Entrained polymer materials with oxygen scavenging agent and zeolite

Abstract

Provided herein is an entrained polymer material comprising a base polymer, an oxygen scavenging agent, and a zeolite. The resulting entrained polymer material will have useful applications, including but not limited to the manufacture of packaging for the protection of oxygen-sensitive contents. Also provided herein are systems and methods for reducing contamination in a product due to oxidation. Also provided herein are related methods of manufacture and methods of use.

Description

ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTENTRAINED POLYMER MATERIALS WITH OXYGEN SCAVENGING AGENT AND ZEOLITECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims priority to U.S. Provisional Application No. 63 / 774,545, titled “ENTRAINED POLYMER MATERIALS WITH OXYGEN SCAVENGING AGENT AND ZEOLITE” and filed on March 19, 2025, and U.S. Provisional Application No.63 / 971,007, titled “ENTRAINED POLYMER MATERIALS WITH OXYGEN SCAVENGING AGENT AND ZEOLITE” and filed on January 29, 2026. Each of the aforementioned priority applications is hereby incorporated by reference in its entirety.FIELD OF THE INVENTION

[0002] Disclosed are entrained polymers comprising an oxygen scavenging agent, including but not limited to organic and inorganic reducing agents, and a zeolite, including but not limited to a molecular sieve. Also disclosed are methods of their use to reduce oxygen levels and maintain properties of packaged oxygen sensitive products. The oxygen scavenging agent and the zeolite are entrained in at least one base polymer with optional channels throughout. Also disclosed herein are related methods of preparation and methods of use.BACKGROUND

[0003] There are many items that are preferably stored, shipped and / or utilized in an environment that must be controlled and / or regulated. The control of moisture, oxygen, ethylene and other gaseous substances may be desirable in medical, diagnostic, industrial chemical, laboratory, electronics and food packaging applications.

[0004] It is well known that regulating the exposure of oxygen-sensitive products to oxygen maintains and enhances the quality and stability or shelf life of the product. In packaging oxygen sensitive materials such as foodstuffs, herbs, beverages, pharmaceuticals, cosmetics, tobacco, cannabis, and others, oxygen contamination can be particularly troublesome. Electronic components and military products such as ammunition and other explosives may also be sensitive to atmospheric oxygen and require special packaging. Care is generally taken to reduce the detrimental or undesirable effects of oxygen on the product.

[0005] In the food and beverage packaging industry, many food products suffer oxygen-initiated degradation - for example, individual portions of prepared foods are marketed in containersATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTmade of plastics, and air entrapped therein, and leaking or transferring into the package after processing, is an acknowledged continuing industry problem. Limiting the exposure of oxygen sensitive food products to oxygen in a packaging system maintains the quality or freshness of the food, reduces spoilage, and extends the food’s shelf life.

[0006] Numerous means for regulating oxygen exposure within packaging containers are used. In the 1960s. packaging containers were developed that envelop a product in an attempt to form a barrier within an oxygen-free package wherein free oxygen is ejected from the product and oxygen external to the package can be precluded. Such containers include modified atmosphere packaging (MAP) and oxygen barrier film packaging. Methods for excluding oxygen involving mechanical means also include vacuum and inert gas packaging. In these procedures, the oxygen is removed by displacement of the entire atmospheric mixture in the package by vacuumizing or flushing the oxygen from the container. In some instances, the package is backfilled with an inert gas. Such systems are used in boiler water treatment, the orange juice and brewing industries, and in modified-atmosphere packaging of food products. This technology, while somewhat equipment intensive, can remove about 90-95% of the oxygen present in air from the product (or its container) prior to or during packaging. However, the removal of the remaining 5-10% of oxygen using this approach requires longer times for vacuum treatment and increasingly larger volumes of higher and higher purity inert gas which must not itself be contaminated with trace levels of oxygen. This makes the removal by such methods of the last traces of oxygen expensive. A further disadvantage of these methods is a tendency to remove volatile product components. This is a particular problem with foods and beverages, wherein such components are often responsible for some or all of the aroma and flavor. These methods do not quantitatively remove all the oxygen from the package because complete evacuation is never achieved and oxygen often remains dissolved or trapped in the packaged product. In addition, when an inert gas backfill is used, the inert gas often brings traces of oxygen back into the package. Such vacuum or flushing methods, especially where inert gas handling is involved, often require machines of considerable cost and sophistication for high-speed packaging. It has proven extremely difficult to remove all traces of oxygen from packages of food products by mechanical means.

[0007] Another method used for regulating oxygen exposure is “active packaging”, whereby the package containing the food product has been modified in some manner to regulate the food’sATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTexposure to oxygen. This concept combines such systems as oxygen regulation (by oxygen scavenging agents), moisture regulators, carbon dioxide (CO2) emitters, carbon dioxide (CO2) absorbers, ethylene absorbers and many more.

[0008] Conventionally, oxygen scavenging agents, desiccants, and other active agents have been used in raw form, e.g., as loose particulates housed in sachets or canisters within packaging, to control the internal environment of the package. For many applications, it is not desired to have such loosely stored active substances. A more uniform scavenging effect throughout the package can be achieved by incorporating the scavenging agent in the package instead of adding a separate scavenger structure such as a sachet to the package. Uniformity may be especially important where there is restricted airflow inside the package. In addition, incorporating the oxygen scavenging agent into the package structure provides a means of intercepting and scavenging oxygen as it permeates the walls of the package, providing in effect an active oxygen barrier, thereby maintaining the lowest possible oxygen level in the package.

[0009] Furthermore, technical challenges are experienced when processing powdery materials, such as oxygen scavenging agents, into polymer films or sheets, such as reduced transparency and deterioration of the mechanical properties of the film or sheet. Improved oxygen scavenging agents are desired in order to reduce such disadvantageous effects or challenges during manufacture.

[0010] To address these problems, active entrained polymers have been developed which comprise active agents. Such polymers can be extruded and / or molded into desired forms, e.g., container liners, plugs, film sheets, pellets and other such structures. Optionally, such active entrained polymers may include channeling agents, such as polyethylene glycol (PEG), which form channels between the surface of the entrained polymer and its interior to transmit a selected material (e.g., moisture) to the entrained active agent (e.g., desiccant to absorb the moisture).

[0011] Entrained polymers may be two phase formulations (i.e.. comprising a base polymer and active agent, without a channeling agent) or three phase formulations (i.e., comprising a base polymer, active agent and channeling agent). Three phase entrained polymers and methods for making the same are described, for example, in U.S. Pat. Nos. 5,911,937, 6,080,350, 6,124,006, 6,130,263, 6,194,079, 6,214,255, 6,486,231, 7,005,459, and U.S. Pat. Pub. No. 2016 / 0039955, each of which is incorporated herein by reference as if fully set forth. These entrained polymers have been conventionally made as extruded products (e.g., pellets or films) or injection moldedATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTcomponents (e.g., pucks, inserts or liners within containers).

[0012] Limited success has been achieved in incorporating oxygen scavenging agents into the walls of packages for various types of foods. Previously developed scavengers include sulfite-based, ascorbate-based and enzyme-based systems as well as oxidizable polyamides and ethylenically unsaturated hydrocarbons. More recent scavengers include incorporation of natural products such as teas or carrots into polymer compositions.

[0013] Antioxidants (such as sulfur dioxide, trihydroxy butyrophenone, butylated hydroxy toluene and butylated hydroxy anisole) and oxygen scavenging agents (such as ascorbic acid, isoascorbic acid and glucose oxidase-catalase) have been used in an attempt to reduce the effects of oxygen contamination. The direct addition of such agents has several disadvantages. Both sulfur dioxide and ascorbates, (when added to beer, for example), can result in production of off-flavors thus negating the intended purpose of the addition.

[0014] Incorporating an oxygen scavenging agent into the packaging structure itself is another means to regulate exposure of a packaged product to oxygen.

[0015] The oxygen scavenging agent can be chosen from a variety of compounds, most of which feature chemical reactivity towards molecular oxygen (O2). Although oxygen is the most recognizable oxidant known to lay people, it is a surprisingly unreactive molecule, relatively speaking. Ozone (O3) and hydrogen peroxide (H2O2), which are formally related to molecular oxygen by addition of either a third oxygen atom or hydrogen, respectively, are significantly more reactive than molecular oxygen. The reaction of many reducing agents with molecular oxygen, even in the presence of a large thermodynamic driving force, can be too slow for their practical use as oxygen scavenging agents.

[0016] For this reason, only a relatively small number of chemical reducing agents provide sufficient kinetic reactivity towards molecular oxygen to provide meaningful oxygen scavenging.

[0017] In contrast to the methods discussed above, which utilize compounds which chemically react with an unwanted compound (including but not limited to molecular oxygen), other methods employ materials which bind reversibly and noncovalently with the unwanted compound, rather than chemically transforming the compound.

[0018] Certain solid materials can noncovalently bind water, and thus remove moisture from a gaseous environment. Included in this class of materials are zeolites, which are compounds that act as molecular sieves and which are widely used for their high adsorption properties and theirATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTthermal, chemical and mechanical stabilities. Certain zeolites can be used for drying solutions, for dehumidifying closed spaces, as well as for drying textiles after the washing process, and as drying components for dishes in dishwashers. Certain zeolites can be used for odor removal, due to their abilities to adsorb volatile organic compounds at trace levels in the atmosphere.

[0019] Zeolites are crystalline aluminosilicates with a 3-dimensional, open anion framework consisting of oxygen- sharing SiC and AIOC tetrahedral structure. Although essentially all zeolites are aluminosilicates, the ratio of alumina to silica varies. Alumina-rich zeolites are attracted to polar molecules such as water, while silica-rich zeolites work better with nonpolar molecules.

[0020] The most common zeolites used for water adsorption in the industry are 3A (potassium or KA) and 4A (sodium or NaA) zeolites, which are LTA-type zeolites, and 13X (sodium or NaX) zeolite, which are FAU-type zeolites. LTA (Linde Type A) is also known as Zeolite A. The principal building units of zeolite A are sodalite cages which are connected by four-membered rings forming a three-dimensional (3D) network. The aluminosilicate framework of zeolite A (LTA-type) can be further described in terms of two types of polyhedra: one being a simple cubic arrangement of eight polyhedra (the double 4-rings); the other being a truncated octahedron of 24 tetrahedra also named 0- cage. Zeolite A has a three-dimensional pore system and molecules can diffuse in all three directions. Normally, zeolite A is present or synthesized in the sodium form, which has a pore opening of about 0.4 nm.

[0021] Despite their impressive properties for binding of water and small organic compounds, zeolites are not expected to have the same activity towards molecular oxygen. The processes that are responsible for the high affinity of water to zeolites, such as polar interactions and hydrogen bonding, are generally unavailable to molecular oxygen, which is a small (0.12 nm bond length) and nonpolar molecule, lacking an acidic hydrogen, or any hydrogen for that matter.

[0022] There remains a need to provide material with the capability of scavenging oxygen. Many uses can be envisioned for such material, including but not limited to inclusion into packaging for the protection of oxygen-sensitive contents.

[0023] Inclusion of a binding agent such as a zeolite or molecular sieve to an oxygen scavenging material would not be expected to improve the efficacy of oxygen scavenging, due both to the low chemical reactivity and the weak noncovalent affinity of zeolites towards oxygen.

[0024] Surprisingly, however, we have found that inclusion of a zeolite into an oxygenATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTscavenging material increases its efficacy of an oxygen scavenging agent incorporated into an entrained polymer.BRIEF SUMMARY

[0025] Accordingly, in one aspect is provided an entrained polymer material comprising a base polymer, an oxygen scavenging agent, and a zeolite.

[0026] In some embodiments, the base polymer is chosen from a polyolefin, a polyamide, and a polyester. In some embodiments, the base polymer is a block copolymer. In some embodiments, the block copolymer comprises polyester segments and polyether segments.

[0027] In some embodiments, the entrained polymer material further comprises a channeling agent. In some embodiments, the channeling agent is chosen from a polyglycol, glycerin polyamine, polyurethane, and polycarboxylic acid, or any combination of the foregoing. In some embodiments, the channeling agent is a water insoluble polymer. In some embodiments, the channeling agent is chosen from propylene oxide polymerisate, propylene oxide polymerisate-monobutyl ether, ethylene vinyl acetate (EVA), nylon, or any combination of the foregoing.

[0028] Also provided herein is a method of manufacturing an entrained polymer material as disclosed herein, the method comprising the step of:extruding a suitable precursor material comprising a molten mix of a polymer, an oxygen scavenging agent, and a zeolite.

[0029] Also provided herein is a container which comprises an entrained polymer material as disclosed herein and an interior space suitable for storage of a product.

[0030] In some embodiments, the entrained polymer material is a film. In some embodiments, the entrained polymer material is a blown film.

[0031] Also provided herein is a method for inhibiting oxidative decomposition of a product, the method comprising storing the product in a container as disclosed herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0032] A full understanding of the disclosure can be gained from the following description of the preferred embodiments when read in conjunction with the accompanying drawings in which:

[0033] FIG. 1 depicts the oxygen scavenging performance of films containing 17% by weight of an oxygen scavenging agent and a zeolite at the following weight percent compositions (a) 0% (b) 10% (c) 20% (d) 30% (e) 40% (f) 50%, along with least-squares fits to the data, horizontalATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTaxis: time (days), vertical axis: decrease in partial volume of O2 (cm3).

[0034] FIG. 2 depicts the oxygen scavenging performance up to 35 days of films containing 17% by weight of an oxygen scavenging agent and a zeolite at the following weight percent compositions (a) 0% (b) 10% (c) 20% (d) 30% (e) 40% (f) 50%; dotted line (g) working capacity, horizontal axis: time (days), vertical axis: decrease in partial volume of O2 (cm3).

[0035] FIG. 3 depicts the time in days required to achieve working capacity of films containing 17% by weight of an oxygen scavenging agent and a zeolite at the following weight percent compositions (a) 0% (b) 10% (c) 20% (d) 30% (e) 40% (f) 50%.DETAILED DESCRIPTION

[0036] As used herein, the articles “a” and “an” may refer to one or to more than one (e.g. to at least one) of the grammatical object of the article.

[0037] As used herein, “about” may generally refer to an acceptable degree of error for the quantity measured given the nature or precision of the measurements. Example degrees of error are within 5% of a given value or range of values.

[0038] Concentrations, amounts, volumes, percentages and other numerical values may be presented herein in a range format. It is also to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.

[0039] In one aspect, there is provided herein an entrained polymer material comprising a base polymer, an oxygen scavenging agent, and a zeolite.

[0040] In some embodiments, the entrained polymer material is a film. In some embodiments, the film has a thickness from 0.1 mm to 1.0 mm, optionally from 0.15 mm to 0.8 mm, optionally from 0.20 mm to 0.6 mm, optionally from 0.25 mm to 0.4 mm, optionally 0.3 mm.

[0041] In one aspect, there is provided herein a blown film entrained polymer material comprising a base polymer, an oxygen scavenging agent, and a zeolite.

[0042] In some embodiments, the oxygen scavenging agent comprises a chemical reducing agent. In some embodiments, the chemical reducing agent is a 1- or 2-electron reducing agent. In some embodiments, the chemical reducing agent produces hydrogen peroxide (H2O2) or water from the reduction of oxygen. In some embodiments, the oxygen scavenging agent comprises aATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTneutral metal. In some embodiments, the oxygen scavenging agent comprises a low-valent metal ion, including but not limited to Fe2+, Sn2+, and Ti3+. In some embodiments, the neutral metal is in monolithic, granulated, or powdered form. In some embodiments, the oxygen scavenging agent is a naturally occurring antioxidant. In some embodiments, the oxygen scavenging agent comprises a vicinal diol (RC(OH)=C(OH)R’) or keto equivalent. In some embodiments, the oxygen scavenging agent provides a vicinal diketone (RC(=O)-C(=O)-R’) from the reduction of oxygen. In some embodiments, the oxygen scavenging agent is chosen from a polyolefin, a phenol, a hydroquinone, and a porphyrin. In some embodiments, the oxygen scavenging agent comprises an organic sulfur-containing compound, including but not limited to a thioether, a thiolester, and a thiol. In some embodiments, the oxygen scavenging agent comprises an organic phosphorus-containing compound, including but not limited to a phosphine and a phosphite. In some embodiments, the oxygen scavenging agent further comprises a catalyst. In some embodiments, the oxygen scavenging agent further comprises a pH-buffering material.

[0043] In some embodiments, the oxygen scavenging agent comprises a polyene. In some embodiments, the oxygen scavenging agent comprises a conjugated polyene, optionally comprising 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 olefins in conjugation. In some embodiments, the oxygen scavenging agent comprises a compound chosen from retinol, retinal, and carotene. In some embodiments, the oxygen scavenging agent comprises a compound chosen from a porphyrin and a heme.

[0044] In certain embodiments, the oxygen scavenging agent is a free radical trap. Without wishing to be bound by theory, certain free radical traps can reduce the amount of reactive oxygen species (“ROS”), either by reducing their rate of formation, or removing them from the medium. Some free radical traps transfer a hydrogen to a radical species. Certain free radical traps contain phenol moieties, such as BHA. BHT, caffeic acid, ferulic acid, and a-tocopherol. Certain free radical traps are enols, such as ascorbic acid (Vitamin C). Certain free radical traps contain a weak X-H bond (X=N, O, S), including but not limited to thiols, uric acid, and bilirubin. Certain free radical traps contain polyene moieties. such as such as [3-carotene and other carotenoids. Certain free radical traps contain conjugated or nonconjugated dienes, such as a-terpinene and y-terpinene, respectively, as well as certain unsaturated fats and fatty acids.

[0045] In some embodiments, the oxygen scavenging agent comprises ascorbic acid, which is the 4R, 5S isomer of 3,4,5,6-tetrahydroxy-2-oxohexanoic acid, as shown in Table 1.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTTable 1.OH OH O OH OH OH0\6 U\ 4 2 JLH0\ 6 45>J\ 25 3 Y ^OH3 OHOH O OH O3,4,5 ,6-tetrahydroxy-2-oxohexanoic acid (4S,5S)-3,4,5,6-tetrahydroxy-2-oxohexanoic acid(L-Ascorbic Acid)

[0046] L-Ascorbic acid can exist as (open) acid and (closed) lactone forms, as shown in Equation (1), below:

[0047] The parent acid, 3,4,5,6-tetrahydroxy-2-oxohexanoic acid, has three chiral centers, at the carbons labelled 3. 4, and 5, following organic chemical nomenclature, in the acid structure shown in Equation (I). Of the three chiral centers, C3 is readily epimerized due to the adjacent ketone. In contrast, C4 and C5 both represent non-interconverting stereocenters, giving rise to a total four isolable stereoisomers, each of which potentially existing in equilibrium with the lactone form, as shown in Equation (II), below:

[0048] Of the four isolable stereoisomers, D-ascorbic acid is the enantiomer of L-ascorbic acid. The other two isomers are D-isoascorbic acid, the 5R epimer of ascorbic acid, as well as its enantiomer, L-isoascorbic acid. A person of skill will appreciate that each of the four stereoisomers will be expected to behave similarly as reducing agents and / or radical traps. AllATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTpossible mixtures of the four enantiomers are contemplated with this disclosure, including isolated enantiomers of either ascorbic acid or isoascorbic acid or mixtures thereof, D / L racemic mixtures either ascorbic acid or isoascorbic acid acid or mixtures thereof, and intermediate compositions of either ascorbic acid or isoascorbic acid acid having arbitrary enantiomeric excess, and mixtures thereof.

[0049] Any of the four stereoisomers may be provided as any one of the carboxylic acid, a salt of the carboxylic acid, an ester, or a lactone, or mixtures thereof. No limitation is envisaged on the type of ester; suitable esters may include alkyl esters, Ci-Cs alkyl esters, methyl esters, ethyl esters, isopropyl esters, and / -butyl esters. The choice of ester may be determined by ease of hydrolysis to the acid, compliance of the alcohol product (e.g., methanol, ethanol) with regulations and best practices for the particular application, and desired water or lipid solubility.

[0050] In some embodiments, the activity of ascorbic acid as a reducing agent can be modulated by adjusting the pH of the environment. Ascorbic acid is a dibasic acid with pKai= 4.1 and pKa2 = 11.8; suitable choice of acids, bases, or buffers can vary the relative amounts of the neutral acid, the monoanion, and the dianion, each of which has different rates of reaction. Furthermore, inclusion of catalytically active metals, including but not limited to salts of nickel, cobalt, iron, copper, and manganese or, in some embodiments, Fe(III) or Cu(II), can be expected to change the rate of reaction. Alternatively, the inclusion of metal ion scavengers, such as EDTA, can be expected to change the rate of reaction. By either of these strategies, the potency of ascorbic acid over time can be adjusted so as to meet particular requirements. Alternatively, controlled hydrolysis of an ascorbic acid ester may provide a pathway for controlling the potency of ascorbic acid over time.

[0051] In some embodiments, the oxygen scavenging agent comprises a partially unsaturated derivative of polyethylene. In some embodiments, the oxygen scavenging agent comprises polyethylene interspersed with -(CHR'=CHR2)- units, wherein R1and R2are each independently a hydrogen atom, an alkyl group that is optionally substituted, an aryl group that is optionally substituted, an alkylaryl group that is optionally substituted, -COOR3, -OCOR4, a cyano group or a halogen atom, and R3and R4are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In some embodiments, neighboring (CHR'=CHR2) units are separated by three or more methylene (-CH2-) units.

[0052] In some embodiments, the oxygen scavenging agent is a material disclosed in USATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT7,893,145, incorporated herein by reference. Tn some embodiments, the oxygen scavenging agent has a structural unit represented by Formula (III):wherein:R1and R2are each independently a hydrogen atom, an alkyl group that is optionally substituted, an aryl group that is optionally substituted, an alkylaryl group that is optionally substituted, — COOR3, — OCOR4, a cyano group or a halogen atom, and R3and R4are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0053] In some embodiments, the oxygen scavenging agent is a ring-opening metathesis polymer of a cyclic olefin having 7 or more carbon atoms. Tn some embodiments, the oxygen scavenging agent is a ring-opening metathesis polymer of a substituted or unsubstituted cyclooctene. In some embodiment, the average molecular weight of the polymer is 1000 amu or less.

[0054] In some embodiments, the oxygen scavenging agent is Visparent (Evonik), optionally Visparent El 00.

[0055] In some embodiments, the zeolite is an aluminosilicate or a silicoaluminophosphate containing compensating cations selected from the group comprising sodium, magnesium, lithium, potassium, calcium, zinc, manganese and iron.

[0056] In some embodiments, the zeolite is an LTA-type or FAU-type zeolite.

[0057] In some embodiments, the zeolite comprises magnesium, lithium or both.

[0058] In some embodiments, the zeolite is present in an amount of at least 5% or greater by weight, optionally at least 10% or greater, optionally at least 15% or greater, optionally at least 20% or greater, optionally at least 25% or greater, optionally at least 30% or greater, optionally at least 35% or greater, optionally at least 40% or greater, optionally at least 45% or greater by weight with respect to the total weight of the entrained polymer material.

[0059] In some embodiments, the zeolite is present in an amount of at most 70% or less byATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTweight, optionally at most 65% or less by weight, optionally at most 60% or less by weight, optionally at most 55% or less by weight, optionally at most 50% or less, optionally at most 45% or less, optionally at most 40% or less, optionally at most 35% or less, optionally at most 30% or less, optionally at most 25% or less, optionally at most 20% or less by weight with respect to the total weight of the entrained polymer material.

[0060] In some embodiments, the zeolite is present in an amount of from 40% to 70% by weight with respect to the total weight of the entrained polymer material, optionally from 40% to 65%, optionally from 40% to 60%, optionally from 40% to 55%, optionally from 40% to 50%.

[0061] In some embodiments, the oxygen scavenging agent is present in an amount of at least 8% or greater by weight, optionally at least 10% or greater by weight, optionally at least 12% or greater by weight, optionally at least 14% or greater by weight, optionally at least 16% or greater by weight with respect to the total weight of the entrained polymer material.

[0062] In some embodiments, the oxygen scavenging agent is present in an amount of at most 30% or less by weight, optionally at most 26% or less by weight, optionally at most 22% or less by weight, optionally at most 20% or less by weight, optionally at most 18% or less by weight, optionally at most 16% or less by weight, optionally at most 14% or less by weight, optionally at most 12% or less by weight with respect to the total weight of the entrained polymer material.

[0063] In some embodiments, the oxygen scavenging agent is present in an amount of from 5% to 30% by weight with respect to the total weight of the entrained polymer material, optionally from 5% to 25%, optionally from 5% to 20%, optionally 15%, 16%, 17%, 18%, 19% or 20%.

[0064] In some embodiments, the base polymer is present in an amount of at most 90% or less by weight, optionally at most 85% or less by weight, optionally at most 80% or less by weight, optionally at most 75% or less by weight, optionally at most 70% or less by weight, optionally at most 65% or less by weight, optionally at most 60% or less by weight, optionally at most 55% or less by weight, optionally at most 50% or less by weight, optionally at most 45% or less by weight, optionally at most 40% or less by weight, optionally at most 35% or less by weight with respect to the total weight of the entrained polymer material.

[0065] In some embodiments, the base polymer is present in an amount of at least 10% or more by weight, optionally at least 15% or more by weight, optionally at least 20% or more by weight, optionally at least 25% or more by weight, optionally at least 30% or more by weight, optionally at least 35% or more by weight, optionally at least 40% or more by weight with respect to theATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTtotal weight of the entrained polymer material.

[0066] In some embodiments, the entrained polymer material further comprises a channeling agent. In some embodiments, the channeling agent is chosen from a polyglycol such as polyethylene glycol (PEG), ethylene- vinyl alcohol (EVOH), polyvinyl alcohol (PVOH), glycerin polyamine, polyurethane and polycarboxylic acid including polyacrylic acid or polymethacrylic acid.

[0067] In some embodiments, the channeling agent is a water insoluble polymer, such as a propylene oxide polymerisate-monobutyl ether, such as Polyglykol BO 1 / 240, produced by CLARIANT. In other embodiments, the channeling agent could be a propylene oxide polymerisate monobutyl ether, such as Polyglykol B01 / 20, produced by CLARIANT, propylene oxide polymerisate, such as Polyglykol DO 1 / 240, produced by CLARIANT, ethylene vinyl acetate (EVA), nylon 6, nylon 66, or any combination of the foregoing.

[0068] In some embodiments, the base polymer is chosen from a polyolefin, a polyamide, and a polyester. In some embodiments, the base polymer is chosen from a polyolefin and a polyester. In some embodiments, the base polymer is chosen from polyethylene, polypropylene, a polyethylene / polypropylene copolymer, and poly(lactic acid).

[0069] In some embodiments, the base polymer comprises at least one block copolymer.

[0070] In some embodiments, the base polymer comprises a block copolymer that comprises a block of ester monomers. In some further embodiments, the base polymer comprises a block copolymer that comprises a block of poly(alkylene) terephthalate monomers. In some further embodiments, the alkylene is chosen from ethylene, propylene, and butylene.

[0071] In some embodiments, the base polymer comprises a block copolymer that comprises a block of polyether glycols.

[0072] In some embodiments, the base polymer comprises a copolyether-ester composition consisting essentially of long chain ester units having Formula I:-OGO-C(=O)-R-C(=O)- (I)and short chain ester units having Formula II:-ODO-C(=O)-R-C(=O)- (I)joined head-to-tail through ester linkages;wherein G is a divalent radical corresponding to removal of hydroxyl groups from a poly(alkylene oxide) glycol, with molecular weight from 400 to 6000 amu, optionally from 400ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTto 4000 amu, and D is divalent radical corresponding to removal of hydroxyl groups from a diol with molecular weight less than 250 amu, and R is a divalent radical corresponding to removal of carboxyl groups from a dicarboxylic acid with molecular weight less than about 300.

[0073] In some embodiments, the short chain ester units comprise 45% to 65%, inclusive by weight of the copolyether-ester composition.

[0074] In some embodiments, the poly(alkylene oxide) glycol is poly(trimethylene oxide) glycol. In some embodiments, the poly(alkylene oxide) glycol is poly(tetramethylene oxide) glycol.

[0075] In some embodiments, the diol is 1,3-propanediol. In some embodiments, the diol consists of at least 70% of 1,4-butanediol. In some embodiments, the diol is 1,4-butanediol.

[0076] In some embodiments, the dicarboxylic acid is benzenedicarboxylic acid. In some embodiments, the dicarboxylic acid consists of at least 70% terephthalic acid. In some embodiments, the dicarboxylic acid is terephthalic acid.

[0077] In some embodiments, the base polymer further comprises poly(butylene terephthalate).

[0078] In some embodiments, the base polymer comprises a block copolymer that contains both a block of ester monomers and a block of polyether glycols. In some embodiments, the base polymer comprises a HYTREL® block copolymer. In some embodiments, the base polymer comprises HYTREL® 7246.

[0079] In some embodiments, the base polymer comprises a block copolymer having a density from 1.1 to 1.4 g / cm3, optionally from 1.2 to 1.3 g / cm3, optionally from 1.24 to 1.28 g / cm3, optionally about 1.26 g / cm3.

[0080] In some embodiments, the base polymer comprises a block copolymer having a melt mass-flow rate (2.16 kg and 100 °C; ISO 1133) from 10 g / 10 min to 16 g / 10 min, inclusive, optionally from 11 g / 10 min to 15 g / 10 min, optionally from 12 g / 10 min to 14 g / 10 min, optionally about 13 g / 10 min.

[0081] In some embodiments, the base polymer comprises a block copolymer having a melt volume-flow rate (2.16 kg and 100 °C; ISO 1133) from 8 cm3 / 10 min to 16 cm3 / 10 min, optionally from 10 cm3 / 10 min to 14 cm3 / 10 min, optionally from 11 cm3 / 10 min to 13 cm3 / 10 min, optionally about 12 cm3 / 10 min.

[0082] In some embodiments, the base polymer comprises a block copolymer having a nominal strain at break (IO 527-1 / -2) from 500% to 560%, optionally from 510% to 550%, optionally from 520% to 540%, optionally about 530%.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT

[0083] In some embodiments, the base polymer comprises a block copolymer having a flexural modulus (ISO 178, 23 °C) from 500 MPa to 600 MPa, optionally from 520 MPa to 580 MPa, optionally from 530 MPa to 570 MPa, optionally from 540 MPa to 560 MPa, optionally about 550 MPa.

[0084] In some embodiments, the base polymer comprises an ethylene I alpha-olefin copolymer. In some further embodiments, the alpha-olefin is chosen from propylene. 1 -butene, 1 -pentene; 1-pentene with one or more methyl, ethyl, or propyl substituents; 1 -hexene; 1 -hexene with one or more methyl, ethyl, or propyl substituents; 1 -heptene; 1 -heptene with one or more methyl, ethyl, or propyl substituents; 1-octene; 1-octene with one or more methyl, ethyl, or propyl substituents; 1 -nonene; 1 -nonene with one or more methyl, ethyl, or propyl substituents; ethyl, methyl, or dimethyl-substituted 1-decene; 1-dodecene; and styrene. In some further embodiments, the alpha-olefin is chosen from propylene, 1 -butene, 1 -pentene, 1 -hexene, 1 -heptene, 1-octene, 1-nonene, 1-decene, and 1-dodecene.

[0085] In some embodiments, the base polymer comprises a copolymer derived from ethylene and one or more C3-C20 , optionally C3-C12 alpha olefin comonomers. In some embodiments, the copolymer consists of from 5% to 15% by mass, of comonomer. In some embodiments, the molecular weight distribution Mw / Mnis from 2 to 3. In some embodiments, the molecular weight distribution Mz / Mwis less than 2, inclusive. In some embodiments, the density of the copolymer is less than 0.916 g I cm3.

[0086] In some embodiments, the base polymer comprises a metallocene polyolefin. In some embodiments, the base polymer comprises a VLDPE.

[0087] In some embodiments, the base polymer comprises a polyolefin having a density from 0.880 to 0.920 g / cm3, optionally from 0.890 to 0.910 g I cm3, optionally from 0.895tod 0.905 g I cm3, optionally about 0.90 g / cm3.

[0088] In some embodiments, the base polymer comprises a polyolefin having a melt flow index (ASTM D1238) from 14 to 20 g / 10 min, optionally from 15 to 19 g / 10 min, optionally from 16 to 18 g / 10 min, optionally about 17 g / 10 min.

[0089] In some embodiments, the base polymer comprises a polyolefin having a tensile yield strength (MD, ASTM D882) from 4.9 to 5.5 MPa, optionally from 5.0 to 5.4 MPa, optionally from 5.1 to 5.3 MPa, optionally from 5.15 to 5.25 MPa, optionally about 5.17 MPa.

[0090] In some embodiments, the base polymer comprises a polyolefin having a tensile yieldATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTstrength (TD, ASTM D882) from 4.3 to 4.8 MPa, optionally from 4.4 to 4.7 MPa, optionally from 4.45 to 4.65 MPa, optionally from 4.5 to 4.6 MPa, optionally about 4.55 MPa.

[0091] In some embodiments, the base polymer comprises a polyolefin having an elongation at break (MD, ASTM D882) from 580% to 640%, optionally between 590% and 630%, inclusive, optionally from 600% to 620%, optionally about 610%.

[0092] In some embodiments, the base polymer comprises a polyolefin having an elongation at break (TD, ASTM D882) from 740% to 800%, optionally from 750% to 790%, optionally from 760% to 780%, optionally about 770%.

[0093] In some embodiments, the base polymer comprises a polyolefin having a secant modulus (MD, ASTM D882) from 0.067 GPa to 0.070 GPa, optionally from 0.0683 GPa to 0.0693 GPa, optionally from 0.0686 GPa to 0.0692 GPa, optionally from 0.0688 GPa to 0.0690 GPa. optionally about 0.0689 GPa.

[0094] In some embodiments, the base polymer comprises a polyolefin having a secant modulus (TD, ASTM D882) from 0.750 GPa to 0.765 GPa, optionally from 0.755 GPa to 0.761 GPa, optionally from 0.756 GPa to 0.760 GPa, optionally from 0.757 GPa to 0.759 GPa, optionally about 0.758 GPa.

[0095] In some embodiments, the base polymer comprises a polyolefin having an Elmendorf tear strength (MD, ASTM D1922) from 300 g to 360 g, optionally from 310 g to 350 g, optionally from 320 g to 340 g. optionally about 330 g.

[0096] In some embodiments, the base polymer comprises a polyolefin having an Elmendorf tear strength (TD, ASTM D1922) from 500 g to 360 g, optionally from 510 g to 550 g, optionally from 520 g to 540 g. optionally about 530 g.

[0097] In some embodiments, the base polymer comprises a polyolefin having a peak melting temperature from 92 °C to 98 °C, optionally from 93 °C to 97 °C, optionally from 94 °C to 96 °C, optionally about 95 °C.

[0098] In some embodiments, the base polymer comprises a polyolefin having a haze (ASTM D1003) from 0.20% to 0.40%, optionally from 0.25% to 0.35%, optionally from 0.28% to 0.32%, optionally about 0.30%.

[0099] In some embodiments, the base polymer comprises a polyolefin having a gloss (ASTM D2457) from 90% to 96%, optionally from 91% to 95%, optionally from 92% to 94%, optionally about 93%.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT

[0100] In some embodiments, the base polymer comprises a copolymer derived from ethylene and one or more C3-C20 , optionally C3-C12 alpha olefin comonomers. In some embodiments, the copolymer consists of from 5% to 15% by mass, inclusive, of comonomer. In some embodiments, the molecular weight distribution MwI Mnis from 2 to 3. In some embodiments, the molecular weight distribution Mz / Mwis less than 2, inclusive. In some embodiments, the density of the copolymer is less than 0.916 g / cm3.

[0101] In some embodiments, the base polymer comprises a metallocene polyolefin. In some embodiments, the base polymer comprises a VLDPE.

[0102] In some embodiments, the base polymer comprises two block copolymers. In some further embodiments, one of the two block copolymers is an ethylene / alpha-olefin copolymer as disclosed herein. In some further embodiments, the base polymer comprises EXACT™ 3040. In some further embodiments, one of the two block copolymers is a block copolymer that contains both a block of ester monomers and a block of polyether glycols as disclosed herein. In some further embodiments, the base polymer comprises HYTREL® 7246. In some further embodiments, the base polymer comprises both EXACT™ 3040 and HYTREL® 7246. In some further embodiments, the base polymer consists of a mixture of EXACT™ 3040 and HYTREL® 7246.

[0103] In some embodiments, the base polymer comprises both a polyolefin and a polyester. In some embodiments, the polyolefin ranges from 10% and 40% by weight of the total composition, optionally from 15% to 30%. In some embodiments, the polyester ranges from 20% and 80% by weight of the total composition, optionally from 25% to 70%, optionally 30% and 60%. In some embodiments, the polyolefin has formula (-CH2CHR-)n, and R is chosen from H and n-Ci-walkyl. In some embodiments, the polyester has formula (( CH2)mCOO)n, and m is chosen from 1, 2, 3, 4, and 5. In some embodiments, the polyester has formula (-CHRCOO-)n, and R is chosen from H and w-Ci-ioalkyl.

[0104] In some embodiments, the base polymer is a thermoplastic. In some embodiments, the base polymer is a thermoplastic elastomer. In some embodiments, the thermoplastic elastomer is a thermoplastic polyamide elastomer. In some embodiments, the thermoplastic elastomer is a thermoplastic polyester elastomer. In some embodiments, the thermoplastic elastomer is a thermoplastic polyolefin elastomer. In some embodiments, the thermoplastic elastomer is a thermoplastic polystyrene elastomer. In some embodiments, the thermoplastic elastomer is aATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTthermoplastic polyurethane elastomer. In some embodiments, the thermoplastic elastomer is a thermoplastic elastomer vulcanizate. In some embodiments, the thermoplastic elastomer is an unclassified thermoplastic polyamide elastomer. In some embodiments, the thermoplastic elastomer is a block copolymer.

[0105] In some embodiments, the base polymer is chosen from polypropylene, polyethylene, polyhydroxyalkanoates (PHA), polylactic acid (PLA), polybutylene succinate (PBS), polyisoprene, polyhexene, polybutadiene, polybutene, polysiloxane, polycarbonate, polyamide, ethylene-vinyl acetate copolymer, ethylene-methacrylate copolymer, polyvinyl chloride (PVC), polystyrene, polyester, polyanhydride, polyacrylonitrile, polysulfone, polyacrylic ester, acrylic, polyurethane, poly acetal, polyvinylpyrrolidone (PVP), a copolymer, or a combination thereof.

[0106] In some embodiments, the base polymer is a block copolymer. In some embodiments, the block copolymer comprises polyester segments and polyether segments. In some embodiments, the polyester segment is poly(alkylene terephthalate). In some embodiments, the polyester segment is poly(butylene terephthalate). In some embodiments, the polyether segment is a poly(alkylene glycol). In some embodiments, the polyether segment is chosen from polyethylene glycol, polypropylene glycol, and poly tetramethylene glycol. In some embodiments, the polyether segment is one or more long chain glycols. In some embodiments, the block copolymer includes a hard crystalline segment and a soft amorphous segment. In some embodiments, the block co-polymer exhibits high thermal stability.

[0107] In some embodiments, the base polymer is HYTREL®, a thermoplastic polyester elastomer from DuPont. HYTREL® is a block copolymer, consisting of segments of polybutylene terephthalate and segments of poly ether. In some embodiments, the base polymer is HYTREL® 7246.

[0108] In some embodiments, the base polymer has the formula (-CHR-X-)„ with -X- chosen from -CH2-, -COO-. and -CONH-, and R chosen from H and Ci-ioalkyl.

[0109] In some embodiments, the base polymer has a formula chosen from (-CHRCH2-L and (-CHRCOO-)ra. with R chosen from H and Ci-ioalkyl. In some embodiments, R is chosen from H, CH3, C2H5, C4H9, CeHi3, and CsHn. In some embodiments, R is chosen from C2H5, C4H9, and CeHi3.

[0110] In some embodiments, a film of the material measuring 1 cm2in area and 0.3 mm thick, when stored in a 120 cm3bottle for 7 days at 40 °C and ambient pressure, will scavenge anATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTamount of oxygen having partial volume of 0.2 cm3or greater, optionally 0.4 cm3or greater, optionally 0.6 cm3or greater, optionally 0.8 cm3or greater, optionally 1.0 cm3or greater, optionally 1.2 cm3or greater.

[0111] In some embodiments, a film of the material measuring 1 cm2in area and 0.3 mm thick, when stored in a 120 cm3bottle for 7 days at 40 °C and ambient pressure, will scavenge an amount of oxygen that is at least 100% greater than a comparable material lacking zeolite, optionally at least 200% greater, optionally at least 300% greater, optionally at least 400% greater, optionally at least 500% greater, optionally at least 600% greater, optionally at least 700% greater.

[0112] In some embodiments, a film of the material measuring 1 cm2in area and 0.3 mm thick, when stored in a 120 cm3bottle for 7 days at 40 °C and ambient pressure, will decrease the partial pressure of oxygen by 0.004 atm or greater, optionally 0.005 atm or greater, optionally 0.006 atm or greater, optionally 0.007 atm or greater.

[0113] In some embodiments, a film of the material having thickness of 0.3 mm, when stored in a bottle for 7 days at 40 °C and ambient pressure, the film measuring 0.08 cm2in surface area per cm3volume of the bottle, will decrease the partial pressure of oxygen by 0.004 atm or greater, optionally 0.005 atm or greater, optionally 0.006 atm or greater, optionally 0.007 atm or greater.

[0114] In some embodiments, a film of the material measuring 1 cm2in area and 0.3 mm thick, when stored in a 120 cm3bottle for 7 days at 40 °C and ambient pressure, will decrease the partial pressure of oxygen by an amount whose absolute value is at least 100% greater than for a comparable material lacking zeolite, optionally at least 200% greater, optionally at least 300% greater, optionally at least 400% greater, optionally at least 500% greater, optionally at least 600% greater, optionally at least 700% greater.

[0115] In some embodiments, a film of the material, when stored in a bottle for 7 days, the film having a thickness of 0.3 mm and measuring 0.08 cm2in surface area per cm3volume of the bottle, will decrease the partial pressure of oxygen at 40 °C and ambient pressure by an amount whose absolute value is at least 100% greater than for a comparable material lacking zeolite, optionally at least 200% greater, optionally at least 300% greater, optionally at least 400% greater, optionally at least 500% greater, optionally at least 600% greater, optionally at least 700% greater.

[0116] In some embodiments, storage of a film of the material in a 120 cm3bottle for 7 days, theATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTfilm measuring 1 cm2in area and 0.3 mm thick, will result in a partial pressure of oxygen in the headspace that is 80% or less, optionally 70% or less, optionally 60% or less, optionally 50% or less, optionally 40% or less, optionally 30% or less, than for a comparable entrained polymer material lacking zeolite.

[0117] In some embodiments, storage of a film of the material in a bottle for 7 days, the film having thickness of 0.3 mm and measuring 0.08 cm2in surface area per cm3volume of the bottle, will result in a partial pressure of oxygen in the headspace that is 80% or less, optionally 70% or less, optionally 60% or less, optionally 50% or less, optionally 40% or less, optionally 30% or less, than for a comparable entrained polymer material lacking zeolite.

[0118] Also provided herein is a method of manufacturing an entrained polymer material as disclosed herein, the method comprising the steps of:extruding a suitable precursor material comprising a molten mix of a polymer, an oxygen scavenging agent, and a zeolite.

[0119] Also provided herein is a method of manufacturing a blown film entrained polymer as disclosed herein, the method comprising the steps of:extruding a suitable precursor material comprising a molten mix of a polymer and an oxygen scavenging agent in a screw extruder with warming;passing the warmed extruded material through a tubular die;expanding and stretching the warmed extruded material with positive pressure; and allowing the expanded and stretched extruded material to cool.

[0120] Also provided herein is a container which comprises an entrained polymer material as disclosed herein and an interior space suitable for storage of a product. In some embodiments, the container comprises at least one article, the at least one article comprising an entrained polymer material as disclosed herein, located within the interior space. In some embodiments, inclusion of the product within the container creates a headspace formed by the interior space that is not occupied by the product. In some embodiments, the container comprises a bottom surface, a top opening, and one or more sidewalls extending in a vertical direction from the bottom surface to the top opening. In some embodiments, the container further comprises a cover to close and / or seal the container.

[0121] Also provided herein is a method for inhibiting oxidative decomposition of a product, the method comprising storing the product in a container as disclosed herein.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT

[0122] In some embodiments, the entrained polymer material is provided as a film. In some embodiments, the film has a thickness from 0.1 mm to 1.0 mm, inclusive, optionally from 0.15 mm to 0.8 mm, inclusive, optionally from 0.20 mm to 0.6 mm, optionally from 0.25 mm to 0.4 mm, optionally about 0.3 mm.

[0123] In some embodiments, the film measures 0.20 cm2in surface area or less, per cm3volume of the container, optionally 0.16 cm2in surface area or less, optionally 0.12 cm2in surface area or less, optionally 0.10 cm2in surface area or less.

[0124] In some embodiments, inclusion of the product within the container creates a headspace formed by the interior space that is not occupied by the product. In some embodiments, the volume of the headspace is 30% or less of the total volume of the container, optionally 20% or less, optionally 10% or less, optionally 5% or less.

[0125] In some embodiments, the film measures 0.20 cm2in surface area or less, per cm3volume of headspace in the container, optionally 0.16 cm2in surface area or less, optionally 0.12 cm2in surface area or less, optionally 0.10 cm2in surface area or less.

[0126] In some embodiments, upon storage of the product, the initial partial pressure of oxygen in the headspace is 0.21 atm or less, optionally 0.15 atm or less, optionally 0.10 atm or less, optionally 0.05 atm or less, optionally 0.02 atm or less, optionally 0.01 atm or less.

[0127] In some embodiments, at 7 days of storage of the product, the partial pressure of oxygen in the headspace is no more than 300% of the initial partial pressure of oxygen, optionally no more than 200%, optionally no more than 150%, optionally no more than 100%, optionally no more than 75%, optionally no more than 50%.

[0128] In some embodiments, at 28 days of storage of the product, the partial pressure of oxygen in the headspace is no more than 300% of the initial partial pressure of oxygen, optionally no more than 200%, optionally no more than 150%, optionally no more than 100%, optionally no more than 75%, optionally no more than 50%.

[0129] In some embodiments, at 7 days of storage of the product, the partial pressure of oxygen in the headspace is 0.15 atm or less, optionally 0.12 atm or less, optionally 0.10 atm or less, optionally 0.08 atm or less, optionally 0.06 atm or less, optionally 0.04 atm or less.

[0130] In some embodiments, at 28 days of storage of the product, the partial pressure of oxygen in the headspace is 0.15 atm or less, optionally 0.12 atm or less, optionally 0.10 atm or less, optionally 0.08 atm or less, optionally 0.06 atm or less, optionally 0.04 atm or less.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT

[0131] In some embodiments, at 7 days of storage of the product in the container, the partial pressure of oxygen in the headspace is 80% or less, optionally 70% or less, optionally 60% or less, optionally 50% or less, optionally 40% or less, optionally 30% or less, of the partial pressure of oxygen in the headspace at 7 days of storage of the same product in a comparable container, the container comprising a comparable entrained polymer material lacking zeolite.

[0132] In some embodiments, at 28 days of storage of the product in the container, the partial pressure of oxygen in the headspace is 80% or less, optionally 70% or less, optionally 60% or less, optionally 50% or less, optionally 40% or less, optionally 30% or less, of the partial pressure of oxygen in the headspace at 7 days of storage of the same product in a comparable container, the container comprising a comparable entrained polymer material lacking zeolite.

[0133] Provided is an entrained polymer material comprising:a base polymer;an oxygen scavenging agent; and40% to 70% of a particulate by weight with respect to the total weight of the entrained polymer material.

[0134] In some embodiments, the size of the particulate is from 4 pm to 841 pm, optionally from 5 pm to 707 pm, optionally from 6 pm to 595 pm, optionally from 7 pm to 500 pm, optionally from 7 pm to 354 pm, optionally from 7 pm to 250 pm, optionally from 7 pm to 149 pm, optionally from 7 pm to 44 pm. Without wishing to be bound by theory, high loading of particle provides an increase in surface area, which improves the effectiveness of the entrained polymer material.

[0135] In some embodiments, the particulate is calcium carbonate, a zeolite, an alumino silicate, a fine silica, or a glass bead.

[0136] In some embodiments, the particulate is present in an amount of from 40% to 70% by weight with respect to the total weight of the entrained polymer material, optionally from 40% to 65%, optionally from 40% to 60%, optionally from 40% to 55%, optionally from 40% to 50%.

[0137] In some embodiments, the oxygen scavenging agent is present in an amount of from 5% to 30% by weight with respect to the total weight of the entrained polymer material, optionally from 5% to 25%, optionally from 5% to 20%, optionally 15%, 16%, 17%, 18%, 19% or 20%.

[0138] Provided is a method of increasing oxygen scavenger speed rate in an entrained polymer material comprising:ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTproviding 40% to 70% of a particulate by weight with respect to the total weight of the entrained polymer material.

[0139] In some embodiments, the particulate is calcium carbonate, a zeolite, an alumino silicate, a fine silica, or a glass bead.

[0140] In some embodiments, the oxygen scavenging agent is present in an amount of from 5% to 30% by weight with respect to the total weight of the entrained polymer material, optionally from 5% to 25%, optionally from 5% to 20%, optionally 15%, 16%, 17%, 18%, 19% or 20%.

[0141] In some embodiments, the particulate is present in an amount of from 40% to 70% by weight with respect to the total weight of the entrained polymer material, optionally from 40% to 65%, optionally from 40% to 60%, optionally from 40% to 55%, optionally from 40% to 50%.

[0142] In some embodiments, the oxygen scavenger speed rate of the entrained polymer material increases by up to 750 %, optionally by up to 700%, optionally by up to 600%, optionally by up to 500%, optionally by up to 400%, optionally by up to 300%, optionally by up to 200%, optionally by up to 100%. when the particulate is included in the entrained polymer material, as compared to the entrained polymer material without the particulate.

[0143] Also provided are embodiments wherein any embodiment above may be combined with any one or more of these embodiments, provided the combination is not mutually exclusive.

[0144] As used herein, two embodiments are “mutually exclusive” when one is defined to be something which is different than the other. For example, an embodiment wherein two groups combine to form a cycloalkyl is mutually exclusive with an embodiment in which one group is ethyl the other group is hydrogen. Similarly, an embodiment wherein one group is CEE is mutually exclusive with an embodiment wherein the same group is NH.Definitions

[0145] As used herein, the term “active” is defined as capable of acting on, interacting with or reacting with a selected material (e.g„ moisture or oxygen) according to the disclosure.Examples of such actions or interactions may include absorption, adsorption or release of the selected material.

[0146] As used herein, the term “active agent” is defined as a material that (1) is immiscible with the base polymer, and when mixed and heated with the base polymer or the base polymer and the channeling agent, will not melt, i.e., has a melting point that is higher than the melting point for either the base polymer or the channeling agent, and (2) acts on, interacts or reacts with aATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTselected material. The term “active agent” may include but is not limited to materials that absorb, adsorb or release the selected material(s). Active agents according to the disclosure may be in the form of particles, preferably minerals, but the disclosure should generally not be viewed as limited only to particulate active agents (unless a respective claim recites otherwise).

[0147] The term” acyl”, as used herein, refers to a group having the formular RC(=O)-, wherein R is alkyl or aryl.

[0148] The term “alkyl”, as used herein, refers to a saturated, singly unsaturated, or multiply unsaturated linear hydrocarbon group. Unless otherwise indicated, the term embraces to all possible stereo- and regioisomers. In some embodiments, an alkyl group has the formula CmH(2m+i), with m from 1 to 16, optionally from 1 to 14, optionally from 1 to 12, optionally from 1 to 10, optionally from 1 to 6, optionally from 1 to 6, optionally from 1 to 4. In some embodiments, an alkyl group is chosen from -CEE and -(CEOmCHs, with m from 1 to 16, optionally from 1 to 14, optionally from 1 to 12, optionally from 1 to 10, optionally from 1 to 6, optionally from 1 to 6, optionally from 1 to 4. In some embodiments, the alkyl group is chosen between -CH3 and -CH2CH3. In some embodiments, the alkyl group is -CH3. The alkyl group may be specified by indicating the number of carbons. By way of example, Ci-ioalkyl refers to an alkyl group with from 1 to 10 carbon atoms.

[0149] The term “aryl”, as used herein, refers to a mono- or polycyclic hydrocarbon group wherein each cycle (ring) is aromatic. Unless otherwise indicated, the term embraces to all possible regioisomers. Exemplary aryl groups include phenyl, and naphthyl.

[0150] The term “carboxy”, as used herein, refers to -COOH.

[0151] The term “cycloalkyl”, as used herein, refers to a saturated, singly unsaturated, or multiply unsaturated mono- or polycyclic hydrocarbon group, wherein at least one cycle (ring) is nonaromatic. Exemplary cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl. Unless otherwise indicated, the term embraces to all possible stereo- and regioisomers.

[0152] The term “heterocycloalkyl”, as used herein, refers to a saturated, singly unsaturated, or multiply unsaturated mono- or polycyclic group containing at least one heteroatom, wherein at least one cycle (ring) is nonaromatic. In some embodiments, the heteroatom is chosen from N, O, and S. Unless otherwise indicated, the term embraces to all possible stereo- and regioisomers. Exemplary cycloalkyl groups include pyrrolidinyl, pyranyl, and tetrahydrofuranyl.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT

[0153] The term “heteroaryl”, as used herein, refers to a mono- or polycyclic group containing at least one heteroatom, wherein each cycle (ring) is aromatic. In some embodiments, the heteroatom is chosen from N. O, and S. Unless otherwise indicated, the term embraces to all possible regioisomers. Exemplary heteroaryl groups include furyl, pyridyl, and thienyl.

[0154] The term "carbonyl”, as defined herein, refers to the -C(=O) fragment. The term “oxy” refers to the -O- fragment.

[0155] The term “cyano”, as defined herein, refers to -CN.

[0156] The term “hydroxy”, as defined herein, refers to -OH. The term “oxo”, as defined herein, refers to =0, i.e. an oxygen double bonded to a single atom.

[0157] Groups containing multiple terms are defined by the identity of individual terms, read right to left. By way of example, “arylalkyl” refers to the group R1R2-, wherein R1is aryl, and R2is alkyl. By way of example, “alkyloxy” (often referred to as “alkoxy”) refers to the group R-O-, wherein R is alkyl.

[0158] As used herein, a substituted alkyl group refers to an alkyl group in which one or more hydrogens of the alkyl group is substituted with groups X, each individually chosen unless specified otherwise. In some embodiments, X is chosen from halo, cyano, hydroxy, oxo, acyl, acyloxy, alkyl, alkoxy, aryl, aryloxy, cycloalkyl, cycloalkyloxy, heterocycloalkyl, heterocycloalkyloxy, heteroaryl, and heteroaryloxy, with each of these terms as defined herein. In some embodiments, X is chosen from halo, cyano, hydroxy, oxo, acyl, alkyl, aryl, cycloalkyl, heterocycloalkyl, and heteroaryl, with each of these terms as defined herein. In some embodiments, X is chosen from halo, cyano, hydroxy, and oxo, with each of these terms as defined herein.

[0159] As used herein, the term “partial pressure” for a particular gas in a mixture of a plurality of gases is defined as the pressure of the gas multiplied by the mole fraction of the particular gas. By way of example, for a volume of gas held at 1 atm pressure and containing a 0.2 mole fraction of O2, the partial pressure of oxygen, represented as P(C>2), would be 1 atm x 0.2 = 0.2 atm.

[0160] As used herein, the term “partial volume” for a particular gas in a mixture of a plurality of gases is defined as the total volume of the gas multiplied by the mole fraction of the particular gas. By way of example, for a 5 L volume of gas containing a 0.2 mole fraction of O2. the partial volume of oxygen, represented as V(C>2), would be 5 L x 0.2 = 1 L of O2.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT

[0161] As used herein, the term “polymer” refers to a compound composed of a linear chain of monomers. A polymer can be further defined as a “hompolymer”, which is composed of identical monomers, and may be represented as (-A-)re, with integer subscript n indicating the degree of polymerization.

[0162] Degree of polymerization is often provided as subscript n to a monomer A, giving (-A-)„ or a similar expression. It will be understood that the number of monomers for individual molecules in a quantity of polymeric material can deviate from the degree of polymerization. In general, integer subscript n , termed the degree of polymerization, is without limit, and represents the average number of monomers in each polymer molecule in a polymer material. It will further be understood that the expression (-X-)« is frequently used in the art to represent a polymeric material, and the absence of an accompanying numeric value or range for n in a particular expression should be construed as having a degree of polymerization without limit. In some embodiments, n is below 5000, optionally below 2000, optionally below 1000, optionally below 500, optionally below 200, optionally below 100, optionally below 50. In some embodiments, the degree of polymerization is greater than 50, optionally greater than 100, optionally greater than 200, optionally greater than 500, optionally greater than 1000. In some embodiments, n is from 50 to 5000, optionally from 100 to 2500, optionally from 200 to 2000, optionally from 500 to 1500. In some embodiments, the degree of polymerization is from 100 to 5000. In some embodiments, the degree of polymerization is from 200 to 2000. In some embodiments, the degree of polymerization is from 500 to 5000.

[0163] A polymer can be further defined as a “copolymer”, which is composed of two or more types of monomers, for example “A” and “B”. The term “copolymer” can further be subdivided into “random copolymers”, for which no regular pattern exists for occurrence of either “A” or “B” in a polymer chain, “alternating copolymers”, which may be represented as -A-B-A-B- etc., and “block copolymers”, which consist of contiguous sequences of monomers interspersed with each other, e.g. -A-A-A-B-B-B-A-A-A- etc. In general, the number of each type of monomer in contiguous sequences of the monomer is without limit, and the number need not be uniform in either the quantity of polymer or in an individual strand. Unless otherwise indicated, the degree of polymerization n for a copolymer represents the average number of monomers, of all types, in each polymer molecule in a polymer material.

[0164] As used herein, the term “polyolefin” refers to a polymer with formula (-CH2CHR-)„,ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTwith R chosen from H, alkyl, chloro, aryl, hydroxy, acyloxy, acetoxy, carboxy, and alkoxycarbonyl. In some embodiments, R is chosen from H, alkyl, and phenyl. In some embodiments, R is chosen from H and Ci-ioalkyL In some embodiments, R is chosen from H and CH3. In some embodiments, the polyolefin is chosen from polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very-low-density polyethylene (VLDPE), ultra-low-density polyethylene (ULDPE), and medium-density polyethylene (MDPE).

[0165] As used herein, the term “polyester” refers to a polymer with formula (-X-COO-),,. with X being a bivalent organic moiety. In some embodiments, the polyester has the formula(-CHRCOO-)n, with R chosen from H and Ci-ioalkyl. In some embodiments, the polyester has the formula ((-CH2)mCOO-)n, wherein m is chosen from 1, 2, 3, 4, and 5. In some embodiments, the polyester has the formula (-OOC-Y-COO-Z)„, with Y and Z both being bivalent organic moieties. In some embodiments, Y = 1,4-phenylene. In some embodiments, Z is chosen from ethylene, butylene (tetramethylene), hexylene (hexamethylene), and 1,4-cyclohexenedimethylene. In some embodiments, the polyester is polyethylene terephthalate (“PET”). In some embodiments, the polyester is poly-1, 4-cyclohexylene-dimethylene terephthalate (“PCDT”).

[0166] As used herein, the term “oxygen scavenging agent” is defined as an active agent that can reduce the amount of oxygen in a gaseous environment. An oxygen scavenging agent can act by any mechanism, including but not limited to chemical reduction (z'.e., transfer of one or more electrons from a reducing agent), reductive dissociation of the 0-0 bond, and coordination of a mono- or dinuclear oxygen species to a metal center.

[0167] As used herein, the term “base polymer” is a polymer optionally having a gas transmission rate of a selected material that is substantially lower than, lower than or substantially equivalent to, that of the channeling agent. By way of example, such a transmission rate would be a water vapor transmission rate in embodiments where the selected material is moisture and the active agent is a water absorbing desiccant. The primary function of the base polymer is to provide structure for the entrained polymer. Suitable base polymers may include thermoplastic polymers, e.g., polyolefins such as polypropylene and polyethylene, polyisoprene, polybutadiene, polybutene, polysiloxane, polycarbonates, polyamides, ethylene- vinyl acetate copolymers, ethylene-methacrylate copolymer, poly (vinyl chloride), polystyrene, polyesters, poly anhydrides, polyacrylonitrile, polysulfones, polyacrylic ester, acrylic, polyurethane andATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTpolyacetal, or copolymers or mixtures thereof. A base polymer may comprise two or more chemically distinct polymers. By way of example, a base polymer may comprise a mixture of a polyolefin and a polyester.

[0168] Referring to such a comparison of the base polymer and channeling agent water vapor transmission rate, in one embodiment, the channeling agent has a water vapor transmission rate of at least two times that of the base polymer. In another embodiment, the channeling agent has a water vapor transmission rate of at least five times that of the base polymer. In another embodiment, the channeling agent has a water vapor transmission rate of at least ten times that of the base polymer. In still another embodiment, the channeling agent has a water vapor transmission rate of at least twenty times that of the base polymer. In still another embodiment, the channeling agent has a water vapor transmission rate of at least fifty times that of the base polymer. In still another embodiment, the channeling agent has a water vapor transmission rate of at least one hundred times that of the base polymer.

[0169] As used herein, the term “channeling agent” or “channeling agents” is defined as a material that is immiscible with the base polymer and has an affinity to transport a gas phase substance at a faster rate than the base polymer. Optionally, a channeling agent is capable of forming channels through the entrained polymer when formed by mixing the channeling agent with the base polymer. Optionally, such channels are capable of transmitting a selected material through the entrained polymer at a faster rate than in solely the base polymer.

[0170] As used herein, the term “channels” or “interconnecting channels” is defined as passages formed of the channeling agent that penetrate through the base polymer and may be interconnected with each other.

[0171] As used herein, the term “entrained polymer” is defined as a monolithic material formed of at least a base polymer with an active agent and optionally also a channeling agent entrained or distributed throughout. An entrained polymer thus includes two-phase polymers and three phase polymers.

[0172] As used herein, the term “monolithic,” “monolithic structure” or “monolithic composition” is defined as a composition or material that does not consist of two or more discrete macroscopic layers or portions. Accordingly, a “monolithic composition” does not include a multi-layer composite (although it may be part of a multi-layer composite).

[0173] As used herein, the term “organic” refers to a compound that contains carbon. OrganicATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTcompounds may therefore be a synthetic compound, a naturally occurring compound, or a chemically modified naturally occurring compound.

[0174] As used herein, the term “phase” is defined as a portion or component of a monolithic structure or composition that is uniformly distributed throughout, to give the structure or composition it’s monolithic characteristics.

[0175] As used herein, the term “selected material” is defined as a material that is acted upon by. or interacts or reacts with an active agent and is capable of being transmitted through the channels of an entrained polymer. For example, in embodiments in which a desiccant is used as an active agent, the selected material may be moisture or a gas that can be absorbed by the desiccant. In embodiments in which a releasing material is used as an active agent, the selected material may be an agent released by the releasing material, such as moisture, fragrance, or an antimicrobial agent. In embodiments in which an adsorbing material is used as an active agent, the selected material may be certain volatile organic compounds and the adsorbing material may be activated carbon.

[0176] As used herein, the term “three phase” is defined as a monolithic composition or structure comprising three or more phases. An example of a three phase composition according to the disclosure would be an entrained polymer formed of a base polymer, active agent, and channeling agent. Optionally, a three phase composition or structure may include an additional phase, e.g., a colorant (thus “three phase” indicates at least three phases, including a base polymer, active agent and channeling agent).

[0177] Suitable channeling agents may include a polyglycol such as polyethylene glycol (PEG), ethylene-vinyl alcohol (EVOH), polyvinyl alcohol (PVOH), glycerin polyamine, polyurethane and polycarboxylic acid including polyacrylic acid or polymethacrylic acid. Alternatively, the channeling agent 35 can be, for example, a water insoluble polymer, such as a propylene oxide polymerisate-monobutyl ether, such as Polyglykol B01 / 240. produced by CLARIANT. In other embodiments, the channeling agent could be a propylene oxide polymerisate monobutyl ether, such as Polyglykol B01 / 20, produced by CLARIANT, propylene oxide polymerisate, such as Polyglykol DO 1 / 240, produced by CLARIANT, ethylene vinyl acetate (EVA), nylon 6, nylon 66, or any combination of the foregoing.

[0178] In some embodiments, the base polymer ranges from 10% to 90% by weight of the total composition, optionally from 20% to 80% by weight. When an optional channeling agent isATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTemployed, the channeling agent may be provided in a range of 2% to 15% by weight, optionally 2% to 10%, optionally about 5%.

[0179] It is believed that the higher the active agent concentration in the mixture, the greater the absorption, adsorption or releasing capacity (as the case may be) will be of the final composition. However, too high an active agent concentration could cause the entrained polymer to be more brittle and the molten mixture of active agent, base polymer and channeling agent to be more difficult to process. In one embodiment, the active agent loading level can range from 10% to 80%, optionally 35% to 70%, optionally from 40% to 60%, optionally from 45% to 55% by weight with respect to the total weight of the entrained polymer material.

[0180] In some embodiments, the active agent loading level can range from 10% to 70%, optionally 30% to 60%, optionally from 35% to 50% by weight with respect to the total weight of the entrained polymer material.

[0181] In any embodiment, the active agent is preferably a particulate, granular and / or mineralbased material and is optionally present in at least 35% to 70%, optionally from 40% to 60%. optionally from 45% to 55% by weight with respect to the total weight of the entrained polymer material.

[0182] In some embodiments, the active agent loading level can range from 10% to 60%, optionally 20% to 50%, optionally from 25% to 45% by weight with respect to the total weight of the entrained polymer material.

[0183] In some embodiments, the active agent loading level can range from 10% to 50%, optionally 15% to 45%, optionally from 20% to 40%, optionally from 25% to 35%, by weight with respect to the total weight of the entrained polymer material.

[0184] Optionally, channeling agent may be provided in a range of 2% to 15% by weight, optionally 2-12%, optionally 5-12%, optionally about 10%, optionally about 9%, optionally about 8%, optionally about 7%, optionally about 6%. optionally about 5%, optionally about 4%, optionally about 3%, optionally about 2%. Optionally, the base polymer may range from 10% to 65% by weight of the total composition, optionally from 20% to 45% by weight, optionally from 25% to 35% by weight. Optionally, a colorant is added, e.g„ at about 0.5-2% or at about 1% by weight of the total composition. Combination of any of the above ranges with respect to the base polymer, active agent, channeling agent, and colorant is contemplated.

[0185] In some embodiments, the entrained polymer is positioned in a container andATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTsubstantially all of the interior-facing part of the container is composed of the entrained polymer. In some embodiments, the container is fabricated so that the entrained polymer is located below the level of a liquid medium contained in the package, thereby providing direct contact between the active agent and the liquid medium.

[0186] Embodiments described herein as “comprising” one or more features may also be considered as disclosure of the corresponding embodiments “consisting of’ and / or “consisting essentially of’ such features.EXEMPLARY EMBODIMENTS

[0187] The following exemplary embodiments further describe optional aspects of the presently disclosed technology and are part of this Detailed Description. These exemplary embodiments are set forth in a format substantially akin to claims (each with numerical designations followed by a capital letter), although they are not technically claims of the present application. The following exemplary embodiments refer to each other in dependent relationships as “embodiments” instead of “claims.”Entrained Polymers-Zeolite

[0188] 1A. An entrained polymer material comprising:a base polymer;an oxygen scavenging agent; and40% to 70% of a zeolite by weight with respect to the total weight of the entrained polymer material.

[0189] 2 A. The entrained polymer material of embodiment 1A, wherein the oxygen scavenging agent comprises a chemical reducing agent.

[0190] 3A. The entrained polymer material of embodiment 2A, wherein the oxygen scavenging agent comprises a 1- or 2-electron chemical reducing agent.

[0191] 4A. The entrained polymer material of embodiment 2A or 3A, wherein the chemical reducing agent produces, from the reduction of oxygen, a compound chosen from hydrogen peroxide and water.

[0192] 5A. The entrained polymer material of any one of embodiments 2A - 4A, wherein the chemical reducing agent is a neutral metal.

[0193] 6A. The entrained polymer material of embodiment 5 A, wherein the neutral metal is in monolithic, granular, or powdered form.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT

[0194] 7A. The entrained polymer material as recited in embodiment 5A or 6A, wherein the neutral metal is Fe°.

[0195] 8A. The entrained polymer material of any one of embodiments 2A - 4A, wherein the chemical reducing agent is a low valent metal ion.

[0196] 9A. The entrained polymer material of any one of embodiments 2A - 4A, wherein the chemical reducing agent is an organic compound.

[0197] 10A. The entrained polymer material of embodiment 9A, wherein the organic compound is chosen from an organic phosphorus containing compound and an organic sulfur containing compound.

[0198] 11 A. The entrained polymer material of embodiment 9 A, wherein the organic compound is a sugar.

[0199] 12 A. The entrained polymer material of embodiment 11 A, wherein the sugar comprises an available reducing end.

[0200] 13 A. The entrained polymer material of embodiment 9A, wherein the organic compound comprises a polyene.

[0201] 14A. The entrained polymer material of embodiment 13 A, wherein the polyene contains 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 olefins in conjugation.

[0202] 15 A. The entrained polymer material of embodiment 9A, wherein the organic compound is chosen from a porphyrin and a heme.

[0203] 16 A. The entrained polymer material of embodiment 9A, wherein the chemical reducing agent is a polymer.

[0204] 17A. The entrained polymer material of embodiment 16A, wherein the polymer is an optionally substituted, optionally partially unsaturated polyethylene.

[0205] 18 A. The entrained polymer material of embodiment 17 A, wherein the optionally partially unsaturated polyethylene is substituted with one or more R1. wherein:each R1is independently a hydrogen atom, an alkyl group that is optionally substituted, an aryl group that is optionally substituted, an alkylaryl group that is optionally substituted, -COOR3, -OCOR4, a cyano group or a halogen atom, and R3and R4are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0206] 19 A. The entrained polymer material of embodiment 18 A, wherein the polymerATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTcomprises polyethylene interspersed with -(CHR^CHR2)- units, wherein:R1and R2are each independently a hydrogen atom, an alkyl group that is optionally substituted, an aryl group that is optionally substituted, an alkylaryl group that is optionally substituted, -COOR3, -OCOR4, a cyano group or a halogen atom, and R3and R4are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0207] 20A. The entrained polymer material of embodiment 19A, wherein:neighboring -(CHRJ=CHR2)- units are separated by three or more methylene units.

[0208] 21 A. The entrained polymer material of embodiment 16A, wherein the polymer has a structural unit represented by Formula:wherein:R1and R2are each independently a hydrogen atom, an alkyl group that is optionally substituted, an aryl group that is optionally substituted, an alkylaryl group that is optionally substituted, — COOR3, — OCOR4, a cyano group or a halogen atom, and R3and R4are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0209] 22A. The entrained polymer material of embodiment 16A, wherein the polymer is a ring-opening metathesis polymer of a cyclic olefin having 7 or 8 carbon atoms.

[0210] 23 A. The entrained polymer material of embodiment 16A, wherein the polymer is a polyoctenylene.

[0211] 24A. The entrained polymer material of embodiment 9A, wherein the organic compound is an a-hydroxyketone, or a tautomer thereof.

[0212] 25A. The entrained polymer material of embodiment 24A, wherein the organic compound is an a-keto- -hydroxycarboxylic acid, or a salt, tautomer, ester, or lactone thereof.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT

[0213] 26A. The entrained polymer material of embodiment 25 A, wherein the organic compound is 2-keto-3,4,5,6-tetrahydroxyhexanoic acid, or a salt, tautomer, ester, or lactone thereof.

[0214] 27A. The entrained polymer material of embodiment 26A, wherein the organic compound is chosen from D-ascorbic acid, L-ascorbic acid, D-isoascorbic acid, and L-isoascorbic acid, and salts, tautomers, esters, lactones of any of the foregoing, and mixtures thereof.

[0215] 28A. The entrained polymer material of embodiment 25A, wherein the ester is a Ci-Ce ester.

[0216] 29A. The entrained polymer material of embodiment 27A, wherein the organic compound is chosen from the lactone form of any one of D-ascorbic acid, L-ascorbic acid, D-isoascorbic acid, and L-isoascorbic acid, and mixtures thereof.

[0217] 30A. The entrained polymer material of embodiment 27A, wherein the organic compound is L-ascorbic acid, or a salt, tautomer, ester, or lactone thereof.

[0218] 31 A. The entrained polymer material of embodiment 30 A, wherein the organic compound is L-ascorbic acid, or a salt, tautomer, or lactone thereof.

[0219] 32A. The entrained polymer material of embodiment 31 A, wherein the organic compound is the lactone form of L-ascorbic acid.

[0220] 33A. The entrained polymer material of any one of embodiments 1A-32A, wherein the zeolite is present in an amount of at least 40% or greater, optionally at least 45% or greater, optionally at least 50% or greater, optionally at least 55% or greater, optionally at least 60% or greater, optionally at least 65% or greater by weight with respect to the total weight of the entrained polymer material.

[0221] 34A. The entrained polymer material of any one of embodiments 1A-33A, wherein the zeolite is present in an amount of at most 70% or less by weight, optionally at most 65% or less, optionally at most 60% or less, optionally at most 55% or less, optionally at most 50% or less, optionally at most 45% or less, optionally at most 44% or less, optionally at most 43% or less, optionally at most 42% or less, optionally at most 41% or less, optionally at most 40% or less by weight with respect to the total weight of the entrained polymer material.

[0222] 35A. The entrained polymer material of any one of embodiments 1A-34A, wherein the oxygen scavenging agent is present in an amount of at least 8% or greater by weight, optionally at least 10% or greater by weight, optionally at least 12% or greater by weight, optionally at leastATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT14% or greater by weight, optionally at least 16% or greater by weight with respect to the total weight of the entrained polymer material.

[0223] 36A. The entrained polymer material of any one of embodiments 1A-35A, wherein the oxygen scavenging agent is present in an amount of at most 30% or less by weight, optionally at most 26% or less by weight, optionally at most 22% or less by weight, optionally at most 20% or less by weight, optionally at most 18% or less by weight, optionally at most 16% or less by weight, optionally at most 14% or less by weight, optionally at most 12% or less by weight with respect to the total weight of the entrained polymer material.

[0224] 37A. The entrained polymer material of any one of embodiments 1A-36A, wherein a film of the material measuring 1 cm2in area and 0.3 mm thick, when stored in a 120 cm3bottle at 40 °C and ambient pressure, will scavenge an amount of oxygen over 7 days having partial volume of 0.2 cm3or greater, optionally 0.4 cm3or greater, optionally 0.6 cm3or greater, optionally 0.8 cm3or greater, optionally 1.0 cm3or greater, optionally 1.2 cm3or greater.

[0225] 38A. The entrained polymer material of any one of embodiments 1A-37A, wherein a film of the material measuring 1 cm2in area and 0.3 mm thick, when stored in a 120 cm3bottle at 40 °C and ambient pressure, will scavenge an amount of oxygen over 7 days that is at least 100% greater than a comparable material lacking zeolite, optionally at least 200% greater, optionally at least 300% greater, optionally at least 400% greater, optionally at least 500% greater, optionally at least 600% greater, optionally at least 700% greater.

[0226] 39A. The entrained polymer material of any one of embodiments 1 A-38A, wherein the base polymer ranges from 10% to 90% by weight of the total composition, optionally from 20% to 80% by weight.

[0227] 40A. The entrained polymer material of any one of embodiments 1A-39A, wherein the the base polymer is present in an amount of at most 90% or less by weight, optionally at most 85% or less by weight, optionally at most 80% or less by weight, optionally at most 75% or less by weight, optionally at most 70% or less by weight, optionally at most 65% or less by weight, optionally at most 60% or less by weight, optionally at most 55% or less by weight, optionally at most 50% or less by weight, optionally at most 45% or less by weight, optionally at most 40% or less by weight, optionally at most 35% or less by weight with respect to the total weight of the entrained polymer material.

[0228] 41 A. The entrained polymer material of any one of embodiments 1A-40A, wherein theATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTthe base polymer is present in an amount of at least 10% or more by weight, optionally at least 15% or more by weight, optionally at least 20% or more by weight, optionally at least 25% or more by weight, optionally at least 30% or more by weight, optionally at least 35% or more by weight, optionally at least 40% or more by weight with respect to the total weight of the entrained polymer material.

[0229] 42A. The entrained polymer material of any one of embodiments 1A-41A, further comprising a channeling agent.

[0230] 43A. The entrained polymer material of embodiment 42A, wherein the channeling agent is chosen from a polyglycol, glycerin polyamine, polyurethane, and polycarboxylic acid, or any combination of the foregoing.

[0231] 44A. The entrained polymer material of embodiment 42A, wherein the channeling agent is chosen from propylene oxide polymerisate, propylene oxide polymerisate-monobutyl ether, ethylene vinyl acetate (EVA), nylon, or any combination of the foregoing.

[0232] 45 A. The entrained polymer material of any one of embodiments 42A - 44A, wherein the channeling agent is present in a range of 2% to 15% by weight, optionally 2% to 10%, optionally about 5%.

[0233] 46 A. A blown film comprising the material of any one of embodiments 1A - 45 A.

[0234] 47A. A method of manufacturing the blown film of embodiment 46A, the method comprising the steps of:extruding a suitable precursor material comprising a molten mix of a base polymer, an oxygen scavenging agent, and a zeolite in a screw extruder with warming; passing the warmed extruded material through a tubular die;expanding and stretching the warmed extruded material with positive pressure; and allowing the expanded and stretched extruded material to cool.

[0235] 48A. The method of embodiment 47A, wherein the extrusion is performed with a rotation speed of from 5 rpm to 35 rpm, optionally from 10 rpm to 30 rpm, optionally from 10 rpm to 25 rpm, optionally from 10 rpm to 20 rpm.

[0236] 49A. The method of embodiment 47A, wherein the extrusion is performed at a temperature from 140 °C to 180 °C, optionally from 145 °C to 175 °C, optionally from 150 °C to 170 °C, inclusive, optionally from 150 °C to 165 °C.

[0237] 50A. The method of embodiment 47 A, wherein the method includes coextrusion of atATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTleast two layers for forming the expanded and stretched extruded material.

[0238] 51 A. The method of embodiment 50 A, wherein at least one layer includes a polymer material without the oxygen scavenging agent.

[0239] 52A. The material produced by the method of any one of embodiments 47A-51 A.

[0240] 53A. A container comprising:the entrained polymer material as recited in any one of embodiments 1A - 45A, and an interior space suitable for storage.

[0241] 54A. The container of embodiment 53A, comprising at least one article, the at least one article comprising the entrained polymer material of any one of embodiments 1A- 45A.

[0242] 55A. The container of embodiment 53A or 54A, further comprising a bottom surface, a top opening, and one or more sidewalls extending in a vertical direction from the bottom surface to the top opening.

[0243] 56A. The container of any one of embodiments 53A - 55A, further comprising a cover to close and I or seal the container.

[0244] 57A. The container of any one of embodiments 53A - 55A, wherein the entrained polymer is a film.

[0245] 58 A. The container of embodiment 57 A, wherein the film has a thickness from 0.1 mm to E0 mm, optionally from 0.15 mm to 0.8 mm, optionally from 0.20 mm to 0.6 mm, optionally from 0.25 mm to 0.4 mm, optionally about 0.3 mm.

[0246] 59A. The film of embodiment 57A or 58A, wherein the film measures 0.20 cm2in surface area or less, per cm3volume of the container, optionally 0.16 cm2in surface area or less, optionally 0.12 cm2in surface area or less, optionally 0.10 cm2in surface area or less.

[0247] 60A. A method for inhibiting oxidative decomposition of a product, the method comprising storing the product in the container of any one of embodiments 53A- 56A.

[0248] 61 A. The method of embodiment 60 A, wherein inclusion of the product within the container creates a headspace formed by the interior space that is not occupied by the product.

[0249] 62A. The method of embodiments 61 A, wherein the entrained polymer is provided as a film having a thickness of from 0.1 mm to 1.0 mm, optionally from 0.15 mm to 0.8 mm, optionally from 0.20 mm to 0.6 mm, optionally from 0.25 mm to 0.4 mm, optionally about 0.3 mm.

[0250] 63A. The method of embodiment 62A, wherein the film measures 0.20 cm2in surfaceATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTarea or less, per cm3volume of headspace in the container, optionally 0.16 cm2in surface area or less, optionally 0.12 cm2in surface area or less, optionally 0.10 cm2in surface area or less.

[0251] 64A. The method of any one of embodiments 61 A - 63A, wherein the initial partial pressure of oxygen in the headspace is 0.21 atm or less, optionally 0.15 atm or less, optionally 0.10 atm or less, optionally 0.05 atm or less, optionally 0.02 atm or less, optionally 0.01 atm or less.

[0252] 65A. The method of embodiment 64A, wherein:at 7 days of storage of the product, the partial pressure of oxygen in the headspace is no more than 300% of the initial partial pressure of oxygen, optionally no more than 200%, optionally no more than 150%. optionally no more than 100%, optionally no more than 75%, optionally no more than 50%.

[0253] 66A. The method of embodiment 64A, wherein:at 7 days of storage, the partial pressure of oxygen in the headspace is 0.15 atm or less, optionally 0.12 atm or less, optionally 0.10 atm or less, optionally 0.08 atm or less, optionally 0.06 atm or less, optionally 0.04 atm or less.

[0254] 67A. The method of embodiment 64A, wherein:at 7 days of storage of the product in the container, the partial pressure of oxygen in the headspace is 80% or less, optionally 70% or less, optionally 60% or less, optionally 50% or less, optionally 40% or less, optionally 30% or less, of the partial pressure of oxygen in the headspace at 7 days of storage of the same product in a comparable container, the container comprising a comparable entrained polymer material lacking zeolite.

[0255] 68A. The method of embodiment 64A, wherein:at 28 days of storage of the product in the container, the partial pressure of oxygen in the headspace is 80% or less, optionally 70% or less, optionally 60% or less, optionally 50% or less, optionally 40% or less, optionally 30% or less, of the partial pressure of oxygen in the headspace at 7 days of storage of the same product in a comparable container, the container comprising a comparable entrained polymer material lacking zeolite.

[0256] 69A. Any one of the previous embodiments, wherein the oxygen scavenging agent is present in an amount of from 5% to 30% by weight with respect to the total weight of the entrained polymer material, optionally from 5% to 25%, optionally from 5% to 20%, optionallyATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT15%, 16%, 17%, 18%, 19% or 20%.

[0257] 70 A. Any one of the previous embodiments, wherein the zeolite is present in an amount of from 40% to 70% by weight with respect to the total weight of the entrained polymer material, optionally from 40% to 65%, optionally from 40% to 60%, optionally from 40% to 55%, optionally from 40% to 50%.Entrained Polymers-Particles

[0258] IB. An entrained polymer material comprising:a base polymer;an oxygen scavenging agent; and40% to 70% of a particulate by weight with respect to the total weight of the entrained polymer material.

[0259] 2B. The entrained polymer material of embodiment IB, wherein the size of the particulate is from 4 pm to 841 pm, optionally from 5 pm to 707 pm, optionally from 6 pm to 595 pm, optionally from 7 pm to 500 pm, optionally from 7 pm to 354 pm, optionally from 7 pm to 250 pm, optionally from 7 pm to 149 pm, optionally from 7 pm to 44 pm.

[0260] 3B. The entrained polymer material of embodiment IB or 2B, wherein the particulate is calcium carbonate, a zeolite, an alumino silicate, a fine silica, or a glass bead.

[0261] 4B. The entrained polymer material of any one of embodiments 1B-3B, wherein the oxygen scavenging agent comprises a chemical reducing agent.

[0262] 5B. The entrained polymer material of embodiment 4B, wherein the oxygen scavenging agent comprises a 1- or 2-electron chemical reducing agent.

[0263] 6B. The entrained polymer material of embodiment 4B or 5B, wherein the chemical reducing agent produces, from the reduction of oxygen, a compound chosen from hydrogen peroxide and water.

[0264] 7B. The entrained polymer material of any one of embodiments 4B - 46B wherein the chemical reducing agent is a neutral metal.

[0265] 8B. The entrained polymer material of embodiment 7B, wherein the neutral metal is in monolithic, granular, or powdered form.

[0266] 9B. The entrained polymer material as recited in embodiment 7B or 8B, wherein the neutral metal is Fe°.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT

[0267] 1 OB . The entrained polymer material of any one of embodiments 4B - 6B wherein the chemical reducing agent is a low valent metal ion.

[0268] 1 IB. The entrained polymer material of any one of embodiments 4B - 6B, wherein the chemical reducing agent is an organic compound.

[0269] 12B. The entrained polymer material of embodiment 1 IB, wherein the organic compound is chosen from an organic phosphorus containing compound and an organic sulfur containing compound.

[0270] 13B. The entrained polymer material of embodiment 1 IB, wherein the organic compound is a sugar.

[0271] 14B. The entrained polymer material of embodiment 13B, wherein the sugar comprises an available reducing end.

[0272] 15B. The entrained polymer material of embodiment 1 IB, wherein the organic compound comprises a polyene.

[0273] 16B. The entrained polymer material of embodiment 15B, wherein the polyene contains 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 olefins in conjugation.

[0274] 17B. The entrained polymer material of embodiment 1 IB, wherein the organic compound is chosen from a porphyrin and a heme.

[0275] 18B. The entrained polymer material of embodiment 1 IB, wherein the chemical reducing agent is a polymer.

[0276] 19B. The entrained polymer material of embodiment 18B, wherein the polymer is an optionally substituted, optionally partially unsaturated polyethylene.

[0277] 20B. The entrained polymer material of embodiment 19B, wherein the optionally partially unsaturated polyethylene is substituted with one or more R1, wherein:each R1is independently a hydrogen atom, an alkyl group that is optionally substituted, an aryl group that is optionally substituted, an alkylaryl group that is optionally substituted, -COOR3, -OCOR4, a cyano group or a halogen atom, and R3and R4are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0278] 2 IB. The entrained polymer material of embodiment 20B, wherein the polymer comprises polyethylene interspersed with -(CHR '=CHR2)- units, wherein:ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTR1and R2are each independently a hydrogen atom, an alkyl group that is optionally substituted, an aryl group that is optionally substituted, an alkylaryl group that is optionally substituted, -COOR3. -OCOR4, a cyano group or a halogen atom, and R3and R4are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0279] 22B. The entrained polymer material of embodiment 21B, wherein:neighboring -(CHRJ=CHR2)- units are separated by three or more methylene units.

[0280] 23B. The entrained polymer material of embodiment 18B, wherein the polymer has a structural unit represented by Formula:wherein:R1and R2are each independently a hydrogen atom, an alkyl group that is optionally substituted, an aryl group that is optionally substituted, an alkylaryl group that is optionally substituted, — COOR3, — OCOR4, a cyano group or a halogen atom, and R3and R4are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0281] 24B. The entrained polymer material of embodiment 18B, wherein the polymer is a ring-opening metathesis polymer of a cyclic olefin having 7 or 8 carbon atoms.

[0282] 25B. The entrained polymer material of embodiment 18B, wherein the polymer is a polyoctenylene.

[0283] 26B. The entrained polymer material of embodiment 1 IB, wherein the organic compound is an a-hydroxyketone, or a tautomer thereof.

[0284] 27B. The entrained polymer material of embodiment 26B, wherein the organic compound is an a-keto-P-hydroxycarboxylic acid, or a salt, tautomer, ester, or lactone thereof.

[0285] 28B. The entrained polymer material of embodiment 27B, wherein the organicATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTcompound is 2-keto-3,4,5,6-tetrahydroxyhexanoic acid, or a salt, tautomer, ester, or lactone thereof.

[0286] 29B. The entrained polymer material of embodiment 28B, wherein the organic compound is chosen from D-ascorbic acid, L-ascorbic acid, D-isoascorbic acid, and L-isoascorbic acid, and salts, tautomers, esters, lactones of any of the foregoing, and mixtures thereof.

[0287] 30B. The entrained polymer material of embodiment 27B, wherein the ester is a Ci-Ce ester.

[0288] 3 IB. The entrained polymer material of embodiment 29B, wherein the organic compound is chosen from the lactone form of any one of D-ascorbic acid, L-ascorbic acid, D-isoascorbic acid, and L-isoascorbic acid, and mixtures thereof.

[0289] 32B. The entrained polymer material of embodiment 29B, wherein the organic compound is L-ascorbic acid, or a salt, tautomer, ester, or lactone thereof.

[0290] 33B. The entrained polymer material of embodiment 32B, wherein the organic compound is L-ascorbic acid, or a salt, tautomer, or lactone thereof.

[0291] 34B. The entrained polymer material of embodiment 33B, wherein the organic compound is the lactone form of L-ascorbic acid.

[0292] 35B. The entrained polymer material of any one of embodiments 1B-34B, wherein the particulate is present in an amount of at least 40% or greater, optionally at least 45% or greater, optionally at least 50% or greater, optionally at least 55% or greater, optionally at least 60% or greater, optionally at least 65% or greater by weight with respect to the total weight of the entrained polymer material.

[0293] 36B. The entrained polymer material of any one of embodiments 1B-35B, wherein the particulate is present in an amount of at most 70% or less by weight, optionally at most 65% or less, optionally at most 60% or less, optionally at most 55% or less, optionally at most 50% or less, optionally at most 45% or less, optionally at most 44% or less, optionally at most 43% or less, optionally at most 42% or less, optionally at most 41% or less, optionally at most 40% or less by weight with respect to the total weight of the entrained polymer material.

[0294] 37B. The entrained polymer material of any one of embodiments 1B-36B, wherein the oxygen scavenging agent is present in an amount of at least 8% or greater by weight, optionally at least 10% or greater by weight, optionally at least 12% or greater by weight, optionally at least 14% or greater by weight, optionally at least 16% or greater by weight with respect to the totalATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTweight of the entrained polymer material.

[0295] 38B. The entrained polymer material of any one of embodiments 1B-37B, wherein the oxygen scavenging agent is present in an amount of at most 30% or less by weight, optionally at most 26% or less by weight, optionally at most 22% or less by weight, optionally at most 20% or less by weight, optionally at most 18% or less by weight, optionally at most 16% or less by weight, optionally at most 14% or less by weight, optionally at most 12% or less by weight with respect to the total weight of the entrained polymer material.

[0296] 39B. The entrained polymer material of any one of embodiments 1B-38B, wherein a film of the material measuring 1 cm2in area and 0.3 mm thick, when stored in a 120 cm3bottle at 40 °C and ambient pressure, will scavenge an amount of oxygen over 7 days having partial volume of 0.2 cm3or greater, optionally 0.4 cm3or greater, optionally 0.6 cm3or greater, optionally 0.8 cm3or greater, optionally 1.0 cm3or greater, optionally 1.2 cm3or greater.

[0297] 40B. The entrained polymer material of any one of embodiments 1B-39B, wherein a film of the material measuring 1 cm2in area and 0.3 mm thick, when stored in a 120 cm3bottle at 40 °C and ambient pressure, will scavenge an amount of oxygen over 7 days that is at least 100% greater than a comparable material lacking particulate, optionally at least 200% greater, optionally at least 300% greater, optionally at least 400% greater, optionally at least 500% greater, optionally at least 600% greater, optionally at least 700% greater.

[0298] 4 IB. The entrained polymer material of any one of embodiments 1B-40B, wherein the base polymer ranges from 10% to 90% by weight of the total composition, optionally from 20% to 80% by weight.

[0299] 42B. The entrained polymer material of any one of embodiments 1B-41B, wherein the the base polymer is present in an amount of at most 90% or less by weight, optionally at most 85% or less by weight, optionally at most 80% or less by weight, optionally at most 75% or less by weight, optionally at most 70% or less by weight, optionally at most 65% or less by weight, optionally at most 60% or less by weight, optionally at most 55% or less by weight, optionally at most 50% or less by weight, optionally at most 45% or less by weight, optionally at most 40% or less by weight, optionally at most 35% or less by weight with respect to the total weight of the entrained polymer material.

[0300] 43B. The entrained polymer material of any one of embodiments 1B-42B, wherein the the base polymer is present in an amount of at least 10% or more by weight, optionally at leastATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT15% or more by weight, optionally at least 20% or more by weight, optionally at least 25% or more by weight, optionally at least 30% or more by weight, optionally at least 35% or more by weight, optionally at least 40% or more by weight with respect to the total weight of the entrained polymer material.

[0301] 44B. The entrained polymer material of any one of embodiments 1B-43B, further comprising a channeling agent.

[0302] 45B. The entrained polymer material of embodiment 44B, wherein the channeling agent is chosen from a polyglycol, glycerin polyamine, polyurethane, and polycarboxylic acid, or any combination of the foregoing.

[0303] 46B. The entrained polymer material of embodiment 44B, wherein the channeling agent is chosen from propylene oxide polymerisate, propylene oxide polymerisate-monobutyl ether, ethylene vinyl acetate (EVA), nylon, or any combination of the foregoing.

[0304] 47B. The entrained polymer material of any one of embodiments 44B - 46B, wherein the channeling agent is present in a range of 2% to 15% by weight, optionally 2% to 10%, optionally about 5%.

[0305] 48B. A blown film comprising the material of any one of embodiments IB - 47B.

[0306] 49B. A method of manufacturing the blown film of embodiment 48B, the method comprising the steps of:extruding a suitable precursor material comprising a molten mix of a base polymer, an oxygen scavenging agent, and a particulate in a screw extruder with warming; passing the warmed extruded material through a tubular die;expanding and stretching the warmed extruded material with positive pressure; and allowing the expanded and stretched extruded material to cool.

[0307] 50B. The method of embodiment 49B, wherein the extrusion is performed with a rotation speed of from 5 rpm to 35 rpm, optionally from 10 rpm to 30 rpm, optionally from 10 rpm to 25 rpm, optionally from 10 rpm to 20 rpm.

[0308] 5 IB. The method of embodiment 49B, wherein the extrusion is performed at a temperature from 140 °C to 180 °C, optionally from 145 °C to 175 °C, optionally from 150 °C to 170 °C, inclusive, optionally from 150 °C to 165 °C.

[0309] 52B. The method of embodiment 49B, wherein the method includes coextrusion of at least two layers for forming the expanded and stretched extruded material.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT

[0310] 53B. The method of embodiment 52B, wherein at least one layer includes a polymer material without the oxygen scavenging agent.

[0311] 54B. The material produced by the method of any one of embodiments 49B-53B.

[0312] 55B. A container comprising:the entrained polymer material as recited in any one of embodiments IB - 47B, and an interior space suitable for storage.

[0313] 56B. The container of embodiment 55B, comprising at least one article, the at least one article comprising the entrained polymer material of any one of embodiments IB- 47B.

[0314] 57B. The container of embodiment 55B or 56B, further comprising a bottom surface, a top opening, and one or more sidewalls extending in a vertical direction from the bottom surface to the top opening.

[0315] 58B. The container of any one of embodiments 55B - 57B, further comprising a cover to close and I or seal the container.

[0316] 59B. The container of any one of embodiments 55B - 57B, wherein the entrained polymer is a film.

[0317] 60B. The container of embodiment 59B, wherein the film has a thickness from 0.1 mm to 1.0 mm, optionally from 0.15 mm to 0.8 mm, optionally from 0.20 mm to 0.6 mm, optionally from 0.25 mm to 0.4 mm, optionally about 0.3 mm.

[0318] 61B. The film of embodiment 59B or 60B, wherein the film measures 0.20 cm2in surface area or less, per cm3volume of the container, optionally 0.16 cm2in surface area or less, optionally 0.12 cm2in surface area or less, optionally 0.10 cm2in surface area or less.

[0319] 62B. A method for inhibiting oxidative decomposition of a product, the method comprising storing the product in the container of any one of embodiments 55B- 58B.

[0320] 63B. The method of embodiment 62B, wherein inclusion of the product within the container creates a headspace formed by the interior space that is not occupied by the product.

[0321] 64B. The method of embodiments 63B, wherein the entrained polymer is provided as a film having a thickness of from 0.1 mm to 1.0 mm, optionally from 0.15 mm to 0.8 mm, optionally from 0.20 mm to 0.6 mm, optionally from 0.25 mm to 0.4 mm, optionally about 0.3 mm.

[0322] 65B. The method of embodiment 64B, wherein the film measures 0.20 cm2in surface area or less, per cm3volume of headspace in the container, optionally 0.16 cm2in surface area orATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTless, optionally 0.12 cm2in surface area or less, optionally 0.10 cm2in surface area or less.

[0323] 66B. The method of any one of embodiments 63B - 65B, wherein the initial partial pressure of oxygen in the headspace is 0.21 atm or less, optionally 0.15 atm or less, optionally 0.10 atm or less, optionally 0.05 atm or less, optionally 0.02 atm or less, optionally 0.01 atm or less.

[0324] 67B. The method of embodiment 66B, wherein:at 7 days of storage of the product, the partial pressure of oxygen in the headspace is no more than 300% of the initial partial pressure of oxygen, optionally no more than 200%, optionally no more than 150%, optionally no more than 100%, optionally no more than 75%, optionally no more than 50%.

[0325] 68B. The method of embodiment 66B, wherein:at 7 days of storage, the partial pressure of oxygen in the headspace is 0.15 atm or less, optionally 0.12 atm or less, optionally 0.10 atm or less, optionally 0.08 atm or less, optionally 0.06 atm or less, optionally 0.04 atm or less.

[0326] 69B. The method of embodiment 66B, wherein:at 7 days of storage of the product in the container, the partial pressure of oxygen in the headspace is 80% or less, optionally 70% or less, optionally 60% or less, optionally 50% or less, optionally 40% or less, optionally 30% or less, of the partial pressure of oxygen in the headspace at 7 days of storage of the same product in a comparable container, the container comprising a comparable entrained polymer material lacking particulate.

[0327] 70B. The method of embodiment 66B, wherein:at 28 days of storage of the product in the container, the partial pressure of oxygen in the headspace is 80% or less, optionally 70% or less, optionally 60% or less, optionally 50% or less, optionally 40% or less, optionally 30% or less, of the partial pressure of oxygen in the headspace at 7 days of storage of the same product in a comparable container, the container comprising a comparable entrained polymer material lacking particulate.

[0328] 7 IB. A method of increasing oxygen scavenger speed rate in an entrained polymer material comprising:ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTproviding 40% to 70% of a particulate by weight with respect to the total weight of the entrained polymer material.

[0329] 72B. The method of embodiment 7 IB, wherein the particulate is calcium carbonate, a zeolite, an alumino silicate, a fine silica, or a glass bead.

[0330] 73B. The method of any one of embodiments 71B-72B, wherein the oxygen scavenger speed rate of the entrained polymer material increases by up to 750 %, optionally by up to 700%. optionally by up to 600%, optionally by up to 500%, optionally by up to 400%, optionally by up to 300%, optionally by up to 200%, optionally by up to 100%, when the particulate is included in the entrained polymer material, as compared to the entrained polymer material without the particulate.

[0331] 74B. Any one of the previous embodiments, wherein the oxygen scavenging agent is present in an amount of from 5% to 30% by weight with respect to the total weight of the entrained polymer material, optionally from 5% to 25%, optionally from 5% to 20%, optionally 15%, 16%, 17%. 18%, 19% or 20%.

[0332] 75B. Any one of the previous embodiments, wherein the particulate is present in an amount of from 40% to 70% by weight with respect to the total weight of the entrained polymer material, optionally from 40% to 65%, optionally from 40% to 60%, optionally from 40% to 55%, optionally from 40% to 50%.

[0333] Various aspects of the disclosure will be illustrated in more detail with reference to the following Examples, but it should be understood that the present disclosure is not deemed to be limited thereto.EXAMPLESExample 1. Formulations: Polyolefin.

[0334] The following polyolefins (CHRCH2),,, combined with an oxygen scavenging agent and a zeolite have been prepared. The oxygen scavenging agent was a cyclooctene-based ring-opening metathesis polymer as described in US 7,893,145. The oxygen scavenging agent used was Visparent E100 (Evonik). The catalyst was a masterbatch containing 5% cobalt neodecanoate and 95% ExxonMobil Exceed™ PP9074MED. The base polymer was the EXACT™ 3040 ethylene / hexene copolymer material. The zeolite was a 3 Angstrom pore size material from SYLOSIV (3A molecular sieve).

[0335] Table 2 shows the compositions tested, where the percentages in the table are weightATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTpercentages.Table 2, Compositions.Oxygen BaseScavenger Catalyst Masterbatch Polymer Zeolite1 17.0% 3.0% 80.0% 0.0%2 17.0% 3.0% 70.0% 10.0%3 17.0% 3.0% 60.0% 20.0%4 17.0% 3.0% 50.0% 30.0%5 17.0% 3.0% 40.0% 40.0%6 17.0% 3.0% 30.0% 50.0%Example 2. Measurement of oxygen concentration.

[0336] Non-invasive Oxysense® OxyDot oxygen sensors were employed to measure oxygen concentrations. The OxyDot sensor contains a fluorescent dye whose fluorescence lifetime and emission intensity are correlated with oxygen concentration. To determine oxygen concentration, an OxyDot sensor is attached to the inside of a container having a headspace therein. The sensor is illuminated with a pulsed blue light from an LED. The blue light is absorbed by the sensor and red light is emitted. The red light is detected by a photo-detector and the characteristics of the fluorescence lifetime are measured. One or more calibration curves are constructed from standard samples with known concentrations of oxygen to identify the correlation between fluorescence lifetime and oxygen concentration. From the calibration curves and fluorescence emission data, the concentration of oxygen in a headspace can be found.Example 3. Experimen tal determination of oxygen scavenging

[0337] Samples of the film measuring 1 cm2in area and 0.3 mm thick were placed in a 120 cm3bottle equipped with the OxyDot oxygen sensor described above. The bottle was sealed with ambient air under atmospheric pressure and held at 40 °C. Oxygen concentration was determined periodically from the OxyDot measurements.

[0338] For purposes of calculation, a starting oxygen concentration of 21% was used, corresponding to a partial pressure of oxygen, P(O2) of 0.21 atm. The partial volume of oxygen, based on the bottle size, was calculated. Scavenging of oxygen was determined as the decrease in partial volume of oxygen at any given time.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT

[0339] Data are provided in Table 3, below, in units of partial volume (cm3) of scavenged oxygen. It will be noted that two readings were taken at t = 1 day. Compared to the remaining data points, these values were anomalously high; a satisfactory explanation for this behaviour has not been determined.Table 3. Oxygen scavenging performance.Time, Weight % zeolitedays 0% 10% 20% 30% 40% 50%1 0.286 0.301 0.120 0.469 0.658 0.4791 0.540 0.384 0.397 0.257 0.526 0.6702 0.020 0.020 0.029 0.026 0.102 0.2893 0.041 0.071 0.104 0.146 0.246 0.5464 0.067 0.129 0.221 0.258 0.450 0.7527 0.137 0.356 0.448 0.504 0.738 1.2128 0.161 0.454 0.658 0.728 0.945 1.5049 0.185 0.554 0.874 0.982 1.146 1.81010 0.209 0.649 1.050 1.230 1.334 2.06711 0.240 0.752 1.216 1.448 1.548 2.274

[0340] The set of data, up to t = 11 days, but excluding the t = 1 day points, is depicted in FIG. 1.Also provided in FIG. 1 are least-squares fits, to order 3 polynomials, of oxygen scavenging for each sample. Each fit is to a cubic equation having the form:y = a + bt + ct2+ dt3with y = oxygen scavenging, in partial volume, and t = time in days.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTTable 4, Parameters for least-squares fitsParameter Weight % zeolite(x 106) 0% 10% 20% 30% 40% 50%a -3.05 x IO'3-2.27 x 10’3-2.31 x IO'3-8.21 x IO'3-1.64 x IO'2-7.07 x IO'3b 8.83 x IO'3-5.39 x IO'37.97 x IO'32.03 x IO'27.84 x IO'21.75 x IO'1c 2.23 x 10'31.06 x IO'28.90 x IO'38.33 x IO’33.79 x IO'3-1.53 x IO'3d -9.56 x 10'5-3.49 x IO'46.04 x IO'51.49 x IO'41.84 x IO'44.31 x IO'4

[0341] R2for 0%: 0.9965

[0342] R2for 10%: 0.9997

[0343] R2for 20%: 0.9928

[0344] R2for 30%: 0.9893

[0345] R2for 40%: 0.9930

[0346] R2for 50%: 0.9956

[0347] Also provided below are least-squares fits, to order 8 polynomials, of oxygen scavenging for each sample. Each fit is to a cubic equation having the form:y = a + bt + ct2+ dt3+ et4+ ft5+ gt6+ ht7+ jt8with y = oxygen scavenging, in partial volume, and t = time in days.Table 5. Parameters for least-squares fits.Parameter Weight % zeolite0% 10% 20% 30% 40% 50% a -1.5552 x IO'3-6.7429 x IO'42.4570 x IO'32.3633 x IO'36.4789 x IO'3-8.6534 x IO'3b 9.1151 x IO’32.7805 x IO'32.2374 x IO'31.9996 x IO’22.0154 x IO’21.2985 x IO’1c 2.3591 x IO'31.7170 x IO'34.6125 x IO'3-4.5653 x IO'32.2726 x IO'21.9706 x IO'2d -1.7117 x IO’42.6714 x IO'32.4015 x IO'34.7665 x IO'3-1.5219 x IO’3-1.8345 x IO’3e 7.7292 x IO'6-4.4394 x IO'4-3.0713 x IO'4-5.4324 x IO’43.5945 x IO'55.9317 x IO'5f -2.5618 x IO’73.1952 x IO’51.4834 x 1 O'52.6016 x IO'51.1171 x IO’7-6.5183 x IO'7g 6.5973 x IO'9-1.1943 x IO'6-3.2441 x IO'7-5.7788 x IO'7-1.8152 x IO'82.8510 x IO'13h-1.0738 x IO'102.2619 x IO'82.7170 x IO'94.9300 x IO'92.9595 x IO'10-8.4231 x IO'15ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTj 7.2241 x 10'13-1.7145 x IO'10-7.5323 x 10'13-7.3064 x IO'13-1.9937 x IO'121.1610 x IO'16

[0348] R2for 0%: 0.9994

[0349] R2for 10%: 0.9991

[0350] R2for 20%: 0.9992

[0351] R2for 30%: 0.9984

[0352] R2for 40%: 0.9992

[0353] R2for 50%: 0.9982

[0354] FIG. 2 depicts the experiment of Example 3, extended to 35 days.

[0355] FIG. 3 depicts the time, in days, required for oxygen scavenging of each film to reach the working capacity. Data are also provided in Table 6. Comparison of the performance of films (a) and (b) reveals that incorporation of 10% zeolite to a formula lacking zeolite improves performance from 34.6 days to 12.5 days.Table 6. Time, in days, to reach working capacity.Film Weight % zeolite Time(a) 0% 34.6(b) 10% 12.5(c) 20% 9.0(d) 30% 8.3(e) 40% 7.2(0 50% 4.6Example 4. Polyolefin with Particulates.

[0356] Polyolefins (CHRCFEjn, combined with an oxygen scavenging agent and a particulate are prepared. The oxygen scavenging agent is a cyclooctene-based ring-opening metathesis polymer as described in US 7,893,145. The oxygen scavenging agent used is Visparent E100 (Evonik). The catalyst is a masterbatch containing 5% cobalt salt and 95% polyethylene. The base polymer is a polyethylene material. The particulate is calcium carbonate, a zeolite, an alumino silicate, a fine silica, or a glass bead.

[0357] Injection molding compound is loaded at up to 70% of particle by weight. InjectionATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTmolded parts are made from the compound.

[0358] The films and compounds are tested as described in the previous Examples.

[0359] All references, patents or applications. U.S. or foreign, cited in the application are hereby incorporated by reference as if written herein in their entireties. Where any inconsistencies arise, material literally disclosed herein controls.

[0360] From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

[0361] While the disclosed concept has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims

ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTCLAIMSWhat is claimed is:

1. An entrained polymer material comprising:a base polymer;5% to 20% of an oxygen scavenging agent by weight with respect to the total weight of the entrained polymer material; and40% to 70% of a zeolite by weight with respect to the total weight of the entrained polymer material.

2. The entrained polymer material of claim 1, wherein the oxygen scavenging agent comprises a chemical reducing agent.

3. The entrained polymer material of claim 1, wherein the zeolite is present in an amount of 30% to 50% by weight with respect to the total weight of the entrained polymer material.

4. The entrained polymer material of claim 1, wherein the zeolite is present in an amount of 40 to 50% by weight with respect to the total weight of the entrained polymer material.

5. The entrained polymer material of claim 1, wherein the oxygen scavenging agent is present in an amount of 10% to 20% by weight with respect to the total weight of the entrained polymer material.

6. The entrained polymer material of claim 1, wherein the oxygen scavenging agent is present in an amount of 15% to 20% by weight with respect to the total weight of the entrained polymer material.

7. The entrained polymer material of claim 1, wherein a film of the material measuring 1 cm2in area and 0.3 mm thick, when stored in a 120 cm3bottle at 40 °C and ambient pressure, will scavenge an amount of oxygen over 7 days having partial volume of 0.2 cm3or greater, optionally 0.4 cm3or greater, optionally 0.6 cm3or greater, optionally 0.8 cm3or greater, optionally 1.0 cm3or greater, optionally 1.2 cm3or greater.

8. The entrained polymer material of claim 1, wherein a film of the material measuring 1 cm2in area and 0.3 mm thick, when stored in a 120 cm3bottle at 40 °C and ambientATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENTpressure, will scavenge an amount of oxygen over 7 days that is at least 100% greater than a comparable material lacking zeolite, optionally at least 200% greater, optionally at least 300% greater, optionally at least 400% greater, optionally at least 500% greater, optionally at least 600% greater, optionally at least 700% greater.

9. The entrained polymer material of claim 1, wherein the base polymer ranges from 10% to 90% by weight of the total composition, optionally from 20% to 80% by weight.

10. The entrained polymer material of claim 1, further comprising a channeling agent.

11. The entrained polymer material of claim 10, wherein the channeling agent is chosen from a polyglycol, glycerin polyamine, polyurethane, and polycarboxylic acid, or any combination of the foregoing.

12. The entrained polymer material of claim 10, wherein the channeling agent is chosen from propylene oxide polymerisate, propylene oxide polymerisate-monobutyl ether, ethylene vinyl acetate (EVA), nylon, or any combination of the foregoing.

13. The entrained polymer material of any one of claims 10 - 12, wherein the channeling agent is present in a range of from 2% to 15% by weight, optionally from 2% to 10%, optionally about 5%.

14. A blown film comprising the material of any one of claims 1 - 13.

15. A method of manufacturing the blown film of claim 14, the method comprising the steps of:extruding a suitable precursor material comprising a molten mix of a base polymer, an oxygen scavenging agent, and a zeolite in a screw extruder with warming; passing the warmed extruded material through a tubular die;expanding and stretching the warmed extruded material with positive pressure; and allowing the expanded and stretched extruded material to cool.

16. The method of claim 15, wherein the extrusion is performed with a rotation speed of from 5 rpm to 35 rpm, optionally from 10 rpm to 30 rpm, optionally from 10 rpm to 25 rpm, optionally from 10 rpm to 20 rpm.ATTORNEY DOCKET NO.: CSP-0671PC(310316-02780) PATENT17. The method of claim 15, wherein the extrusion is performed at a temperature from 140 °C to 180 °C, optionally from 145 °C to 175 °C, optionally from 150 °C to 170 °C, inclusive, optionally from 150 °C to 165 °C.

18. The method of claim 15, wherein the method includes coextrusion of at least two layers for forming the expanded and stretched extruded material.

19. The method of claim 18, wherein at least one layer includes a polymer material without the oxygen scavenging agent.

20. The material produced by the method of any one of claims 15-19.

21. A container comprising:the entrained polymer material as recited in any one of claims 1 - 13, andan interior space suitable for storage.

22. The container of claim 21, comprising at least one article, the at least one article comprising the entrained polymer material of any one of claims 1 - 13.

23. The container of any one of claims 21 -22, wherein the entrained polymer is a film.

24. A method for inhibiting oxidative decomposition of a product, the method comprising storing the product in the container of any one of claims 21 - 23.

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