US20040146674A1 - Acetaldehyde scavenging by addition of active scavengers to bottle closures - Google Patents
Acetaldehyde scavenging by addition of active scavengers to bottle closures Download PDFInfo
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- US20040146674A1 US20040146674A1 US10/353,411 US35341103A US2004146674A1 US 20040146674 A1 US20040146674 A1 US 20040146674A1 US 35341103 A US35341103 A US 35341103A US 2004146674 A1 US2004146674 A1 US 2004146674A1
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- closure
- nylon
- acetaldehyde
- scavenger
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Classifications
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01D—CONSTRUCTION OF BRIDGES, ELEVATED ROADWAYS OR VIADUCTS; ASSEMBLY OF BRIDGES
- E01D21/00—Methods or apparatus specially adapted for erecting or assembling bridges
-
- 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
- B65D51/00—Closures not otherwise provided for
- B65D51/24—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01D—CONSTRUCTION OF BRIDGES, ELEVATED ROADWAYS OR VIADUCTS; ASSEMBLY OF BRIDGES
- E01D19/00—Structural or constructional details of bridges
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
Definitions
- the invention pertains to compositions containing acetaldehyde scavengers in polyethylene terephthalate packaging, and more particularly to polyethylene terephthalate packaging closures containing acetaldehyde scavengers.
- PET polyethylene terephthalate
- AA residual acetaldehyde
- the amount of acetaldehyde formed is a function of the temperature and the time that the polymer is held in the melt, the polymerization catalyst and stabilizers used in the manufacturing process, the molecular weight of the polymer, the end group concentration of the polymer, the process used to form the finished package and the variables of that process such as temperature, shear rate, residence time, etc.
- a portion of the AA produced remains within the quenched polymer/package and can migrate from and through the container wall and enter the package's contents.
- AA is a naturally occurring flavorant which is used in number of food and beverage items, consumers may find the flavor undesirable in some foods and beverages.
- the fruity flavor that AA can impart may be considered undesirable in a bottled water where the consumer expects a “clean” taste.
- the taste threshold for AA in water is in the 10 to 20 parts per billion range, requiring bottle perform AA concentrations of 1 to 2 parts per million. Over time, the residual AA leaches into the water, imparting an undesirable taste and smell to the product. It is not surprising, therefore, that there has been a considerable amount of work done to produce PET with lower levels of AA.
- the additional acetaldehyde formed and the residual acetaldehyde in the walls of the container can, over time, migrate out of the polymer into the vapor space above the contents contained in the package.
- Small amounts of acetaldehyde in the vapor space e.g. in the range of 5 to 250 ppb can affect the taste of some beverages, including water.
- AA scavenger additive levels in the package resin may not be sufficient to effectively eliminate all acetaldehyde in the resin, resulting in small amounts of acetaldehyde migrating into the container's vapor space and it's contents over time.
- a threaded closure for a polyethylene terephthalate container for holding fluids comprising a polymer and a acetaldehyde scavenger effective to react with acetaldehyde under closure conditions.
- Closure conditions are conditions effective to seal the closure against the body of the container.
- a closure for a polyethylene terephthalate container comprising a liner having a vapor surface disposed in direct contact with a vapor space above a fluid in the container, said liner comprising a compound effective to react with acetaldehyde under closure conditions comprising a polyoxyalkylene amine; a polyamidoamine; a polyamide; a polyesteramide; anthranilic acid; anthranilamide; salicyclamide; salicylanilide; o-phenylenediamine; 3,4-diaminobenzoic acid; o-mercaptobenzamide; 4,5-dihydroxy-2,7-naphthalenedisulfonic acid; biuret; 2-amino-2-methyl-1,3-propanediol; aniline; 1-amino-2-indole; a thiol containing an active sulfur hydrogen atom; activated carbon; alumina; silica; amine functionalized silica
- a package comprising a polyethylene terephthalate bottle containing a fluid, a closure, and a vapor space in contact with the closure and above the fluid, said closure comprising a compound effective to react with acetaldehyde under closure conditions.
- This invention details a robust method for scavenging aldehydes, such as acetaldehyde, from the vapor space of the packaged food or beverage using a process that is independent of the resin end group population, the processing conditions used in the fabrication of the main body of the package and which does not impact the appearance or performance of the polyester container.
- aldehydes such as acetaldehyde
- polyester packaging solutions involve two primary components: the sealable container body, and a closure, or cap.
- the closure is typically produced from a polymer other than PET; although it need not be in all cases.
- the closure composition is a thermoplastic polymer, and is selected from among polyethylene, polypropylene, poly (vinyl chloride) polymers, copolymers of ethylene and a vinyl ester, such as polyethylene vinyl acetate (“EVA”), ethylene vinyl alcohol, polyester polymers and copolymers, in particular polyethylene terephthalate, and olefin homopolymer and copolymers, polyurethane, polycarbonates, polyacrylates, polyethers, polyketones, polyarylates and the like.
- EVA polyethylene vinyl acetate
- polyester polymers and copolymers in particular polyethylene terephthalate
- olefin homopolymer and copolymers polyurethane, polycarbonates, polyacrylates, polyethers, polyketones, polyarylates and the
- closures are plastic screw threaded caps, and most of these are injection molded.
- the closure must be capable of providing a sealing contact with the body of the container to prevent the vapor overhead from escaping. Providing a sealed package is especially important to preserve carbonation, and to keep the contents sanitary.
- the container may be provided in the form of different shaped articles. Suitable containers include rigid plastic containers such as juice containers, carbonated soft drink containers, water bottles and any other type of container for fluids; sealable thermoformed trays, and flexible sealable bags.
- rigid plastic containers such as juice containers, carbonated soft drink containers, water bottles and any other type of container for fluids; sealable thermoformed trays, and flexible sealable bags.
- the shape of the packaging and the nature of the packaging material are not limited so the material used in the body of the container may be a type of plastic which generates or allows the migration of an aldehyde out of the plastic, and the packaging is adapted to be sealed with a closure.
- the container comprises a polyester, and more preferably a polyethylene terephthalate composition (PET) or polyethylene naphthalate composition (PEN). Copolyesters and blends of PET and PEN can also be used. Multi-layer containers comprised of at least one PET layer can also be used.
- PET polyethylene terephthalate composition
- PEN polyethylene naphthalate composition
- Suitable polyesters are generally known in the art and may be formed from aromatic dicarboxylic acids, esters of dicarboxylic acids, anhydrides of dicarboxylic esters, glycols, and mixtures thereof.
- Suitable partially aromatic polyesters are formed from repeat units comprising terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, dimethyl-2,6-naphthalenedicarboxylate, 2,6-naphthalenedicarboxylic acid, 1,2-, 1,3- and 1,4-phenylene dioxydiacetic acid, ethylene glycol, diethylene glycol, 1,4-cyclohexane-dimethanol, 1,4-butanediol, and mixtures thereof.
- the term “repeat units from dicarboxylic acid” include repeat units from the esters and anhydrides of said dicarboxylic acids.
- Preferred polyesters comprise repeat units comprising terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, dimethyl-2,6-naphthalenedicarboxylate and mixtures thereof. More preferably the polyesters used in the body of the container comprise at least about 50 mol % and most preferably at least about 70 mol % and most preferably at least about 85 mole % terephthalic acid in the dicarboxylic acid component. In the most preferred embodiment, PET polyesters comprise at least about 90 mole % terephthalic acid or dimethyl terephthalate and at least about 90 mole % ethylene glycol residues
- the dicarboxylic acid component of the polyester may optionally be modified with up to about 50 mole percent of one or more different dicarboxylic acids other than terephthalic acid or suitable synthetic equivalents such as dimethyl terephthalate.
- 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.
- the polyester component may optionally be modified with up to about 15 mole percent, of one or more different diols other than ethylene glycol.
- additional diols include cycloaliphatic diols preferably having 6 to 20 carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms.
- diols to be included with ethylene glycol are: diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, propane-1,3-diol, butane-1,2-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-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3), hexanediol-(1,3), 1,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxy-cyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-((4
- the polyethylene terephthalate resin may also contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art.
- trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art.
- the polyesters useful as the polymer for the container body have an ItV of about 0.55 to about 1.5 dL/g, preferably from 0.65 to about 1.1 dL/g, when measured as a solution of polymer dissolved in a mixture comprised of 60% by weight phenol and 40% by weight of 1,1,2,2-tetrachloroethane.
- the acetaldehyde scavenger can be blended into the closure material of the container, it can be incorporated into the liner material, it can be deposited as a coating onto the inner surface of the closure, or it can be laminated onto the inner surface of the closure facing the vapor space. If desired, the scavenger may also be placed between the lid and the liner as a separate layer. In the event that the scavenger layer is disposed between the inner surface of the closure and a liner, the liner in this case should be permeable to acetaldehyde or any other aldehyde species to be scavenged. Otherwise, there are no constraints placed on the nature of the liner material used.
- the liner is typically used to provide a tight seal against the container body, preventing the exchange of gases to and from the contents of the package. Many of the liners are self weldable with the application of heat at low temperatures.
- the liner also may contain antiblock and antifog additives, as well as oxygen scavengers. A wide variety of materials can be used as a liner.
- Examples of useful polymers for liners can be selected from the among suitable materials used to make the closure, that is, thermoplastic polymers such as ethylene vinylacetate (EVA) having a vinyl acetate/ethylene weight ratio of 5-20%:1%, PVC, polyurethane, PET, and polyolefins such as polyethylene, including LDPE, branched or unbranched, having a density ranging from about 0.915-0.925, LLDPE having a density ranging from 0.920 to 0.924, and very low density polyethylene having density below 0.910 where sealability is desired, or HDPE having a density ranging from about — 0.94 to — 0.96 g/cc where sealability is not critical parameter; homopolymers of polypropylene or copolymers of polypropylene with ethylene having an ethylene content of 3-10% by weight; acrylates and methacrylate polymers from compounds such as ethylene (meth)acrylic acid, ethylene acrylic acid, and ethylene n-butyl acrylate, and the salt
- a liner in contact with the closure for a polyethylene terephthalate package.
- One surface of the liner contacts the inner surface of the closure, while the other surface of the liner, the vapor surface, is disposed and faces the vapor space above a fluid in the container.
- the liner material containing the scavenging compound is in direct contact with the vapor space on its vapor surface, meaning that in this embodiment, the acetaldehyde does not need to penetrate an intermediate layer to contact the liner containing the scavenger because the liner contacts the vapor space directly without the presence of a polymer layer or other barrier between the vapor space and the liner.
- the scavenger is incorporated into the liner polymer or coated on the liner polymer, preferably incorporated into the liner polymer.
- the presence of the scavenger in the liner may be due to blending the scavenger with the liner polymer or by pre-reacting the scavenger with the liner polymer or by co-polymerizing the scavenger with the liner polymer during polymerization of the liner polymer such that the scavenger is reacted into the backbone of the polymer or grafted onto the liner polymer backbone.
- the scavenger reacts with acetaldehyde contained in a vapor space under closure conditions. Closure conditions are conditions effective to seal the closure against the body of the container.
- the preferred package is a bottle, and in particular a polyethylene terephthalate bottle containing a fluid such as water.
- a process for reducing acetaldehyde levels in a vapor space located between a closure sealed to a polyethylene terephthalate container and the contents contained within a polyethylene terephthalate container comprising contacting a) a vapor comprising acetaldehyde in the vapor space with b) a closure comprising a compound effective for scavenging acetaldehyde, and continuously scavenging acetaldehyde from the vapor at a temperature less 50° C., preferably less than 40° C.
- the process of the invention may be used to scavenge acetaldehyde at 25° C. or less and even 15° C. or less.
- the temperature values are measured by the temperature to which the vapor space is subjected for at least 0.5 hours, which is about the time necessary to equilibrate the temperature of the package contents with ambient surroundings. Since the temperature values are measured by the applied temperature, the temperature values are independent of the pressure generated inside the sealed package.
- a sealed closure is meant the conventional seal applied to the package for the market into which the package is sold.
- This process is unlike conventional scavenging schemes which attempt to capture acetaldehyde in the polymer melt during melt phase manufacture or during injection blow molding as a liquid/gas interaction.
- the scavenger compound operates to scavenge acetaldehyde in a solid/gas interaction, wherein the scavenger operates in the solid phase to scavenge acetaldehyde from a gas phase.
- the process of the invention provides for acetaldehyde capture at lower temperatures.
- the process Since many beverages are refrigerated, the process has the advantage of scavenging at a wide range of lower temperatures, even down to temperatures above the freezing temperatures of the package contents. Finally, the process of the invention provides for the continual scavenging of acetaldehyde. Thus, scavenging will continue for so long as a significant amount of acetaldehyde migrates into the container vapor space or until such time as the closure is unsealed.
- Acetaldehyde will continuously migrate from the liquid phase into the vapor space because as the acetaldehyde is captured by the scavenger, more acetaldehyde will diffuse into the vapor space, thus providing a continuous process for-scavenging acetaldehyde rather than a one time scavenging as experienced in the melt applications.
- a polyethylene terephthalate package a closure, and a vapor space above the fluid and in contact with the closure, where the closure itself contains a compound effective to react with acetaldehyde under closure conditions.
- a liner is not needed and the scavenger is incorporated directly into the closure itself.
- the process for incorporating the scavenger into the closure or the liner can be any conventional process known for combining two compounds or polymers. Typical processes include dry blending pellets into an extruder or injection molding machine by the addition of the scavenger neat or as a concentrate or in a carrier to a feed of bulk polymer to the extruder. Alternatively, the scavenger can be added neat, as a concentrate, or in a carrier to a suitable reaction vessel used to manufacture the closure or liner resin. If desired, the scavenger can be deposited onto a support such as silica or a zeolite, which is then compounded into a polymer melt used to make the closure or liner.
- a support such as silica or a zeolite
- the invention also comprises a process for reducing acetaldehyde levels in a vapor space located between a closure and contents contained within a polyethylene terephthalate container, comprising sealing the polyethylene terephthalate container with a closure containing a compound effective to react with the acetaldehyde in the vapor space.
- the scavenger may be blended with the polymer material or may be copolymerized, reacted onto, or grafted onto the polymer backbone.
- scavenging acetaldehyde many of the scavengers are capable of scavenging other aldehydes or ketones, which would be useful in other applications.
- aldehydes and ketones include formaldehyde, propionaldehyde, acrolein, butyraldehyde, benzaldehyde, acetone, cylopentanone, and the like.
- Suitable scavenger materials include polyoxyalkylene amines, polyamidoamines, polyamides, polyesteramides, anthranilic acid, anthranilamide, salicyclamide, salicylanilide, o-phenylenediamine, 3,4-diaminobenzoic acid, o-mercaptobenzamide, 4,5-dihydroxy-2,7-naphthalenedisulfonic acid, biuret, 2-amino-2-methyl-1,3-propanediol, aniline, and 1-amino-2-indole, thiols containing an active sulfur hydrogen atom, activated carbon, alumina, silica, silica functionalized with amine groups, talc, and zeolites, polyfunctional organic species containing both a primary, secondary or tertiary amine group and a carboxylic acid, phenolic, amide, ester, or thiol groups, each of which are capable of being reacted into the
- the polyoxyalkylene polyamines include diamines and triamines, which may optionally be functionalized with hydroxyl and aminoalcohol groups, having a number average molecular weight ranging form 400 to 6000, preferably from 1,000 to 3,000.
- Examples include polyoxyethylene diamine, amino group-containing polymers such as amino group-terminated polyethers, for example, aminoethyletherified or aminopropyl-etherified polyethylene glycol and/or polypropylene glycol, and the polyoxyalkylene polyamines known as Jeffamine® amines.
- suitable polyamides include those having a molecular weight suitable for film formation and an It.V of 0.4 dL/g or more. These include poly(m-xylylene adipamide), poly(hexamethylene adipamide), polycaprolactam, poly(hexamethylene isophthalamide), and poly(hexamethylene isophthalamide-co-terephthalamide).
- the polyamides may also contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, pyromellitic dianhydride, or other polyamide forming polyacids and polyamines known in the art.
- Preferred low molecular weight aliphatic polyamides include polycapramide (nylon 6), poly- ⁇ -aminoheptanoic acid (nylon 7), poly- ⁇ -aminonanoic acid (nylon 9), polyundecane-amide (nylon 11), polyaurylactam (nylon 12), polyethylene-adipamide (nylon 2,6), polytetramethylene-adipamide (nylon 4,6), polyhexamethylene-adipamide (nylon 6,6), polyhexamethylene-sebacamide (nylon 6,10), polyhexamethylene-dodecamide (nylon 6,12), polyoctamethylene-adipamide (nylon 8,6), polydecamethylene-adipamide (nylon 10,6), polydodecamethylene-adipamide (nylon 12,6) and polydodecamethylene-sebacamide (nylon 12,8).
- the preferred polyamides are low molecular weight partially aromatic polyamides having a number average molecular weight of less than 15,000, more preferably less than 13,000, and most preferably less than 11,000, and low molecular weight aliphatic polyamides having a number average molecular weight of less than 7,000, and combinations thereof.
- partially aromatic polyamide it is meant that the amide linkage of the partially aromatic polyamide contains at least one aromatic ring and a nonaromatic species.
- the partially aromatic polyamides have an It.V. of less than 0.85 dL/g.
- the It.V. of the partially aromatic polyamides is less than 0.75 dL/g and the number average molecular weight is less than 13,000.
- the aliphatic polyamides have an It.V. of less than 1.15 dL/g.
- the It.V. of the aliphatic polyamides is less than 0.85 dL/g and the number average molecular weight is less than 6,000.
- the most preferred polyamide is poly(m-xylylene adipamide) having an inherent viscosity in 60/40 phenol/tetrachloroethane of 0.2 to 0.4 dL/g.
- the low molecular weight polyamides are generally prepared by melt phase polymerization from a diacid-diamine complex which may be prepared either in situ or in a separate step. In either method, the diacid and diamine are used as starting materials. Alternatively, an ester form of the diacid may be used, preferably the dimethyl ester. If the ester is used, the reaction must be carried out at a relatively low temperature, generally 80 to 120° C., until the ester is converted to an amide. The mixture is then heated to the polymerization temperature.
- caprolactam either caprolactam or 6-aminocaproic acid can be used as a starting material and the polymerization may be catalyzed by the addition of adipic acid/hexamethylene diamine salt which results in a nylon 6/66 copolymer.
- adipic acid/hexamethylene diamine salt which results in a nylon 6/66 copolymer.
- the molecular weight is controlled by the diacid-diamine ratio. An excess of diamine produces a higher concentration of terminal amino groups. If the diacid-diamine complex is prepared in a separate step, excess diamine is added prior to the polymerization.
- the polymerization can be carried out either at atmospheric pressure or at elevated pressures.
- the preferred ones include: poly(m-xylylene adipamide), poly(hexamethylene isophthalamide), poly(hexamethylene adipamide-co-isophthalamide), poly(hexamethylene adipamide-co-terephthalamide), and poly(hexamethylene isophthalamide-co-terephthalamide).
- the most preferred low molecular weight partially aromatic polyamide is poly(m-xylylene adipamide) having a number average molecular weight of about 4,000 to about 7,000 and an inherent viscosity of about 0.3 to about 0.6 dL/g.
- Preferred low molecular weight aliphatic polyamides include poly(hexamethylene adipamide) and poly(caprolactam).
- the most preferred low molecular weight aliphatic polyamide is poly(hexamethylene adipamide) having a number average molecular weight of about 3,000 to about 6,000 and an inherent viscosity of 0.4 to 0.9 dL/g.
- Low molecular weight partially aromatic polyamides are preferred over the aliphatic polyamides where clarity and dispersibility are crucial.
- the present invention provides an acetaldehyde scavenger, which contains functionality capable of reacting with the polymer backbone to provide a covalently bound scavenger.
- This scavenger could be mono or difunctional, providing an end capper or a monomer, respectively.
- functional groups used to react the scavenger into the polymer chain include hydroxyl, ester, amide, amine, or any other group capable of reacting with the selected polymer and having at least one unbound group capable of reacting with acetaldehyde.
- Preferred examples of a scavenger capable of reacting with the polymer backbone are shown in the following representative formulas:
- R is independently H, alkyl, aryl, substituted alkyl or heteroaryl.
- the level of scavenger selected should be based on the anticipated amount of aldehyde present in the vapor space of the container and generated from the walls of the container. Generally, the minimal level of scavenger selected should be slightly more than one mole of scavenger per mole of acetaldehyde. Higher levels may be required when such factors as mixing of the scavenger in a support, diffusion of the aldehyde through the support and desired rate of scavenging are considered.
- Typical amounts of scavenger begin at 25 ppm, more preferred are at least 50 ppm, based on the weight of the polymer used to make either the closure or liner, depending on where the scavenger is incorporated. Usually, no more than 2000 ppm, and in many cases not more than 500 ppm of scavenger are needed to effectively scavenge the acetaldehyde generated from the small residual amount migrating from the walls of the container into the vapor space.
- a closure for a polyethylene terephthalate container comprising a polymer and a compound effective to react with acetaldehyde under closure conditions in an amount ranging from 25 ppm to 2000 ppm, preferably 50 to 500 ppm.
- a polyethylene terephthalate package comprising a polyethylene terephthalate container and a closure, said closure comprising a polymer and a compound effective to react with acetaldehyde under closure conditions in an amount ranging from 25 ppm to 2000 ppm, preferably 50 to 500 ppm.
- scavenger Although not more than 2000 ppm of scavenger is needed to effectively reduce the amount of acetaldehyde in the vapor space to acceptable levels, more can be used if the polyethylene terephthalate is of particularly poor quality, or if no scavenger has been added to the container polymer to reduce as far a possible the level of acetaldehyde within the polymer itself, or, more commonly, if the liner material or the closure material itself generates acetaldehyde. For example, many liners used as oxygen barriers generate aldehydes such as acetaldehyde.
- a liner or closure containing a scavenger in an amount as high as 50 wt %, but commonly not more than about 10 wt. %, and in many instances not more than about 5 wt. %, based on the weight of the closure polymer or the liner polymer, especially in applications requiring the use of oxygen barrier compounds or polymers which generate or contribute to the generation of acetaldehyde.
- compositions of the present invention can be added to enhance the performance properties of the blends.
- impact modifiers for example, impact modifiers, surface lubricants, denesting agents, stabilizers, antioxidants, ultraviolet light absorbing agents, metal deactivators, colorants, phosphate stabilizers, fillers, and the like, can be included herein. All of these additives and the use thereof are well known in the art and do not require extensive discussions. Therefore, only a limited number will be referred to, it being understood that any of these compounds can be used so long as they do not hinder the present invention from accomplishing its objectives.
- Desirable additives also include impact modifiers and antioxidants.
- typical commercially available impact modifiers well-known in the art and useful in this invention include ethylene/propylene terpolymers, styrene based block copolymers, and various acrylic core/shell type impact modifiers.
- the impact modifiers may be used in conventional amounts from 0.1 to 25 weight percent of the overall composition and preferably in amounts from 0.1 to 10 weight percent of the composition.
- Examples of typical commercially available antioxidants useful in this invention include, but are not limited to, hindered phenols, phosphites, diphosphites, polyphosphites, and mixtures thereof. Combinations of aromatic and aliphatic phosphite compounds may also be included.
- PET inherent viscosity was measured at 25° C. using 0.50 grams of polymer per 100 ml of a solvent consisting of 60% by weight phenol and 40% by weight tetrachloroethane.
- PET having a 0.72 dL/g inherent viscosity as measured in a 60% phenol/40% 1,1,2,2-tetrachloroethane solution (manufactured by Eastman Chemical Company) was dried for 8 hours at 60° C. and 29 inches of mercury vacuum.
- the dried polymer was then extruded using a DACA 1/4′′ twin-screw extruder.
- the extruder's temperature was set at 300° C. and the recirculation time within the extruder was three minutes.
- the extrudate was collected in a dewar-flask containing liquid nitrogen.
- the cold extrudate was then ground using a Wiley mill to produce a coarse grind.
- the ground material was screened and material which passed an 8-mesh screen but was retained on a 16-mesh screen was collected.
- Two grams of the screened PET was placed into a series of 20-ml headspace vials (Drachrom Catalog number DC-3120) which contained a pre-measured amount of the acetaldehyde scavenger being screened in an amount stated in Table 1.
- the vial was immediately capped with a standard septum cap (Drachrom Part No. DC-3127CAP) and placed into the sample feed carousel of a Hewlett Packard model 7694 Headspace sampler which was in turn connected to a Hewlett Packard Model 6890 gas chromatograph.
- the instrument was programmed to execute a variation of the industry standard French National Acetaldehyde generation test.
- the sample vials were heated to 150° C. for sixty minutes to drive the AA from each sample into the vial's head-space.
- the vapor was then sampled and injected into the instrument's sample loop that was maintained at 160° C. Helium was used as the carrier gas.
- the vapor space above the liquid is sampled via a gas-sampling syringe. Approximately 5 ml of gas was removed and injected into a 1-ml sample loop of a GC.
- the GC instrument used was an Alligent model 5890A gas chromatograph fitted with a gas sampling valve.
- the instrument's column was a Chrompack Poraplot Q. Detection was done with a flame ionization detector.
- the instrument's oven temperature was set to 145° C. Following sample injection the temperature was held at 145° for five minutes and then ramped up at 10° C./minute until the final temperature of 210° C. was reached.
- control specimens are also prepared by inserting a disk prepared from extruded polyethylene containing no additive.
- Table 2 illustrates the relative scavenging effects of several of the compounds: TABLE 2 Headspace AA concentration (gAA/10 6 g Loading (Weight % polymer, ppm) After 7 of Additive in Days at Room Compound Polyethylene) Temperature Blank 0 111 Carbon 0.2 wt % 19 Anthranilamide 2.7 wt % 6 Anthranilic Acid 2.8 wt % 2 Activated Carbon 4.2 wt % 0
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- Food Science & Technology (AREA)
- Structural Engineering (AREA)
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- Closures For Containers (AREA)
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- Packaging Of Annular Or Rod-Shaped Articles, Wearing Apparel, Cassettes, Or The Like (AREA)
Priority Applications (16)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/353,411 US20040146674A1 (en) | 2003-01-29 | 2003-01-29 | Acetaldehyde scavenging by addition of active scavengers to bottle closures |
TW092128295A TW200413508A (en) | 2003-01-29 | 2003-10-13 | Acetaldehyde scavenging by addition of active scavengers to bottle closures |
ARP030103827A AR041680A1 (es) | 2003-01-29 | 2003-10-21 | Depuracion de acetaldehidos mediante la adicion de depuradores activos a los cierres de las botellas |
MXPA03011437A MXPA03011437A (es) | 2003-01-29 | 2003-12-10 | Depuracion de acetaldehido por la adicion de depuradores activos a tapas de botellas. |
CNA2003101242372A CN1530416A (zh) | 2003-01-29 | 2003-12-29 | 向瓶密封盖中添加活性清除剂清除乙醛的方法 |
ES04000992T ES2271706T3 (es) | 2003-01-29 | 2004-01-19 | Eliminacion de acetaldehido por adicion de secuestrantes activos a cierres de botella. |
AT04000992T ATE344764T1 (de) | 2003-01-29 | 2004-01-19 | Flaschenverschlüsse mit acetaldehydaufnehmenden komponenten |
DE602004018839T DE602004018839D1 (de) | 2003-01-29 | 2004-01-19 | Flaschenverschlüsse mit acetaldehydaufnehmenden Komponenten |
EP04000992A EP1442993B8 (fr) | 2003-01-29 | 2004-01-19 | Bouchons de bouteilles comprenant des agents absorbant l'acétaldéhyde |
DE602004003073T DE602004003073T2 (de) | 2003-01-29 | 2004-01-19 | Flaschenverschlüsse mit acetaldehydaufnehmenden Komponenten |
ES06016967T ES2317383T3 (es) | 2003-01-29 | 2004-01-19 | Eliminacion de acetaldehido por adicion de secuestrantes activos a cierres de botella. |
AT06016967T ATE419191T1 (de) | 2003-01-29 | 2004-01-19 | Flaschenverschlüsse mit acetaldehydaufnehmenden komponenten |
EP06016967A EP1739026B1 (fr) | 2003-01-29 | 2004-01-19 | Bouchons de bouteilles comprenant des agents absorbant l'acétaldéhyde |
JP2004019942A JP2004231964A (ja) | 2003-01-29 | 2004-01-28 | ボトルクロージャーへの活性スカベンジャーの添加によるアセトアルデヒドの捕捉 |
KR1020040005732A KR20040070057A (ko) | 2003-01-29 | 2004-01-29 | 보틀 클로저에 활성 스캐빈저의 첨가에 의한아세트알데히드의 스캐빈징 |
US11/527,238 US20070020418A1 (en) | 2003-01-29 | 2006-09-25 | Acetaldehyde scavenging by addition of active scavengers to bottle closures |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/353,411 US20040146674A1 (en) | 2003-01-29 | 2003-01-29 | Acetaldehyde scavenging by addition of active scavengers to bottle closures |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US11/527,238 Continuation US20070020418A1 (en) | 2003-01-29 | 2006-09-25 | Acetaldehyde scavenging by addition of active scavengers to bottle closures |
Publications (1)
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US20040146674A1 true US20040146674A1 (en) | 2004-07-29 |
Family
ID=32655525
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/353,411 Abandoned US20040146674A1 (en) | 2003-01-29 | 2003-01-29 | Acetaldehyde scavenging by addition of active scavengers to bottle closures |
US11/527,238 Abandoned US20070020418A1 (en) | 2003-01-29 | 2006-09-25 | Acetaldehyde scavenging by addition of active scavengers to bottle closures |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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US11/527,238 Abandoned US20070020418A1 (en) | 2003-01-29 | 2006-09-25 | Acetaldehyde scavenging by addition of active scavengers to bottle closures |
Country Status (11)
Country | Link |
---|---|
US (2) | US20040146674A1 (fr) |
EP (2) | EP1739026B1 (fr) |
JP (1) | JP2004231964A (fr) |
KR (1) | KR20040070057A (fr) |
CN (1) | CN1530416A (fr) |
AR (1) | AR041680A1 (fr) |
AT (2) | ATE419191T1 (fr) |
DE (2) | DE602004003073T2 (fr) |
ES (2) | ES2317383T3 (fr) |
MX (1) | MXPA03011437A (fr) |
TW (1) | TW200413508A (fr) |
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US20050228125A1 (en) * | 2004-04-07 | 2005-10-13 | Clariant Gmbh | Copolymerizable polyalkylene glycol macromonomers, and the preparation and use thereof |
US20080146710A1 (en) * | 2006-12-18 | 2008-06-19 | Qiwen Han | Waterborne adhesive |
US20080197528A1 (en) * | 2007-02-20 | 2008-08-21 | Wood Willard E | Combination of Substituted Cyclodextrin Compound and Activated Carbon |
US20090298985A1 (en) * | 2005-10-01 | 2009-12-03 | David John Kemmish | Themoplastic Polymer Additive Compositions |
US20120241406A1 (en) * | 2011-03-25 | 2012-09-27 | Beuerle Frederick C | Barrier system for wide mouth containers |
IL266406B1 (en) * | 2016-11-03 | 2023-03-01 | Coca Cola Co | A toxic substance that feeds on manure with ptf and 1,3-propanediol produced from polymers |
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MX342800B (es) * | 2005-02-15 | 2016-10-13 | Plastipak Packaging Inc | Composiciones depuradoras de oxigeno y envase que comprende dichas composiciones. |
CN101688020B (zh) | 2007-05-10 | 2014-01-01 | 康斯达国际公司 | 氧清除分子、包含所述氧清除分子的制品及其使用方法 |
JP2009074058A (ja) * | 2007-08-29 | 2009-04-09 | Asahi Fiber Glass Co Ltd | アルデヒド捕捉剤及びそれを用いた建築材料 |
EP2406320A1 (fr) * | 2009-03-13 | 2012-01-18 | Basf Se | Mélanges stabilisés de polyester et de polyamide |
KR20150021031A (ko) | 2012-04-30 | 2015-02-27 | 프라스틱팩 팩키징, 인코퍼레이티드 | 산소 제거 조성물 |
TWI503552B (zh) * | 2014-03-26 | 2015-10-11 | Ipworks Technology Corp | 測試探針及其製造方法 |
US11338983B2 (en) | 2014-08-22 | 2022-05-24 | Plastipak Packaging, Inc. | Oxygen scavenging compositions, articles containing same, and methods of their use |
US10351692B2 (en) | 2014-10-17 | 2019-07-16 | Plastipak Packaging, Inc. | Oxygen scavengers, compositions comprising the scavengers, and articles made from the compositions |
WO2017057463A1 (fr) * | 2015-10-02 | 2017-04-06 | 三菱瓦斯化学株式会社 | Récipient multicouche et procédé de production pour ce dernier, procédé de production de récipient monocouche, et procédé de production de résine polyester recyclée |
KR101980944B1 (ko) * | 2016-10-31 | 2019-05-21 | 삼성에스디아이 주식회사 | 포토레지스트 제거용 조성물 및 이를 이용한 포토레지스트 제거 방법 |
CN111234474A (zh) * | 2020-01-17 | 2020-06-05 | 上海翰晖新材料有限公司 | 一种pet瓶用乙醛去除剂及pet瓶乙醛去除方法 |
ES1278834Y (es) * | 2021-08-18 | 2021-12-30 | Dsigntank Sl | Tapon de plastico y carbon activo |
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Cited By (12)
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US20050228125A1 (en) * | 2004-04-07 | 2005-10-13 | Clariant Gmbh | Copolymerizable polyalkylene glycol macromonomers, and the preparation and use thereof |
US7514501B2 (en) * | 2004-04-07 | 2009-04-07 | Clariant Produckte (Deutschland) Gmbh | Copolymerizable polyalkylene glycol macromonomers, and the preparation and use thereof |
US20090298985A1 (en) * | 2005-10-01 | 2009-12-03 | David John Kemmish | Themoplastic Polymer Additive Compositions |
US20080146710A1 (en) * | 2006-12-18 | 2008-06-19 | Qiwen Han | Waterborne adhesive |
US7871488B2 (en) * | 2006-12-18 | 2011-01-18 | Henkel Ag & Co. Kgaa | Waterborne adhesive |
US20080197528A1 (en) * | 2007-02-20 | 2008-08-21 | Wood Willard E | Combination of Substituted Cyclodextrin Compound and Activated Carbon |
US10323131B2 (en) | 2007-02-20 | 2019-06-18 | Cellresin Technologies, Llc | Combination of substituted cyclodextrin compound and activated carbon |
US20120241406A1 (en) * | 2011-03-25 | 2012-09-27 | Beuerle Frederick C | Barrier system for wide mouth containers |
US9707732B2 (en) * | 2011-03-25 | 2017-07-18 | Amcor Limited | Barrier system for wide mouth containers |
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Also Published As
Publication number | Publication date |
---|---|
EP1442993B1 (fr) | 2006-11-08 |
DE602004003073D1 (de) | 2006-12-21 |
EP1442993B8 (fr) | 2007-03-14 |
EP1739026A1 (fr) | 2007-01-03 |
ATE419191T1 (de) | 2009-01-15 |
ES2317383T3 (es) | 2009-04-16 |
DE602004018839D1 (de) | 2009-02-12 |
MXPA03011437A (es) | 2004-08-04 |
DE602004003073T2 (de) | 2007-03-01 |
AR041680A1 (es) | 2005-05-26 |
EP1739026B1 (fr) | 2008-12-31 |
US20070020418A1 (en) | 2007-01-25 |
CN1530416A (zh) | 2004-09-22 |
ATE344764T1 (de) | 2006-11-15 |
ES2271706T3 (es) | 2007-04-16 |
TW200413508A (en) | 2004-08-01 |
JP2004231964A (ja) | 2004-08-19 |
KR20040070057A (ko) | 2004-08-06 |
EP1442993A1 (fr) | 2004-08-04 |
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Owner name: EASTMAN CHEMICAL COMPANY, TENNESSEE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HOWELL, EARL EDMONDSON, JR.;PONASIK, JAMES ALLEN, JR.;REEL/FRAME:013613/0004 Effective date: 20030421 |
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STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |