WO1997030122A1 - Bouteilles pour boissons en polymere rigide dotees d'une resistance amelioree a l'elution de permeants - Google Patents

Bouteilles pour boissons en polymere rigide dotees d'une resistance amelioree a l'elution de permeants Download PDF

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Publication number
WO1997030122A1
WO1997030122A1 PCT/US1997/002579 US9702579W WO9730122A1 WO 1997030122 A1 WO1997030122 A1 WO 1997030122A1 US 9702579 W US9702579 W US 9702579W WO 9730122 A1 WO9730122 A1 WO 9730122A1
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Prior art keywords
cyclodextrin
container
thermoplastic
layer
polymer
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PCT/US1997/002579
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English (en)
Inventor
Willard E. Wood
Neil J. Beaverson
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Cellresin Technologies, L.L.C.
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Publication of WO1997030122A1 publication Critical patent/WO1997030122A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16—Cyclodextrin; Derivatives thereof

Definitions

  • the invention relates to a beverage bottle comprising a rigid thermoplastic onolayer, bilayer or multilayer container having in at least one layer an amount of a substituted or modified cyclodextrin that prevents the passage of a permeant, or the elution of a soluble material from the thermoplastic into the liquid container contents.
  • the invention also relates to biaxially oriented thermoformed polyolefin or polyester thermoplastic beverage containers resistant to the movement or passage of a permeant into the beverage and resistant to the extraction or elution of beverage soluble materials from the polyester web into the beverage.
  • thermoplastic beverage containers have been known for many years .
  • high density polyethylene milk containers that have a capacity of a quart, a gallon or other common sizes. These containers typically comprise high density polyethylene.
  • High density polyethylene is made from an ethylene stream using a Ziegler-Natta catalyst in either liquid phase or gas phase processes.
  • Other vinyl polymers can also be used in formulating these beverage containers including polymers made from such monomers including ethylene, propylene, butylene, butadiene, styrene and others. Such materials often contain small concentrations of residual monomers, contaminants in the olefin feed, catalyst residues and other contaminants.
  • Such containers are typically blow molded using common thermoforming technology to shape a preform into a finished bottle or container.
  • Biaxially oriented blow molded thermoformed polyester beverage containers are disclosed in J. Agranoff (Ed) Modern Plastics, Encyclopedia, Vol. 16, No. 10A, P. (84) pp. 192-194. These beverage containers are typically made from a polyester material. Such polyesters are commonly made from a diol such as ethylene glycol, 1,4-butane diol, 1, 4-cyclohexane diol and other diols copolymerized with an organic diacid compound or lower diester thereof such as terephthalic acid, 2, 6-naphthalene dicarboxylic acid etc.
  • a diol such as ethylene glycol, 1,4-butane diol, 1, 4-cyclohexane diol and other diols copolymerized with an organic diacid compound or lower diester thereof such as terephthalic acid, 2, 6-naphthalene dicarboxylic acid etc.
  • the condensation/polymerization reaction occurs between the dicarboxylic acid, or a dimethyl ester thereof and the glycol material in a heat driven reaction that releases water or methanol as a reaction by-product leaving the high molecular weight polyester material.
  • bulk polyester is injection blow molded over a steel- core rod or are formed into a preform containing the polyester.
  • the preform is introduced into a blow molding machine wherein the polyester is heated and blown to an appropriate shape and volume for a beverage container the preform can be a single layer material, can be a bilayer or multilayer preform.
  • Such preforms can form bilayer or multilayer bottles.
  • the thermoplastic polyester is a high molecular weight material, but can contain a large variety of relatively low molecular weight compound, substantially less than 500 grams per mole. These compounds can be extractable into beverage within the container. These beverage extractable materials typically comprise impurities in feed streams of the diol or diacid used in making the polyester. Further, the extractable materials can comprise degradation by-products of the polymerization reaction, the preform molding process or the thermoforming blow molding process. Further, the extractable materials can contain residual diester, diol or diacid materials including methanol, ethylene glycol, terephthalic acid, dimethyl terephthalic, 2,6- naphthalene dicarboxylic acid and esters or ethers thereof.
  • Relatively low molecular weight oligomeric linear or cyclic diesters, triesters or higher esters made by reacting one mole of ethylene glycol with one mole of terephthalic acid may be present.
  • These relatively low molecular oligomers can comprise two or more moles of diol combined with two or more moles of diacid.
  • Schiono, Journal of Polymer Science : Polymer Chemistry Edition, Vol. 17, pp. 4123-4127 (1979) , John Wiley & Sons, Inc. discusses the separation and identification of PET impurities comprising poly(ethylene terephthalate) oligomers by gel permeation chromatography. Bartl et al .
  • Beverages containing these soluble/extractables when consumed by the public, can exhibit an off-taste, a changed taste or even, in some cases, reduced taste due to the presence of extractable compounds.
  • the extractable compounds can add to or interfere with the perception of either the aroma note or flavor notes from the beverage material. Additionally, some substantial concern exists with respect to the toxicity or carcinogenicity of any organic material that can be extracted into beverages for human consumption.
  • the technology relating to compositions used in the manufacture of beverage containers is rich and varied. In large part, the technology is related to coated and uncoated polyolefin containers and to coated and uncoated polyester that reduce the permeability of gasses such as carbon dioxide increasing shelf life.
  • the art also relates to manufacturing methods and to bottle shape and bottom configuration.
  • Deaf et al., U.S. Pat. No. 5,330,808 teach the addition of a fluoroelastomer to a polyolefin bottle to introduce a glossy surface onto the-bottle.
  • Visioli et al . U.S. Pat. No. 5,350,788 teach methods for reducing odors in recycled plastics.
  • Visioli et al. disclose the use of nitrogen compounds including polyalkylenimine and polyethylenimine to act as odor scavengers in polyethylene materials containing a large proportion of recycled polymer.
  • Wyeth et al., United States Pat. No. 3,733,309 show a blow molding machine that forms a layer of polyester that is blown in a blow mold.
  • Addleman, United States Pat. No. 4,127,633 teaches polyethylene terephthalate preforms which are heated and coated with a polyvinylidene chloride copolymer latex that forms a vapor or gas barrier.
  • Halek et al . United States Pat. No. 4,223,128 teaches a process for preparing polyethylene terephthalate polymers useful in beverage containers.
  • Bonnebat et al . United States Pat. No.
  • 4,385,089 teaches a process for preparing biaxially oriented hollow thermoplastic shaped articles in bottles using a biaxial draw and blow molding technique.
  • a preform is blow molded and then maintained in contact with hot walls of a mold to at least partially reduce internal residual stresses in the preform.
  • the preform can be cooled and then blown to the proper size in a second blow molding operation.
  • Gartland et al . United States Pat. No. 4,463,121 teaches a polyethylene terephthalate polyolefin alloy having increased impact resistance, high temperature, dimensional stability and improved mold release.
  • Ryder, United States Pat. No. 4,473,515 teaches an improved injection blow molding apparatus and method.
  • a parison or preform is formed on a cooled rod from hot thermoplastic material.
  • the preform is cooled and then transformed to a blow molding position.
  • the parison is then stretched, biaxally oriented, cooled and removed from the device.
  • Nilsson, United States Pat. No. 4,381,277 teaches a method for manufacturing a thermoplastic container comprising a laminated thermoplastic film from a preform.
  • the preform has a thermoplastic layer and a barrier layer which is sufficiently transformed from a preformed shape and formed to a container.
  • Jakobsen et al. United States Pat. No. 4,374,878 teaches a tubular preform used to produce a container. The preform is converted into a bottle.
  • 4,370,368 teaches a plastic bottle comprising a thermoplastic comprising vinylidene chloride and an acrylic monomer and other vinyl monomers to obtain improved oxygen, moisture or water vapor barrier properties.
  • the bottle can be made by casting an aqueous latex in a bottle mold, drying the cast latex or coating a preform with the aqueous latex prior to bottle formation.
  • Kuhfuss et al . United States Pat. No. 4,459,400 teaches a poly(ester-amid) composition useful in a variety of applications including packaging materials.
  • Maruhashi et al . United States Pat. No. 4,393,106 teaches laminated or plastic containers and methods for manufacturing the container.
  • the laminate comprises a moldable plastic material n a coating layer.
  • thermoplastic polymer materials for beverage containers that can substantially reduce the passage of permeants in the extractable materials that pass into beverages intended for human consumption.
  • the barrier or trapping properties of polymeric beverage bottles preferably polyolefin or polyester biaxially oriented polymeric beverage container can be improved.
  • the resistance to extraction of soluble materials from the bulk polymer into the beverage can be improved, without any important reduction- and clarity, processability or structural properties, through the use of a modified cyclodextrin or compatible cyclodextrin derivative incorporated into or coated on the beverage container polymer material.
  • the cyclodextrin material can increase the barrier properties of the polymer material by trapping permeants in an internal hydrophobic space in the cyclodextrin molecule .
  • any small molecule or oligomer impurity present in the container thermoplastic, that can be extracted by the beverage can also be trapped in the cyclodextrin before the impurity material can migrate to the beverage.
  • the cyclodextrin material can be incorporated, dispersed or suspended in the bulk polymer used to make the plastic bottle, the cyclodextrin can be incorporated, suspended or dispersed in a second thermoplastic layer than can be coextruded with the thermoplastic material forming the bottle.
  • the cyclodextrin material can be used in an aqueous or solvent based liquid coating material that can be added to the bottle in the preform stage or in the fully formed bottle stage.
  • Preferred containers comprise a high density polyethylene milk container and a PET/polyacrylonitrile bilayer bottle or container.
  • the cyclodextrin material is used in the form of a compatible derivatized cyclodextrin.
  • the cyclodextrin molecule without a compatible substituent often is not sufficiently compatible in the bulk polymer material to result in a clear, useful trapping or barrier layer in the packaging material.
  • the compatible cyclodextrin derivative is a compound substantially free of an inclusion complex.
  • substantially free of an inclusion complex means that the quantity of the dispersed cyclodextrin material in the bulk polymer contains a large fraction having cyclodextrin free of a polymer contaminant, a permeant or other inclusion compound in the interior of the cyclodextrin molecule.
  • a cyclodextrin compound is typically added and blended in the bulk polymer without any inclusion compound but some complexing can occur during manufacture. Such complexing can occur as polymer impurities and degradation materials become the inclusion compound in a cyclodextrin inclusion complex.
  • the preferred cyclodextrin is a derivatized cyclodextrin having at least one substituent group bonded to the cyclodextrin molecule that is compatible with the bulk polymer.
  • Cyclodextrin is a cyclic dextrin molecule having six or more glucose moieties in the molecule.
  • the cyclodextrin is an alpha cyclodextrin ( ⁇ -CD) , a beta cyclodextrin (,3-CD) , and delta cyclodextrin ( ⁇ -CD) or mixtures thereof.
  • the derivatization of the cyclodextrin molecule results in improved blending into the thermoplastic bulk polymer with no loss in clarity, processability, or structural or packaging property in the bulk polymer.
  • the substituents on the cyclodextrin molecule are selected to possess a composition, structure and polarity to match that of the polymer to ensure the cyclodextrin is sufficiently compatible in the polymer material.
  • derivatized cyclodextrin can be blended into thermoplastic polymer, formed into semirigid or rigid containers of the invention using conventional thermoplastic blow molding/thermoforming manufacturing techniques.
  • the cyclodextrin material used in a variety of aspects of the invention can be used in forming such thermoplastic beverage containers without any substantial reduction in structural properties.
  • the first aspect of the invention comprises a thermoplastic polymer pellet having a major proportion of the thermoplastic beverage polyester material having a sufficient amount of the cyclodextrin material to improve barrier properties and to serve as a trap for polymer impurities.
  • a second aspect of the invention comprises a thermoplastic beverage container comprising a thermoplastic polyester having a major proportion of the polymeric material and a minor but effective amount of the cyclodextrin material to improve barrier properties and to act as a trap for polymer impurities.
  • the third aspect of the invention comprises a beverage container comprising a major proportion of a structural thermoplastic polymer having a second laminate layer comprising a thermoplastic layer comprising a thermoplastic polymer and an effective amount of a cyclodextrin material to improve barrier properties to the beverage container and to act as a trap for polymer purities in the laminate structure of the beverage container.
  • a last aspect of the invention comprises a beverage container comprising a thermoplastic structure having an internal coating comprising a film forming material having an effective amount of a cyclodextrin material that can provide and improve barrier properties or act as a trap for the impurities in the beverage container.
  • FIGURE 1 is a graphical representation of the dimensions of the cyclodextrin molecule without derivatization.
  • the central pore comprises the hydrophilic space or volume within the cyclodextrin molecule that can be the site for absorption of a permeant or contaminant.
  • the alpha, beta and gamma cyclodextrins are shown.
  • FIGURE 2 is an isometric view of a two liter polyester bottle having a second layer on the thermoplastic comprising a polymer and an effective amount of cyclodextrin derivative.
  • the polyester material useful in common engineering plastics of the invention is a condensation/polymerization product of a diacid and a polyol .
  • the product preferably employs an aromatic compound diacid such as a phthalate or naphthalate.
  • the major diacids used in the polymers of the invention are terephthalic acid (1,4-benzyene dicarboxylic acid) or 2, 6-naphthalene dicarboxylic acid.
  • polyesters are typically referred to as aromatic-aliphatic or aromatic according to the copolymerized diol.
  • PET polyethylene terephthalate chemical abstract No. 25038-59-9
  • PBT poly (butylene terephthalate) chemical abstract No. 24968-12-5
  • Poly(bisphenol A- phthalate) is called an aromatic polyester resin or a polyarlate resin.
  • PET, PBT and poly (ethylene-2, 6- naphthalene dicarboxylate resins) are the largest volume aromatic aliphatic products.
  • Other aromatic aliphatic products include Eastman Kodak's Kodar ® resin which is a PET resin modified with isophalate and dimethyl cyclohexane.
  • Polyarlate resins are a lower volume special resins for high temperature (HDT) end uses.
  • a preferred polyethylene terephthalic resin is typically made by a transesterification reaction of dimethyl terephthalate with ethylene glycol or 1,4- butane diol in the presence of a trace amount of a metal ion catalyst .
  • the methanol byproduct from the transesterification is collected overhead and the neat resin is extruded from the reactor in a batch of continuous process.
  • the product PET resin has an intrinsic viscosity (77) that ranges from about 0.72-0.85 dL/g.
  • Often bottle grade PET resin, during manufacture, is heated under inert ambient atmosphere to promote further polymerization in the resin.
  • Polyester bottles are typically produced by injection blow molding. Two manufacturing techniques are typically used. In one method, a preform is made by injection mold techniques in a preformed shape having the neck and screw-cap portion of the bottle in approximately useful size but having the body of the preform substantially smaller than the final bottle shape. A single component or bilayer preform can be used. The preform is then inserted into a blow molding machine where it is heated and then blown into the appropriate shape. Alternatively, the resin can be injection below molded over a steel-core rod. The neck of the bottle is formed with the proper shaped received closures (cap) and resin is provided around the temperature conditioned rod for the blowing step. The rod with the resin is indexed into the molding and the resin is blown away from the rod against the mold walls. The resin cools in contact with the mold while into the transparent bottle. The finished bottle is ejected and the rod is moved again in the injection molding station. This process is favored for single cylindrical bottles but typically can not be used to introduce complex shapes such as handles into a bottle.
  • the most common machine involves a four station apparatus that can inject resin, blow the resin into the appropriate shape, strip the formed container from the rod and recondition the core rod prior to the repeat of the process.
  • Such containers are typically manufactured with the closure fitment portion comprising a threaded neck adapted to a metal screw cap.
  • the bottle bottom typically has a lobed design such as a four lobe or five lobe design to permit the bottle be placed in a stable upright position.
  • the molded bottles, having a hemispherical bottom can be adhesively bonded to a polyethylene or polypropylene base cut to provide placement stability.
  • thermoplastic films of the invention contain a modified substituted or derivatized cyclodextrin having pendent moieties or substituents that render the cyclodextrin material compatible with the thermoplastic polyester polymer.
  • compatible means that the cyclodextrin material can be uniformly dispersed into the melt polymer, can retain the ability to trap or complex permeant materials or polymer impurity, and can reside in the polymer without substantial reductions in polymer film barrier properties or container forming characteristics.
  • Compatibility can be determined by measuring polymer characteristics such as tensile strength, tear resistance, etc., permeability or transmission rates for permeants, surface smoothness, clarity, etc.
  • Qualitative compatibility screening can be obtained by preparing small batches (100 grams-one kilogram of thermoplastic and substituted cyclodextrin) .
  • the blended material is extruded at production temperatures as a linear strand extrudate having a diameter of about one to five mm.
  • Incompatible cyclodextrin materials will not disperse uniformly in the melt and can be seen in the transparent melt polymer immediately upon extrusion from the extrusion head.
  • the incompatible cyclodextrin can degrade at extrusion temperatures and produce a characteristic "burnt flour" odor in an extrusion. Further, we have found that incompatible cyclodextrin can cause substantial melt fracture in the extrudate which can be detected by visual inspection.
  • Cyclodextrin is a cyclic oligosaccharide consisting of at least five, preferably six glucopyranose units joined by c.(l- * 4) linkages. Although cyclodextrin with up to twelve glucose residues are known, the three most common homologs ( ⁇ x cyclodextrin, ⁇ cyclodextrin and ⁇ cyclodextrin) having 6, 7 and 8 residues have been used.
  • Cyclodextrin is produced by a highly selective enzymatic synthesis. They commonly consist of six, seven, or eight glucose monomers arranged in a donut shaped ring, which are denoted a , ⁇ , or ⁇ cyclodextrin respectively (See Figure 1) .
  • the specific coupling of the glucose monomers gives the cyclodextrin a rigid, truncated conical molecular structure with a hollow interior of a specific volume.
  • This internal cavity which is lipophilic (i.e.,) is attractive to hydrocarbon materials (in aqueous systems is hydrophobic) when compared to the exterior, is a key structural feature of the cyclodextrin, providing the ability to complex molecules (e.g., aromatics, alcohols, halides and hydrogen halides, carboxylic acids and their esters, etc.) .
  • the complexed molecule must satisfy the size criterion of fitting at least partially into the cyclodextrin internal cavity, resulting in an inclusion complex.
  • the oligosaccharide ring forms a torus, as a truncated cone, with primary hydroxyl groups of each glucose residue lying on a narrow end of the torus.
  • the secondary glucopyranose hydroxyl groups are located on the wide end.
  • the torus interior is hydrophobic due to the presence of methylene (-CH 2 -) and ether (-0-) groups.
  • the parent cyclodextrin molecule, and useful derivatives, can be represented by the following formula (the ring carbons show conventional numbering) in which the vacant bonds represent the balance of the cyclic molecule:
  • Cyclodextrin molecules have available for reaction with a chemical reagent the primary hydroxyl at the six position, of the glucose moiety, and at the secondary hydroxyl in the two and three position. Because of the geometry of the cyclodextrin molecule, and the chemistry of the ring substituents, all hydroxyl groups are not equal in reactivity. However, with care and effective reaction conditions, the cyclodextrin molecule can be reacted to obtain a derivatized molecule having all hydroxyl groups derivatized with a single substituent type. Such a derivative is a persubstituted cyclodextrin.
  • Cyclodextrin with selected substituents (i.e.) substituted only on the primary hydroxyl or selectively substituted only at one or both the secondary hydroxyl groups can also be synthesized if desired. Further directed synthesis of a derivatized molecule with two different substituents or three different substituents is also possible. These substituents can be placed at random or directed to a specific hydroxyl.
  • the cyclodextrin molecule needs to contain sufficient thermoplastic compatible substituent groups on the molecule to insure that the cyclodextrin material can be uniformly dispersed into the thermoplastic and when formed into a clear film, sheet or rigid structure, does not detract from the polymer physical properties.
  • the preferred preparatory scheme for producing a derivatized cyclodextrin material having a functional group compatible with the thermoplastic polymer involves reactions at the primary or secondary hydroxyls of the cyclodextrin molecule. Broadly we have found that a broad range of pendant substituent moieties can be used on the molecule.
  • These derivatized cyclodextrin molecules can include acylated cyclodextrin, alkylated cyclodextrin, cyclodextrin esters such as tosylates, mesylate and other related sulfo derivatives, hydrocarbyl-amino cyclodextrin, alkyl phosphono and alkyl phosphato cyclodextrin, imidazoyl substituted cyclodextrin, pyridine substituted cyclodextrin, hydrocarbyl sulphur containing functional group cyclodextrin, silicon-containing functional group substituted cyclodextrin, carbonate and carbonate substituted cyclodextrin, carboxylic acid and related substituted cyclodextrin and others.
  • the substituent moiety must include a region that provides compatibility to the derivatized material.
  • Acyl groups that can be used as compatibilizing functional groups include acetyl, propionyl, butyryl, trifluoroacetyl, benzoyl, acryloyl and other well known groups .
  • the formation of such groups on either the primary or secondary ring hydroxyls of the cyclodextrin molecule involve well known reactions.
  • the acylation reaction can be conducted using the appropriate acid anhydride, acid chloride, and well known synthetic protocols.
  • Peracylated cyclodextrin can be made.
  • cyclodextrin having less than all of available hydroxyls substituted with such groups can be made with 21 into a useful pellet. The pellet is then formed into a preform shape which is then converted into a biaxally oriented beverage container.
  • Two techniques are typically used in manufacturing the bottles.
  • a machine is used that converts the resin pellet into a preform formed on a heated rod. After conditioning, the preform is blown using the rod and in conjunction with the balance of the manufacturing equipment into the bottle.
  • a second technique involves forming a preform from thermoplastic resin. Removing the resin from the preform manufacturing site and transferring the preform to a blow molding apparatus. The preform is then blown in biaxally oriented into a useful container shape.
  • the container can be self-supporting with a lobed bottom or can be adhesively bonded to a polyethylene or polypropylene base cup support.
  • the finished beverage container can be at least a two layer laminate material .
  • the laminate can contain in one layer a polyester material and in a second layer a barrier polymer.
  • the derivatized cyclodextrin material can be in either layer or in both layers.
  • a beverage container can comprise a biaxally oriented beverage container having a coating on the interior of the bottle.
  • the coating can be placed in the preform having sufficient thickness to adequately cover the interior of the beverage container after blowing. Alternatively, the coating can be formed on the interior of the container after blow molding.
  • Raw material used in any of the thermoforming procedures is a pelletized thermoplastic polyester or polyolefin.
  • the product of the transesterification reaction producing a thermoplastic polyester is in the form of a melt.
  • the melt can be easily reduced to a useful pellet or other small diameter flake or particulate.
  • the flake or particulate polyester can then be dried and blended with the derivatized cyclodextrin material until uniform and then melt 22 extruded under conditions that obtain a uniform dispersion or solution of the modified or derivatized cyclodextrin and polyester material .
  • the resulting polyester pellet is typically substantially clear, uniform and of conventional dimensions.
  • the pellet preferably contains about 0.01 to about 10 wt-% of the modified cyclodextrin, preferably about 0.1 to about 5 wt-% of the modified cyclodextrin and under certain circumstances, the polyester can contain between 0.5 and 2 wt-% of the cyclodextrin material.
  • the polyester pellet containing the modified cyclodextrin material then can be incorporated into the conventional preform or parison blow molding techniques. The products of these techniques contain similar proportions of materials .
  • Biaxially oriented PET plastic carbonated soft drink bottle which is produced from polyethylene terephthalate using methods taught in Wyeth et al., United States Pat. No. 3,733,309 issued May 15, 1973 and entitled "Biaxially Oriented Poly (Ethylene Terephthalate) Bottle.”
  • the majority of the biaxially oriented PET beverage bottles are presently being produced by the so-called two stage "reheat blow” method, using a separate machine for each stage.
  • PET parisons or preforms are first injection molded in a cooled mold, at melt temperatures of about 540°F.
  • nitrogen containing substituents include dialkylamino such as dimethylamino, diethylamino, piperidino, piperizino, quaternary substituted alkyl or aryl ammonium chloride substituents, halogen derivatives of cyclodextrins can be manufactured as a feed stock for the manufacture of a cyclodextrin molecule substituted with a compatibilizing derivative.
  • the primary or secondary hydroxyl groups are substituted with a halogen group such as fluoro, chloro, bromo, iodo or other substituents. The most likely position for halogen substitution is the primary hydroxyl at the 6-position.
  • Hydrocarbyl substituted phosphono or hydrocarbyl substituted phosphato groups can be used to introduce compatible derivatives onto the cyclodextrin.
  • the cyclodextrin molecule can be substituted with alkyl phosphato, aryl phosphato groups.
  • the 2, and 3, secondary hydroxyls can be branched using an alkyl phosphato group.
  • the cyclodextrin molecule can be substituted with heterocyclic nuclei including pendent imidazole groups, histidine, imidazole groups, pyridino and substituted pyridino groups .
  • Cyclodextrin derivatives can be modified with sulfur containing functional groups to introduce compatibilizing substituents onto the cyclodextrin.
  • sulfur containing groups manufactured based on sulfhydryl chemistry can be used to derivatize cyclodextrin.
  • Such sulfur containing groups include methylthio (-SMe) , propylthio (-SPr) , t-butylthio (-S-C (CH 3 ) 3 ) , hydroxyethylthio (-S-CH 2 CH 2 OH) , imidazolylmethylthio, phenylthio, substituted phenylthio, aminoalkylthio and others.
  • cyclodextrin having substituents ending with a hydroxyl aldehyde ketone or carboxylic acid functionality can be prepared.
  • groups include hydroxyethyl, 3- hydroxypropyl, methyloxylethyl and corresponding oxeme isomers, formyl methyl and its oxeme isomers, carbylmethoxy (-O-CH 2 -C0 2 H) , carbylmethoxymethyl ester (- 0-CH 2 C0 2 -CH 3 ) .
  • Cyclodextrin with derivatives formed using silicone chemistry can contain compatibilizing functional groups.
  • Silicone groups generally refer to groups with a single substituted silicon atom or a repeating silicone-oxygen backbone with substituent groups. Typically, a significantly proportion of silicone atoms in the silicone substituent bear hydrocarbyl (alkyl or aryl) substituents. Silicone substituted materials generally have increased thermal and oxidative stability and chemical inertness. Further, the silicone groups increase resistance to weathering, add dielectric strength and improve surface tension.
  • the molecular structure of the silicone group can be varied because the silicone group can have a single silicon atom or two to twenty silicon atoms in the silicone moiety, can be linear or branched, have a large number of repeating silicone-oxygen groups and can be further substituted with a variety of functional groups.
  • the simple silicone containing substituent moieties are preferred including trimethylsilyl, mixed methyl-phenyl silyl groups, etc.
  • the preferred cyclodextrin derivative containing polyester beverage containers of the invention are commonly made by incorporating the modified cyclodextrin into a polyolefin or polyester resin that is then formed 17 one or more of the balance of the available hydroxyls substituted with other functional groups.
  • Cyclodextrin materials can also be reacted with alkylating agents to produced an alkylated cyclodextrin.
  • Alkylating groups can be used to produce peralkylated cyclodextrin using sufficient reaction conditions exhaustively react available hydroxyl groups with the alkylating agent. Further, depending on the alkylating agent, the cyclodextrin molecule used in the reaction conditions, cyclodextrin substituted at less than all of the available hydroxyls can be produced.
  • alkyl groups useful in forming the alkylated cyclodextrin include methyl, propyl, benzyl, isopropyl, tertiary butyl, allyl, trityl, alkyl-benzyl and other common alkyl groups .
  • Such alkyl groups can be made using conventional preparatory methods, such as reacting the hydroxyl group under appropriate conditions with an alkyl halide, or with an alkylating alkyl sulfate reactant .
  • Tosyl (4-methylbenzene sulfonyl) mesyl (methane sulfonyl) or other related alkyl or aryl sulfonyl forming reagents can be used in manufacturing compatibilized cyclodextrin molecules for use in thermoplastic resins.
  • the primary -OH groups of the cyclodextrin molecules are more readily reacted than the secondary groups.
  • the molecule can be substituted on virtually any position to form useful compositions.
  • Such sulfonyl containing functional groups can be used to derivatize either of the secondary hydroxyl groups or the primary hydroxyl group of any of the glucose moieties in the cyclodextrin molecule.
  • the reactions can be conducted using a sulfonyl chloride reactant that can effectively react with either primary or secondary hydroxyl.
  • the sulfonyl chloride is used at appropriate mole ratios depending on the number of target hydroxyl groups in the molecule requiring 18 substitution. Both symmetrical (per substituted compounds with a single sulfonyl moiety) or unsymmetrical (the primary and secondary hydroxyls substituted with a mixture of groups including sulfonyl derivatives) can be prepared using known reaction conditions.
  • Sulfonyl groups can be combined with acyl or alkyl groups generically as selected by the experimenter.
  • monosubstituted cyclodextrin can be made wherein a single glucose moiety in the ring contains between one and three sulfonyl substituents. The balance of the cyclodextrin molecule remaining unreacted.
  • Amino and other azido derivatives of cyclodextrin having pendent thermoplastic polymer containing moieties can be used in the sheet, film or container of the invention.
  • the sulfonyl derivatized cyclodextrin molecule can be used to generate the amino derivative from the sulfonyl group substituted cyclodextrin molecule via nucleophilic displacement of the sulfonate group by an azide (N 3 "1 ) ion.
  • the azido derivatives are subsequently converted into substituted amino compounds by reduction. Large numbers of these azido or amino cyclodextrin derivatives have been manufactured.
  • Such derivatives can be manufactured in symmetrical substituted amine groups (those derivatives with two or more amino or azido groups symmetrically disposed on the cyclodextrin skeleton or as a symmetrically substituted amine or azide derivatized cyclodextrin molecule. Due to the nucleophilic displacement reaction that produces the nitrogen containing groups, the primary hydroxyl group at the 6-carbon atom is the most likely site for introduction of a nitrogen containing group.
  • nitrogen containing groups examples include acetylamino groups (-NHAc) , alkylamino including methylamino, ethylamino, butylamino, isobutylamino, isopropylamino, hexylamino, and other alkylamino substituents-.
  • the amino or alkylamino having a threaded bottle neck finish at its open ended top are heated uniformly in an oven to its orientation temperature, which for PET is about 190°F (87.78°C) to 200°F (93.33°C) (which is below PET's melting point) .
  • the temperature conditioned parisons are then placed within cooled bottle blow molds which clamp the parisons by their necks upon closing off the blow molds.
  • Metal pushrods are then inserted and pushed into the parisons through their open necks, and the parisons, whose initial lengths are shorter than that of the finished bottle, are stretched axially against the bottom of the blow molds to their final lengths, thereby effecting axial or longitudinal orientation.
  • Radial or so-called "hoop direction” orientation is next achieved by introducing compressed air inside the axially stretched parisons to expand them outward and into contact with the cooled surfaces of the bottle blow molds. After cooling sufficiently for subsequent handling, the blow molds open and the biaxially oriented bottles are ejected from the machine.
  • the reheating step can be avoided if a so-called in-line single stage injection blow molding process were utilized to make biaxially oriented hollow articles using a single "hot parison" injection stretch-blow molding machine.
  • the parison is formed by injection molding, cooled to orientation temperature, and then stretched axially and blown radially to its final product shape, without ever being allowed to cool to room temperature.
  • a number of such in-line "hot parison" injection stretch blowing methods and apparatus have been disclosed in the paten literature and as such constitute the prior art.
  • a hot thermoplastic parison is first formed by injection molding the thermoplastic material, at a temperature above its melting point, over a generally cylindrical core, called an inner sleeve, which is positioned in the female cavity of an injection mold.
  • the parison is then cooled, while on the core and within the injection mold, by suitable cooling means located therein, down to a narrow temperature range, which includes the preferred orientation temperature of the material being processed, said temperature range being relatively uniform and covering all points across the thickness and at the surfaces of the parison, and said temperature range also being below the thermoplastic materials homogenous melting temperature.
  • the narrow temperature range for PET parisons would be about 190°F.
  • the uniformly cooled parison is then removed from the injection mold and transferred, while still on the inner core, to a blow mold having cooling means therein. While in transit, or after being positioned within the closed blow molds, the parison is stretched axially by the outward extension of a valve located within the inner core over which the parison had been previously molded. Next, the parison is inflated, while positioned within the blow molds, thus stretching the parison along a second axis or direction of axial stretching. Stretching the thermoplastic parison at its orientation temperature, by longitudinal or axial extension of a valve within the core rod, and by radial inflation, sometimes referred to as "hoop stretching, " yields a biaxially oriented hollow article.
  • the parison must first be brought to orientation temperature throughout its entire thickness. If the metal surfaces of the core and injection mold cavity are maintained at temperatures at or slightly below the orientation temperature range of the thermoplastic to be processed, 190°F (87.78°C) to 200°F (93.33°C) . for PET, the parison will eventually be cooled to an equilibrium temperature condition corresponding to the desired orientation temperature range, across its thickness, wile it is still in the injection mold. However, the rate of cooling of the parison within the injection mold will be extremely slow because of the small temperature differential between the parison, the core, and the mold surfaces.
  • the speed of operation of the apparatus will be limited by the long injection molding cycle required.
  • the core and injection mold cavities are maintained at a much lower temperature, conventionally about 35°F (1.67°C) to 40°F (4.44°C) . for PET, the rate of cooling will be increased substantially, but an uneven temperature distribution will be created across the thickness of the parison.
  • Such rapid cooling of the parison if accomplished within an economical and commercially feasible cycle time, will result in surface temperatures of the parison which are substantially below the orientation temperature range of the thermoplastic being processed and will actually approach the temperature of the core and the injection mold, while the middle or mid-point of the parison walls will be substantially above the desired orientation temperature range. Therefore, satisfactory orientation will not be achieved during the stretching and blowing of parisons which have such substantial mal-distributions of temperatures across their thickness, major portions of which lie outside the orientation temperature range of the thermoplastic being processed.
  • a parison is formed on a first core in an injection mold, cooled in the injection mold, transferred on said first core to a pre-blow mold and partially expanded against the inner surfaces of the pre-blow mold to a shape intermediate that of the parison and that of the finished article.
  • cooling is effected on the first core in the pre- blow mold to a uniform temperature across its thickness within the desired orientation temperature range of the thermoplastic being molded.
  • the temperature conditioned parison is then transferred to a second blow core and later transferred to a third mold where it is axially stretched and expanded in the third mold, which is the final blow mold, to form a hollow biaxially oriented article.
  • Separate parisons may be simultaneously injection molded, preblown, and cooled to orientation temperature, and finally stretch-blown, if multiple sets of cores and molds are utilized. Because the parison is not conditioned to a uniform orientation temperature across its thickness in the injection mold, the injection mold can operate at a reasonable and economical production rate. However, the necessity for additional preblow molds and additional cores and transfer means greatly complicates the apparatus and requires greater capital investment.
  • pre- blowing to an intermediate shape is actually somewhat self-defeating in that it sacrifices the amount of orientation which may be subsequently imparted to the parison, since the degree of orientation which may be imposed is directly proportional to the amount of stretch which takes place after the parison has been brought to the desired orientation temperature, which in this case takes place in the pre-blow mold.
  • the amount of orientation-stretching which can be accomplished from stretching the parison' s intermediate shape to its final shape is less than if the parison was stretched, at orientation temperature, from its original shape to its final shape.
  • the cooled parison is then conditioned or tempered in the temperature controlled tempering mold to equalize the temperature distribution across the walls of the parison and attain a uniform temperature distribution corresponding to the desired orientation temperature of the thermoplastic material being molded.
  • the tempering is aided by insertion of a separate stretch-blow core into and against the parison, to provide pressure contact between the parison and the tempering mold, thereby speeding heat transfer between the two.
  • the temperature conditioned parison is then transferred on the stretch-blow core to a third mold, which is the stretch blow mold, and is finally axially stretched by telescoping extension of said stretch-blow core, and then radially expanded and cooled in said stretch-blow mold, to form a biaxially oriented hollow article.
  • the parison need not be conditioned to a uniform orientation temperature across its wall thickness in the injection mold, the parison may be removed from the injection mold early, and the injection molding step can be operated at a reasonable rate, and much faster then otherwise would be possible.
  • the necessity for additional cores, molds, and transfer means greatly complicates the apparatus and substantially adds to the costs.
  • a method for producing biaxially oriented hollow plastic articles in a rotary type injection molding machine having at least four stations, wherein a parison is formed on a first core within an injection mold at the injection station, cooled in the injection mold to a temperature above the orientation temperature, indexed to an interim station on said first core where the parison is preblown against the cold surfaces of an interim mold, which is larger than the shape of the original parison but smaller than the shape of the final desired article, cooled in the interim mold to the optimum orientation temperature, indexed on said first core to a blow station and positioned within the final blow mold whose cavity is in the shape of the final desired article.
  • the preblown parison is then axially stretched in the closed final blow mold by extension by a poppet valve stem located within said first core rod, and finally radially expanded outward to its final shape, against the cavity walls of the blow mold, and then cooled to a suitable ejection temperature.
  • the core rod and biaxially oriented article are indexed to an ejection station, where the biaxially oriented article is removed.
  • Marcus, United States Pat. No. 4,065,246, teaches another injection blow molding process employing at least three stations wherein the parison is formed on a core in an injection mold, cooled to the desired orientation temperature range while in the injection mold, transferred on the same core to the final blow mold and allowed to dwell therein to bring the parison to uniform orientation temperature while the outer tip of the parison is in contact with a temperature controlled stop, and the remainder of the parison, except for the inner surface of its tip, is expanded slightly off the core to aid in the removal of the first core from said parison, by momentarily introducing low pressure air inside the parison.
  • Marcus teaches that lubricant may be used to aid in removal of the first core from the parison.
  • the first core is removed from the partially expanded parison, and a second core is inserted and extended outwardly therein to stretch the parison longitudinally and thereby axially orient the parison.
  • High pressure air is then introduced within the axially stretched parison to expand it radially outward until it contacts the cool surfaces of the blow mold cavity where it assumes its final shape and is cooled to a suitable ejection temperature.
  • the biaxially oriented article is then transferred on said second core to an ejection station where it is ejected from the apparatus.
  • This process avoids the duplication of molds but requires the duplication of cores and transfer means, and extra stations, all of which add complexities and additional costs .
  • the methods disclosed in these patents are typical beverage container manufacturing methods. However, any method that can conveniently manufacture PET beverage container can be used with the pellets of the invention.
  • a laminated bottle can be made having an exterior layer typically comprising a thermoplastic with an interior layer comprising a barrier polymer.
  • Either the barrier polymer or the polyester material or both can contain the modified or derivatized cyclodextrin material as a permeant trapping molecule or as a contaminate trapping molecule.
  • the barrier polymer material can be any conventional thermoplastic that can be formed with polyethylene terephthalate into a laminate beverage container.
  • Thermoplastic materials can be formed into barrier film layer in the bottle using a variety of processes. These methods are well known manufacturing procedures.
  • the characteristics in the polymer thermoplastics that lead to successful barrier film formation are as follows. Skilled artisans manufacturing thermoplastic polymers have learned to tailor the polymer material for thermoplastic processing and particular end use application by controlling molecular weight (the melt index has been selected by the thermoplastic industry as a measure of molecular weight -- melt index is inversely proportional to molecular weight, density and crystallinity) .
  • melt index has been selected by the thermoplastic industry as a measure of molecular weight -- melt index is inversely proportional to molecular weight, density and crystallinity
  • blown thermoplastic extrusion polyolefins LDPE, LLDPE, HDPE
  • LDPE blown thermoplastic extrusion polyolefins
  • polypropylene, nylon, nitriles and polycarbonate are sometimes used to make blown film.
  • Polyolefins typically have a melt index from 0.2 to 3 grams/10 mins . , a density of about 0.910 to about 0.940 grams/cc, and a molecular weight that can range from about 200,000 to 500,000.
  • the polymer most often used are olefin based — chiefly polyethylene and polypropylene (melt index from about 0.1 to 4, preferably 0.4 to 4 grams/10 mins. and a molecular weight of about 200,000 to 600,000) .
  • Polyesters and nylons can also be used.
  • molten thermoplastic resin or monomer dispersion are typically produced from polyethylene or polypropylene. Occasionally, nylon, polyester and PVC are cast.
  • dispersions are polymerized to an optimum crystallinity and molecular weight before coating.
  • thermoplastic materials include polyacrylonitrile, poly(acrylonitrile-co-butadiene-co-styrene) polymers, acrylic polymers such as the polymethylmethacrylate, poly-n-butyl acrylate, poly(ethylene-co-acrylic acid) , poly(ethylene-co-methacrylate) , etc.; cellophane, cellulosics including cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate and cellulose triacetate, etc.; fluoropolymers including polytetrafluoroethylene (teflon) , poly(ethylene-co- tetrafluoroethylene) copolymers, (tetrafluoroethylene- co- propylene) copolymers, polyvinyl fluoride polymers, etc., polyamides such as nylon 6, nylon 6,6, etc.; polycarbonates; polyesters such as poly(ethylene-co- terephthalate) , poly(
  • a preform in making a laminate preform material having an exterior layer of a poly(ethylene-terephthalate) and an interior layer of a barrier polymer, a preform can be made through sequential injection molding techniques.
  • the first step involves the injection molding of a first preformed section.
  • the preform section can comprise either the barrier polymer or the polyethylene terephthalate container material .
  • the preform can then be transferred to a second station wherein the complimentary polymer is either injection molded on the interior of the preform (barrier polymer inside PET) or formed on the exterior of the preform (PET over the barrier polymer) .
  • Such a multi-step formation can also be done on a single machine having the appropriate internal working components for such injection molding operations.
  • the preforms must be cooled to a sufficient temperature to permit successful manufacture. Additional layers can be used if desired, however, the preferably container is a two layer construction.
  • the two or more layer preform material is then subjected to a reheat blow molding operation.
  • the preform is reheated to a desirable temperature sufficient to permit blow molding into the desired shape. Not only does the blow molding operation achieved biaxial orientation of the layers, thereby improving strength, but also produces the desired end product, and shaped bottom if desired.
  • the heat source is used either in the interior of or around the exterior of the bottle preform to reach an appropriate blow molding temperature.
  • the injection molded by component preform is subject to a final forming operation including biaxial orientation through stretch blow molding at a temperature from about at an elevated blow molding temperature that is typically 95- 150°C.
  • a isothermal temperature profile across the layers of thermoplastic is desired.
  • the temperature of blow molding should be sufficient to achieve satisfactory blow molding of both thermoplastic resins.
  • the cyclodextrin materials can be incorporated into a barrier cellulosic web by coating the cellulosic web or a similar structure containing a cellulosic layer with a liquid coating composition containing an effective amount of a cyclodextrin or substituted cyclodextrin.
  • a liquid coating composition containing an effective amount of a cyclodextrin or substituted cyclodextrin.
  • Such coating compositions are typically formed using a liquid medium.
  • Liquid mediums can include an aqueous medium or organic solvent media.
  • Aqueous media are typically formed by combining water with additives and components that can form a useful coatable aqueous dispersion.
  • Solvent based dispersions based on organic solvents can be made using known corresponding solvent base coating technology.
  • coatings can be formed either on a film which is later laminated on a film which is later laminated onto the cellulosic web or can be coated to form a film on the cellulosic web.
  • Such coating processes involve the application of liquid to a traveling cellulosic web.
  • Such coating processes commonly use machines having an application section and a metering section. Careful control of the amount and thickness of the coating obtains optimized barrier layers without waste of material.
  • a number of coating machines are known such as tension sensitive coaters, for example, coaters using a metering rod, tension insensitive coating stations that can maintain coat weight even as web tensions vary, brush coating methods, air knife coaters, etc.
  • Such coating machines can be used to coat one or both sides of a flexible film or one or both sides of a cellulosic web.
  • Coating machines described above commonly apply a liquid composition containing a film forming material, additives that can help form and maintain the coating composition along with the effective amount of the cyclodextrin or substituted cyclodextrin material.
  • the film forming materials are often called a binder.
  • binders exist in the final coating as a polymer of high molecular weight.
  • Thermoplastic polymers or crosslinking polymers can both be used.
  • Such binders are grouped into certain overlapping classes including acrylic, vinyl, alkyl, polyester, etc.
  • the compositions described above are materials that can be used in forming the polymer films also have corresponding materials that can be used in the formation of aqueous and solvent based coating compositions.
  • Such coating compositions can be made by combining the liquid medium with solid materials containing the polymer, the cyclodextrin and a variety of useful additives.
  • the cyclodextrin materials added to the coating composition as part of the solids component .
  • the solids present in the coating composition can contain from about 0.01 to about 10 wt% of the cyclodextrin compound, preferably about 0.1 wt% to 5 wt%, most preferably about 0.1 wt% to about 2 wt% of the cyclodextrin material based on the total solids in the solvent based dispersion composition.
  • a useful barrier layer can also be made by coating the interior of either a preform or a formed container with a coating typically made from an aqueous dispersion or suspension of a useful polymer material containing the modified cyclodextrin material.
  • the preform or container is heated to 40° to 80°C, and in coated with an aqueous dispersion of a polymer, and dried.
  • the coating is applied at a temperature of 40° to 100°C, preferably 50° to 90°C. If the temperature is below 40°C, little advantage is obtained compared with coating a preform at a room temperature where only a very thin coating, e.g-. about 3 ⁇ m thickness, of insufficient adhesion is obtained. If the preform is heat to above 90°C, then crystallization is likely to be induced which impairs satisfactory conversion of the preform into a biaxially oriented container during the blow molding operation and also gives rise to distortion of the container as a result of uneven relaxation of molding strains.
  • solvents that may be used include acetone, chloroform ethyl acetate, m-cresol and trichloroethylene.
  • an adherent and uniform coating of greater thickness e.g. of the order of 20 to 30 ⁇ m may be produced in a single coating step. If this thickness coating is inadequate, the coated perform may be given further coats after drying to give the necessary thickness. Preferably the coated article is reheated to 40 to 80°C before applying such further coats.
  • the drying is preferably conducted using an infra-red heater operating at a temperature below 1000°C.
  • an infra-red heater operating at a temperature below 1000°C.
  • the radiation will be absorbed by the water in the aqueous dispersion without unduly heating the PET preform itself: the water thus tends to act as a filter against infra-red radiation.
  • the preform or bottle may be rotated so as to provide even heating and also to provide an even thickness coating.
  • a PET preform in the form of a tube having one closed end may be mounted with its longitudinal axis horizontal and rotated about this longitudinal axis .
  • the preform or bottle may be mounted with its longitudinal axis horizontal and rotated about the longitudinal axis. As it rotates it is first heated by an infra-red heater to 40° to 90°C and then it picks up a coating of the aqueous dispersion from a coating point, e.g.
  • a flexible doctor knife then the water is evaporated off, and the coated preform heated to 40° to 90°C, by means of one or more infra-red heaters mounted adjacent the rotating article so that the coating is dried and the preform reheated before one revolution of the preform is completed: hence on reaching the coating point on completion of one revolution, a further coating of the aqueous dispersion is applied over the dried coating.
  • a multilayer coating may be formed as a spiral on the preform.
  • the coating may be applied to the interior or exterior surface and may be applied by spraying or dip coating.
  • coating the interior is advantageous particularly where the resultant bottle is intended to contain carbonated beverages.
  • the resultant bottle is intended to contain carbonated beverages.
  • it presents a barrier layer between the beverage and bottle wall and so reduces the amount of carbon dioxide absorbed by the polyethylene terephthlate itself.
  • This enables thinner coatings to be employed to achieve a specified carbon dioxide loss.
  • it is possible to employ a coating on the interior of the preform of thickness only half that which would be required on the outside of the preform to give a similar carbon dioxide loss.
  • the polymer dispersion may be any of those that are customarily employed for application of barrier coatings to plastic materials.
  • it is an aqueous dispersion of a copolymer of vinylidene chloride with acrylonitrile and/or methyl acrylate optionally containing units derived from other monomers such as methyl methacrylate, vinyl chloride, acrylic acid or itaconic acid.
  • Particularly useful vinylidene chloride copolymers are those containing 5 to 10% by weight of units derived from acrylonitrile and/or methyl acrylate, and optionally containing up to 10% by weight of units derived from an unsaturated carboxylic acid such as acrylic acid.
  • the dispersions may preferably contain surfactants such as sodium alkyl sulphonates.
  • the containers of the invention can be used to distribute a variety of beverages including milk (skim, 1%, 2%, chocolate) , orange juice, carbonated beverages, water, flavored water, carbonated water, beer, mixed alcoholic drinks, distilled spirits, wines, 200 proof grain or absolute alcohol; fruit juices such as apple, tomato, pear, etc.; distilled water, etc.
  • Figure 1 is a generally isometric view of a conceptual representation of the dimensions of the various cyclodextrin molecules.
  • Figure 1 shows an , ⁇ and ⁇ cyclodextrin showing the dimensions of the exterior of the cyclodextrin ring along with the dimensions of the interior pore volume that can act as a trapping site for permeants or polymer impurities.
  • View 1 shows that the primary and secondary hydroxyls exist on the edge of the circular form. This suggests that the interior of the cyclodextrin is relatively hydrophobic and adapted to complex and contain hydrophobic molecules.
  • Figure 2 is a side view of a substantially transparent two liter carbonated beverage container.
  • the container generally shown at 20 comprises a body 22, a base 24 and a cap portion 26.
  • the overall shape of the container is formed in a thermoplastic blow molding operation.
  • Base 24 is a self-supporting base formed during bottle manufacture.
  • Such a bottle can contain either a second layer prepared from a parison having a second thermoplastic material formed during parison formation or can have a second layer derived from a liquid coating material.
  • the liquid coating material can be either a parison coating or a bottle coating.
  • the cyclodextrin material can be melt blended into thermoplastic materials smoothly resulting in clear extrudable thermoplastic materials with the cyclodextrin materials uniformly distributed throughout the thermoplastic. Further, we have found that the cyclodextrin derivatives can be combined with a broad variety of thermoplastic films.
  • the cyclodextrin materials can be incorporated into the films in a broad range of cyclodextrin concentrations.
  • the cyclodextrin containing thermoplastic materials can be blown into films of varying thickness and can be blown free of melt fracture or other film or sheet variation.
  • the barrier properties i.e.
  • modified ⁇ CO acetylated and trimethylsilyl ether derivatives
  • machinability of the extruded plastic material is effected somewhat causing some surface defects, thereby reducing the barrier properties of the film.
  • (3) Films containing a modified ⁇ CO composition reduce aromatic permeants by 35% at 72°F (22.22°C) and 38% at 105°F (40.56°C) ; aliphatic permeants were reduced by only 9% at 72°F (22.22°C) . These results would improve significantly if worst case shelf-life testing conditions were not used to test the films.
  • Complexation rates were different for aromatic and aliphatic permeants.
  • Films containing modified jSCD had better complexation rates for aromatics (gasoline-type compounds) than aliphatic (printing ink- type compounds) . Conversely, film coating had significantly better complexation of aliphatic compound than aromatic compounds.
  • CD containing acrylic coatings were the star performers reducing aliphatic permeants from 46% to 88%, while aromatics were reduced by 29%.
  • the nine modified cyclodextrin and milled cyclodextrin LLDPE profiles were examined under an optical microscope at 50X and 200X magnification. The microscopic examination was used to visually check for compatibility between LLDPE resin and cyclodextrin. Of the ten cyclodextrin candidates tested, three (acetylated, octanyl succinate and trimethylsilyl ether) were found visually to be compatible with the LLDPE resin. Complexed residual film volatiles were measured using cryotrapping procedure to test 5% ⁇ CO film sample and three extruded profiles containing 1% (wt/wt) acetylated ⁇ CO octanyl succinate ⁇ CO and trimethylsilyl ether.
  • the method consists of three separate steps; the first two are carried out simultaneously while the third, an instrumental technique for separating and detecting volatile organic compounds, is conducted after one and two.
  • an inert pure, dry gas is used to strip volatiles from the sample.
  • the sample is heated at 120°C.
  • the sample is spiked with a surrogate (benzene-d6) immediately prior to the analysis.
  • Benzene-d 6 serves as an internal QC surrogate to correct each set of test data for recovery.
  • the second step concentrates the volatiles removed from the sample by freezing the compounds from the stripping gas in a headspace vial immersed in a liquid nitrogen trap.
  • an internal standard (toluene-d8) is injected directly into the headspace vial and the vial is capped immediately.
  • Method and system blanks are interspersed with samples and treated in the same manner as samples to monitor contamination.
  • the concentrated organic components are then separated, identified and quantitated by heated headspace high resolution gas chromatography/mass spectrometry (HRGC/MS) .
  • HRGC/MS heated headspace high resolution gas chromatography/mass spectrometry
  • acetylated, octanyl succinate and trimethylsilyl ether were shown to effectively complex trace volatile organics inherent in the LLDPE resin.
  • One percent loadings of acetylated and trimethylsilyl ether (TMSE) ⁇ CO showed approximately 50% of the residual LPDE organic volatiles were complexed, while the octanyl succinate CD did not complex residual LLDPE resin volatiles. Milled ⁇ CO was found to be less effective (28%) than the acetylated and TMSE modified ⁇ CD's.
  • Plastic packaging materials all interact to some degree with the food product they protect.
  • the main mode of interaction of plastic packaging of food is through the migration of organic molecules from the environment through the polymer film into the head space of the package where they are absorbed by the food product .
  • Migration or transfer of organic molecules of the package to the food, during storage, is effected by environmental conditions such as temperature, storage time, and other environmental factors (e.g., humidity, type of organic molecules and concentration thereof) .
  • Migration can have both quality (consumer resistance) and toxicological influence.
  • the objective of packaging film testing is to measure how specific barriers may influence the quality of packaged individual foods .
  • the relative humidity can affect the film' s performance especially in low-water-activity food products. Because a packaging film during actual end-use conditions will be separating two moisture extremes, relative humidity in the permeation device was controlled on both sides of the film. The environment side, representing the outside of the package, was maintained at 60% relative humidity, and the sample side, representing the inside of a package containing a low-water-activity product, at 0.25.
  • a combination of permeants was used to measure the function and performance of the CD.
  • a combination was used to be realistic, since gasoline (principally an aromatic hydrocarbon mixture) and printing ink solvents (principally an aliphatic hydrocarbon mixture) are not formed from a single compound but are a mixture of compounds.
  • the aromatic permeant contained ethanol (20 ppm) , toluene (3 ppm) , p-xylene (2 ppm) , o-xylene (1 ppm) , trimethyl-benzene (0.5 ppm) and naphthalene (0.5 ppm) .
  • the aliphatic permeant a commercial paint solvent blend containing approximately twenty (20) individual compounds, was 20 ppm.
  • the permeation test device consists of two glass permeation cells or flasks with cavities of 1200 ml (environment cell or feed side) and 300 ml (sample cell or permeating side) .
  • the 1% TMSE ,5CD film was slightly better than the 1% acetylated ⁇ CO film (24% -vs- 26%) for removing aromatic permeants at 72°F (22.22°C) adding more modified CD appeared to have no improvement.
  • both 1% TMSE jSCD and 1% acetylated ⁇ CO are approximately 13% more effective removing aromatic permeants than 72°F (22.22°C) .
  • the 1% TMSE film was again slightly better than the 1% film (36% -vs- 31%) for removing aromatic permeants.
  • the 1% TMSE film was more effective initially removing aliphatic permeants than the 1% acetylated ⁇ CD film at 72°F (22.22°C) . But for the duration of the test, 1% TMSE ⁇ CO was worse than the control while 1% acetylated ⁇ CO removed only 6% of the aliphatic permeants.
  • a reduction in aromatic and aliphatic vapors by the hydroxyethyl ⁇ CO coating is greater in the first several hours of exposure to the vapor and then diminishes over the next 20 hours of testing.
  • Higher removal of aliphatic vapors than aromatic vapors was achieved by the hydroxyethyl jSCD coating; this is believed to be a function of the difference in their molecular size (i.e., aliphatic compounds are smaller than aromatic compounds) .
  • Aliphatic permeants were reduced by 46% as compared to the control over the 20 hour test period. Reduction of aromatic vapors was 29% as compared to the control over the 17 hour test period.
  • the Rev. 1 coated hydroxyethyl ⁇ CO reduced the aliphatic permeants by 87% as compared to the control over the 20 hour test period. It is not known if the method of coating the film was responsible for the additional 41% reduction over the other hydroxyethyl ⁇ CO coated film.
  • the hydroxyethyl ⁇ CO coating was slightly better for removing aromatic permeants than the hydroxypropyl ⁇ CO coating (29% -vs- 20%) at 72°F (22.22°C) .
  • Example II Trimethyl Silyl Ether of ⁇ -cyclodextrin Into a rotary evaporator equipped with a 4000 milliliter round bottom flask and a nitrogen atmosphere, introduced at a rate of 100 milliliters N 2 per minute, was placed three liters of dimethylformamide. Into the dimethylformamide was placed 750 grams of ⁇ - cyclodextrin. The ⁇ -cyclodextrin was rotated and dissolved in dimethylformamide at 60°C. After dissolution, the flask was removed from the rotary evaporator and the contents were cooled to approximately 18°C.
  • HMDS- Pierce Chemical No. 84769 hexamethyldisilylazine
  • TMCS trimethylchlorosilane
  • the flask and its contents were placed on the rotary evaporator, heated to 60°C while maintaining an inert nitrogen atmosphere flow of 100 milliliters of N 2 per minute through the rotary evaporator.
  • the reaction was continued for four hours followed by removal of solvent, leaving 308 grams of dry material.
  • the material was removed from the flask by filtering, washing the filtrate with deionized water to remove the silylation products, vacuum oven drying (75°C at 0.3 inches of Hg) and stored as a powdered material and maintained for subsequent compounding with a thermoplastic material.
  • Table IA displays typical pelletizing extruder conditions.
  • the films were blown as follows. A thermal plastic tube was extruded through a first die. The tube was then collapsed by a second die and layered by rollers into the film. The extruded tube was then inflated using air under pressure blown through an air inlet tube. The thermoplastic was melted in the extruder. The extruder temperature is taken at the mixing zone. The melt temperature is taken in the melt zone while the die temperature is taken in the die. The extrudate is cooled using an air blown cooling stream from a cooling ring.
  • the foregoing general description is representative of the Kiefel blown film extruder, 40 mm die diameter, used in the actual preparation of the blown film.
  • the film is manufactured according to the above protocol and reported in Table IB. The film was tested for transmission rates at a variety of environmental conditions. Environmental test conditions are shown below in Table II.
  • Aromatic/Alcohol Aromatic/Alcohol
  • thermoplastic films of the invention substantially improves the barrier properties by reducing transmission rate of a variety of permeants .
  • the data showing the improvement in transmission rate is shown below in the following data tables.
  • Control Film 0.5% CS-001 (Roll #7) 1% CS-001 (Roll #5) 2% CS-001 (Roll #8) m 0 . 001 in .
  • aqueous coatings containing hydroxypropyl ⁇ CO These coatings can be used to coat the interior or exterior of a bottle.
  • One of the coatings was prepared from a 10% acrylic emulsion (a polyacrylic acid polymer having a molecular weight of about 150,000 purchased from Polysciences, Inc.) .
  • the 10% acrylic emulsion contained hydroxypropyl ⁇ CO at a 5% and 10% by weight loading.
  • These solutions were used to hand-coat test film samples by laminating two films.
  • the coatings were applied to linear low density polyethylene film sheet containing 0.5% acetylated ⁇ CO (Roll No. 7) and to a second film sheet containing 2% acetylated / SCD (Roll No.
  • a second coating was prepared from a vinylidene chloride latex (PVDC, 60 wt-% solids) purchased from Dagax Laboratories, Inc.
  • PVDC latex coating was prepared with two levels of hydroxypropyl ⁇ CO - 10% and 20% by weight of the derivatized cyclodextrin. These solutions were used to hand-coat linear low density polyethylene test film samples by laminating the two films together. The coatings were applied to two control film sheets (rolled into one) using a hand roller and laminated together. The films were not stretched during lamination process. All coated samples were placed in a vacuum laminating press to remove air bubbles between the film sheets. The PVDC coating thickness was approximately 0.0004 inch (.0001 mm) .
  • a PVDC coated control was prepared in an identical manner but without hydroxypropyl / SCD.
  • This method involves experimental techniques designed to measure the permeability of selected organic molecules through food packaging films, using a static concentration gradient .
  • the test methodology simulates accelerated shelf-life testing conditions by implementing various storage humidities, product water activities and temperature conditions and using organic molecule concentrations found in previously tested food products to simulate outside-the-package organic vapors in the permeation test cell. This procedure allows for the determination of the following compounds: ethanol, toluene, p-xylene, o-xylene, 1, 2,4-trimethyl benzene, naphthalene, naphtha solvent blend, etc.
  • Permeant Test Compounds In a typical permeation experiment, three steps are involved. They are (a) the instrument sensitivity calibration, (b) film testing to measure transmission and diffusion rates, and (c) the quality control of the permeation experiment. Film samples are tested in a closed-volume permeation device. High-resolution gas chromatograph (HRGC) operated with a flame ionization detector (FID) is used to measure the change in the cumulative penetrant concentration as a function of time.
  • HRGC High-resolution gas chromatograph
  • FID flame ionization detector
  • Sample-side and environment-side test compound concentrations are calculated from each compound's response factor or calibration curve. Concentrations are then volume-corrected for each specific set of permeation cells if permeant mass is desired.
  • the cumulative penetrant concentration is plotted as a function of time on both the upstream (environment) and downstream (sample) side of the film.
  • the diffusion rate and transmission rate of the permeant are calculated from the permeation curve data.
  • Reagent water Water in which interferences are not observed at the MDL of the chemical analytes of interest.
  • a water purification system is used to generate reagent water which has been boiled to 80% volume, capped, and allowed to cool to room temperature before use.
  • Ethanol/Aromatic Standard solution Ethanol (0.6030 gram) , toluene (0.1722 gram) , p-xylene (0.1327 gram) , o-xylene (0.0666 gram) , trimethylbenzene (0.0375 gram) and naphthalene (0.0400 gram) package in 1 ml sealed glass ampules .
  • Naphtha blends standard is a commercial paint solvent blend containing approximately twenty (20) individual aliphatic hydrocarbon compounds obtained from Sunnyside Corporation, Consumer Products Division, Wheeling, IL.
  • Triton X-100 Nonylphenol nonionic surface active agent (Rohm and Hass) . 2.0 Standards Preparation
  • a stock permeant test standard solution is used. These standards are prepared by weight from neat certified reference compounds, actual weight and weight percent are shown.
  • the working ethanol/aromatic standard is prepared by injecting 250 ul of the stock standard solution into 100 ml of reagent water containing 0.1 gram of surfactant (Triton X-100) . It is important that the Triton X-100 is completely dissolved in the reagent water prior to adding the permeant stock standard. This will insure dispersing the test compounds in the water.
  • the working standard should be mixed thoroughly each time an aliquot is dispensed. It is advisable to transfer the working standard to crimp-top vials with no headspace to minimize losses due to the large headspace in the volumetric flask used to prepare the standard.
  • a working naphtha blend standard is prepared by injecting 800 ⁇ L of the "neat" naphtha solvent blend into 100 milliliters of reagent water containing 0.2 gram of surfactant (Triton X-100) .
  • An opened stock standard solution should be transferred from the glass snap-cap vial to a crimp-top vial for short-term storage.
  • the vials may be stored in an explosion-proof refrigerator or freezer.
  • Calibration standards are prepared at a minimum of three concentration levels by adding volumes of the working standard to a volumetric flask and diluting to volume with reagent water.
  • One of the standards is prepared at a concentration near, but above, the method detection limit. The other concentrations correspond to the expected range of concentrations found in the environment and sample side cells .
  • each flask is fitted with a rubber septum.
  • the film test specimen is cut to the inside diameter of the aluminum seal ring using a template.
  • the film test specimen diameter is important to prevent diffusion losses along the cut edge circumference.
  • the film sample, aluminum seals, and testing flask is assembled.
  • the test cell is prepared. First the sample flask and environment flask are flushed with dry compressed air to remove humidity in the sample and environment flasks. This is done by puncturing the sample system and environment septum with a needle and tubing assembly which permits a controlled flow of dry air through both flasks simultaneously. The clamp rings are loosely fitted to the flasks to eliminate pressure buildup on either side of the film. After flushing both flasks for approximately 10 minutes, the needles are removed and the clamp rings tightened, sealing the film between the two flasks. Rubber faced aluminum spacers are used to ensure a gas tight fit.
  • the sample side is injected with 2 ⁇ L of water per 300 ml flask volume. Since the sample flasks vary in volume, the water is varied to correspond to the volume variations. The 2 ⁇ L of water in the 300 ml flask volume is comparable to a 0.25 water activity product at 72°F (22.22°C) .
  • 40 ⁇ L, the permeation ethanol/aromatic working standard or 40 ⁇ L of the naphtha blend working standard prepared according to section 2.2 is injected into the environmental flask. Either of these working standards will produce a 60% relative humidity at 72°F (22.22°C) with a permeant concentration (parts per million-volume/volume) in the 1200 ml volume flask indicated in Table I.
  • a sample from the group is removed from the oven.
  • the environmental flask is analyzed first, using a heated six-port sampling valve fitted with a 1 ml loop.
  • the loop is flushed with a 1 ml volume of the environment-side or sample-side air.
  • the loop is injected onto the capillary column.
  • the GC/FID system is started manually following the injection. Up to eight 1 ml sample injections may be taken from the sample and environment side of a single permeation experiment. Sample side and environment side test compound concentrations are calculated from each compound's calibration curve or response factor (equation 1 or 3) . Concentrations are then volume-corrected for each specific set of permeation flasks if permeant mass is desired. 4.0 Sample Analysis
  • the six-port sampling valve temperature is set to 105°C.
  • a three point calibration is prepared using standards in the range of the following test compounds:
  • Naphtha Solvent Blend 4.0 - 40 To prepare a calibration standard, add an appropriate volume of the working standard solution to an aliquot of reagent water in a volumetric flask.
  • the naphtha solvent blend is a commercial paint solvent containing approximately twenty (20) individual aliphatic hydrocarbon compounds .
  • the response versus concentration is determined by totaling the area under each of the twenty individual peaks .
  • Method of least squares is used to fit a straight line to the calibration curve.
  • the slope of each test compound's calibration curve is then calculated for determining the unknown concentration.
  • the average response factor may be used in place of the calibration curve.
  • the working calibration curve or response factor must be verified on each working day by measurement of one or more calibration standards. If the response of any compound varies more than 20%, the test must be repeated using a fresh calibration standard. If the results still do not agree, generate a new calibration curve.
  • Calibration standards and method detection samples are prepared in the environment flask only. This is accomplished by using a 1/2 inch (.127 mm) plastic disk and aluminum sheet disk the diameter of the environment flange in place of the sample flask. A single sealing ring is placed onto the environmental glass flange followed by an aluminum sheet, and then the plastic disk.
  • the environment flask is flushed with dry compressed air to remove humidity in the sample and environment flask. This is done by puncturing the environment septa with a needle and tubing assembly which permits a controlled flow of dry air through the flask.
  • the clamp rings are loosely fitted to the flask to eliminate pressure buildup. After flushing both flasks for approximately 10 minutes, the needle is removed and the clamp rings tightened, sealing the aluminum sheet against the seal ring.
  • the environment flask is removed from the oven.
  • the environmental flask is analyzed using a heated six-port sampling valve fitted with a 1 ml loop.
  • the loop is flushed with a 1 ml volume of the environment-side or sample-side air.
  • the loop is injected onto the capillary column .
  • the GC/FID system is started manually following the inj ection . 4 .4 Calculation of Results
  • Test Compound Response Factor Sample -side and environment -side test compound concentrations are calculated for each compound' s calibration curve slope or response factor (RF) . Concentrations are then volume-corrected for each specific set of permeation cells if permeant mass is desired .
  • the cumulative penetrant mass is plotted as a function of time on both the upstream (environment) and downstream (sample) side of the film.
  • the diffusion rate and transmission rate of the permeant area calculated from the transmission curve data.
  • the permeability coefficient, R is usually characteristic for the permeant-polymer system. This is the case with the permeation of many gases, such as hydrogen, nitrogen, oxygen, and carbon dioxide, through many polymers. If a permeant interacts with polymer molecules, as is the case with the permeant test compounds used in this method, P is no longer constant and may depend on the pressure, film thickness, and other conditions. In such cases, a single value of P does not represent the characteristic permeability of the polymer membrane and it is necessary to know the dependency of P on all possible variables in order to obtain the complete profile of the permeability of the polymer. In these cases, the transmission rate, Q, is often used for practical purposes, when the saturated vapor pressure of the permeant at a specified temperature is applied across the film . Permeability of films to water and organic compounds is often expressed this way.
  • Q is represented in units of gm-0.001 inches 100 in 2 -day.
  • the pressure-drop across the film from environment side to sample side is principally due to water vapor pressure.
  • the water concentration or humidity does not remain constant and is not measured during the time intervals the organic compounds are analyzed, and therefore the pressure across the membrane is not determined.
  • thermoplastic films containing a variety of compatible cyclodextrin derivatives shows that the invention can be embodied in a variety of different thermoplastic films. Further, a variety of different compatible derivatized cyclodextrin materials can be used in the invention. Lastly, the films can be manufactured using a variety of film manufacturing techniques including extrusion and aqueous dispersion coating to produce useful barriers. Migration from Food and Beverage Packaging Materials
  • the migration of trace amounts of reaction and degradation byproducts, additives, oligomers and monomers from food and beverage packaging can affect consumer acceptance, product qulaity and regulatory approval of candidate packaging materials.
  • Tests were conducted to measure the transfer of these substances from packaging films with and without acetylated cyclodextrin using a method from The Center for Food Safety and applied Nutrition of the U.S. Food and Drug Administration (FDA) .
  • the method simulates the expected migration of these substances in a packaging film to a particular food type, but the packaging test material is subjected to accelerated testing which simulates migration occurring to real food under normal conditions of packaging and storage.
  • HDPE high density poyethylene
  • One of the films contained 0.5% (wt/wt) acetylated a cyclodextrin, two contained a acetylated ⁇ cyclodextrin at 0.5% and 1.0% loading levels, and two contained a mixture of acetylated and ⁇ cyclodextrin at 0.5% and 1.0% loading levels.
  • the sixth film was a control made from the same batch of HDPE (DOW 640) and additives (Dynamar FX-9613 processing additive; Irgafos 168 and Irganox 1076 antioxidants) but without cyclodextrin.
  • the films were fabricated by blown film extrusion and had a normal thickness of 2 mil.
  • Migration testing was conducted according to FDA guidelines for food-simulating liquids.
  • the migration cells were for single sided flexible film and conform to ASTM F34-92.
  • the food simulating liquid was 8% ethanol in deionized water and test temperature 40°C.
  • the food-simulating liquid (FSL) was withdrawn from the extraction cell after seven days.
  • the FSL was reduced in volume, exhcnaged with methylene chloride and then analyzed by gas chromatography using flame ionization detection.
  • the gas chromatograms of the six test film FSL extracts are provided in the attached figures.
  • the peaks indicated in the chromatograms are migrants that diffused from the HDPE film into the FSL.
  • the reduction in the migrant amount was determined quantitatively by comparison of the gas chromatographic total peak areas from 4 minutes to 30 minutes.
  • Film samples containing acetylated cyclodextrin were compared to the control film made from the same HDPE resin and additives but without cyclodextrin.
  • the percent reduction of extractable migrants in the 8% ethanol FSL was determined using the following equation:
  • Food that comes into direct contact with polymeric packaging materials may result in the transfer or migration of volatiles into the stored food product.
  • package materials are approved for direct food contact, they can impart flavors to the food.
  • Volatiles can become incorporated into the pellets during the manufacturing process. When these pellets are converted to film, the flavor of the film can be affected by the residual volatiles.
  • the method consists of three separate steps; the first two are carried out simultaneously while the third, an instrumental technique for separating and detecting volatile organic compounds, is conducted after one and two.
  • an inert pure, dry gas is used to strip volatiles from the sample.
  • the sample is heated at 120°C.
  • the sample is spiked with a surrogate (benzene-d6) immediately prior to the analysis.
  • Benzene-d6 serves as an internal ZC surrogate to correct each set of test data for recovery.
  • the second step concentrates the volatiles removed from the sample by freezing the compounds from the stripping gas in a headspace vial immersed in a liquid nitrogen trap.
  • an internal standard (toluene-d8) is injected directly into the headspace vial and the vial is capped immediately.
  • Method and system blanks are interspersed with samples and treated in the same manner as samples to monitor contamination.
  • the concentrated organic components are then separated, identified and quantitated by heated headspace high resolution gas chromatography-mass spectrometry (HRGC/MS) .
  • HRGC/MS heated headspace high resolution gas chromatography-mass spectrometry

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Wrappers (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Les boissons gazeuses peuvent contenir une concentration relativement réduite de matières solubles dans l'eau provenant de récipients à boissons formés à chaud orientés biaxialement. Ces récipients peuvent comporter un matériau barrière pour les perméants et un piège efficace pour les matières solubles dans l'eau, lesquelles peuvent s'échapper du thermoplastique par extraction dans la boisson gazeuse. Ce matériau de récipient amélioré comprend une bande polyester thermoplastique formée par soufflage contenant une matière cyclodextrine modifiée compatible, ladite matière comportant des fractions latérales ou des substituants qui rendent la cyclodextrine compatible avec le thermoplastique du récipient. La matière cyclodextrine, une fois ajoutée à la matière polymère, agit comme une barrière et retient les matières extractibles au fur et à mesure qu'elles filtrent à travers le polyester thermoplastique. La molécule de cyclodextrine est munie d'une grande cavité centrale dont les propriétés augmentent la probabilité que des molécules organiques soient absorbées et retenues dans le pore central. Le polyester ainsi obtenu est relativement résistant à toute extraction par la boisson gazeuse de matières solubles provenant de la matière polyester.
PCT/US1997/002579 1996-02-20 1997-02-20 Bouteilles pour boissons en polymere rigide dotees d'une resistance amelioree a l'elution de permeants WO1997030122A1 (fr)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000001527A1 (fr) * 1998-07-06 2000-01-13 Cellresin Technologies, Llc Bande cellulosique avec barriere pour les permeants ou piege pour les contaminants
WO2000064648A1 (fr) * 1999-04-22 2000-11-02 Vinpac International Pty Ltd Elements de fermeture traites 2
WO2000064647A1 (fr) * 1999-04-22 2000-11-02 Vinpac International Pty Ltd Fermetures traitees
WO2000064649A1 (fr) * 1999-04-22 2000-11-02 Vinpac International Pty Ltd Fermetures traitees (3)
NL1013488C2 (nl) 1999-11-04 2001-05-07 Campina Melkunie Bv Fles voor zuivelproduct.
WO2001032514A1 (fr) 1999-11-04 2001-05-10 Campina Melkunie B.V. Bouteille pour produits laitiers sensibles a la lumiere
AU776471B2 (en) * 1999-04-22 2004-09-09 Vinpac International Pty Ltd Treated closures 2
US7001661B2 (en) 2001-08-15 2006-02-21 Cellresin Technologies, Llc. Packaging material
US7470464B2 (en) 2003-09-05 2008-12-30 Cellresin Technologies, Llc Fiber material having improved malodor scavenger properties
US8629215B2 (en) 2009-03-30 2014-01-14 Cellresin Technologies, Llc Malodor absorbent polymer and fiber
CN110698732A (zh) * 2019-09-29 2020-01-17 界首市蒙特普休闲用品有限公司 一种改性β-环糊精制备可降解仿生鱼饵的方法

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JPH03215031A (ja) * 1990-01-19 1991-09-20 Kyoraku Co Ltd 包装用多層構造体
US5177129A (en) * 1991-04-22 1993-01-05 The Valspar Corporation Interior can coating compositions containing cyclodextrins
WO1996000260A1 (fr) * 1994-06-23 1996-01-04 Aspen Research Corporation Materiau barriere comprenant un polymere thermoplastique et un derive de cyclodextrine compatible

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JPH03215031A (ja) * 1990-01-19 1991-09-20 Kyoraku Co Ltd 包装用多層構造体
US5177129A (en) * 1991-04-22 1993-01-05 The Valspar Corporation Interior can coating compositions containing cyclodextrins
WO1996000260A1 (fr) * 1994-06-23 1996-01-04 Aspen Research Corporation Materiau barriere comprenant un polymere thermoplastique et un derive de cyclodextrine compatible

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000001527A1 (fr) * 1998-07-06 2000-01-13 Cellresin Technologies, Llc Bande cellulosique avec barriere pour les permeants ou piege pour les contaminants
WO2000064648A1 (fr) * 1999-04-22 2000-11-02 Vinpac International Pty Ltd Elements de fermeture traites 2
WO2000064647A1 (fr) * 1999-04-22 2000-11-02 Vinpac International Pty Ltd Fermetures traitees
WO2000064649A1 (fr) * 1999-04-22 2000-11-02 Vinpac International Pty Ltd Fermetures traitees (3)
AU776471B2 (en) * 1999-04-22 2004-09-09 Vinpac International Pty Ltd Treated closures 2
NL1013488C2 (nl) 1999-11-04 2001-05-07 Campina Melkunie Bv Fles voor zuivelproduct.
WO2001032514A1 (fr) 1999-11-04 2001-05-10 Campina Melkunie B.V. Bouteille pour produits laitiers sensibles a la lumiere
US7001661B2 (en) 2001-08-15 2006-02-21 Cellresin Technologies, Llc. Packaging material
US7470464B2 (en) 2003-09-05 2008-12-30 Cellresin Technologies, Llc Fiber material having improved malodor scavenger properties
US8629215B2 (en) 2009-03-30 2014-01-14 Cellresin Technologies, Llc Malodor absorbent polymer and fiber
CN110698732A (zh) * 2019-09-29 2020-01-17 界首市蒙特普休闲用品有限公司 一种改性β-环糊精制备可降解仿生鱼饵的方法
CN110698732B (zh) * 2019-09-29 2021-05-04 界首市蒙特普休闲用品有限公司 一种改性β-环糊精制备可降解仿生鱼饵的方法

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