction process. Alternatively, attrition testing can occur on every nth drum, e.g. every fifth drum.
• the compacted pellets of the present invention can have the attrition test specifications following the last step of compaction and sifting as shown in Table 1.
• the attrition test results of Table 1 can be obtained as follows: a) a 50 g sample is placed onto the top 4-mesh screen of a 4/12/30/Pan stack and shaken 3 minutes using the Rotap; b) after Rotap, material on each screen is weighed and converted to a percentage of the entire sample; c) material in the pan (the initial ⁇ 30 mesh fines) is discarded; d) sample on the remaining screens is combined back together, and 25 g of this combined sample is placed onto the 30-mesh screen along with five pennys; e) the screen stack is placed in the Rotap, and shaken for 3 minutes; and f) ⁇ 30 mesh material in the pan after the attrition test is weighed and converted to a percentage.
• the invention relates to methods of making an article comprising the steps of (1) combining polyester pellets with transition metal compacted pellets in a melt processing zone; wherein the transition metal compacted pellets comprise an oxygen scavenger composition present in an amount greater than about 85 weight percent and a transition metal master batch composition present in an amount greater than about 10 weight percent; wherein the let down ratio of the transition metal compacted pellets is greater than about 1%; (2) forming a melt; and (3) extruding the melt, thereby forming the article.
• extrusion is injection molding.
• extrusion is sheet or film extrusions.
• the article is a preform.
• the article is a bottle.
• the method further comprises addition of one or more additives selected from colorants, acetaldehyde scavengers, reheat agents, UV absorbers or inhibitors, stabilizers, thermal stabilizers, and nonionic colorant harmonizers.
• the additive is a visually effective amount of colorant in the melt processing zone.
• the additive is a nonionic colorant harmonizer in an amount of from about 0.010 to about 10 weight percent in the melt processing zone.
• the nonionic colorant harmonizer is an aliphatic ester having 6 to 24 carbons.
• the method further comprises a first stream comprising the transition metal to a melt processing zone for making the article, a second stream comprising polyester polymer particles, and optionally a third stream comprising other additives such as colorant, acetaldehyde scavengers, reheat agents, UV absorbers or inhibitors, stabilizers, thermal stabilizers; and wherein first, second and optional third streams are fed to a melt processing zone for making the article.
• the polyester pellets comprise polyethylene terephthalate or a copolymer thereof.
• the polyester pellets and the transition metal compacted pellets are combined in the melt processing zone as individual streams or as pellet/pellet dry blends, or as combinations thereof.
• the let down ratio of the transition metal compacted pellets is from about 1.3% to about 3.5%.
• the let down ratio of the transition metal compacted pellets is from about 1.5% to about 3.0%.
• the let down ratio of the transition metal compacted pellets is from about 2.5% to about 3.0%.
• the let down ratio of the transition metal compacted pellets is from about 1.3% to about 1.8%.
• the let down ratio of the transition metal compacted pellets is from about 1.3% to about 1.6%.
• articles such as bottle performs are prepared from polyester polymer particles (e.g. PET) and the transition metal compacted pellet by feeding them into the melt processing zone as individual streams or as combined streams of particle/particle dry blends.
• polyester polymer particles e.g. PET
• transition metal compacted pellet obtained by the methods described in the invention, into an melt processing zone, forming a melt, and forming an article directly from the melt.
• a blend comprising solid polyester particles comprising polyester polymers and a solid transition metal compacted pellets can be simultaneously dried in a drying zone, under conditions effective to at least partially remove moisture from the blend.
• the moisture level of the blend of solid polyester particles and transition metal compacted pellets can be reduced down to less than 0.015 wt. %, or less than 0.010 wt. %, or less than 0.005 wt. %.
• radiant or convective heat, or electromagnetic or microwave radiation, or any other source for removal of moisture is emitted from a drying zone or is passed through at least a portion of the mechanical drying zone and contacts the particle blend to remove at least a portion of surface and/or internal water moisture.
• the articles obtained by the concentrates of the invention may be extruded products such as sheets and fibers, or injection molded articles such as bottle preforms and other shapes.
• the articles produced from the melt processing zone are the preforms, sheets, and trays for packaging food, pharmaceuticals, medical supplies, and beverages.
• Suitable articles include vessels and films, such as flexible sheet films, flexible bags, pouches, semi-rigid and rigid containers such as bottles (e.g. PET bottles) or metal cans, or combinations thereof.
• Typical flexible films and bags include those used to package various food items and can be made up of one or a multiplicity of layers to form the overall film or bag-like packaging material.
• the composition of the present invention can be used in one, some or all of the layers of such packaging material.
• Specific articles include preforms, containers and films for packaging of food, beverages, cosmetics, pharmaceuticals, and personal care products where a high oxygen barrier is needed.
• beverage containers are bottles for holding water and carbonated soft drinks, and the invention is particularly useful in bottle applications containing juices, sport drinks, beer or any other beverage where oxygen detrimentally affects the flavor, fragrance, performance (e.g., vitamin degradation), or color of the drink.
• the compositions are also particularly useful as a sheet for thermoforming into rigid packages and films for flexible structures. Rigid packages include food trays and lids.
• Examples of food tray applications include dual ovenable food trays, or cold storage food trays, both in the base container and in the lidding (whether a thermoformed lid or a film), where the freshness of the food contents can decay with the ingress of oxygen.
• the compositions can also be used in the manufacture of cosmetic containers and containers for pharmaceuticals or medical devices.
• suitable articles include rigid or semi-rigid articles including plastic, such as those utilized for juices, soft drinks, as well as thermoformed trays or cup normally having thickness in the range of from 100 to 1000 micrometers.
• the walls of such articles can comprise single or multiple layers of materials.
• the article can also take the form of a bottle or can, or a crown, cap, crown or cap liner, plastisol or gasket.
• the composition of the present invention can be used as an integral layer or portion of, or as an external or internal coating or liner of, the formed semi-rigid or rigid packaging article.
• the composition can be extruded as a film along with the rigid article itself, e.g., by coextrusion, extrusion coating, or an extrusion lamination process, so as to form the liner in situ during article production; or alternatively can be adhered by heat and/or pressure, by adhesive, or by any other suitable method.
• the permeability of the composition for oxygen is advantageously not more than about 3.0, or about 1.7, or about 0.7, or about 0.2, or about 0.03 cm 3 -mm/(m 2 -atm-day). In some aspects, the permeability of the composition is not more than about three-quarters of that in the absence of the amide compound. In some aspects, the permeability is not more than about one half, one-tenth in certain embodiments, one twenty-fifth in other embodiments, and not more than one-hundredth of that in the absence of the amide compound.
• articles for packaging other oxygen-sensitive products can also benefit from the present invention.
• Such products would include pharmaceuticals, oxygen sensitive medical products, corrodible metals or products, electronic devices and the like.
• Oxygen permeability of an article can be maintained for a longer period of time by storing the article in a sealed container or under an inert atmosphere such as nitrogen prior to use with oxygen sensitive materials.
• the articles can be made by various methods known in the art.
• the articles are prepared by melt processing methods (i.e., a melt of the composition).
• melt processing methods i.e., a melt of the composition.
• Such processes generally include injection molding, stretch blow molding, extrusion, thermoforming, extrusion blow molding, and (specifically for multilayer structures) co-extrusion and lamination using adhesive tie layers.
• Orientation, e.g., by stretch blow molding, of the polymer can be used with phthalate polyesters because of the known mechanical advantages that result.
• the melt processing zone for making the article can be operated under customary conditions effective for making the intended articles, such as preforms, bottles, trays, and other articles mentioned above.
• such conditions are effective to process the melt without substantially increasing the intrinsic viscosity of the melt and which are ineffective at promoting transesterification reactions.
• suitable operating conditions effective to establish a physical blend of the base polymer, oxidizable organic component, and transition metal are temperatures in the melt processing zone within a range of about 250° C. to about 300° C. at a total cycle time of less than about 6 minutes, and typically without the application of vacuum and under a positive pressure ranging from about 0 psig (pound-force per square inch gauge) to about 900 psig.
• the residence time of the melt on the screw can range from about 1 to about 4 minutes.
• PET DAK C61A PET; 1600 lb
• the extruder used in this study was a 50 mm twin screw extruder that had a 5 heat zones, 11 barrel sections. The configuration of was such that barrel section #1 was closet to the gear box and barrel section #11 was closest to the die.
• PET was loaded into barrel section #1; cobalt pastilles (Shepherd Chemical Company, Norwood, Ohio; cobalt neodecanoate, 20.5% Co by weight; referred to hereinafter as CoNDA) were loaded with a side stuffer into barrel section #4 (where turbo-mixing element sections of the screw were co-located); atmospheric vent at barrel section #6; and vacuum was pulled at barrel section #10 with a vacuum of 30′′ Hg.
• CoNDA cobalt pastilles
• barrel section #4 where turbo-mixing element sections of the screw were co-located
• atmospheric vent at barrel section #6
• vacuum was pulled at barrel section #10 with a vacuum of 30′′ Hg.
• the system ended with a 14-hole (4 mm) die.
• Pre-dried PET was hand-loaded into feed hoppers above the extruder, with PET extruded at 338 lbs/hour.
• the CoNDA pastilles were dropped into the funnel hopper of a high capacity, twin auger side stuffer (the maximum rate was about 40% of extruder capacity).
• the CoNDA pastilles were fed into the side stuffer using a high capacity Brabender vibratory feeder at a rate of 15% (weight percent of the CoNDA pastille) from the upper mezzanine (maximum rate about 6000 lbs/hour).
• the resulting extrusion was fed onto a pre-wetted surface, and then quenched by hand periodically with water from a stainless steel beaker.
• cake samples were taken by collection of the extruded material into a large metal pan containing minimal water to expedite cooling.
• the rate of feeding of the CoNDA pastilles into the extrusion mixture was sequentially increased from 15% to 17%, 19%, and 21%, with cake samples collected as described herein.
• the metal pans were floated in a water bath during this time and periodically sprayed with water to facilitate cooling of the samples. It was noted that surprisingly the viscosity notably decreased when the CoNDA component of the mixture reached 21%.
• the aspects of viscosity noted were an obvious change in the viscosity of the die drool, notably thinner extruded streams, and the flow pattern of extrudate when collected on a solid surface.
• the extrusion rate was 428 lbs/hour when the change in viscosity was noted.
• Samples of the transition metal master batch composition comprising 21% CoNDA pastille and 79% PET were analyzed by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) at Gas Technology Institute (Des Plaines, Ill.).
• the samples were microwave digested in a sulfuric acid/nitric acid solution.
• ICP-OES analysis of the samples at least two spectral lines were used and ytrrium was used as an internal standard. Analysis was carried out on triplicate samples and the results averaged. Results were obtained as shown in Table 2.
• transition metal master batch compositions prepared in this manner can be further processed (e.g. milling, pellitization, or pulverization) to pellets, granules, particulates or powders using methods known to one skilled in the art.
• transition metal master batch compositions that have been processed to a powder or fine particulate form can be used in the preparation of transition metal compact compositions according to the ratios of transition metal master batch compositions and powdered oxygen scavenger described in Table 3, wherein the oxygen scavenger exemplified is Constar International DC-300. It is understood that other oxygen scavengers in fine particulate or powder form can be substituted as required by the specific application or end-use. Briefly, the powdered transition metal master batch compositions are combined with a powdered oxygen scavenger, e.g. Constar International DC-300, physically blended to obtain a homogenous mixture, and then compacted into pellets comprising transition metal compact compositions and an oxygen scavenger to provide transition metal compacted pellets.
• a powdered oxygen scavenger e.g. Constar International DC-300
• the transition metal compacted pellets can then be used in the production of preforms, e.g. a preform can be manufactured by blending the transition metal compacted pellets with a suitable preform polymer, e.g. PET, and then formed into a suitable preform by blow extrusion.
• a preform can be manufactured by blending the transition metal compacted pellets with a suitable preform polymer, e.g. PET, and then formed into a suitable preform by blow extrusion.
• the transition metal compacted pellets can be used in various end-use applications such as manufacture of bottle performs. For example, as shown in Table 3 , the transition metal compacted pellets of varied cobalt and oxygen scavenger levels can be utilized to obtain the desired or preferred cobalt levels in the bottle perform.

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