Enhanced lubrication in polyolefin closure with polyolefin grafted cyclodextrin.

IMPROVED LUBRICATION IN POLYOLEFIN SEAL WITH

CYCLODEXTRIN GRAFTED IN POLYOLEFIN

Related Requests

This application is a continuation application in part of U.S. Serial No. 10 / 672,297 filed September 25, 2003, the application of which is a utility application claiming priority from provisional patent application No. 60 / 432,523 filed December 10, 2002, now abandoned, the applications of which are incorporated herein by reference.

Field of Invention

The invention relates to polymer materials containing grafted cyclodextrin and a lubricant used in a variety of end uses. The invention relates to a polymer closure composition, film, polymer thick webs, rigid or semi-rigid sheets, microelement barrier covers, and other useful polymer forms. The invention also relates to packaging materials, closures, lids, lid liners, containers, and other thermoplastic container technology.

BACKGROUND OF THE INVENTION

The development of high-performance polymer-based packaging materials and structures has allowed the evolution of

<img file="MX347751B_D0001.tif" />

IMPI

MEXICAN INSTITUTE

- two . ... . ... HEARD LAFROflEDAD lightweight flexible films and rigid containers, boflffNlse^{TO THE}and trays that protect the contents against the ingress of organic vapors, aromas, humidity, oxygen and other gases. The purpose is to make the underlying technologies transparent while simultaneously reducing the financial and environmental costs of these products to the end consumer. There is still a considerable need for polymer materials and packaging systems that provide increased shelf life stability under a wide range of storage conditions and food products. The present invention relates to barrier structures for food packaging that are useful in providing the extended shelf life of the product.

The sheer size of the packaging industry makes up an attractive market with incredible numbers of technical challenges, for example, loss of flavor from stripping, staining from odor and flavor release, oxygen ingress, odor control, photodegradation (loss of value due to a sensitivity to light), moisture loss, source reduction / waste recycling, and environmental / social considerations. As innovations in fundamental polymer science increase, applications for new packaging expand considerably as well as the complexity of solutions, thus providing an ever-growing market for innovations. Current estimates suggest that the dollar value of the polymers used to make packaging adds up to more

<img file="MX347751B_D0002.tif" />

MEXICAN INSTITUTE

The exploitation of the $ 19 billion po4l in 2002.

define how a packaging material has provided substantial advantages to producers, retailers and consumers over traditional glass, aluminum and metal materials since its introduction in the 1950's. The driving force for innovation has been to develop a consumer demand for convenient and transportable packaging, while continuing to improve functional properties to protect freshness, quality and safety at a cost-effective price through the use of more innovative technologies, complex materials and structures. .

The globalization of the food industry and its packaging suppliers present challenges from a regulatory point of view since the materials to be exported must meet the requirements of any country to which the product is transported. For the packaging innovator introducing novel packaging technologies, this represents a massive, long-term and costly commitment. Regulatory agencies require that the materials, which are being manufactured, meet strict safety standards for both human and environmental exposure.

Packaging materials have been the target of consumer and environmental activist groups as they are a major contributor to the solid waste stream; These materials make up more than a third of the total waste generated in the United States. In many cases, manufacturers want to achieve source reduction and cost reduction through

- 4 IMPI

MEXICAN INSTITUTE g

OF PROPERTY combination of polyolefin layers of different barrier materials (eg nylon, polyvinylidene chloride - PVDC, alWITOT ethylene vinyl - VEO, etc.) in order to achieve the desired barrier properties and gauge; packaging film metallization is yet another technique. In some cases, these approaches create incompatibility problems for pre-consumer in-plant scrap recycling and post-consumer plastic recycling streams. Environmental considerations clearly influence current packaging technologies and will certainly continue to do so in the future.

In today's competitive markets, all technology innovations are driven by intense competition and therefore must meet industry target and cost constraints. The main cost guidelines in today's packaging are raw materials. Innovative new value technology leads packaging to be weighed against added cost.

The invention provides a polyolefin having a cyclodextrin grafted to lessen regulatory concerns because cyclodextrin is covalently linked to food safety concerns that removes polymers related to cyclodextrin migration. The present invention provides an innovative functional material with significant property improvements, which is compatible with source reduction, in-plant scratch recycling, and post-consumer recycling.

<img file="MX347751B_D0003.tif" />

<img file="MX347751B_D0004.tif" />

- 5 MEXICAN INSTITUTE OF INDUSTRY PROPERTY!

The invention forms compatible functionalized cyclodextrin (CD) / polyolefin compositions by grafting an unmodified, primary cyclodextrin onto a polyolefin, using extrusion processing in order to reduce both material, manufacturing and regulatory costs, and decrease the impact on the environment that the synthetic route otherwise takes to synthesize a compatible cyclodextrin derivative.

The invention also provides a commercial polyolefin material that has higher crystallinity and lower surface energy to effectively change the cleavage of compounds in direct contact with the polymer, especially nonpolar compounds (eg, alkanes, aromatics, and terpenes and sesquiterpenes. ).

Containers of liquid and solid contents that can be emptied require a closure system in order to maintain the integrity of the product within the container. The receptacle maintains the character of any product within the container free from external contamination. In addition, the closure maintains volatile components such as charring from sparkling water and carbonated beverages and can also ensure that the product does not interact with the atmosphere in any way to degrade the quality of the product. Such closures are either closure liners, snap caps, or screw (threaded) caps or closures. In making a screw or threaded container closure, the container typically

<img file="MX347751B_D0005.tif" />

- 6 thermoplastic and closure are formed so

IMPI

MEXICAN WSTmJTO DE LA FROHEDAD IfíDUSTMIAl thermoplastic.

container can be filled with product and closed with the closure. The closures may include screw caps and snap-fit ​​closures or liners for the closure which may comprise a valved post and others. In screw closures, the cap is typically placed on the container with automated equipment that imposes a specific degree of torque on the cap to ensure complete and permanent sealing. The caps are designed to be removable by a user through the application of a turning force with a designated degree of torque in such a way that the vast majority of users can remove the cap, including the elderly, children and others. Lubricants have been incorporated, for some time, into all closure structures to ensure removal with a torque that is acceptable to most users. Lubricants can also aid in the installation or removal of other types of closures. Such lubricants are typically formulated in the thermoplastic closure material. Sufficient lubricant is used in the formulation to ensure that at least some of the lubricant appears at the interface between the thermoplastic cap and the surface of the thermoplastic bottle. As long as a sufficient amount of that lubricant appears at the interface point, the lubricant can promote the installation and removal of the cap at sufficient torque for most users.

BRIEF DESCRIPTION OF THE INVENTION

<img file="MX347751B_D0006.tif" />

IMPI

INSTITUI · MIXICANC DE LA MONEDAD INDUSTRIAL

The invention relates to novel functional polyolefin compositions and structures containing a lubricant and cyclodextrin elements pendent in the polymer. More particularly, this invention relates to a polyolefin comprising a thermoplastic resin, a lubricant and a reaction product of a functionalized polyolefin and cyclodextrin, in which the cyclodextrin is grafted onto the functionalized polyolefin. The traditional mixing apparatus can be used to convert the resin into functionalized resin. Upon grafting, a functional group such as the hydroxyl functionality of the cyclodextrin reacts with a reactive functional group on the polymer to form a bond between the cyclodextrin and the polymer. In a preferred mode, an anhydride or epoxide component of the functionalized polyolefin can be used to form a reaction product. For example, a primary hydroxyl in cyclodextrin reacts with a maleic anhydride element under conditions that convert substantially all anhydride groups to a medium ester. It has been found quite unexpectedly that by such conversion it is possible to significantly change the low molecular weight transport of organic compounds in conventional polyolefin polymers through the use of major cyclodextrins. This invention is also a process for the production of the reaction product of the functionalized polyolefin and the cyclodextrin by fusion grafting with functionalized polyolefin in a customary composition apparatus that forms a compatible composition of

-θ IMPI &lt;

MEXICAN INSTITUTE

FROM THE DUSTRIAL PROPERTY The polar nature of the polymer functionalized with cictTHTüYtTTR ^ and ~ ST polar lubricant migrate to the surface of the closure or lid.

Cyclodextrin graft polymer compositions according to the present invention are useful in cast or drawn structures such as thin films, laminates, semi-rigid films, and rigid containers as well as fibers. For example, these structures provide functional properties for a sealing layer in flexible food packaging, a beverage contact layer for boxes and bottles, plastic closures and layers of sealing elements for bottles and jars of sauces, soups, purees, food. for babies and wine, a non-contact layer in plastic fuel tanks, and polymers used to make fibers, textiles and non-woven compositions for disposable diapers.

We have found that the lubrication of a thermoplastic cap closure can be improved by manufacturing a cap from the formulation comprising polyolefin, an effective amount of a cyclodextrin graft polymer material of the invention combined with a lubricating material. We have found that in use, the proportions discussed below, the grafted cyclodextrin and the lubricating material, in combination, have a higher polarity than the thermoplastic cap and tend to form a surface of improved lubricity on the formed seal. We believe that the combination of the polar nature of the cyclodextrma substitute

<img file="MX347751B_D0007.tif" />

- 9 IMPI

MEXICAN INSTTTVTC

OF THE GRAFTED ΐΝπυίτηίΑΐ PROPERTY and the substantially polar nature of the lubricating material enhance the tendency of the polar materials to migrate out of the bulk polymer and onto the surface of the formed closure structure. In this way, the thermoplastic closure obtains a lubricity that is improved by the cooperation between the grafted cyclodextrin and the lubricating material.

The invention comprises a closure having a surface with an improved concentration of the lubricant compared to the precursor bulk polymer. A second aspect of the invention is a closure or coating formulation comprising a combination of the grafted cyclodextrin and the lubricant. A further aspect of the invention comprises a method for improving the lubricity of thermoplastic closure or coating systems comprising mixing a thermoplastic material with grafted cyclodextrin, and a lubricating composition and forming a cap or coating from the mixed composition. . In this discussion, the term "bulk polymer precursor" refers to the material formed in the closure that typically comprises polyolefin, grafted cyclodextrin, and lubricant and the average concentration of materials in the composition before the lubricant can migrate to the surface of the closure, lining or lid.

DETAILED DESCRIPTION OF THE INVENTION

In summary, the invention comprises a thermoplastic resin, a lubricant and a polyolefin covalently bound to

<img file="MX347751B_D0008.tif" />

- 10 IMPI

INSTITUTO MEXICANO DE LA rMHElML a CD. CD can react with a functional polyolefin.

Polyolefins with a variety of functionalate groups can be used to covalently bind CD. One version is the modification or functionalization of polyolefins where a peroxide initiator is used with various unsaturated polar monomers in order to add chemically reactive elements in the polymer which has an important unexpected application when used in combination with a group of compounds in this present invention, known as cyclodextrins.

Cyclodextrin (CD) is a cyclic oligomer of α-D-glucose formed by the action of certain enzymes, such as cyclodextrin glycotransferase (CGTase). Three cyclodextrins (alpha, beta, and gamma) are commercially available consisting of six, seven, and eight α-1,4-linked glucose monomers, respectively. The most stable three-dimensional molecular configuration for these oligosaccharides is a torus with the smallest and largest aperture of the toroid that presents hydrophilic, primary and secondary groups. The specific coupling of glucose monomers gives CD a rigid, truncated, conical molecular structure with a hollow interior of a specific volume.

Commercial polyolefin functionalization is achieved through the use of solution, melt, and solid state routes known in the art. The process covalently bonds monomers on vinyl polymers or on polyolefin polymers that include copolymers of olefins with other monomers, such as^11_ IMPI ^

MEXICAN INSTITUTE

DI THE PIOPFETY as vinyl monomers, constituting predominantly the olefin portion. The polyolefins useful in this invention include poly (ethylene) or PE, poly (propylene) or PP, poly (ethylene-co-propylene) or PEP, ethylene / methyl acrylate copolymer and ethylene / ethyl acrylate copolymer. . Polyolefins can be functionally modified with unsaturated compounds such as unsaturated anhydrides and carboxylic acids. Additionally, there are terpolymers of ethylene-acrylate (ethyl or butyl) -maleic anhydride and ethylene-methyl acrylate-glycidyl methacrylate. Any grade of vinyl polymer packaging can be used.

Functionalized polyolefins have extensive industrial applications, such as the coextrusion of binder resins in multilayer films and bottles for the food industry, compatibilizers for designing polymers and plastic fuel tank binder resins for the automotive industry, flexibilization and compatibilization of halogen-free polymers for cables and fillers used in roof construction. Functionalized polyolefins useful in the present invention are maleate polyethylene and polypropylene (Orevac ™ and Lotryl ™ from ATOCINA, Plexar® resins from EQUISTAR, Fusabond® resins from DuPont, OPTM resins from MANAS and EXXELORTM from Exxon / Mobil), functionalized EP, EVA and EPDM (such as ethylene-propylene-butadiene or ethylene-propylene-1,4-hexadiene polymers) ethylene-octene, ethylene-n-butyl acrylate-maleic anhydride copolymers, ethylene-ethylacrylate-maleic anhydride terpolymers, and

- 12 IMPI

<img file="MX347751B_D0009.tif" />

copolymers

INSTITUTO MEXICANO of ethylene-glycidyl methacrylate and the ethylene-propylene-1,4-hexadiene polymer can be represented as:

- (CH₂CH₂)_X - (CHCH₂)_Y - (CHCH₂)_zch₃ where x, y, and z are selected so as to obtain about 70 to 90% by weight of ethylene, about 10 to 30% by weight of propylene, and up to about 5% by weight of 1,4-hexadiene. The vacant links are linked to similar groups, H or end groups.

The olefin compositions of the invention with pendant CD elements can be extruded, laminated, or molded into a variety of useful films, sheets, closure liners and caps, structures, or shapes using conventional processing technology.

The compositions of this invention can be prepared by using reactive extrusion by feeding a dry cyclodextrin, or derivative thereof, (&lt;0.10% moisture), a functionalized polyolefin and optionally a second polyolefin, in an extruder at such temperatures that the cyclodextrin reacts with the functionalized polyolefin as the molten polymer and cyclodextrin are transported through the extruder to form a reaction product containing, for example, a group

INSTITUTO MEXICANC?

OF THE nOFIBOAD

INDUSTRIAL ester that covalently binds cyclodextrin to polyolefin. The ratio of functionalized polyolefin to non-functionalized polyolefin can be adjusted for a specific application and conversion process. The present invention is directed to a stoichiometric reaction product of a cyclodextrin and a graft-linking agent (i.e., anhydride, epoxide, etc.), resulting in a modified polymer, especially suitable as a main batch that can be left behind. with one or more thermoplastic polymers and thermoplastic elastomers, non-functionalized, in a weight ratio of one (1) part of the main batch composition to ten (10) to twenty (20) parts of non-functionalized polymer. In other words, the mixture of polymer and main batch, or functionalized polymer, after mixing, may contain approximately 0.01 to 10% by weight of the CD-functionalized polymer, in certain applications the polymer may contain approximately 0.02 to 8% by weight of the Functionalized material, about 0.02 to 5% by weight of the functionalized material or about 0.02 to 2% by weight of the functionalized material. A maleic acid, fumaric acid, or maleic anhydride functionalized material is useful for the binding of CD to polyolefin. The stoichiometric ratio for fusion grafting is calculated on a gram-mole basis (gram-formula-weight) where one (1) gram-mole of CD (alpha, beta, or gamma) is equivalent to one (1) gram- mole of the grafted anhydride, glycidyl and carboxylic acid element.

<img file="MX347751B_D0010.tif" />

<img file="MX347751B_D0011.tif" />

mexican institute

Fumaric acid can be used as the graft by reinstalling and dehydration of fumaric acid as shown:

<img file="MX347751B_D0012.tif" />

<img file="MX347751B_D0013.tif" />

<img file="MX347751B_D0014.tif" />

OR

<img file="MX347751B_D0015.tif" />

<img file="MX347751B_D0016.tif" />

IMPI

IMSTTTVTO MEXICANA the WWS

The

- Maleic anhydride can be grafted onto olefinic by using a reaction "ene in c.ugl f" The olefinic character of the polymer reacts with maleic anhydride in order to add the anhydride to the polymer chain, the reaction is exemplified in model structure, as follows.

<img file="MX347751B_D0017.tif" />

<img file="MX347751B_D0018.tif" />

Maleic anhydride can be grafted onto the olefinic polymer using a free radical reaction by cleavage of the polyolefin which forms a free radical that can combine with maleic anhydride to form the anhydride.

<img file="MX347751B_D0019.tif" />

^1βIMPI

INSTITUTO MEXICANO grafted, the free radical mechanism is exemplified comd '^ANDÁt¿KSra¡ÍAL

-CH₂CH₂CH₂CH₂CH₂CH₂Oh₂CH₂Free Radical Initiator

<img file="MX347751B_D0020.tif" />

resulting in a grafted material. The reaction can occur either at an unsaturated carbon in the backbone or at an unsaturated carbon in a group sloping towards the polymer backbone.

The inventive composition may be processed by any of the conventional mixing or compounding processes known for mixing polymer particulates in the art of

ΙΜΡΙ «* 'NSTlTUTOMEXJCANi ___ thermoplastic processing. The grafting process of¹¹^ * ^ Subject invention is carried out in any conventional batch mixer, twin screw or single screw extruder capable of homogeneously melting and mixing the process components to produce a covalently bonded CD. The grafting reaction is conveniently carried out in the extruder or mixer of the invention.

The preferred twin screw mixer is configured with multiple barrel segments for in-line additive composition and optional devolatilization. A feeder, preferably a gravimetric feeder, is used to feed the functionalized polyolefin into the first barrel zone of the extruder. A second additive feeder, either gravimetric or volumetric, is used to feed the dry cyclodextrin stream from the dispersive cylinder segment. Care must be taken during the compounding process to avoid the portion of atmospheric moisture by the CD. The twin screw mixer is set up with two kneading sections. The kneading sections are separated along the screw so that the first kneading section fuses the resin and mixes it, and the second kneading section allows dispersive mixing with minimal tearing of the resin. The conveying section in the first zone has an increasing slope followed by dispersive screw elements. After the dispersive section, a short section is used to transport the melt without increasing the temperature and followed again by distributive mixing elements before the composition leaves the mixer.

<img file="MX347751B_D0021.tif" />

IMPI

MEXICAN INSTITUTE

OF INDUSTRIAL PROPERTY

Alternatively, the cyclodextrin can be measured in the first cylinder zone together with functionized resin granules from the gravimetric feeder. In this case, the cylinder segments can be reduced and the dispersive mixing cylinder elements can move upward. The resin can be devolatilized in any configuration by drawing a vacuum into a downstream cylinder segment before the resin is pumped out through a filament nozzle. The molten polymer filaments are passed into a water bath and two air scrubs before entering the filament cutter. The purpose of the mixing step is to reduce the introduction of moisture while ensuring a consistent feed of the cyclodextrin with good dispersion in the functionalized resin.

In the present invention, when preparing a functionalized polyolefin / CD master batch, the use of a cyclodextrin material having low or reduced moisture content is important. When a main batch composition is produced, it may collect some water in the water bath and may require drying in a hot air fluidized bed, an air oven, or a vacuum oven before being used in a conversion process. The downstream process, as well as the application, dictates the residual moisture content of the main batch. After the main batch is made up, the moisture content of CD can be varied to carry out various aspects of the invention. Surprisingly, the barrier properties of a material

IMPI

- 19 INSTITUTE MRX1CANO Di LA MPHEDAD INDUSTRIAL made from a functionalized polyolefin / main batch of CDs left on virgin binder material are not maximized if dry cyclodextrin material is used. The absence of moisture in cyclodextrin leads to greater complexing of residual impurities inherent in all thermoplastic resins. The presence of some moisture in the cyclodextrin reduces complexing during the mixing and converting processing steps. Moisture levels in cyclodextrin between 0.5% and 2% in the main batch will generally reduce or substantially prevent the complexing of residual resin impurities. Furthermore, these moisture levels in cyclodextrin do not adversely affect polymer morphology or cause other adverse barrier effect, such as matrix holes, microscopic voids, etc. The presence of some moisture in the cyclodextrin does not prevent or reduce the formation of inclusion complex with diffusion permeants.

Chemical graft CD molecules on functionalized polyolefin polymers economically produce a barrier or selective barrier structure with properties capable of adaptation based on CD pore size (alpha, beta or gamma), whether the CD is found or unmodified, and the concentration of the grafted CD in the finished polymer. These unique properties include reducing the transport of low molecular weight impurities inherent in polymers, improving the intrinsic organic vapor barrier properties of the polymer, changing the

<img file="MX347751B_D0022.tif" />

- 20 polymer surface energy and change, therefore, polar and nonpolar organic d at the interface, and increased polymer crystallinity, an important polymer characteristic, especially in olefinic polymers. These property improvements add significant value to commercial merchandise resins. These improvements come with additional benefits that cannot be achieved with compatible cyclodextrin derivatives - pending elements or substitutes that make the CD material compatible with the thermoplastic polymer - known in the art (US Patent Nos. 5,492,947, 5,603,974, 5,837,339 and 5,928,745) which also achieve reduced migrants and barrier properties. The present novel CD-grafted polymers have additional benefits including significant changes in polymer surface energy, increased polymer crystallinity, significantly lower implementation costs, lower regulatory safety concerns, and, in some cases, a more barrier polymer. environmentally 'green'Vsocially responsible.

For this invention, a compatible CD means that the CD material contains at least one pendant group capable of reacting with either anhydride or epoxide-functionalized polyolefin. Additionally, the CD material can be uniformly dispersed in the molten functionalized polyolefin, can reside in the polymer without reductions in the intrinsic barrier properties of the polyolefin, and can retain the ability to trap complex diffusion permeants or migrating polymer impurities.

- 21 and can change the surface energy of the polymer, splitting organic molecules and improve the crystallinity of the polymer.

We have found that polyolefin-incompatible CD such as unmodified a-, β- and γ-CD can be dispersed in functionalized polyolefins, covalently bound to the functionalized polyolefin forming a compatible composition without microscopic particles or decomposition of the unmodified CD during mixing or during subsequent conversion steps. Furthermore, we have found that covalently bonded unmodified CD functionalized polyolefins do not cause melt fracture by visual inspection of the extrudate. Finally, the transverse cut polyolefin extrudate, examined by light microscopy, is shown free of CD agglomerates.

Cyclodextrin

Cyclodextrin is a cyclic oligosaccharide consisting of at least six glucopyranose units linked by alpha (1 -&gt; 4) bonds. Although cyclodextrin with up to twelve glucose residues is known, the three most common homologues (alpha cyclodextrin, beta cyclodextrin, and gamma cyclodextrin) having 6, 7 and 8 residues have been used.

Cyclodextrin is produced by highly selective enzymatic synthesis. It consists of six, seven, or eight glucose monomers installed in a donut-shaped ring, denoted alpha, beta, or gamma cyclodextrin, respectively (See FIGS. 1A, 1B, and 1C, respectively). The coupling

<img file="MX347751B_D0023.tif" />

conical, truncated, rigid molecular structure, with a hollow inteTTUI · a specific volume. This internal cavity, which is lipophilic (that is, it is attractive to hydrocarbon materials when compared to the exterior, is a key structural feature of cyclodextrin, which provides the ability to complex molecules (e.g. aromatics, alcohols, halides). and hydrogen halides, carboxylic acids and their esters, etc.). The complexed molecule must meet the size criteria to at least partially fit into the internal cyclodextrin cavity, resulting in an inclusion complex.

<td colspan="4">TYPICAL PROPERTIES OF CYCLODEXTRIN</td>

<td>CD PROPERTIES</td><td>a-CD</td><td>β-CD</td><td>γ-CD</td>

<td>Degree of polymerization (n =)</td><td> 6</td><td> 7</td><td> 8</td>

<td>Molecular Size (A °)</td><td></td><td></td><td></td>

<td>inside diameter</td><td> 5.7</td><td> 7.8</td><td> 9.5</td>

<td>external diameter</td><td> 13.7</td><td> 15.3</td><td> 16.9</td>

<td>height</td><td> 7.0</td><td> 7.0</td><td> 7.0</td>

<td>Specific rotation [a]²⁵or</td><td> + 150.5</td><td> + 162.5</td><td> + 177.4</td>

<td>Iodine complex color</td><td>Blue</td><td>Yellow</td><td></td>

<td>Yellowish</td><td></td><td></td><td>Coffee</td>

<td>Solubility in distilled water</td><td> 14.50</td><td> 1.85</td><td> 23.20</td>

<td>(g / 100 mL) 25 ° C</td><td></td><td></td><td></td>

The oligosaccharide ring forms a torus, like a cone

- 23 IMPI

MEXICAN INSTITUTE

OF THE PROPERTY

INDUSTRIAL truncated, with primary hydroxyl groups from each glucose residue lying at a narrow end of the torus. Secondary glucopyranose hydroxyl groups are located at the broad end. The major cyclodextrin molecule and useful derivatives can be represented by the following formula (ring carbons show conventional numbering) in which vacant bonds represent the remainder of the cyclic molecule:

<img file="MX347751B_D0024.tif" />

where Ri and R₂ they are primary or secondary hydroxyl, as shown.

The internal cavity size of the DC (i.e. alpha, beta or gamma) must be considered and the modification of the functional group must be adequate to change the desired bulk polymer and surface polymer characteristics in addition to the formation of a complex of inclusion with target volatiles or impurities. To achieve a specific result, more than one cavity size and functional group may be necessary.

According to the present invention, cyclodextrin is a compound substantially free of an inclusion complex. For this invention, the term "substantially free of a

<img file="MX347751B_D0025.tif" />

- 24 INSTITUTO MEXICANO inclusion complex ”means that the quantity of the mateYI ^ N ^ wlSD '^ dispersed in the bulk polymer contains a large frannion gn ^ ti ^ ne

CD free of a polymer contaminant in the central pore of the cyclodextrin ring (see FIG. 1A). The central pore is used as a binding site for permeants. Once used, the core pore may acquire a permeant or other inclusion compound but some complexing may occur during manufacture. Such complexing can occur as residual polymer impurities and degrading materials are converted to the inclusion compound in the CD inclusion complex.

CD molecules have available for reaction with a functionalized polyolefin at the primary hydroxyl at position six of the glucose element and at the secondary hydroxyl at positions two and three. Due to the geometry of the CD molecule and the chemistry of the ring substitute, not all hydroxyl groups are equal in reactivity. However, with gentle and efficient reaction conditions, the dried CD molecule can react to obtain grafted CD. CD with selected substitute (ie) substituted only on the primary hydroxyl or selectively substituted only on one or both secondary hydroxyl groups, can also be grafted if desired. Directed synthesis of a molecule derived with two different substitutes or three different substitutes is also possible. These substitutes can be placed randomly or targeted to a specific hydroxyl. In addition, alcohol derivatives of CD (eg, hydroxyethyl and hydroxypropyl) and amino derivatives can

- 25 react to make a grafted CD.

<img file="MX347751B_D0026.tif" />

The preferred preparatory scheme for the production of a grafted CD polyolefin material, which has compatibility with the polyolefin resin, involves reactions at the primary or secondary hydrophiles of the CD molecule. It is understood that a hydroxyl functionality of the CD reacts with the anhydride or epoxide component of the functionalized polyolefin to form a reaction product. The formation of an ester or ether bond in any of the ring hydrophils, primary or secondary, of the CD molecule involves well known reactions. Furthermore, DC having less than all available hydrophiles, substituted with derivative groups, can be grafted with one or more of the rest of the available hydrophiles. The primary-OH groups of cyclodextrin molecules react more easily than secondary groups. However, the molecule can be substituted at virtually any position in order to form useful compositions. We have widely found that a wide range of pendant surrogate elements can be used in the molecule. These derived cyclodextrin molecules can include alkylated cyclodextrin, hydrocarbyl-amino cyclodextrin, and others. The surrogate element must include a region that provides compatibility with the derived material.

Amino and other azide derivatives of cyclodextrin, which have pendant thermoplastic polymer containing elements, can be used in the sheet, film or container of the invention.

- 26 MEXICAN INSTITUTE

The sulfonyl-derived cyclodextrin molecule can generate the amino derivative from Tnoloula-da. sulfonyl group substituted cyclodextrin through nucleophilic displacement of the sulfonate group by an azide ion (Ν₃'¹). The azide derivatives are subsequently converted to substituted amino compounds by reduction. Such derivatives can be made into symmetric substituted amino groups (those derivatives with two or more azide amino groups symmetrically placed on the cyclodextrin backbone or as a symmetrically substituted azide or amine derived cyclodextrin molecule. Due to the nucleophilic shift reaction produced by nitrogen-containing groups, the primary hydroxyl group at carbon 6 is the most likely site for introduction of a nitrogen-containing group. Examples of nitrogen-containing groups that may be useful in the invention include acetylamino (-NHAc), alkylamino groups including methylamino, ethylamine, butylamino, isobutylamino, isopropylamino, hexylamino, and other alkylamino substitutes. The amino or alkylamino substitutes can be further reactive with other compounds that react with the nitrogen atom to further derivatize the amino group. Other possible nitrogen-containing substitutes include dialkylamino such as dimethylamino, diethylamino, piperidino, and piperizino.

The cyclodextrin molecule can be substituted with heterocyclic nuclei including pendant imidazole groups,

- 27 IMPI INSTITUTO MEXICANO histidine, imidazole groups, pyridino and pyridino groups substituicRJ ^^^

Cyclodextrin derivatives can be modified with ____________ sulfur containing functional groups to introduce compatibilizing substitutes into the cyclodextrin. Sulfur-containing groups made on the basis of sulfhydryl chemistry can be used to derive cyclodextrin. Such sulfur-containing groups include hydroxieti Iti or (-S — CH2CH₂OH), imidazolylmethylthio, aminoalkylthio and others.

Applications and Uses

Long established food packaging concepts are limited to their ability to extend the shelf life of food products. The innovative food packaging concepts of the present invention interact with the environmental interior of the packaging and respond by changing its properties to maintain, adjust or enhance the specific packaging headspace atmosphere or reduce the loss of flavor in the food to the packaging. by “desbroze” (that is, capture of volatile components by the polymeric packaging material from the food) thus adding quality to the product and prolonging the shelf life. The most notable group of technologies in use today to control gasket headspace oxygen are oxygen scavengers.

Multilayer or composite packaging, including eaves top boxes, depend on

INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL essential layers of plastic that add resistance, barrier to other materials in the structure and sealing ability. By way of example, top eaves milk and juice boxes are specifically set forth in US Patent Nos. 5,816,487, 5,508,075, 5,616,353, 6,193,827 and 6,372,317 as waterproof containers. Although these familiar eaves-top boxes have been used extensively throughout the United States to contain juices, they are associated with some problems. Most of the food contact with inner polyolefin or sealing layers that release low molecular weight, volatile, organic aroma and flavor compounds from the food to the polymer, based on the sorbet mechanism, have been and continue being the subject of considerable attention and concern. Sorbing can result in loss of aroma and flavor volatiles associated with product quality. Cyclodextrin modified anhydride functionalized polymers effectively address these problems related to poor organic barrier, surface hydrophobicity, and food flavor stripping over conventional polyolefin blends. The invention described herein is particularly useful for containers constructed from laminates that have an internal food contact surface capable of heat sealing, which allows for significant flavor retention in fruit juices contained therein over the shelf life. in product deposit.

IMPI

- 29 INJTTTVTO MBUCANC M LA CURRENCY INDUSTRY l

In properly designed food packaging, the polymers must absorb a minimal amount of the critical flavors while meeting all other performance requirements. Loss of flavor due to absorption in the packaging polymer is generally assumed to be detrimental to product quality. In contrast, the fruit juice industry has designed liquid packages to take advantage of sorbing losses through struggles to remove flavor-eliminating precursors. The present invention relates to the use of the packaging food contact polymer layer, as illustrated by the example of juices, to selectively remove undesirable flavors from packaged foods while reducing the loss of food compounds. important flavor. The food packaging contact layer can be constructed of cyclodextrin modified anhydride functionalized polymers to effectively address problems related to poor organic aroma / flavor barrier, unwanted food flavor stripping, and removal of offensive odors / aromas from the interior. of food packaging produced by lipid oxidation, lipid hydrolysis and protein / amino acid breakdown of the packaged food. These active packaging polymer enhancements are significant over conventional polyolefins and can greatly improve the taste of foods over the shelf life of the product.

Packaging laminates have been used by

- 30 many years for packaging food products.

<img file="MX347751B_D0027.tif" />

Widely known and used is a cardboard-based structure, which is covered with various barrier materials and sealants. The contact layer for food packaging of the present invention is capable of heat sealing, thus providing a useful barrier structure for converting a reservoir material into boxes and similar food retention packages that require heat sealing. The barrier structure of the present invention is particularly useful in the packaging of orange juice and similar citrus products. Anhydride-functionalized, cyclodextrin-modified polymers lead to the improved interfacial interaction of conventional polyolefin polymers such as changing division coefficients, polymer solubility coefficients due to hydrophobicity, increased crystallinity, and proportion of a selective scavenging function.

As the plastics industry has matured, it has developed numerous specialty food packaging applications. A large number of multi-layer and single-layer structures are available for storing food or non-food, liquid or solid products. The need continues for high performance value-added packaging that is capable of maintaining or improving a specific internal packaging environment in order to ensure improved quality, safety and shelf life while also achieving this objective from transparent films and progressively thinner. The

<img file="MX347751B_D0028.tif" />

-31- IMPI

MEXICAN INSTITUTE

Of LA RaOREtiAS current low oxygen barrier packaging methods ^ Hb eliminate all deteriorating chemical reactions pFóducidáJi μ'σι—— ..

stored food or packaging, so undesirable chemical by-products such as odor and flavor traces continue to be produced in residual amounts, and these are effectively retained in the head space of the packaging re-absorbed by the product, reducing the quality of the product. product flavor and shelf life. When the ratio (rate) of the total concentration of these compounds goes too far out of line, they contribute to the flavor detachment of foods.

Low and intermediate moisture foods comprise a large portion of self-stable foods such as cereals, crunchy foods, cookies, salty snacks, etc. They contain fat, protein, starches, and undergo many damaging chemical reactions. The most important chemical changes are associated with hydrolytic reactions, enzymatic action, oxidative reactions, particularly lipid oxidation that alters the taste of many foods that contain lipids and non-enzymatic caramels. The chemical compounds produced from these reactions vary widely in their chemical and physical properties. They also vary in their impact on flavor. Some are responsible for pleasant aromas, while others produce offensive odors and tastes, often causing significant food storage problems. Therefore, the removal of all these compounds will cause the flavor fading or the removal of

<img file="MX347751B_D0029.tif" />

IMPI ΐΝίτπυτο Mexican some and others will cause flavor imbalance - a food flavor. —-------- In breakfast cereals, for example, accelerated shelf life studies using high temperature and low humidity produce various spoilage chemicals.

Cyclodextrins can reduce the headspace build-up of volatile chemical family compounds (ie aromatics, alkanes, alkenes, and ketones) in addition to aldehydes that cannot be removed by traditional antioxidants and oxygen and aldehyde scavengers. Cyclodextrins can trap hydroperoxides and other compounds that are produced by oxidation of the sealant polymer during extrusion and are known to be detrimental to flavor quality. In addition, the grafted CD / polyolefin can specify the selective cleavage of unwanted flavor release compounds from the headspace surrounding the food stored in the sealant polymer layer without significantly affecting preferred desirable flavors and thus preventing flavor fading. The CD pore is an effective trap for a broad spectrum of undesirable odors that are known to cause flavor defects in packaged foods.

A large proportion of harvested fresh fruits, vegetables and cut flowers are lost due to leakage resulting from increased levels of ethylene gas in the headspace of the package. One of the ways to delay the ripening of fruits, vegetables and the quality of fresh flowers is to reduce ethylene gas.

Τ

33- IMPI

MEXICAN INSTITUTE

OF THE PROPERTY generated. The ethylene absorption capacity of a film! F1? H5lé^LLDPE can be improved by having a thin, contaete inner layer¹, with a functionalized LDPE and cyclodextrin. The cyclodextrin grafted polymers can be used as the food contact layer in the headspace surrounding the product and maintain adequate humidity (generally greater than 80% RH) so that unwanted enzymatic action and wrinkling do not take place. If the product is sealed in enzyme film, the levels of O₂ in the headspace they will drop to low levels where anaerobic respiration takes place, forming undesirable odor and taste compounds such as ethanol, acetaldehyde and organic acids. The advantage of grafting cyclodextrin onto the polyolefin is that a high concentration of CD can be used in the dermal LDPE layer to improve the cleavage of ethylene gas and other organoleptic precursors from the headspace without degrading the intrinsic properties of the olefin barrier humidity and gases.

The closure can be made of a thermoplastic material and can comprise grafted CD and lubricant. Suitable thermoplastic materials for the cap include polypropylene, polyethylene such as linear low-density polyethylene, PET, polystyrene, and the like. The closure is made by conventional means understood by those skilled in the art. The closure is preferably a copolymer of ethylene polyethylene and a C4.10 olefin monomer. Preferred materials have the following characteristics:

<img file="MX347751B_D0030.tif" />

- 34 Physical Properties

IMPI

INSTITUTO MEXICANO DG LA INDUSTRIAL PROPERTY

<td>Prqpledacl</td><td>, Npmminal value.</td><td>Units</td><td>Proof</td>

<td>Fusion Index</td><td>1.5 to 5</td><td>g / 10 min</td><td>ASTM D 1238</td>

<td>Density</td><td> 0.93 - 0.97</td><td>g / cc</td><td>ASTM D 1505</td>

<td>Resistance to Traction @ Fracture</td><td> 10-20</td><td>(MPa)</td><td>ASTM D 638</td>

<td>Tensile Strength @ Performance</td><td> 20 - 30</td><td>(MPa)</td><td>ASTM D 638</td>

<td>Elongation @ Yield</td><td> 10-600</td><td> %</td><td>ASTM D 638</td>

<td>Bending coefficient</td><td> 140,000-200,000</td><td>psi</td><td>ASTM D 790</td>

The closure also includes a thermoplastic liner positioned within the closure shell against the top cover of the closure. The liner creates a waterproof seal between the mouth of the container and the closure when the closure is screwed tightly onto the neck of the container. The liner includes a raised outer ring that directly contacts the mouth of the container and a central grooved portion within the outer ring.

The thermoplastic coating is made and deposited inside the closure by conventional means. For example, the liner may be compression molded and then inserted into the closure shell or the liner may be formed in situ by deposition of heated thermoplastic liner material on the closure shell and pressing the thermoplastic material against the top shell of the closure.

Suitable thermoplastics to form the polymer matrix of the coating include ethylene vinyl acetate (EVA),

<img file="MX347751B_D0031.tif" />

polyvinyl chloride (PVC), PET, polyethylene,

IMPI

MEXICAN INSTITUTE

OF THE PROPERTY „. · INDUSTRIAL polypropylene, polyurethane, copolymers of vinyl chloride and acetate, ethyl cellulose, cellulose acetate, cellulose acetate butyrate, terpolymers, alkylacrylates, copolymers and terpolymers of styrene, polyamides, polyesters and other polyolefinas. The matrix may comprise grafted CD and lubricant.

The thermoplastic liner material also includes conventional additives known to those skilled in the art and, in accordance with this invention, includes a substantially fully ethylenically saturated lubricant or slip agent. The thermoplastic coating composition is substantially free of an ethylenically unsaturated slip agent or any ethylenically unsaturated compound. The slip agent (s) and other compounds in the coating must be sufficiently saturated so that any oxygen, such as ozone, in the container does not react with the slip agent (s) or slip agents or other compounds and produce a level of aldehydes, such as nonanal, sufficient to be detected by human taste. The organic slip agent or slip agents in the coating desirably have an iodine value of less than 10, more desirably have an iodine value of less than 5, more desirably have an iodine value of less than 1, and even more desirably have an iodine value of 0. The iodine value is a number that expresses the percentage, in grams per 100 grams, of

-³⁶- WICKED

INSTITUTO MEXICANO iodine absorbed by a substance and is a measure of the number of unsaturated bonds present in a nrgánirQ. The _______________ value of iodine is determined according to ASTM D 1959, the Wijs method.

The container shell, closure shell, and liner are substantially free of an ethylenically unsaturated compound. By ethylenically saturated, it is meant that the compound does not possess carbon-carbon double or triple bonds. Instead, carbon bonds also bind to elements such as hydrogen, fluorine, or silicone. Desirably, the container shell, closure shell, and liner are at least 99.98% by weight free of ethylenically unsaturated compound. More desirably, the container shell, closure shell, and liner are at least 99.99% by weight, free of ethylenically unsaturated compound. Preferably, the container liner, the closure liner, and the liner are 100% by weight free of ethylenically unsaturated compound.

Suitable ethylenically saturated slip agents for coating include fatty acid amide C₁₀.₂4 such as behenamide (a monounsaturated Ci (Z) -13-docosenoic fatty acid amide₃), polysiloxane, fluoropolymers, paraffin wax, carbocera, synthetic mineral oil, and mixtures thereof. The fatty acid amide can be of the structure:

<img file="MX347751B_D0032.tif" />

<img file="MX347751B_D0033.tif" />

- 37 O

II rc-nh₂

INSTITUTO MEXICANO DE LA PROPIBDAD INDUSTRIAL where R is alkyl Ο₈.₂₄ or mono-, di- or tri-unsaturated alkenyl. Generally, suitable slip agents of the present invention include any ethylenically saturated organic compound that meets the requirements for a slip agent. A slip agent is a material that is incorporated into the polymer matrix of the liner and lubricates the outer surface of the liner so that the closure can be easily removed from the neck of the container, even when screwed tightly onto the neck of the container. . Desirably, the slip agent is present in the liner in an amount of from about 0.1 to about 4% or about 0.2 to 3% by weight of the closure or liner. For example, the closure or liner may comprise about 98 parts of polyolefin copolymer, polyethylene copolymer, or other such resin, 2 parts of behenamide, and 0.1 part of a blue or other colorant.

Although the closure typically includes a liner, sealable closures can be made without liner. In such a case, the polymer matrix of the closure shell includes a slip agent. The same saturated slip agents described above are suitable in an uncoated closure and are desirably present in the polymer matrix of the closure therein.

- 38 quantities than in the coating. Although it is not 'tf ^^^ SpArel

INDUSTRIAL container shell could include slip agent.

High barrier coating materials are typically composite compositions containing a thermoplastic (typically an olefin) and dispersed in the thermoplastic are elastomeric materials (typically a butyl rubber, a styrene butadiene rubber, or an acrylic rubber) that form a composition of thermoplastic elastomer material. These thermoplastic compositions are made in shapes that allow them to function as a closure element for a vertical sack, jar, or bottle made of metal, glass, or plastic. Screw cap plastic closure shells used to seal carbonated soft drinks, carbonated waters, etc., contain a two-component system comprising a PP screw cap shell and a monolayer liner normally produced from LDPE and EVA to provide a positive seal. The closure shells for non-carbonated beverages (eg water) are made from PP as a single piece that functions as both a screw cap and liner. The closure shells and coating compositions contain some additional performance additives - lubricants, antistatics, plasticizers, heat stabilizers, antioxidants and pigments. One additive in particular, a common polymer lubricant called erucamide, an amide of (Z) -13-docosenoic acid, improves melt flow properties and reduces stickiness.³⁹'IMPIAS ^MUICánor coating and the shell to the bottle by decreasing the tCni ^^^TOpes&gt; ^ release. The additives that work on the surface of the jimer are traditionally migratory and migration occurs over time.

The surface of the polymeric shells and lining of the container can become a source of chemical precursors susceptible to ozonolysis of residual ozone.

Ozonization is commonly used throughout the world to disinfect drinking water stored in bottles. Residual ozone, typically at ppb levels, remains in the water after bottling. Ozone reacts with unsaturated compounds that form unstable organic ozonides, which rapidly decompose to oxygen compounds, such as aldehydes, ketones, and peroxides, or react rapidly with oxidizing or reducing agents. The unsaturated chemical bonds in erucamide and oleamides, which migrate to the surface of the closure polymer and to a lesser extent the unsaturated olefin monomers and oligomers exposed on the surface, produce an organoleptic defect often described as a "plastic" taste. ”. Plastic flavor release can be associated with the presence of part per billion (ppb) levels of human threshold organoleptic compounds, particularly Cvso aldehydes such as hexanal, heptanal, octanal, nonanal, and decanal. The residual organoleptic volatiles that are produced either from chemical oxidation by ozone or through thermo-oxidation or photo-oxidation of the coating or closure, can be efficiently complexed by dispersion «- IMPL ·

ΙΝΓΤΤΤυΤΟ MEXICAN 1

OF THE NOFIETY 'of a functionalized polyolefin / CD den traite *¹ the coating or closure composition, preventing its migration to the drink. The present invention relates to container lining and shell compositions for retaining a food, beverage or pharmaceutical containing grafted cyclodextrin in order to reduce the release of flavor and migrating organoleptic odors and the ingress of permeants, thus improving the taste of the product. stored.

The present invention is directed to a process by which improved anhydride functionalized polymers are produced, most notably maleic anhydride grafted polyolefins. For improvement, the anhydride-functionalized polymer is modified by reaction with a CD under conditions that can convert all, when necessary, or a portion of the anhydride groups to the corresponding middle ester. Although graft diesters and middle esters of dicarboxylic acids or their anhydrides, such as maleic acid or maleic anhydride, are known to on various polymer substrates, CD graft polyolefin polymer compositions onto a functionalized polyolefin exhibit a substantial increase in crystallinity and improve the interfacial interaction of conventional polyolefin polymers such as change of division coefficients, surface energy due to hydrophobicity, polymer barrier enhancement, and proportion of a selective scavenging function. Cyclodextrin-grafted polymers can

<img file="MX347751B_D0034.tif" />

⁴¹ ΙΜΡ I

MEXICAN INSTITUTE

GIVES THE PRCWSDAD used in various structures and types of food packaging^Nrf) Yes^l extend the shelf life of the product, in fibers -pai a · i reduce bad odors and as a barrier to organic permeants in a variety of applications.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGURE 1 is a graphical representation of the dimensions of a non-shunted cyclodextrin molecule. The central pore comprises the hydrophilic space, central pore, or volume within the cyclodextrin molecule that can act as a site for absorption of a permeant or such contaminant. In the FIGURE, α, β, or γ-cyclodextrin is shown. Such cyclodextrins have hydroxyl groups formed at the perimeter of the molecule that are available for reaction with anhydride and epoxide groups on functionalized polyolefins.

FIGURE 2 is a micrograph of a molded coupon of NA-204 (LDPE).

FIGURE 3 is a micrograph of a molded coupon of NA-204 (LDPE) composed with 2.78% by weight alpha cyclodextrin.

FIGURE 4 is a micrograph of a molded coupon of NA-204 (LDPE) composed with 3.30% by weight of beta cyclodextrin.

FIGURE 5 is a micrograph of a PX 175 molded coupon composed with 2.78% by weight alpha cyclodextrin.

<img file="MX347751B_D0035.tif" />

-42- IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

FIGURE 6 is a micrograph of a PX 175 molded coupon composed with 2.78% by weight beta cyclodextrin.

FIGURE 7 is a Permeation Cell schematic

Static Closed Volume by Organic Vapor.

FIGURE 8 is a drawing of a closed volume permeation profile.

Experimental Section

Chemical grafting of cyclodextrin molecules onto functionalized polyolefin polymers produces an adaptive barrier with unique properties including reduced mass transport of low molecular weight compounds, change of polymer surface energy, realization of polar organic compound cleavage / non-polar and increased crystallinity of the polymer The grafted CD polymer, when combined with polar lubricant, forms an improved surface lubricated layer.

The foregoing discussion illustrates various compositions of this invention and application to a beverage contact layer for eaves top boxes and bottles, plastic closures and sealing elements, and the sealant layers for flexible films.

Compatibility Test

Qualitative Sample Preparation

Five polyolefin samples with and without unmodified aCD and β-CD were mixed and compatibility was visually verified.

IMPI

<img file="MX347751B_D0036.tif" />

- 43 Mexican institute,, _Λ .. x,. _ __. xx_j_j __: _______ _ X 95 W «&lt;» WI.

from to CD by using an oplico ™ microscope method 'Two test coupons containing α-CD and β-CD of poo or stoichiometric fillers (2.78% by weight and 3.20% by weight) were mixed in an ethylene mixture -maleic anhydride / LDPE copolymer (Plexar 175, Equistar Chemicals LP) by using a Brabender Plasticorder Mixing Bowl. A Brabender mixing bowl consists of two counter-rotating roller blades in a number-eight configured bowl. Two additional test coupons containing the same weight loading of α-CD and β-CD used in the Plexar samples were mixed with LDPE (NA-204, Equistar Chemicals LP), the same LDPE used in the Plexar mixture. And finally, a fifth control sample of NA-204 LDPE resin was also mixed in a Brabender Plasticorder Mixing Bowl but without CD. All resins were dried at 85 ° C for 2 hours under vacuum (&lt;0.Γ Hg) before mixing, while α-CD and β-CD cyclodextrins were dried in a circulating air oven at 105 ° C. for 30 minutes.

Low Density Polyethylene (LDPE) Alpha Cyclodextrin Blend and Ethylene Maleic Anhydride / LDPE Copolymer Blend (EMA / LDPE)

One hundred and eleven hundredths gms of alpha cyclodextrin (batch

60P122, Wacker Chemie) were mixed in 39.89 gms of LDPE (NA204, lot ET626241, Equistar Chemicals, LP) or EMA / LDPE (Plexar PX 175, lot CL590803E1, Equistar Chemicals, LP) using

- 44 IMPI ^ the use of a Brabender Plasticorde Mixing Bowl ^ dftS ^^ SDAS &lt;»ιπκιτηι» ι ^ 4. ^ ¾,

INDUSTRIAL minutes at 130 ° C and 80 rpm. The material was then cast into 4.45 cm x 1.59 cm x 0.10 cm sample coupons with an Atlas Laboratory Mix Former set at 140 rpm, 150 ° C for 2 minutes, with a molding temperature of 90 ° C.

Low Density Polyethylene (LOPE) Beta Cyclodextrin Blend and Ethylene Maleic Anhydride / LDPE Copolymer Blend (EMA / LDPE)

One hundred thirty-one hundredths gms of beta cyclodextrin (lot 70P162, Wacker Chemie) were mixed in 39.69 gms of LDPE (NA204, lot ET626241, Equistar Chemicals, LP) or EMA / LDPE (Plexar PX 175, lot CL590803E1, Equistar Chemicals, LP ) by using a Brabender Plastícorder Mixing Bowl for 5 minutes at 130 ° C and 80 rpm. The material was then cast into 4.45 cm x 1.59 cm x 0.10 cm sample coupons with an Atlas Laboratory Mix Former set at 140 rpm, 150 ° C for 2 minutes, with a molding temperature of 90 ° C.

Photographic Procedure

A stereomicroscope with a camera (film

Polaroid type 57), at ~ 10.6x amplification. The illumination was an incident halogen spot at approximately 45 ° to the horizon of the plastic surface. A black piece of paper (inner shield polaroid film) was used as the background, for

- 45 ΙΜΡΠ control diffuse light. Photographs were scanned using default brightness and contrast settings (ie no adjustment) and saved with JPEGs. Because the photos were very flat in contrast, all images were adjusted the same amount using GIMP: "-115 in brightness and" +65 "in contrast. Dark artifacts in all photographs come from dust in the microscope optics.

Microscopic examination was used to visually verify compatibility between polyethylene resin and cyclodextrin. The results show that both alpha and beta cyclodextrins mixed in LDPE resin and cast into thin translucent coupons produce agglomerates and particles in the polymer matrix that are visible by microscopic examination (FIGURES 3 and 4). Microscopic results for alpha and beta cyclodextrins mixed on a stoichiometric weight basis in anhydride functionalized LDPE and cast into thin translucent coupons produce agglomerates or microscopic particles (FIGURES 4 and 5). Functionalized polyolefin / CD materials show the same clarity as LDPE resin (FIGURE 2).

Polyolefin Crystallinity and Surface Energy Examination Polyolefin Crystallinity

The degree of crystallinity affects the fundamental physical properties of the polymer. Crystallinity was measured by Differential Scanning Calorimetry (DSC) by heat quantification

<img file="MX347751B_D0037.tif" />

IMPI

MEXICAN INSTITUTE

Samples Wf &amp; W

- 46 associated with melting (mixing) the polymer.

contain stoichiometric weight loads of β-CD were mixed ao. »!

Brabender Plasticorder Mixing Bowl and analyzed by DSC over a temperature range of 20 ° C to 160 ° C. All samples were subjected to an initial term treatment from room temperature to 160 ° C in order to impart equivalent thermal history to all samples. After heat treatment, the samples were then subjected to a controlled cooling program of 160 ° C to -20 ° C followed by a controlled heating program of 20 ° C to 160 ° C. The second heats of fusion, AHm, and the cold crystallization AHc, are determined from integration of the areas (J / g) under the peaks. The percent crystallinity was determined from the following equation:

% Crystallinity = [AHm - AHc] / AHm °

[The reference heat of fusion (AHm °) for polyethylene is 293.6 J / g]

Two LDPE resins (NA 204 and NA 214, Equistar Chemicals, LP) and three maleic anhydride functionalized resins (Plexar PX 175, PX 5125, PX 1856 and PX 1857 resins, Equistar Chemicals, LP) and the four Plexar resins composed of a Stoichiometric loading of β-CD (3.2% by weight, 3.2% by weight, 4.6% by weight and 2.3% by weight, respectively) were analyzed by DSC. All samples were subjected to identical processing conditions (thermal history) in order to eliminate processing effects. The percent crystallinity results are provided in Table 1.

- 47 PI

The results clearly show maleic anhydride functionally grafted with RaGD._Li.e has significantly higher crystallinity than the maleic anhydride functionalized LDPE compound without CD.

Surface Energy per Dynamic Contact Angle

The absorption and division coefficients of various compounds are highly correlated with molecular structure.

PE has a very high affinity for non-polar flavor compounds, more miscible in PE, they are preferentially absorbed from the beverage. We hypothesize that by changing the surface energy of the polymer by grafting CD onto a functionalized polyolefin, the surface polarity is increased, thus decreasing the equilibrium division coefficient and increasing non-polar flavor retention. To accomplish this, the food contact layer must selectively divide the flavors released from the packaged food while reducing the loss of important flavor compounds.

Cyclodextrin grafted polyolefin surfaces were measured using a variation of the Willhelmy slip technique. In this test method, a liquid with a known surface tension is used to determine the contact angle of an uncharacterized material. The technique measures the force exerted on the material to be characterized, extrapolated to the moment of contact, the contact angle uses the following force

<img file="MX347751B_D0038.tif" />

IMPI of equation (F), surface tension (y) and the perimeter of T8KféftS ^^ is:

F = yp eos (Θ)

Two LDPE resins (NA 204 and NA 214, Equistar Chemicals, LP) and three resins functioned with maleic anhydride (Plexar PX 175, PX 5125 and PX 1856 resins, Equistar Chemicals, LP). The three Plexar resins mixed with α-CD and β-CD stoichiometric weight fillers (2.78% by weight and 3.2% by weight) were analyzed for dynamic contact angle. All samples were subjected to identical molding conditions in order to eliminate the effects of processing on surface conditions, ie, contaminants and texture. The large area of ​​the 4.45 cm x 1.59 cm x 0.10 cm test sample coupons is "averaged." The samples were examined on an Instron equipped with a 50 gmf load cell. The samples to be examined were lowered into a +18 Mohm beaker of water (polar liquid) and reagent grade toluene (non-polar) and separated. The liquid volume used was approximately 200 mL maintained at 24 ° C + during the test. The Instron crosshead travel was 2mm / min and the degree of travel was 12mm. Data files were imported into EXCEL for data analysis and contact angle calculation. The tripled results are average results that are provided in Table 1.

The results show a reduction in the contact angle of a CD grafted polyolefin compared to the⁴⁹IMPI

INSTITUTO MEXICANO same functionalized polyolefin without CD when tested

The decrease in contact angle indicated a change in the surface energy of the CD-grafted polyolefin that makes the material slightly more hydrophilic. Additionally, when samples are examined in toluene, the surface tension of a CD grafted polyolefin compared to the same functionalized polyolefin without CD showed a decrease indicating a less hydrophobic surface.

<img file="MX347751B_D0039.tif" />

Table 1

Summary of Physical Test Data for Low Density Polyethylene (LDPE), Ethylene Maleic Anhydride / LDPE Copolymer Blend, and Maleic β-C Anhydride Grafted Ethylene Copolymer Blend.

<td rowspan="2">Sample ID</td><td colspan="3">Bulk Polymer Properties</td>

<td>Fusion Peak # 1% Crystallinity</td><td>Fusion Peak # 2% Crystallinity</td><td>% of Total Crystallinity</td>

<td>NA 204</td><td> 25.0%</td><td> 3.8%</td><td> 28.8%</td>

<td>PX 175</td><td> 31.7%</td><td> 9.5%</td><td> 41.2%</td>

<td>PX 175 + 3.2% βCD Grafted</td><td> 33.1%</td><td> 8.7%</td><td> 41.8%</td>

<td>PX 5125</td><td> 21.4%</td><td> 21.9%</td><td> 43.2%</td>

<td>PX 5125 + 3.2% β-CD grafted</td><td> 21.7%</td><td> 23.4%</td><td> 45.1%</td>

<td>NA 214</td><td> 38.6%</td><td>ND</td><td> 38.6%</td>

<td>PX 1856</td><td> 23.3%</td><td> 7.7%</td><td> 31.0%</td>

<td>PX 1856 + 4.6% β-CD Grafted</td><td> 29.2%</td><td> 10.6%</td><td> 39.8%</td>

<img file="MX347751B_D0040.tif" />

- 50 IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<td rowspan="3">Sample ID</td><td colspan="3">Properties of Limero to Gran I</td>

<td rowspan="2">HzO Lead Contact Angle</td><td rowspan="2">Angle of - H Retreat Contact₂OR</td><td></td>

<td>surface Dyn / cm (Toluene)</td>

<td>NA 204</td><td> 104.1</td><td> 75.7</td><td> 31.90</td>

<td>PX 175</td><td> 101.1</td><td> 75.3</td><td> 31.25</td>

<td>PX 175 + 3.2% βCD Grafted</td><td> 95.7</td><td> 63.5</td><td> 30.88</td>

<td>PX 5125</td><td> 97.5</td><td> 76.8</td><td> 31.52</td>

<td>PX 5125 + 3.2% grafted βCD</td><td> 98.3</td><td> 71.1</td><td> 32.93</td>

<td>NA 214</td><td> 101.8</td><td> 71.0</td><td> 31.83</td>

<td>PX 1856</td><td> 99.7</td><td> 72.3</td><td> 30.54</td>

<td>PX 1856 + 4.6% βCD Grafted</td><td> 93.6</td><td> 62.9</td><td> 31.12</td>

Equilibrium Division Coefficients Example I

Selective absorption of flavor compound by packaging contact materials continues to be a problem, especially in packaged beverages in contact with LDPE. Nonpolar compounds have a very high affinity for LDPE. The coefficient of division of various aroma / flavor compounds in PE is highly correlated with their molecular structure and is greatly influenced by the type of polymer, the degree of crystallinity as well as the structure of the solute, and the chain length and polarity of the solute. A "non-concentrated" single strength commercial orange juice was used to measure the splitting of the flavor compound into CD-grafted LDPE and non-CD-grafted LDPE.

Materials

Two blends of ethylene-51 IMPI maleic anhydride / LDPE copolymer (Plexar 5125 and Plexar

Chemicals, LP) with an unmodified β-CD stoichiometric loading (3.20% by weight) using a Brabender Plasticorder Mixing Bowl. A third LDPE resin control sample was also mixed in a Brabender Plasticorder Mixing Bowl but without CD. All resins were dried at 85 ° C for 2 hours under vacuum (&lt;0.1 "Hg) before use, while the β-CD cyclodextrin was dried in a circulating air oven at 105 ° C for 30 minutes.

Beta / LDPE Grafted EMA Blend (Sample 1A) - Beta Cyclodextrin in Ethylene-Maleic Anhydride / LDPE Copolymer Blend

One hundred thirty-one hundredths gms of beta cyclodextrin (lot 70P162, Wacker Chemie) were mixed in 39.69 gms of EMA / LDPE (Plexar PX 175, lot CL590803E1, Equistar Chemicals, L P.) using a Brabender Plasticorder Mixing Bowl for 5 minutes at 130 ° C and 80 rpm. The material was then cast into 4.45 cm x 1.59 cm x 0.10 cm sample coupons with an Atlas Laboratory Mix Former set at 140 rpm, 150 ° C for 2 minutes, with a molding temperature of 90 ° C.

EMA Grafted with Beta / LDPE Blend (Sample 1B) - Beta Cyclodextrin in Low Density Polyethylene (LDPE) and Ethylene-Maleic Anhydride / LDPE Copolymer Blend (EMA / LDPE)

- 52 LM&gt; S¿

OF INDUSTRIAL PROPERTY

One hundred thirty-one hundredths of beta (lot 70P162, Wacker Chemie) were mixed in 31.75 gms of EMA / LDPE (Plexar PX 175, lot CL590803E1, Equistar Chemicals ”LP) and 7.94 gms of EMA / LDPE (Plexar PX 175, lot CL590803E1, Equistar Chemicals, LP) by using a Brabender Plasticorder Mixing Bowl for 5 minutes at 130 ° C and 80 rpm. The material was then cast into 4.45 cm x 1.59 cm x 0.10 cm sample coupons with an Atlas Laboratory Mix Former set at 140 rpm, 150 ° C for 2 minutes, with a molding temperature of 90 ° C.

The CD-grafted LDPE and control LDPE coupons were placed in hermetically sealed 300 mL glass bottles with a ground glass stopper containing commercial single strength 'unconcentrated orange juice and molded test polymer coupons (4.45 cm x 1.59 cm x 0.10 cm). The bottles were filled and sealed with the stopper to eliminate any headspace and allowed to stand at room temperature in the dark for 8 days. CD-grafted coupons, along with test coupons made from a reference polymer for comparison and orange juice in contact with the coupons, were tested for orange juice flavor compounds at the end of the test period. .

Analytical method

The extraction of volatiles from orange juice and

- 53 τ_τ ντπ * · volatiles absorbed in the polymer coupons meCWamé 'solid phase micro extraction was conducted, using a 75 pm eorboxen · PDMS fiber (Supelco). Aliquots (25 mL) of orange juice were placed in 40 mL glass bottles with plastic screw caps and Teflon-covered spaces, heated to 40 ° C and gently mixed. Samples were equilibrated for 5 minutes prior to fiber insertion and held at 40 ° C throughout the entire 35 min sorbing period. The fiber is removed from the headspace and injected into the high performance gas chromatography equipped with a flame ionization detector. An HP 5890 GC equipped with a 30 mx 0.25 mm id DB5 capillary column (J&amp;W Scientific) was used. The operating conditions were: column kept at 32 ° C for 3 min and then increased at 6 ° C / min up to 200 ° C, the linear velocity of the helium carrier gas was 29 cm / sec. The analysis was conducted in an uninterrupted mode. The unknown flavor peak area is integrated to quantify the concentration and then the unknown flavor concentration is calculated from a standard four-point gauge that covers the concentration range of the samples. Sample concentrations are reported in ppm (pg / g - wt / wt). The flavor concentration is calculated from the slope of the calibration curve or response factor (RF).

Compound Concentration in ppm = (Peak Area X RF) 4- Sample Weight.

Compound Concentration in ppm = (Peak Area) Sample Weight

Calibration Curve Slope

- 54 _c, ...... IMPI

The division coefficient (K_and) was calculated for the corwpttefiSieEsicAde '' OF THE PROPERTY

INDUSTRIAL taste test and contact coupon system of the orange juice-polymer. K values_and were determined by using the following equation:

K_and (differential) = [Cp]_eq/ [Coj]_eq where [Coj]_eq is the concentration of the flavor compound in the juice at equilibrium and [Cp]_eq is the concentration of the flavor compound in the polymer at equilibrium both in (pg / g) determined by analysis. The division coefficients (K_and) are presented in Table 2. The lower is K_and, the lower the affinity of the flavor compound for the polymer, while the higher coefficients reflect a more favorable split in the polymer.

There is a large body of literature that describes the important sensory taste and aroma compounds in orange juice. The division coefficients for thirteen key orange juice aroma / flavor compounds were determined. Orange juice flavor compounds were selected for their contribution to sensory quality. Compounds that contribute to the orange juice aroma and flavor release are also included. The following combinations are responsible for the highest sensory rates: limonene / ethyl butyrate / pear / geranial; limmonne / ethyl butyrate / pear / geranial / beta-pinene. Compounds that contribute to the release of aroma and to the clearing of the same from the orange juice would be beneficial: terpineol / hexanal / 4-vinyl guaiacol. Less is also desirable

<img file="MX347751B_D0041.tif" />

- 55 sorb of limonene and higher sorb of terpineol.

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Limonene

.........

has a coefficient of division in the CD-grafted LDPE resin that is 18% lower than the control polymer, and pear and geranial have division coefficients that are 35% and 23% lower, respectively. Finally, 4-vinyl guaiacol, an undesirable pineapple flavor release, had a coefficient of division that is 10% higher.

Table 2

Equilibrium division coefficients for orange juice aroma and flavor compounds in CD- and LDPE-grafted low-density polyolefins of the commercial contact layer after eight days of storage in commercial orange juice.

<td></td><td>Odor threshold¹ppb in Water</td><td>Flavor Threshold¹ppb in Water</td>

<td>Total Alcohols</td><td></td><td></td>

<td>Linalool</td><td> 5.3</td><td> 3.8</td>

<td>a-Terpineol</td><td> 280</td><td> 300</td>

<td>4-Vinyl guaiacol</td><td>NA</td><td> 75</td>

<td>Total Aldehydes</td><td></td><td></td>

<td>Hexanal</td><td> 9.18</td><td> 3.66</td>

<td>Octanal</td><td> 1.41</td><td> 0.52</td>

<td>Channel</td><td> 0.53</td><td> 1.07</td>

<td>Neral</td><td> 85</td><td> 41.4</td>

<td>Great</td><td>NA</td><td> 40.0</td>

<td>Total esters</td><td></td><td></td>

<td>Ethyl butyrate</td><td> 0.13</td><td> 0.13</td>

<td>Total Hydrocarbons</td><td></td><td></td>

<td>a-Pinene</td><td> 9.5</td><td> 1014</td>

<td>β-Myrcene</td><td> 36</td><td> 42</td>

<td>Limonene</td><td> 60</td><td> 210</td>

<td>Valenceno</td><td>NA</td><td>NA</td>

<td></td><td></td><td></td>

EM Ahmed, RA Dennison, RH Dougherty, PE Shaw, Flavor and Odor Thresholds in Water of Selected Orange Juice Component, J. Agrie. Food Chem., Vol. 25, No. 1, 1978

<img file="MX347751B_D0042.tif" />

<img file="MX347751B_D0043.tif" />

<img file="MX347751B_D0044.tif" />

- 56 i INSTITUTO MEXICANO 'DELA «Ο ™ **? INDUSTRIAL

<td rowspan="2"></td><td colspan="3">DIVISION COEFFICIENTS IN EQJJILIDniO · * ”Ke Temp. 22 ° C</td>

<td>EMA β Grafted / L DPE-1A</td><td>EMA β Grafted / LDPE -1B</td><td>Control Resin</td>

<td>Total Alcohols</td><td>K,</td><td>Ke</td><td>Ke</td>

<td>Linalool</td><td> 862</td><td> 744</td><td> 882</td>

<td>a-Terpineol</td><td> 315</td><td> 292</td><td> 264</td>

<td>4-Vinyl guaiacol</td><td> 493</td><td> 434</td><td> 569</td>

<td>Total Aldehydes</td><td> 54</td><td> 18</td><td> 49</td>

<td>Hexanal</td><td> 3150</td><td> 3249</td><td> 3412</td>

<td>Octanal</td><td> 173</td><td> 151</td><td> 132</td>

<td>Channel</td><td> 477</td><td> 456</td><td> 487</td>

<td>Neral</td><td> 871</td><td> 783</td><td> 400</td>

<td>Genaríal</td><td> 702</td><td> 577</td><td> 1123</td>

<td>Total Esters</td><td> 928</td><td> 1282</td><td> 1269</td>

<td>Ethyl butyrate</td><td> 123</td><td> 116</td><td> 90</td>

<td>Total Hydrocarbons</td><td> 123</td><td> 116</td><td> 90</td>

<td>a-Pinene</td><td> 1907</td><td> 2206</td><td> 2234</td>

<td>β-Myrcene</td><td> 730</td><td> 867</td><td> 815</td>

<td>Limonene</td><td> 651</td><td> 746</td><td> 763</td>

<td>Valenceno</td><td> 452</td><td> 522</td><td> 547</td>

<td></td><td> 74</td><td> 72</td><td> 109</td>

EM Ahmed, RA Denníson, RH Dougherty, PE Shaw, “Flavor and Odor Thresholds in Water of Selected Orange Juice Component, J. Agrie. Food Chem., Vol. 25, No. 1, 1978

Testing of Sealing Materials for Organoleptic Migrants

Example II

Low-level volatiles (eg, monomers, refinery contaminants, etc.) remain as a residue from the polymerization process or after-products of thermo-oxidation (eg, aldehydes and ketones) may be produced during the conversion process. Dispersed in the polymer matrix, these components are capable of migrating into food products in contact with the package through a process generally controlled by Fickian diffusion. These components are typically volatile and mobile enough to be detected by

- 57 ΙΜΡΙ £ ^

INSTITUTE &lt;** ££ ** £ ΟΕ LA MOMBDAO the human nose and give rise to an organoleptic defect often described as a plastic taste "which generally ou cradle id was * ·" · ........ • very undesirable for many consumers. Polyolefins are widely used to seal elements in carbonated water, beer and soft drinks, as well as in numerous layers of sealant for self-stable packaging such as cereals, crunchy foods, cookies, salty snacks, etc. Aldehydes are produced in small amounts when sealant materials are mixed together and subsequently made into coatings and shells. The aim is to show that the CD graft polyolefins mixed in the closure compositions complex the residual oxidation products, such as aldehydes, in the thermoplastic resin during the mixing and molding process preventing them from degassing or migrating from the composition.

Main Batch Material

The CD grafted LDPE was first mixed individually in main batches. A final blend of CD grafted LDPE and the closure coating composition (Polyliner 461, DSChemie, Bremen, Germany) were mixed to provide a CD loading of 0.50% by weight and 0.60% by weight. The final left coating compositions with CD grafted polyolefin were further prepared prior to analysis for residual volatiles.

Two ethylene-maleic anhydride / LDPE copolymer blends were mixed with a stoichiometric weight load

<img file="MX347751B_D0045.tif" />

INSTITUTO MEXICANO of unmodified β-CD (3.20% by weight) through the use of^ANDBrabender Plasticorder Mixing batch prinnjpoioc iing third control sample of the closure coating composition was also mixed in a Brabender Plasticorder Mixing Bowl but without CD. All resins were dried at 85 ° C for 2 hours under vacuum (&lt;0.Γ Hg) before use, while the βCD cyclodextrin was dried in a circulating air oven at 105 ° C for 30 minutes. The following main batch compositions were mixed.

Beta Cyclodextrin Blend in Ethylene Maleic Anhydride / LDPE Copolymer Blend Master Batch (EMA / LDPE)

One hundred thirty-one hundredths gms of beta cyclodextrin (lot 70P162, Wacker Chemie) were mixed in 39.69 gms of EMA / LDPE (Plexar PX 175, lot CL590803E1, Equistar Chemicals, LP) by using a Brabender Plasticorder Mixing Bowl for 5 minutes at 130 ° C and 80 rpm.

Low Density Polyethylene (LOPE) Beta Cyclodextrin Blend and Ethylene Maleic Anhydride / LDPE Copolymer Blend Master Batch (EMA / LDPE)

One hundred thirty-one hundredths of beta cyclodextrin (lot 70P162, Wacker Chemie) were mixed in 31.75 gms of EMA / LDPE (Plexar PX5125, lot CL590803E1, Equistar Chemicals, LP) and 7.94 gms of EMA / LDPE (Plexar PX175, lot CL590803E1 ,

Equistar Chemicals, LP) by using a Mixing Bowl

<img file="MX347751B_D0046.tif" />

- 59 IMPI

INSTITUTO MÍXICAW

OF THE NOFÍPAC '

ΙΝυϊΚΤΙΙΛΙ

Brabender Plasticorder for 5 minutes at 130 ° C and 80 rpm.

Test Compositions

A final test composition was made from the main batch with CD grafting and the closure coating composition was made by mixing the materials in a Brabender Plasticorder Mixing Bowl. The wt% of the seal test compositions are provided in Table 3.

Table 3

CD grafted polyolefin and topcoat wt% compositions are mixed for organoleptic migrant testing

<td>Sample ID</td><td>Description</td><td>A-CD graft</td><td>CD β-CD</td><td>% in P &lt;PX 175</td><td>sso Comp PX 5125</td><td>osition Reves timien t</td>

<td>2A</td><td>Control</td><td></td><td></td><td></td><td></td><td> 100</td>

<td>2B</td><td>0.50% -Mix Grafted with CD</td><td>X</td><td></td><td> 3.7</td><td> 14.8</td><td> 81.5</td>

<td>2 C</td><td>0.60% -Mix Grafted with CD</td><td>X</td><td></td><td> 4.5</td><td> 17.8</td><td> 77.7</td>

<td>2D</td><td>0.50% U-Mix Grafted with CD</td><td></td><td>X</td><td> 3.7</td><td> 14.7</td><td> 81.6</td>

<td>2E</td><td>0.60% -Mix Grafted with CD</td><td></td><td>X</td><td> 4.4</td><td> 17.7</td><td> 77.9</td>

Laboratory Sample Preparation

Granulated Polyliner 461 and CD grafted polyolefin master batch are dry batch mixed on a weight basis. Dry mixed materials are dried in a vacuum oven at &lt;0.1-mm Hg pressure for 2 hours at 85 ° C in order to remove

-⁶° fNSTTTUTO MEXICANO. . ... . . . _____^FROM O-JaS-j®, any residual water of both materials. industrial

A Brabender fusion bowl was used for — mez-offeH^-—— CD-grafted master batch and the closure coating composition mixtures. Reprints from 41 gram batches of pre-dried resins without mixing with CD grafting are passed to flood the melt bowl. The melting bowl temperature was set at 130 ° C. With the blade rpm set at 80, 41 grams of the test material composition is dripped into the bowl. The material is fed into the bowl for a period of 30 seconds.

After another 5 minutes of processing, the screw speed is reduced to zero and the molten resin is removed and collected on aluminum foil. The bowl and roller blades are thoroughly cleaned before starting the next run.

The composite coating test materials are then ground into scratches that are ~ 20 µm thick for examination of organoleptic resin volatiles.

Analytical method

The aldehydes in the test samples prepared in

Brabender are allowed to degas from the resin in the headspace of a flask during confinement at an elevated temperature. An aliquot of air taken from the headspace during the confinement period is analyzed by static headspace gas chromatography using flame ionization detection.

- 61 MEMCANO INSTITUTE

A 0.25 +/- 0.002 g sample of raspadúh ^^^ acre® is placed in a 22-mL glass bottle. The bottle is immediately capped using a butyl rubber gap with Teflon surface and aluminum fold top. Volatiles are desorbed from the sample in the headspace by heating the flask at 85 ° C for 24 hours. The bottle is transferred to a heated headspace sampler (85 ° C) (Hewlett Packard Model 19395A) attached to a Hewlett Packard Model HP-5880 II GC equipped with a Flame Ionization Detector (FID) and computerized data collection. . The J&amp;W Scientific capillary column (DB-5, 30 mx 0.25 mm ID, 1.0 pm film) with hydrogen vehicle flow set at a 20: 1 split ratio. HRGC is used to measure the acetaldehyde concentration in the headspace of the bottle. The peak area of ​​aldehydes is integrated to quantify the concentration and then the concentration is calculated from a standard four-point calibration that covers the concentration range of the samples. Sample concentrations are reported in ppm (pg / g Weight / weight). The aldehyde concentration is calculated from the slope of the calibration curve or response factor (RF) prepared for each aldehyde analyte.

Compound Concentration in ppm = (Peak Area X RF) -? Sample Weight

Compound Concentration in ppm = Peak Area 4- Sample

Tilt Calibration Curve

<img file="MX347751B_D0047.tif" />

- 62 IMPI

MEXICAN INSTITUTE OF PROPERTY

Residual Aldehyde Test Results ^{, NDnsTRIAL}

When heated in a CWIIIad space, the seal test compositions produce part-per-billion and sub-parts-per-billion levels of aldehydes C₄ to C₁₀. Compositions containing CD grafted polyethylene substantially reduce aldehyde concentrations. Aliphatic aldehydes C₄ Total Cio were reduced by 38% and 44% for the α-CD graft compositions of 0.50% by weight and 0.60% by weight, respectively. The related% wt loadings for β-CD graft compositions reduced total aldehydes 31% and 22%, respectively.

Table 4

The Table shows a comparison of saturated aldehydes C₄ to C₁₀ in closure liner material with and without CD graft polyolefin. Aldehyde concentrations are in ng / g or parts per billion.

<td></td><td>2A</td><td>2B</td><td>2 C</td><td>2D</td><td>2E</td>

<td>Channel</td><td> 4.81</td><td> 2.43</td><td> 2.06</td><td> 3.54</td><td> 2.72</td>

<td>Nonanal</td><td> 5.18</td><td> 5.18</td><td> 5.15</td><td> 5.04</td><td> 5.26</td>

<td>Octanal</td><td> 358</td><td> 208</td><td> 185</td><td> 236</td><td> 275</td>

<td>Heptanal</td><td> 0.79</td><td>ND</td><td> 0.66</td><td> 0.60</td><td> 0.57</td>

<td>Hexanal</td><td> 19.2</td><td> 18.8</td><td> 18.1</td><td> 16.9</td><td> 16.7</td>

<td>Butanal</td><td> 29.5</td><td> 25.3</td><td> 22.0</td><td> 26.4</td><td> 25.7</td>

Organoleptic Testing of Sealing Materials Exposed to Water

Ozonized

Example lll

<img file="MX347751B_D0048.tif" />

<img file="MX347751B_D0049.tif" />

- 63 The demand for water

INSTITUTO MEXICANO of purified bottled water has risen sharply around the world.— The μι ULUTrff 'known as ozonation is the commercial method of disinfecting bottled water in the United States. The most common materials used to make bottles and closures are plastics such as polyethylene terephthalate (PET) for the bottle and polyolefins for screw cap liners and shells. A "plastic-like" flavor release and odor release is noticeable in packaged water in all plastic containers. This organoleptic defect is especially noticeable in ozone-treated water. Plastic flavor release in bottled water has been correlated with the presence of low-level aldehyde concentrations (eg, hexanal, heptanal, octanal, nonanal, and decanal) (typically parts per billion). Even before the coating or shell is contacted with ozonated water, low aldehyde concentrations are inherent in thermoplastic materials, as shown in Example 2, due to thermal oxidation degradation during processing. However, substantially higher aldehyde concentrations are measured in water that has been ozonated due to susceptible additives such as erucamide, a common lubricant used in polyolefin sealants. Ozone chemically attacks unsaturated chemical bonds in additives and unsaturated olefin monomers (eg, hexene, octet, decene) and oligomers. A method of

<img file="MX347751B_D0050.tif" />

- 64 iNSTmnroMUiCANo accelerated storage test to measure Ios^from$ iBSSh «1os generated from coating compositions exposed to. ozonated water. The ozone-treated water test method shows that a further reduction in aldehydes can be achieved by incorporating CD-grafted polyolefins into the closure composition.

Main Lot Materials

CD-grafted LDPE was first mixed individually in main batches. A final blend of CD grafted LDPE and the topcoat composition (Polyliner 461, DSChemie, Bremen, Germany) were mixed to provide a CD loading of 0.50% by weight. The final left coating compositions with CD grafted polyolefin were further prepared prior to the ozonated water accelerated storage analysis.

Two ethylene-maleic anhydride / LDPE copolymer blends were mixed with a stoichiometric weight loading of unmodified β-CD (3.30 wt%) using a Brabender Plasticorder Mixing Bowl which forms master batches. A third control sample of the LDPE resin was also mixed in a Brabender Plasticorder Mixing Bowl containing a- and β-CD. All resins were dried at 85 ° C for 2 hours under vacuum (&lt;0.T of Hg) before use, while the β-CD cyclodextrin was dried at 105 ° C for 30 minutes. The following were mixed

<img file="MX347751B_D0051.tif" />

- 65 main batch compositions.

IMPI • ♦ STWUTO M MUCAMO DE LA FtCUIDAD INDUSTRIAL

Beta Cyclodextrin Blend in Ethylene Maleic Anhydride / LDPE Copolymer Blend Master Batch (EMA / LDPE)

One hundred thirty-one hundredths of beta cyclodextrin (lot 70P162, Wacker Chemie) were mixed in 39.69 gms of EMA / LDPE (Plexar PX 5125, lot CL590803E1, Equistar Chemicals, LP) or LDPE (NA204, lot ET626241, Equistar Chemicals, LP ) by using a Brabender Plasticorder Mixing Bowl for 5 minutes at 130 ° C and 80 rpm.

One hundred thirty-one hundredths of beta cyclodextrin (lot 70P162, Wacker Chemie) were mixed in 39.69 gms of EMA / LDPE (Plexar PX 5125, lot CL590803E1, Equistar Chemicals, L P.) and 7.94 gms of EMA / LDPE (Plexar PX175 , lot CL590803E1, Equistar Chemicals, LP) by using a Brabender Plasticorder Mixing Bowl for 5 minutes at 130 ° C and 80 rpm.

Low Density Polyethylene (LDPE) Alpha Cyclodextrin Blend and Ethylene Anhydride Copolymer Blend Master Batch

Maleic / LDPE (EMA / LDPE)

One hundred and eleven hundredths gms of alpha cyclodextrin (batch 60P162, Wacker Chemie) were mixed into 39.89 gms of EMA / LDPE (Plexar PX 5125, batch CL590803E1, Equistar Chemicals, LP) or LDPE (NA204, batch ET626241, Equistar Chemicals, LP) using using a Brabender Plasticorder Mixing Bowl for 5 minutes at

<img file="MX347751B_D0052.tif" />

<img file="MX347751B_D0053.tif" />

130 ° C and 80 rpm.

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Low Density Polyethylene (LDPE) Alpha Cyclodextrin Blend and Ethylene Maleic Anhydride / LDPE Copolymer Blend Master Batch (EMA / LDPE)

One hundred and eleven hundredths gms of alpha cyclodextrin (batch 60P162, Wacker Chemie) were mixed in 31.75 gms of EMA / LDPE (Plexar PX 5125, batch CL590803E1, Equistar Chemicals, LP) and 7.94 gms of EMA / LDPE (Plexar PX175, batch CL590803E1, Equistar Chemicals, LP) by using a Brabender Plasticorder Mixing Bowl for 5 minutes at 130 ° C and 80 rpm.

Closing Test Compositions

A final test composition of the main batch with CD graft and the closure coating composition was made by mixing the resin, the CD graft polymer and the lubricating materials in a Brabender Plasticorder Mixing Bowl for 5 minutes at 130 ° C and 80 rpm. The wt% of the closure test compositions are provided in Table 5. This material was then cast into 4.45 cm x 1.59 cm x 0.10 cm sample coupons with an Atlas Laboratory Mix Former set at 140 rpm, 150 ° C for 2 minutes, with a mold temperature of 90 ° C.

Table 5

CD-grafted polyolefin, CD-containing LDPE and

<img file="MX347751B_D0054.tif" />

wt% compositions of Mexican closure liner ^EC INDUSTRIAL

<td rowspan="3">Sample ID</td><td rowspan="3">Description</td><td colspan="7">% by Weight Composition</td>

<td rowspan="2">Closing liner</td><td colspan="2">Main Lot LOPE</td><td colspan="4">CD graft</td>

<td>a-CD</td><td>β-CD</td><td>aCD PX 175</td><td>β-CD PX 175</td><td>a-CD PX 5125</td><td>PCD PX 512 5</td>

<td>3A</td><td>Control</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>3B</td><td>0.50% a-CD</td><td> 81.5</td><td> 18.5</td><td></td><td></td><td></td><td></td><td></td>

<td>3C</td><td>0.50% a-CD grafted</td><td> 81.5</td><td></td><td></td><td></td><td></td><td> 18.5</td><td></td>

<td>3D</td><td>Mix of 0.50% a-CD Grafted</td><td> 81.5</td><td></td><td></td><td> 3.7</td><td></td><td> 14.8</td><td></td>

<td>3E</td><td>0.50% β-CD</td><td> 81.5</td><td></td><td> 18.5</td><td></td><td></td><td></td><td></td>

<td>3F</td><td>0.50% β-CD grafted</td><td> 81.6</td><td></td><td></td><td></td><td></td><td></td><td> 18. 4</td>

<td>3G</td><td>0.50% β-CD Grafted Mix</td><td> 81.6</td><td></td><td></td><td></td><td> 3.7</td><td></td><td> 14. 7</td>

Sample Preparation

A laboratory system for generating ozone includes passing pure oxygen from a feed gas (5.5 liters / min) to a corona discharge ozone generator that produces high purity ozone. A continuous ozone monitor records the emission from the ozone generator. Ozone is absorbed into water, producing a substantial level of ozone gas dissolved in a given volume of water (approximately 800 ppb ozone). Ozone-containing water is suitable for use in the examination of sealing element materials.

The test involves test coupons of the coating material containing the compositions provided in Table 5, which are exposed to water sterilized with 800 ppb of ozone and stored in glass bottles with 475 mL of DI water.

<img file="MX347751B_D0055.tif" />

IMPI

- 68 INSTITUTO MEXICANO DE LA MONEDAD ozonated, metal threaded caps with aluminum βυβ &amp; ΙΤΓΰΐβ coatings. A 4.45 cm x 1.59 cm x 0.10 cm in cupóirrle μι uebd 'SF solid in the mouth of the bottle. The bottles are stored on their sides where the ozone-treated water is in direct contact with the test coupon for seven days at 40 ° C.

Analytical method

After the storage period, the aqueous content was extracted 3 times with 30 mL of methylene chloride, the methylene chloride extracts were dried through sodium sulfate drying columns, and the volume was reduced to 0.5 mL by using of Kuderna-Danish evaporator. The internal standard acenaphthene (2 ggm) was added to the reduced extract and finally the extracts were analyzed by high performance gas chromatography using flame ionization detection. The aldehyde results are provided in Table 6.

Table 6

A comparison of aldehyde concentrations measured in ozone-treated water in contact with closure coating compositions * containing CD-grafted LDPE and non-CD-grafted LDPE. Aldehyde concentrations found in μgm / L or parts per billion are shown.

<img file="MX347751B_D0056.tif" />

ALDEHYDE CONCENTRATIONS IN WATER ΟΖΟΝ ZAPA

<td></td><td>3A</td><td>3B</td><td>3C</td><td>3D</td><td>3E</td><td>3F</td><td>3G</td>

<td>tr-2 Decennial</td><td> 0.256</td><td> 0.095</td><td> 0.136</td><td> 0.093</td><td> 0.123</td><td> 0.148</td><td> 0.121</td>

<td>Channel</td><td> 0.105</td><td> 0.012</td><td> 0.070</td><td>ND</td><td> 0.043</td><td> 0.131</td><td> 0.022</td>

<td>Nonanal</td><td> 2.822</td><td> 1.806</td><td>ND</td><td> 1.655</td><td> 3.268</td><td> 2.175</td><td> 2.467</td>

<td>Octanal</td><td> 0.192</td><td>ND</td><td>ND</td><td>ND</td><td> 0.017</td><td> 0.082</td><td>ND</td>

Examination of Sealing Materials for Organoleptic Barrier Example IV

A potent odor and flavor mold stain in beer, water and wine has been traced to an environmental pollutant called trichloroanisole (TCA). Sources of TCA have been ship containers, wooden pallets, cardboard bags, and cardboard boxes. TCA is formed from chlorophenols, used in wood preservation, by fungal mutilation. TCA concentrations as low as 5-10 ppt have been detected in aqueous solutions by trained panels and 20-30 ppt in untrained panels.

Organic Vapor Transport

Permeation through a barrier can be explained where the membrane in time (t₀) is initially free of permeating vapor. The penetrating pressure p₂ at the upstream surface of the membrane increases giving a concentration in the surface layer c₂. Diffusion is a measure of how fast permeants in a membrane move through the concentration gradient and the time it takes to reach a

<img file="MX347751B_D0057.tif" />

IMPI uniform state. The downstream pressure, p₁₍ au is negligible in small times relative to the upstream pressure p₂. The amount of vapor that seeps into the film increases linearly with time once the uniform state has been reached. In great times, the upstream pressure p₂ will equal the downstream pressure Pv An illustrative transition profile is provided in FIGURE 8.

The second objective is to show that a compatible cyclodextrin dispersed in PE then formed into a membrane delays organic vapor transport and reduces mass flux as measured in the static test cell in FIGURE 7. Two experimental membranes are examined. The effect of cyclodextrin is measured on a monolayer coating composition membrane at diffusion time (t) when p₂= Pi with TCA.

Main Lot Materials

CD-grafted LDPE was first mixed individually in main batches. A final blend of CD grafted LDPE and closure coating composition (Svelon 477, DSChemie, Bremen, Germany) was mixed to provide a CD loading of 0.50% by weight and 0.60% by weight. The final left coating compositions with CD grafted polyolefin were further prepared prior to analysis for residual volatiles.

Two ethylene-hydroxide copolymer blends

- 71 Maleic IMPI / LDPE (Plexar 1856, Equistar Chemicals, LP) 9®nntr8&gt; ^ ¡3 ^ n

INDUSTRIAL with a stoichiometric weight loading of unmodified α-CD (3.91% by weight) and γ-CD (5.21% by weight) by using a Brabender Plasticorder Mixing Bowl that forms main batches. All resins were dried at 85 ° C for 2 hours under vacuum (&lt;0.1 "Hg) before use, while cyclodextrins were dried at 105 ° C for 30 minutes.

Alpha Cyclodextrin Blend in Ethylene Maleic Anhydride / LDPE Copolymer Blend (EMA / LDPE)

One hundred six tenths gms of alpha cyclodextrin (batch 60P162, Wacker Chemie) were mixed in 39.4 gms of EMA / LDPE (Plexar PX 1856, batch 51080101, Equistar Chemicals, LP) by using a Brabender Plasticorder Mixing Bowl for 5 minutes at 150 ° C and 80 rpm.

Gamma Cyclodextrin Blend in Ethylene Maleic Anhydride / LDPE Copolymer Blend (EMA / LDPE)

Two and fourteen hundredths gms of gamma cyclodextrin (batch 80P0800, Wacker Chemie) were mixed in 38.86 gms of EMA / LDPE (Plexar PX 1856, batch 51080101, Equistar Chemicals, LP) using a Brabender Plasticorder Mixing Bowl for 5 minutes at 150 ° C and 80 rpm.

<img file="MX347751B_D0058.tif" />

- 72 Test Compositions

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

A final test composition of the main batch with CD grafting and the closure coating composition was made by mixing the materials in a Brabender Plasticorder Mixing Bowl for 5 minutes at 130 ° C and 80 rpm. This material was then cast into 4.45 cm x 1.59 cm x 0.10 cm sample coupons with an Atlas Laboratory Mix Former set at 140 rpm, 150 ° C for 2 minutes, with a mold temperature of 90 ° C. The% by weight of the test compositions is provided in Table 7.

Table 7

CD grafted polyolefin and closure liner wt% compositions are shown

<td>Sample ID</td><td>Description</td><td colspan="2">CD a-CD γ-CD graft</td><td colspan="2">Composition% by weight PX 1856 Cover</td>

<td>4A</td><td>Control</td><td></td><td></td><td></td><td> 100</td>

<td>4B</td><td>0.50% a-CD Grafted</td><td>X</td><td></td><td> 12.7</td><td> 87.2</td>

<td>4C</td><td>0.40% -CD γ Grafted</td><td></td><td>X</td><td> 7.7</td><td> 92.3</td>

<td>4D</td><td>0.50% -CD γ Grafted</td><td></td><td>X</td><td> 9.6</td><td> 90.4</td>

Mono-Layer Disc Preparation

A 1.27 cm diameter hole punch is used to cut two coupon discs 4.45 cm x 1.59 cm x 0.10 cm for static permeation testing. Replicate sample thickness should be +/- 5%.

- 73 - IMPI

MEXICAN INSTITUTE

OF PROPERTY Analytical Method for Organic Vapor Permeation ^INDUST*^ITB

The permeation method includes experimental techniques to measure the transport of the organic molecule through a polymer packing structure, using a static concentration gradient. High-resolution gas chromatography (HRGC) operated with electron capture detection (ECD) is used to measure the cumulative downstream penetrating concentration.

Apparatus

Disk samples (0.10 cm thick x 1.27 cm diameter and weighing 128 mg) are tested in a closed volume vapor permeation device (refer to FIGURE 7). The experimental aluminum measuring cell has two compartments (i.e. cells) separated by the disc under study (effective disc area = 5.3 cm²) and covered at both ends using aluminum restraint tops and butyl rubber septa with one side of Teflon®.

The test disk is placed on the top cell, the cell is assembled using an O-ring to seal the test disk tightly and screws to pull the cells, top and bottom, together. The top cell is then covered with a butyl rubber septa and aluminum restriction top with a Teflon® side. Two permeation standards are prepared. The permeating standard contains 2,4,6-trichloroanisole. The permeant disperses

- 74 in a mixture of deionized water and / surfactant.

water / permeating surfactant is injected into the

<img file="MX347751B_D0059.tif" />

lower cell provided a concentration p₂ at₀ shown in Tables 8. The TCA p₂ in lower cell it is expressed in parts per billion - nL / L (vol. vol.) - using gas laws. The lower cell is then immediately covered with an upper part of aluminum restriction and Teflon®-sided butl septa.

Standard concentrations of TCA are prepared by diluting a stock solution of TCA prepared in methanol to 50 mg / mL in a 1% Triton X 100 aqueous solution. The dilutions are prepared such that 5 uL additions of the diluted stock provided the masses (pg) to the 20 mL headspace flasks. The following SPME / GC ECD instrument conditions are used in TCA analysis.

Column: DB-5 (40 meters by 0.18 mm id., 0.18 μιτι film)

Vehicle: Hydrogen

Top pressure: 22 psi (1 mL / min)

Iny mode. No slip (1min)

Temp. Iny: 270 ° C

Total Flow ECD: 60 mL / min

Temp. ECD: 275 ° C

Temp. 50 ° C GC oven for 2 min

10 ° C / min to 225 ° C for 0.5 min

SPME conditions: Heat @ 50 ° C for 30 min

Insert SPME for 30 min @ 50 ° C

<img file="MX347751B_D0060.tif" />

- 75 Fiber SPME (blue, PDMS / DVB)

IMPI

MEXICAN INSTITUTE

OF INDUSTRIAL PROPERTY

Trichloroanisole

ECD-operated HRGC is used to measure the change in cumulative trichloroanisole concentration at time t_1/2 in the upstream cell. The illustrative closed volume static permeation profile is provided in FIGURE 8. At the end of 6 hours, a sample is collected by solid phase microextraction (SPME) from the top cell and analyzed by HRGC / ECD. Trichloroanisole concentration is determined from calibration standards and measured in pL / L or parts per triilon (vol./vol.) Using gas laws. Test cells are prepared and analyzed in triplicate. &lt;.a Table 8 contains the concentration p₂ of TOA in the lower cell at t = 0, and the TOA concentration Ρί in the upper cell at time t_1/2 or 6 hours in the control and the triacetyl gamma cyclodextrin (ΤΑ-γ-CD) sample in two loads.

Table 8

Trichloroanisole concentration is measured by static permeation using headspace HRGC / ECD in a control closure composition containing CD grafted materials - permeation cell temperature maintained at 50 ° C.

- 76 IMPI

<td rowspan="2">Permeating</td><td>Conc. P2 @ Time = 0</td><td colspan="4">OF THE PROPERTY , „„ Industrial Concentration - pi @ Time = 6 hours</td>

<td>All samples</td><td>4A</td><td>4B</td><td>4C--</td><td></td>

<td></td><td>pL / L</td><td>pL / L</td><td>pL / L</td><td>pL / L</td><td>pL / L</td>

<td>2,4,6- Trichloroanisole</td><td> 1310</td><td> 210</td><td> 169</td><td> 136</td><td> 148</td>

<td>Total</td><td> 1310</td><td> 210</td><td> 169</td><td> 136</td><td> 148</td>

<td colspan="6">pL / L = Parts per Million pL / L = Parts per Trillion</td>

Closure compositions containing CD grafted material substantially reduced TCA mass transfer. TCA mass transfer is reduced 18.6% and 34.6% in composite liner composition with 0.40% by weight and 0.50% by weight of grafted LDPE γ-CD, respectively. LDPE γ-CD grafted A 0.50% by weight reduced TCA mass transfer 28.8%. The TCA reduction is both a function of CD (α, β, or γ) isomer and concentration.

Testing of film materials for vapor transport or moisture barrier properties

Example V

For a specific packaging application or package design, it may be important to reduce water transport due to sensitivity of contents or to reduce film gauge for environmental reasons. High-density polyethylene (HDPE) films are commonly used in conjunction with bag-in-box food packaging applications to pack cereals, cookies, and snack foods. The moisture barrier in the structure

<img file="MX347751B_D0061.tif" />

flexible polyolefin plays an important role in

INDUSTRY!

Products from moisture ingress which can lead to sensory changes such as aging and loss of freshness, which shortens the shelf life of the product. A moisture vapor barrier composition may comprise a thermoplastic network comprising a polyolefin polymer and a dispersed functional polyolefin containing pendant cyclodextrin molecules.

Master Lot Materials

An ethylene maleic anhydride copolymer (melt index 7.4 g / 10 min and maleic anhydride functionality of 0.86% by weight) is composed with a stoichiometric weight loading (5.0% by weight) of unmodified β-CD using an extruder of cogiratory composition (Warner Pfleiderer Corporation ZSK-30 mm). It is configured with an upstream feed zone for ethylene-maleic anhydride (EMA) and β-CD copolymer, followed by a mixing section, a feed zone for HDPE, another mixing section with a melt seal, followed by a vacuum section and finally a filament die and transmission section. The EMA copolymer is dried for 6 hours at 95 ° C, at a pressure of &lt;254 centimeters Hg. Cyclodextrin is dried for 28 hours at 105 ° C, at a pressure of &lt;.254 centimeters Hg. Weight loss feeders are used to supply all materials. The cyclodextrin is kept under a nitrogen blanket to prevent moisture pick-up. The feeding zone was at temperature

-^7β- IMPIg

MEXICAN INSTITUTE

OF THE PROPERTY ambient (i.e.), approximately 22 ° C, first the ^x mixing was 150 ° C the other zones were established T'd 12G^P-G: —ta— melting temperature at the nozzle was 204 ° C. The extruder was operated at 300 rpm, and 61% max torque. The muzzle velocity was 22.7 kg per hour. β-CD was fed at 1.18 kg per hour, EMA was fed at 10.18 kg per hour, and HDPE was fed at 11.37 kg per hour. The cyclodextrin also contained a mixture of 3.1% Dynamar 5929 and 0.38% Irganox 1010 and Irgaphos 168. EMA and HDPE copolymer (Petrothene LM 6007) is obtained from Equistar; Irganox and irgaphos antioxidants are obtained from Ciba Specialty Chemicals Corporation; Dynamar lubricant is obtained from the 3M Company, and beta cyclodextrin is obtained from Wacker Biochem Corporation.

Film Preparation

HDPE (LM 6007) and the master batch formulation are made into three films by blown film extrusion. Films are blown on a Killion laboratory scale blown film line. The extruder is equipped with a 25 mm diameter screw (L / D ratio 24: 1) operated at 122 rpm with an output of 3.6 Kg / hour and is pulled at two different speeds producing two different film gauges of 1.4 and 2.2 one thousand. The extruder is fed by virgin HDPE fluid operated only as a control, and with the master batch formulation being pre-mixed with virgin HDPE resin by mechanical spinning to provide two CD weight compositions of 0.50% by weight and 0.35% by weight. .

- 79 IMPI ^

MEXICAN INSTITUTE

Annular Film Nozzle Line ^DThe blown film has a diameter of 31.75 mm and was operated? n ° n. — The bubble of the extruded polymer tube has a diameter of 14.6 cm for both film thicknesses. The two zones of the extruder are operated at 226 ° C and 227 ° C, respectively. The polymer melting temperature is 227 ° C. The extruder for the film die adapter is operated at 227 ° C.

Water-Steam Transmission

The vapor-water permeability through the polymer is at most the same as other vapors. The efficacy of functionalized polyolefin containing pendant cyclodextrin molecules is determined by published ASTM methods (E 96 and F 1249) used to determine a vapor-water transmission rate, which is designated as the time rate of the water vapor flow, under fixed conditions, throughout the unit area, under the relative humidity and temperature conditions of the test. The units accepted are grams per day per square meter (g / (day »m²) or grams per day percent of square inches (g / (day «in²). The test is conducted until the steady state has been reached. The duplicate results of the water vapor transmission rate (WVTR) are provided in Table 9 and 10. Method F ASTM 1249 is used to generate the results of the WVTR test in Table 9 and the results of the WVTR test in Table 10 are generated according to ASTM E 96 Method,

Procedure B-Method of

- 80 water at 23 ° C.

<img file="MX347751B_D0062.tif" />

comprises a comparison of water vapor transmission rates (WVTR) for a control high density polyethylene (HDPE) film and β-CD grafted polyethylene on HDPE film using ASTM Method F 1249.

Table 9

<td rowspan="2"></td><td rowspan="2">Average Film Thickness (mils) +0.05</td><td colspan="2">WVTR (WV Transmission Rate) The rate of time at which water vapor flows normally to surfaces, under steady state conditions, per unit area</td>

<td>gm / m²day</td><td>gm / 1 00 inch²day</td>

<td>Control # 1</td><td> 1.92</td><td> 3.07</td><td> 0.198</td>

<td>Control # 2</td><td> 2.24</td><td> 2.90</td><td> 0.187</td>

<td>0.35% β-CD graft, Rep. # 1</td><td> 2.27</td><td> 2.52</td><td> 0.163</td>

<td>0.35% β-CD graft, Rep. # 2</td><td> 2.25</td><td> 2.53</td><td> 0.163</td>

<td>0.50% β-CD graft, Rep. # 1</td><td> 2.31</td><td> 2.61</td><td> 0.168</td>

<td>0.52% β-CD graft, Rep. # 2</td><td> 2.59</td><td> 2.51</td><td> 0.162</td>

• Test temperature: 37.8 ° C and 0.3 ° C · Test RH: 90% · Sample test area: 50 cm² · Test result accuracy: + 3% • Test results corrected to 760 mm Hg · Average thickness based on five points distributed over the entire test piece

The results in the table above show a substantial reduction in WVTR of the grafted polyolefin CD (0.35% and 0.50% CD) in HDPE (LM 6007) compared to the same control HDPE (LM 6007) without grafted CD. The vapor-water barrier in the CD grafted films of the present invention using ASTM Test Method F 1249 is approximately 15% against the control HDPE.

<img file="MX347751B_D0063.tif" />

<img file="MX347751B_D0064.tif" />

- 81 The following data shows a

INSTITUTO MEXICANO comp ^ g ^ water vapor transmission rates (WVTR) for a control high density polyethylene (HDPE) and β-CD grafted polyethylene on HDPE film using ASTM Method E 96, Procedure B Method Water at 23 ° C

Table 10

<td rowspan="2"></td><td rowspan="2">Average Film Thickness (mils) + 0.05</td><td colspan="2">WVTR (WV Transmission Rate) The rate of time at which water vapor flows normally to surfaces, under steady state conditions, per unit area</td>

<td>gm / m^zday</td><td>gm / 100 inch²day</td>

<td>Control # 1</td><td> 1.39</td><td> 0.484</td><td> 0.031</td>

<td>Control # 2</td><td> 1.40</td><td> 0.496</td><td> 0.032</td>

<td>0.50% β-CD graft, Rep. # 1</td><td> 1.40</td><td> 0.409</td><td> 0.026</td>

<td>0.50% β-CD graft, Rep. # 2</td><td> 1.40</td><td> 0.393</td><td> 0.025</td>

• Test temperature. 23 ° C + 0.5 ° C Test RH: 50% Sample test area: 31.5 cm² • Average thickness based on five points distributed over the entire test piece

A substantial reduction in WVTR of 0.50% CD grafted polyolefin in HDPE (LM 6007) was compared to the same HDPE control (LM 6007) without CD grafted. The improved water vapor barrier in the CD grafted films of the present invention utilizing the ASTM E 96 Test Method (Procedure B - 23 ° C Water Method) is approximately 18% against the control HDPE.

<img file="MX347751B_D0065.tif" />

-⁸²'IMPI

MEXICAN INSTITUTE

Experimental Preparation of P o I or I Closure Materials

Demonstrate Increased Lubricant Concentration in - -

Closing surface

A demonstration of the tendency of claimed materials to increase lubricity at the sealing surface was conducted with a variety of polyolefin materials.

Process

A polyolefin material was formulated and formed into a sealing disc structure in an attempt to compare a variety of formulations. In this procedure, a high-density polyethylene material was combined with a lubricant and beta-cyclodextrin grafted onto a high-density polyethylene master batch. Each main batch comprised mixing a high density polyethylene with 6, 10 or 14% while waiting for a polyethylene with 5% beta-cyclodextrin grafted on the polyethylene to result in formulations containing 0.3, 0.5 and 0.7% by weight of fillers. of the active cyclodextrin material in the composition. Each formulation was formulated to contain 0.5% by weight of erucamide saturated fatty amide lubricant in each formulation. Each formulation was also combined with an effective amount of a blue dye. The formulations were prepared by mixing the material for 5 minutes at 175 ° C at 80 rpm in a Brabender mixing bowl. Test discs [1.125 inches (2.85 cm) diameter x 0.050 inches (0.127 cm) thick] in a shape of

-⁸³- ΙΜΡΠ instituto msxicano And discs were prepared in an Atlas molder using mold &amp; ftSSS ^ auda formulation for 2 minutes at 185 ° C at 140 rpm nn »mold temperature of 95 ° C. These materials were examined for weight, thickness, and surface concentration of erucamide 5 using a solvent extraction procedure, followed by gas chromatography, followed by GC / FID analysis.

σι

Table 11

Polyolefin Copolymer Resin M 4621

<td>% Erucamida</td><td>% CD</td><td>Weight in grams of discs ry 0.75</td><td>r Thickness Day. Mils discs</td><td>0.75 Thickness Dia. Mils discs</td><td>Solvent Extraction mL</td><td>Conc. Erucamide Ug / mL</td><td>Erucamide Total ug</td><td>Erucamide Ug / cm²</td><td>Erucamide ng / L</td><td>Total Amides ng / L</td><td>T otal Acid ng / L</td>

<td> 0.5</td><td> 0.3</td><td> 0.8688</td><td> 45.2</td><td> 43.9</td><td> 5</td><td> 142.3</td><td> 712</td><td> 44.9</td><td> 5.6</td><td> 51.1</td><td> 46.4</td>

<td></td><td></td><td> 0.8693</td><td> 45.0</td><td> 45.5</td><td> 5</td><td> 132.3</td><td> 662</td><td> 41.8</td><td> 5.5</td><td> 66.1</td><td> 52.4</td>

<td> 0.5</td><td> 0.5</td><td> 0.8423</td><td> 44.6</td><td> 44.7</td><td> 5</td><td> 135.4</td><td> 677</td><td> 42.7</td><td> 6.5</td><td> 47.8</td><td> 42.2</td>

<td></td><td></td><td> 0.8587</td><td> 45.2</td><td> 44.3</td><td> 5</td><td> 123.8</td><td> 619</td><td> 39.1</td><td> 9.3</td><td> 58.6</td><td> 66.1</td>

<td> 0.5</td><td> 0.7</td><td> 0.8929</td><td> 45.8</td><td> 45.8</td><td> 5</td><td> 167.4</td><td> 837</td><td> 52.9</td><td> 14.3</td><td> 44.4</td><td> 27.4</td>

<td></td><td></td><td> 0.8633</td><td> 45.3</td><td> 45.9</td><td> 5</td><td> 154.5</td><td> 773</td><td> 48.8</td><td> 2.2</td><td> 79.9</td><td> 47.4</td>

<td> 0.5</td><td> 0</td><td> 0.8903</td><td> 46.0</td><td> 46.4</td><td> 5</td><td> 127.7</td><td> 639</td><td> 40.3</td><td> 6.9</td><td> 59.2</td><td> 31 .2</td>

<td></td><td></td><td> 0.8604</td><td> 44.7</td><td> 46.9</td><td> 5</td><td> 107.3</td><td> 537</td><td> 33.9</td><td> 8.3</td><td> 68.6</td><td> 37.2</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

co

Table 12

Polyolefin Copolymer Resin M 5214

<td>% Erucamida</td><td>% CD</td><td>Weight in Grams of Discs 1 and 0.75 *</td><td>1 'Thickness Dia. Mils discs</td><td>0.75 'Thick Dia. Mils discs</td><td>Solvent Extraction mL</td><td>Conc. Erucamide Ug / mL</td><td>Erucamide Total ug</td><td>Erucamide Ug / cm²</td><td>Erucamide ng / L</td><td>Total Amides ng / L</td><td>Total Acid ng / L</td>

<td> 0.5</td><td> 0.3</td><td> 0.8319</td><td> 45.8</td><td> 43.7</td><td> 5</td><td> 125.8</td><td> 629</td><td> 39.7</td><td> 2.6</td><td> 39.6</td><td> 35.9</td>

<td></td><td></td><td> 0.8492</td><td> 45.3</td><td> 40.9</td><td> 5</td><td> 108.5</td><td> 543</td><td> 34.3</td><td> 3.1</td><td> 32.1</td><td> 20.3</td>

<td> 0.5</td><td> 0.5</td><td> 0.8556</td><td> 46.3</td><td> 44.2</td><td> 5</td><td> 146.4</td><td> 732</td><td> 46.2</td><td> 5.1</td><td> 46.4</td><td> 41.0</td>

<td></td><td></td><td> 0.8315</td><td> 43.5</td><td> 44.5</td><td> 5</td><td> 143.8</td><td> 719</td><td> 45.4</td><td> 4.0</td><td> 39.6</td><td> 33.2</td>

<td> 0.5</td><td> 0.7</td><td> 0.8360</td><td> 42.3</td><td> 49.6</td><td> 5</td><td> 134.6</td><td> 673</td><td> 42.5</td><td> 4.8</td><td> 45.5</td><td> 34.2</td>

<td></td><td></td><td> 0.8079</td><td> 42.8</td><td> 39.4</td><td> 5</td><td> 138.4</td><td> 692</td><td> 43.7</td><td> 5.8</td><td> 41.8</td><td> 31.6</td>

<td> 0.5</td><td> 0</td><td> 0.8482</td><td> 43.0</td><td> 45.3</td><td> 5</td><td> 73.9</td><td> 369.5</td><td> 23.3</td><td> 1.8</td><td> 44.6</td><td> 70.2</td>

<td></td><td></td><td> 0.8106</td><td> 42.3</td><td> 46.5</td><td> 5</td><td> 83.9</td><td> 419.5</td><td> 26.5</td><td> 6.7</td><td> 46.9</td><td> 43.2</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<img file="MX347751B_D0066.tif" />

on

Table 13

Polyethylene Copolymer Resin GA 652-762

Μ U1

ΙΌ

<td>% Erucamida</td><td>% CD</td><td>Weight in grams of discs 1 'and 0.75'</td><td>1 'Thickness Day. Mils discs</td><td>0.75 Thickness Day. Discs thousand s</td><td>Solvent Extraction mL</td><td>Conc. Erucamide Ug / mL</td><td>Erucamide Total ug</td><td>Erucamide Ug / cm²</td><td>Erucamide ng / L</td><td>Total Amides ng / L</td><td>Total Acid ng / L</td>

<td> 0.5</td><td> 0.3</td><td> 0.8093</td><td> 41.7</td><td> 43.5</td><td> 5</td><td> 112.5</td><td> 563</td><td> 35.5</td><td> 7.9</td><td> 60.4</td><td> 47.7</td>

<td></td><td></td><td> 0.8341</td><td> 72.8</td><td> 45.0</td><td> 5</td><td> 142.9</td><td> 715</td><td> 45.1</td><td> 7.2</td><td> 48.0</td><td> 25.0</td>

<td> 0.5</td><td> 0.5</td><td> 0.7870</td><td> 41.8</td><td> 47.2</td><td> 5</td><td> 125.9</td><td> 630</td><td> 39.7</td><td> 3.8</td><td> 66.6</td><td> 52.4</td>

<td></td><td></td><td> 0.8176</td><td> 42.0</td><td> 42.0</td><td> 5</td><td> 115.7</td><td> 579</td><td> 36.5</td><td> 5.9</td><td> 38.0</td><td> 40.5</td>

<td> 0.5</td><td> 0.7</td><td> 0.8184</td><td> 41.3</td><td> 45.9</td><td> 5</td><td> 125.3</td><td> 627</td><td> 39.6</td><td> 10.3</td><td> 88.9</td><td> 44.4</td>

<td></td><td></td><td> 0.8303</td><td> 43.9</td><td> 43.6</td><td> 5</td><td> 146 5</td><td> 733</td><td> 46.3</td><td> 8.7</td><td> 68 5</td><td> 74.6</td>

<td> 0.5</td><td> 0</td><td> 0.8172</td><td> 41.5</td><td> 43.4</td><td> 5</td><td> 110.3</td><td> 552</td><td> 34.8</td><td> 5.0</td><td> 64.7</td><td> 46.0</td>

<td></td><td></td><td> 0.7822</td><td> 41.3</td><td> 43.5</td><td> 5</td><td> 106.9</td><td> 535</td><td> 33.8</td><td> 3.8</td><td> 58.8</td><td> 73.9</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

co

I HEARD

MEXICAN INSTITUTE. of the property 'INDUSTRIA!

<img file="MX347751B_D0067.tif" />

<img file="MX347751B_D0068.tif" />

The summary table of test resultstr ^ '^^^ pi

INDUSTRIAL that from the test discs, the fatty acid lubricant can be extracted from the surface of the test discs at 0.3 to 0.7% by weight of cyclodextrin that can be extracted from the test discs at 0% of grafted cyclodextrin.

ALATHON M 4621 is a high density polyethylene injection molding grade copolymer with a melt index of 2.2, and a density of 0.946. M4621 is a copolymer that provides permanent stress crack resistance and low temperature impact resistance. Typical applications include small, two-piece engine gas tanks, scrap waste drums, and specialty injection molded parts.

Physical properties

<td>Property</td><td>Nominal value</td><td>Units</td><td>Testing method</td>

<td>Fusion Index</td><td> 2.2</td><td>g / 10 min</td><td>ASTM D 1238</td>

<td>Density</td><td> 0.946</td><td>g / cc</td><td>ASTM D 1505</td>

<td>Resistance to Traction @ Fracture</td><td> 2010 (14.5)</td><td>psi (MPa)</td><td>ASTM D 638</td>

<td>Resistance to Traction @ Performance¹</td><td> 3470 (23.9)</td><td>psi (MPa)</td><td>ASTM D 638</td>

<td>Elongation @ Yield¹</td><td> 12</td><td> %</td><td>ASTM D 638</td>

<td>Softening point Vicat</td><td> 253 (123)</td><td>° F (° C)</td><td>ASTM D 1525</td>

ALATHON M 5214 is a high density polyethylene blow molding grade polymer with a melt index of 1.6, and a density of 0.952. The resin is specially designed for bottles of personal care products. M5214

- 87 IMPI

<img file="MX347751B_D0069.tif" />

imparts high gloss to these finished products and is fo ^r 'INDUSTRIAL release molding which makes it very suitable for injection blow molding.

Physical properties

<td>Property</td><td>Nominal value</td><td>Units</td><td>Testing method</td>

<td>index of Fusion</td><td> 1.6</td><td>g / 10 min</td><td>ASTM D 1238</td>

<td>Density</td><td> 0.952</td><td>g / cc</td><td>ASTM D 1505</td>

<td>Tensile Strength @ Fracture</td><td> 3750</td><td>psi</td><td>ASTM D 638</td>

<td>Elongation @ Fracture</td><td> 600</td><td> %</td><td>ASTM D 638</td>

<td>Coefficient of Flexion</td><td> 168,000</td><td>psi</td><td>ASTM D 790</td>

Physical properties

<td>Property</td><td>Nominal value</td><td>Units</td><td>Testing method</td><td>Show</td>

<td>index of Fusion (190 / 2.16)</td><td> 2.0</td><td>g / 10 min</td><td>ASTM D 1238</td><td>Granules</td>

<td>Density</td><td> 0.942</td><td>g / cc</td><td>ASTM D 1505</td><td>Compression molded</td>

<td>Coefficient of Flexion, 1% Secant</td><td> 120,000</td><td>psi</td><td>ASTM D 790</td><td>Rotomoulded²</td>

<td>Tensile Strength @ Yield, Yield, 2'7min³</td><td> 3220</td><td>psi</td><td>ASTM D 638</td><td>Rotomoulded²</td>

<td>Thermal Distortion Temperature @ 66 psi to 264 psi</td><td> 56 42</td><td>° C ° C</td><td>ASTM D 648</td><td>Rotomoulded²</td>

<img file="MX347751B_D0070.tif" />

The specification, figures, examples and data

INDUSTRIAL

<img file="MX347751B_D0071.tif" />

a detailed explanation of the invention as developed to date. However, the invention may take some embodiments without departing from the spirit or the intended scope of the invention. And, accordingly, the invention resides in the claims hereinafter appended.