Removal of oxygen

Abstract

The present invention relates to a formulation for scavenging oxygen comprising: (A) an oxygen scavenging copolymer; and (B) an oil, wherein the oil is selected from, for example, olive oil, macadimia nut oil, avocado oil, patatile oil, Chile hazel oil and / or an oil comprising at least 20% glyceryl oleate.

Description

Technical Field

[0001] The present invention relates to oxygen scavenging, particularly but not limited to scavenging oxygen in packages (such as bottles). Preferred embodiments relate to oxygen scavenging formulations, their combination with compositions, and their uses. Background Art

[0002] There is currently a need for packages that can preserve or extend the shelf life of food, beverages, and other products, and these products are prone to degradation or spoilage due to oxidation during subsequent production and consumption. However, pure PET does not possess the oxygen barrier properties required for certain food or beverage packages. Therefore, it is known to use oxygen scavengers to enhance the oxygen barrier properties of PET packages.

[0003] There is a trade-off between enhancing the oxygen barrier properties and having a negative impact on the high transparency of pure PET. It is undesirable that increasing the loading level of oxygen scavengers in PET to improve the oxygen barrier properties tends to reduce the transparency of PET (i.e., increase haze).

[0004] It is well known that the oxygen barrier properties of PET can be improved by adding polyamides, particularly poly(m -xylylene adipamide) (MXD - 6). However, since PET and MXD - 6 are two very different materials, single - layer containers containing PET / MXD - 6 and substantially pure PET will have an adverse effect on the optical properties of the recycling stream. Therefore, containers containing PET / MXD - 6 can be separated from other containers and then recycled to produce recycled PET of lower quality.

[0005] There is a need for an oxygen scavenging formulation that can be used to achieve very high levels of oxygen scavenging in containers without significantly affecting the optical properties. In this case, it would be very advantageous if bottles containing such a formulation could be recycled directly together with substantially pure PET bottles. Summary of the Invention

[0006] The object of the present invention is to solve the above problems.

[0007] According to a first aspect of the present invention, there is provided an oxygen scavenging formulation, the formulation comprising:

[0008] (A) an oxygen scavenging copolymer;

[0009] (B) an oil, wherein the oil is selected from:

[0010] (a) olive oil;

[0011] (b) macadamia nut oil;

[0012] (c) avocado oil;

[0013] (d) bataua oil;

[0014] (e) gevuina oil;

[0015] (f) PQ oil, comprising:

[0016] (i) less than 25% linoleic acid, and / or

[0017] (ii) less than 10% linolenic acid, and / or

[0018] (iii) greater than 40% oleic acid, and / or

[0019] (iv) greater than 40% monounsaturated fatty acids, and / or

[0020] (v) less than 40% polyunsaturated fatty acids, and / or

[0021] (vi) at least 0.1% squalene;

[0022] (g) RS oil, comprising at least 20% glyceryl oleate.

[0023] As used herein, "ppm" or "parts per million" (or cognate expressions) refers to parts per million by weight of a particular material.

[0024] In one embodiment, the oil may be selected from any of the oils (a) to (f) in (B).

[0025] The percentages of components in the oil (e.g., components in the oils described in (B)) can be evaluated by GC-HRMS. The analysis can be as described below: for example, "Column Selection for the Analysis of Fatty Acid Methyl Esters"; authors: Frank David, Pat Sandra, Allen K Vickers, Agilent Technologies 5989-3760EN and its cited references. The method involves derivatizing fatty acids to methyl esters as described by W.W. Christie, "Gas Chromatography and Lipids, A Practical Guide" (1989), The Oily Press, Ayr, Scotland (ISBN 0-951417-0-X), and then analyzing the fatty acid methyl esters (FAMEs).

[0026] Any grade of olive oil, macadamia nut oil, avocado oil, patawa oil, gevuina oil, and PQ oil can be selected, e.g., virgin, extra-virgin, or highly refined grades of these oils.

[0027] The olive oil may contain less than 25%, preferably less than 15%, more preferably less than 10% of linoleic acid. The olive oil may include at least 1%, preferably at least 3% of linoleic acid.

[0028] The olive oil may contain less than 5.0%, preferably less than 2.0%, more preferably less than 1.0% of linolenic acid. The olive oil may contain at least 0.1%, preferably at least 0.3% of linolenic acid.

[0029] The olive oil may contain at least 40%, preferably at least 50%, more preferably at least 65% of oleic acid. The olive oil may contain less than 85%, preferably less than 82% of oleic acid.

[0030] The olive oil may contain at least 40%, preferably at least 50%, more preferably at least 65% of monounsaturated fatty acids. The olive oil may contain less than 85%, preferably less than 82% of monounsaturated fatty acids.

[0031] The olive oil may contain less than 13%, preferably less than 11% of polyunsaturated fatty acids. The olive oil may contain at least 3% of polyunsaturated fatty acids, such as at least 4% of polyunsaturated fatty acids.

[0032] The olive oil may contain less than 10%, preferably less than 5% of compounds having more than two double bonds.

[0033] The olive oil may contain at least 0.05%, preferably at least 0.1% of squalene. The olive oil may contain less than 2.0%, preferably less than 1.0% of squalene.

[0034] In the olive oil, the total percentage of linoleic acid and linolenic acid may be less than 25%, preferably less than 17%, more preferably less than 12%. The total may be at least 1% or at least 3%.

[0035] The macadamia nut oil may contain less than 25%, preferably less than 15%, more preferably less than 10% of linoleic acid. The macadamia nut oil may contain at least 0.5%, preferably at least 1% of linoleic acid.

[0036] The macadamia nut oil may contain less than 10%, preferably less than 5% of linolenic acid. The macadamia nut oil may contain at least 0.05%, preferably at least 0.1% of linolenic acid.

[0037] The macadamia nut oil may contain at least 40%, preferably at least 45%, more preferably at least 50% of oleic acid. The macadamia nut oil may contain less than 80%, preferably less than 70% of oleic acid.

[0038] The macadamia nut oil may contain at least 40%, preferably at least 50%, more preferably at least 60% of monounsaturated fatty acids. The macadamia nut oil may contain less than 85%, preferably less than 82% of monounsaturated fatty acids.

[0039] The macadamia nut oil may contain less than 13%, preferably less than 11% of polyunsaturated fatty acids. The macadamia nut oil may contain at least 1% of polyunsaturated fatty acids.

[0040] The macadamia nut oil may contain less than 10%, preferably less than 5% of compounds having more than two double bonds.

[0041] The macadamia nut oil may contain less than 2.0%, preferably less than 1.0% of squalene.

[0042] In the macadamia nut oil, the total percentage of linoleic acid and linolenic acid may be less than 25%, preferably less than 17%, more preferably less than 12%. The total may be at least 1%.

[0043] The PQ oil may contain less than 25%, preferably less than 15%, more preferably less than 10% of linoleic acid. The PQ oil may contain at least 1%, preferably at least 3% of linoleic acid.

[0044] The PQ oil may contain less than 10%, preferably less than 5% of linolenic acid. The PQ oil may contain at least 0.1%, preferably at least 0.3% of linolenic acid.

[0045] The PQ oil may contain at least 40%, preferably at least 45%, more preferably at least 50 wt% of oleic acid. The PQ oil may contain less than 80%, preferably less than 70% of oleic acid.

[0046] The PQ oil may contain at least 40%, preferably at least 50%, more preferably at least 60% of monounsaturated fatty acids. The PQ oil may contain less than 85%, preferably less than 80% of monounsaturated fatty acids.

[0047] The PQ oil may contain less than 50%, preferably less than 30%, more preferably less than 15%, especially less than 10% of polyunsaturated fatty acids. The PQ oil may contain at least 2% of polyunsaturated fatty acids.

[0048] The PQ oil may contain less than 30%, preferably less than 20%, more preferably less than 15%, especially less than 10% of compounds having more than two double bonds.

[0049] The PQ oil may contain at least 0.1%, preferably at least 0.2% of squalene. The PQ oil may contain less than 2.0%, preferably less than 1.0% of squalene.

[0050] In the PQ oil, the total percentage of linoleic acid and linolenic acid can be less than 25%, preferably less than 17%, more preferably less than 12%, and especially less than 6%. The total can be at least 1% or at least 2%.

[0051] The PQ oil can contain at least two, preferably at least four, and preferably each of the features (i) to (vi) in feature (f). The PQ oil preferably contains at least the features (i) to (iii) in feature (f).

[0052] The PQ oil preferably has the following features:

[0053] - less than 25% linoleic acid;

[0054] - less than 10% linolenic acid; and

[0055] - more than 40% oleic acid.

[0056] The PQ oil preferably has the following features:

[0057] - 1% to 15%, preferably 2% to 10% linoleic acid;

[0058] - 0.1% to 10%, preferably 0.1% to 5% linolenic acid; and

[0059] - 40% to 80%, preferably 45% to 70% oleic acid.

[0060] The PQ oil preferably has the following features:

[0061] - more than 40% monounsaturated fatty acids;

[0062] - less than 40% polyunsaturated fatty acids; and

[0063] - at least 0.1% squalene.

[0064] The PQ oil preferably has the following features:

[0065] - 40% to 80%, preferably 45% to 75% monounsaturated fatty acids;

[0066] - 3% to 30%, preferably 4% to 15% polyunsaturated fatty acids; and

[0067] - 0.1% to 5.0%, preferably 0.1% to 4.0% squalene.

[0068] The RS oil may contain glycerol monooleate, glycerol dioleate and / or glycerol trioleate. The total percentage of glycerol monooleate, glycerol dioleate and glycerol trioleate in the RS oil is preferably at least 70%, at least 90%, at least 95% or at least 98%.

[0069] In embodiment (I), the RS oil may contain at least 20%, preferably at least 30%, more preferably at least 35% or at least 39% of glycerol monooleate. In some cases, the RS oil may contain at least 90%, at least 95%, at least 99% or about 100% of glycerol monooleate. Suitably, the RS oil may contain less than 90%, less than 70% or less than 50% of glycerol monooleate. In example (I), the RS oil may be glycerol monooleate, as described below.

[0070] In embodiment (I), the RS oil may contain glycerol monooleate as the highest content oil. The remainder may contain other glycerides, such as other glycerol oleates. It may contain 5% to 45% of glycerol dioleate and 5% to 45% of glycerol trioleate, where suitably, the total percentage of dioleate and trioleate is less than 65% or less than 55%.

[0071] In embodiment (II), the RS oil may contain at least 20%, preferably at least 30%, more preferably at least 40% or at least 45% of glycerol trioleate. In some cases, the RS oil may contain at least 90%, at least 95%, at least 99% or about 100% of glycerol trioleate. Suitably, the RS oil may contain less than 90%, less than 70% or less than 50% of glycerol trioleate. In example (II), the RS oil may be glycerol trioleate, as described below.

[0072] In embodiment (II), the RS oil may contain glycerol trioleate as the highest content oil. The remainder may contain other glycerides, such as other glycerol oleates. It may contain 5% to 45% of glycerol monooleate and 5% to 45% of glycerol dioleate, where suitably, the total percentage of glycerol monooleate and glycerol dioleate is less than 65% or less than 55%.

[0073] The oxygen scavenging copolymer preferably comprises an oxygen scavenging segment. The oxygen scavenging copolymer is adapted to be compatible with a packaging resin (such as polyester), so that it can be mixed with a standard packaging resin, thus minimizing costs. It is common practice to use copolymers, more specifically copolycondensates, as packaging and bottling materials. For example, even ordinary polyethylene terephthalate (PET) used for soft drink bottles often contains isophthalic acid bonds in the polymer and can thus be called a copolymer. To avoid this ambiguity, the term oxygen scavenging copolymer will be used to designate a polymer having an oxygen scavenging moiety (OSM) segment, and unmodified PET is defined as a homopolymer or copolymer without OSM segments.

[0074] The oxygen scavenging copolymer preferably comprises a polycondensate segment (and preferably, the copolymer mainly comprises a polycondensate segment) and an OSM segment (and preferably, the copolymer comprises a lower weight % of the OSM segment compared to the weight % of the polycondensate segment).

[0075] The OSM segment only needs to be present in an amount that confers the oxygen scavenging ability required for a particular application. The OSM segment preferably consists of polyolefin oligomer segments incorporated into the oxygen scavenging copolymer. However, other oxygen scavenging moiety segments, such as polypropylene oxide oligomers, methyl side chain aromatic compounds, or other segments that can be readily determined by those skilled in the art, can also be included in the oxygen scavenging copolymer.

[0076] Based on the weight of the oxygen scavenging copolymer, the oxygen scavenging copolymer preferably comprises at least 80 wt% of polyester segments (such as polyethylene terephthalate segments). As described below, the formulations of the first aspect can be mixed with unmodified polyester (such as PET) to produce packaging articles. Since the oxygen scavenging copolymer mainly comprises polyester segments, such as PET segments, the properties of the formed oxygen scavenging copolymer can remain very similar to those of the unmodified polyester (such as PET) used to form the packaging article. In addition, due to the compatibility of the oxygen scavenging copolymer with polyester (such as PET), the preferred oxygen scavenging copolymer remains an integral part of the packaging article. In fact, during the packaging manufacturing process, the oxygen scavenging copolymer can undergo transesterification with unmodified PET. This creates a packaging in which the oxygen scavenging copolymer and unmodified PET cannot be physically separated. However, due to the similarity between unmodified polyester and the oxygen scavenging copolymer, the packaging containing these two materials can be easily recycled with the general recycling stream.

[0077] Based on the weight of the copolymer, the oxygen scavenging copolymer can comprise 0.5 wt% to 20 wt%, preferably 2 wt% to 15 wt%, more preferably 5 wt% to 10 wt% of the OSM segment.

[0078] The OSM segment of the oxygen scavenging copolymer can be prepared by the reaction of an OSM segment precursor with a polyester. The OSM segment precursor can be mono-functionally capped with at least a group capable of entering into a polycondensation polymerization and / or capable of reacting with a previously formed polyester moiety to form a new covalent bond. Alternatively, the OSM segment precursor can react with a polymer end group to provide a copolymer structure. The functionally capped OSM segment precursor can be represented by Formula 1.

[0079] X-(OSM)-Y Formula 1

[0080] Bifunctionality is shown as one possibility in Formula 1, but the OSM segment precursor can be mono-functionally capped or functionalized to a degree greater than 2. Those of ordinary skill in the art will recognize that the commercial availability of the functionally capped OSM segment precursor will eliminate the need to add such functionalization. The OSM segment precursor of Formula 1 is suitably selected to be readily oxidizable at ambient temperature such that its auto-oxidation does not result in the production of significant volatile or extractable by-products. Preferred OSM segment precursors include polyolefin oligomers, polypropylene oxide oligomers, or methyl side-chain aromatic compounds as defined in US6346308 having a molecular weight of 100 to 10,000.

[0081] The OSM segment precursor can include a polybutadiene moiety. When the polybutadiene moiety is incorporated as a segment into the oxygen scavenging copolymer, suitable oxygen scavenging can be advantageously provided. Particularly preferred are OSM segments derived from unhydrogenated polybutadiene oligomers having an M W of 1000 - 3000. In Formula 1, X and Y are generally the same and can be any substance capable of entering into a polycondensation and / or transesterification reaction, such as with a polyester. A non-limiting list of possible species represented by X or Y includes OH, COOH, NH 2 , epoxides, and substituted derivatives thereof capable of undergoing stepwise reactions, condensations, and / or transesterification reactions (e.g., with a polyester).

[0082] In a preferred embodiment, the oxygen scavenging copolymer includes an OSM segment derived from a polyolefin oligomer and / or one that includes a polyolefin oligomer chain. In a particularly preferred embodiment, the oxygen scavenging copolymer includes an OSM segment derived from a polybutadiene oligomer and / or one that includes a polybutadiene oligomer chain. The above OSM segments are suitably covalently bonded to the polyester (e.g., PET) segments of the oxygen scavenging copolymer.

[0083] The oxygen scavenging copolymer may comprise moieties derived from a chain extender or crosslinking agent. Based on the weight of the oxygen scavenging copolymer, the copolymer may comprise from 0.1 wt% to 3 wt%, such as from 0.6 wt% to 1.3 wt% of such moieties. A preferred chain extender or crosslinking agent is pyromellitic dianhydride (PMDA). Inclusion of a chain extender or crosslinking agent is preferably used to prevent molecular weight degradation, thereby increasing the polymer melt viscosity and maintaining the glass transition temperature of the oxygen scavenging copolymer. A high glass transition temperature can be significant because the oxygen scavenging copolymer may exist in solid form at temperatures below the glass transition and can form films and other packaging articles that maintain their shape and mechanical integrity at near ambient temperatures (i.e., about -20°C to 60°C). The oxygen scavenging copolymer is suitably capable of scavenging oxygen at temperatures above and below its glass transition temperature.

[0084] The oxygen scavenging copolymer described above can be prepared by known batch or continuous processes. Those of ordinary skill in the art will recognize that the end functionality of the OSM segment precursor need not be the same as that of the substituted monomer, so long as the reactive incorporation proceeds. For example, in the production of PET, terephthalic acid is copolymerized with ethylene glycol. In this case, substituting the required molar equivalents of the dihydroxy terminated compound of formula 1 in the polycondensation reaction (i.e., substituting an equimolar amount of ethylene glycol) will result in a modified polyester having some OSM segments and fewer ethylene segments in the copolymer.

[0085] The preferred method of the applicant for preparing the oxygen scavenging copolymer is by reactive extrusion because it allows for greater flexibility at a later stage in the overall production scheme of oxygen scavenging bottles and packaging articles. Preparation of the copolymer by reactive extrusion is disclosed in detail in US6083585, which patent is incorporated herein by reference.

[0086] In a preferred embodiment, the oxygen scavenging copolymer can be prepared by reactive extrusion of a mixture comprising about 90 wt% PET (or a PET copolymer containing naphthalate, isophthalate, etc.) and about 10 wt% of an unhydrogenated hydroxy terminated polybutadiene oligomer. The molecular weight of the hydroxy terminated oligomer can range from 100 to 10,000. PMDA can be added to the reaction mixture in the range of about 0.5 wt% - 2.0 wt%, preferably 0.75 wt% - 1.5 wt%.

[0087] A particularly preferred oxygen scavenging copolymer can comprise from about 80 wt% to 90 wt% of PET segments, from about 5 wt% - 12 wt% of polybutadiene segments, and from 0.1 wt% - 2.0 wt% of PMDA-derived moieties.

[0088] In the oxygen-scavenging preparation, the ratio of the weight % of the oxygen-scavenging copolymer to the weight % of the oil (including each oil mentioned in (B), in particular the oils mentioned in (a) to (f) of (B)) can be at least 1.0. It can be less than 30 or less than 15 or less than 11. The ratio is preferably in the range of 1 to 30, preferably 1 to 15, more preferably 2 to 11.

[0089] In the oxygen-scavenging preparation, the sum of the weight % of the oxygen-scavenging copolymer and the weight % of the oil (including each oil mentioned in (B), in particular the oils mentioned in (a) to (f) of (B)) is suitably at least 30% by weight, preferably at least 35% by weight, more preferably at least 40% by weight.

[0090] Preferably, the preparation comprises at least 3% by weight of the oil. The preparation can comprise 3% to 25% by weight of the oil, more preferably 4% to 15% by weight of the oil. Preferably, the preparation contains up to 90% by weight of the oxygen-scavenging copolymer. The preparation can comprise 25% to 90% by weight of the oxygen-scavenging copolymer, more preferably 30% to 86% by weight of the oxygen-scavenging copolymer.

[0091] Preferably, in the preparation, the total weight percentage of olive oil, macadamia nut oil, avocado oil, patawa oil and Chilean hazelnut oil is at least 3%, and can be in the range of 3% to 20%, preferably in the range of 4% to 15%. Preferably, in the preparation, the total weight percentage of the oxygen-scavenging copolymer mentioned in (A), olive oil, macadamia nut oil, avocado oil, patawa oil and Chilean hazelnut oil is at least 35%, preferably at least 40%.

[0092] Preferably, in the preparation, the total weight percentage of olive oil and macadamia nut oil is at least 3%, and can be in the range of 3% to 20%, preferably in the range of 4% to 15%. Preferably, in the preparation, the total weight percentage of the oxygen-scavenging copolymer mentioned in (A), olive oil and macadamia nut oil is at least 35%, preferably at least 40%.

[0093] Preferably, in the preparation, the total weight percentage of the oxygen-scavenging copolymer mentioned in (A) is at least 35%, preferably at least 40%.

[0094] The oxygen-scavenging preparation can also contain a transition metal, such as a transition metal salt. The transition metal can be cobalt, such as cobalt derived from cobalt stearate.

[0095] The preparation may include less than 1.0 wt%, preferably less than 0.6 wt%, and more preferably less than 0.3 wt% of a cobalt moiety. The preparation may include at least 0.05 wt%, preferably at least 0.1 wt%, and more preferably at least 0.15 wt% of a cobalt moiety. The preparation may include 0.05 wt% to 0.4 wt% of a cobalt moiety.

[0096] The preparation for scavenging oxygen may include:

[0097] - 25 wt% to 90 wt% (preferably 30 wt% to 86 wt%) of an oxygen scavenging copolymer, which preferably contains polybutadiene segments;

[0098] - at least 3 wt% (preferably 3 wt% to 20 wt%) of one or more of the oils described in (B) above (especially the oils mentioned in (a) to (f) of (B)); and optionally (but preferably),

[0099] - at least 0.05 wt% (preferably 0.05 wt% to 0.4 wt%) of a cobalt moiety.

[0100] The preparation for scavenging oxygen may include:

[0101] - 25 wt% to 90 wt% (preferably 30 wt% to 86 wt%) of an oxygen scavenging copolymer, which preferably comprises polybutadiene segments;

[0102] - olive oil and / or macadamia nut oil, wherein the total weight percentage of olive oil and macadamia nut oil in the preparation is at least 3 wt% (preferably 3 wt% to 20 wt%); and optionally (but preferably),

[0103] - at least 0.05 wt% (preferably 0.05 wt% to 0.4 wt%) of a cobalt moiety.

[0104] The preparation for scavenging oxygen may include:

[0105] - 25 wt% to 90 wt% by weight (preferably 30 wt% to 86 wt%) of an oxygen scavenging copolymer, which preferably comprises polybutadiene segments;

[0106] - at least 3 wt% (preferably 3 wt% - 20 wt%) of olive oil; and optionally (but preferably),

[0107] - at least 0.05 wt% (preferably 0.05 wt% to 0.4 wt%) of a cobalt moiety.

[0108] The oxygen scavenging formulation can be provided in a range of different forms. In one embodiment, the formulation can comprise a single substance that contains the above components, where the single substance can be a substantially homogeneous mixture or a non-homogeneous mixture. The single substance can be in solid form, such as in particulate form. In such a case, individual particles can comprise the oxygen scavenging copolymer and the oil; and suitably, each particle in the single substance is substantially as described. In another embodiment, the oxygen scavenging formulation can comprise separate first and second components, where the first component can comprise the oxygen scavenging copolymer and optionally the transition metal (if provided); and the second component comprises the oil. In such a case, when the first and second components are contacted with a packaging resin (such as a polyester packaging resin), they can bind together, which packaging resin is designed to provide most of the structure of the packaging material, where the packaging material uses the oxygen scavenging formulation. In another embodiment, the formulation can comprise a blend that contains a first component, where the first component can comprise the oxygen scavenging copolymer and optionally the transition metal (if provided); and a second component that contains the oil, which oil is optionally combined with a carrier (such as a solid carrier for the oil). The blend can be a salt and pepper blend. It can comprise a first solid masterbatch that contains the oxygen scavenging polymer (and optionally a catalyst); and a second solid masterbatch that contains the oil and a solid carrier (such as a polyester, such as PET); where the first masterbatch and the second masterbatch (such as in solid or particulate form) are blended to define a salt and pepper blend.

[0109] Alternatively, the oxygen scavenging formulation can comprise a liquid, such as a liquid masterbatch.

[0110] The formulation, such as one or more of the masterbatches mentioned, can contain additional additives, such as colorants.

[0111] The formulation can be added to a packaging resin (such as a polyester, such as PET) to define a composition that can (such as by melt processing) form a packaging article, such as a preform for a bottle.

[0112] In a second aspect, the invention extends to a composition that comprises a packaging resin (such as a polyester, such as PET); and

[0113] (A) an oxygen scavenging copolymer as described in the first aspect; and

[0114] (B) an oil as described in the first aspect, which is selected from, for example:

[0115] (a) olive oil;

[0116] (b) Macadamia nut oil;

[0117] (c) Avocado oil;

[0118] (d) Patagua oil;

[0119] (e) Chilean hazelnut oil;

[0120] (f) PQ oil as described in the first aspect; and

[0121] (g) RS oil as described in the first aspect.

[0122] The composition can be formed in a melt processing apparatus, for example, in an injection molding apparatus. A preform for a packaging article, such as a container (e.g., a bottle, such as a stretch blow molded bottle), can be made of the composition.

[0123] The composition can comprise:

[0124] (I) A packaging resin (e.g., a polyester, such as PET);

[0125] (II) An oxygen scavenging copolymer as described in the first aspect;

[0126] (III) An oil as described in the first aspect (B) (particularly the oils mentioned in (a) to (f) of (B)).

[0127] The composition can comprise:

[0128] - At least 93 wt%, for example at least 95 wt%, of a packaging resin (e.g., a polyester, such as PET);

[0129] - Less than 7 wt% (preferably less than 5 wt% or less than 4 wt%) of an oxygen scavenging copolymer as described in the first aspect;

[0130] - Less than 2.0 wt% (preferably less than 1.0 wt% or less than 0.6 wt%) of an oil as described in the first aspect (B) (particularly the oils mentioned in (a) to (f) of (B)).

[0131] The composition can comprise at least 0.5 wt% (preferably at least 1.0 wt%) of an oxygen scavenging copolymer as described in the first aspect; and at least 0.1 wt% (preferably at least 0.2 wt%) of an oil as described in the first aspect (B) (particularly the oils mentioned in (a) to (f) of (B)).

[0132] The composition can include:

[0133] - At least 93 wt%, for example at least 95 wt%, of a packaging resin (e.g., a polyester, such as PET);

[0134] - An oxygen scavenging copolymer as described in the first aspect, less than 7 wt% (preferably less than 5 wt% or less than 4 wt%);

[0135] - Olive oil, macadamia nut oil, avocado oil, patawa oil, and / or Chilean hazelnut oil;

[0136] wherein the total weight percentage of olive oil, macadamia nut oil, avocado oil, patawa oil, and Chilean hazelnut oil in the composition is less than 2.0 wt% (preferably less than 1.0 wt% or less than 0.6 wt%).

[0137] The composition may comprise at least 0.5 wt% (preferably at least 1.0 wt%) of the oxygen scavenging copolymer as described in the first aspect; the total weight percentage of olive oil, macadamia nut oil, avocado oil, patawa oil, and Chilean hazelnut oil is at least 0.1 wt% (preferably at least 0.2 wt%).

[0138] The composition may comprise:

[0139] - At least 93 wt%, such as at least 95 wt%, of a packaging resin (e.g., polyester, such as PET);

[0140] - An oxygen scavenging copolymer as described in the first aspect, less than 7 wt% (preferably less than 5 wt% or less than 4 wt%);

[0141] - Less than 2.0 wt% (preferably less than 1.0 wt% or less than 0.6 wt%) of olive oil.

[0142] The composition may comprise at least 0.5 wt% (preferably at least 1.0 wt%) of the oxygen scavenging copolymer as described in the first aspect; and at least 0.1 wt% (preferably at least 0.2 wt%) of olive oil.

[0143] The composition preferably comprises a transition metal catalyst, particularly a cobalt catalyst. The composition preferably comprises at least 0.001 wt%, preferably at least 0.002 wt%, of a cobalt moiety. The composition preferably comprises less than 0.05 wt%, preferably less than 0.01 wt%, of a cobalt moiety. The composition may comprise a cobalt compound, such as cobalt stearate. The composition preferably comprises at least 0.01 wt%, preferably at least 0.02 wt%, of the cobalt compound. The composition preferably comprises less than 0.5 wt%, preferably less than 0.1 wt%, of the cobalt compound.

[0144] Suitably, the composition comprises less than 5% by weight, preferably less than 1% by weight, more preferably about 0% by weight of polyamide; and / or comprises less than 5% by weight, preferably less than 1% by weight, more preferably about 0% by weight of MXD6. Advantageously, by avoiding any significant amount of polyamide and / or MXD6 in the composition (which suitably defines the packaging material, such as a bottle), the packaging material (such as a bottle) can be easily recycled together with the main recycling stream without any significant impact on the optical properties of the recycling stream, while the oxygen scavenging capacity of the formulation and / or composition is at a very high level, thereby providing long-term protection against oxygen spoilage for any contents of the packaging material (such as a bottle).

[0145] The composition of the second aspect can define a packaging material. The packaging material can define or be a component of a container. The container can include an extruded or thermoformed article, such as a tray, such as a tray for food applications. Alternatively, the container can be a preform (suitably a tubular article which is stretch blow molded to define a bottle) or a bottle itself, such as a bottle. Preferred containers, such as preforms or bottles, are single-layer preforms or bottles. Preferably, the container, such as a preform or a bottle (suitably not including any of its closures) comprises at least 90% by weight, more preferably at least 95% by weight, especially at least 99% by weight of the composition.

[0146] According to a third aspect of the present invention, there is provided a method of manufacturing a packaging article, such as a container, such as a preform of a bottle or the bottle itself, the method comprising:

[0147] (I) contacting an oxygen scavenging copolymer, an oil as described in (B) of the first aspect, with a packaging resin (such as a polyester, such as PET); and

[0148] (II) subjecting the components mentioned in (I) to a melt process to define the packaging article.

[0149] The oxygen scavenging copolymer, the oil and the packaging resin can be as described in the first aspect or the second aspect independently.

[0150] The packaging article can have a composition as described in the second aspect.

[0151] The container can be as described in the second aspect.

[0152] The method can include contacting a formulation as described in the first aspect with a packaging resin (such as a polyester, such as PET); and suitably subjecting the mixture to a melt process as in (II).

[0153] The method may comprise selecting at least 95% by weight, preferably at least 97% by weight, of a packaging resin (such as a polyester, such as PET), relative to the weight % of the packaging article (excluding any closures thereof, defined as 100% by weight). The balance of the packaging article (up to 100% by weight) may be defined by the formulation of the first aspect.

[0154] The method is preferably a method of manufacturing a packaging article such as a container, such as a preform of a bottle or the bottle itself, which can be directly recycled with substantially pure PET according to the European PET Bottle Platform (EPBP) protocol. For example, the packaging article can be evaluated as described in Examples 21 to 23.

[0155] In a fourth aspect, the invention extends to a method of recycling a packaging article, the method comprising:

[0156] - selecting a packaging article as described in the second aspect and / or a packaging article made as described in the third aspect; and

[0157] - contacting the packaging article or fragments thereof with other PET to prepare a mixture.

[0158] The mixture may comprise 5 wt% to 50 wt% of the packaging article or fragments thereof and 50 wt% to 95 wt% of other PET. The other PET may be PET without colorants. It preferably does not contain an oxygen scavenging compound. It may be virgin PET.

[0159] In a fifth aspect, the invention extends to recycled PET prepared as described in the fourth aspect.

[0160] In a sixth aspect, there is provided the use of a formulation as described in the first aspect for scavenging oxygen and preparing a composition which can be recycled with virgin PET to prepare a mixture having a b* less than a predetermined level. b* can be evaluated as described in Examples 21 to 23. In a preferred embodiment, the difference in b* between virgin PET and a composite mixture comprising 25 wt% of the composition and 75 wt% of virgin PET is preferably less than 1.5 b* units, as evaluated in Runs 3 and Examples 21 to 23.

[0161] Any aspect of any invention described herein can be combined with any other aspect of any invention described herein, with appropriate modifications if necessary. BRIEF DESCRIPTION OF THE DRAWINGS

[0162] Specific embodiments of the invention will now be described by way of example with reference to the accompanying drawings, in which:

[0163] Figure 1 show the results of the Ingress oxygen scavenging tests of Examples 3 to 6;

[0164] Figure 2 Shows the results of the permeation oxygen scavenging tests of Examples 8 to 10;

[0165] Figure 3 Shows the results of the Pulldown oxygen scavenging tests of Examples 12 to 15;

[0166] Figure 4 Shows the results of the permeation oxygen scavenging tests of Examples 17 to 19;

[0167] Figure 5 Shows the laboratory color values of the plaques of Examples 21 and 22;

[0168] Figure 6 Shows the results of the Pulldown oxygen scavenging tests of Examples 24 to 27;

[0169] Figure 7 Shows the results of the permeation oxygen scavenging tests of Examples 28 to 30, 33 and 35; and

[0170] Figure 8 Shows the results of the Pulldown oxygen scavenging tests of Examples 28 to 35. Detailed Description

[0171] The following materials are mentioned below:

[0172] AMOSORB (trademark) 4020G - A commercially available non-nylon-based low haze oxygen scavenger for polyethylene terephthalate (PET). This material is as described in WO2003 / 035486A1, the content of which is incorporated herein by reference as it describes an oxygen scavenger referred to as "oxygen scavenging concentrate (OS concentrate)" in the above publication.

[0173] AMOSORB (trademark) 4020R - A commercially available non-nylon-based low haze oxygen scavenger for polyethylene terephthalate (PET), similar to AMOSORB 4020G and compliant with WO2003 / 035486A1, but optimized for oxygen scavenging in up to 100% recycled PET (rPET).

[0174] PET-X - Refers to Equippolymers C93, a polyethylene terephthalate (PET) bottle grade polymer.

[0175] Olive oil - Unrefined olive oil purchased from Sigma-Aldrich.

[0176] Macadamia nut oil - Extra virgin cold pressed macadamia nut oil sold under the Pure South Press brand.

[0177] Avocado oil - Extra virgin cold-pressed avocado oil sold under the Mokhado brand.

[0178] Patawa oil - Unrefined cold-pressed patawa oil sold under the Nativilis brand.

[0179] Chilean hazelnut oil - Organic cold-pressed unrefined Chilean hazelnut oil sold under the Biopurus brand.

[0180] Monoolein - Refers to glycerol monooleate from Merck, which contains glycerol monooleate as the component with the highest content (about 43%) and other glycerol oleates (about 23% of glycerol dioleate and about 32% of glycerol trioleate).

[0181] Triolein - Refers to glycerol trioleate from Tokyo Chemical Industries, which contains more than 50% of glycerol trioleate, and the balance of glycerol monooleate and glycerol dioleate.

[0182] Evaluation 1 - "Pulldown" oxygen scavenging test procedure

[0183] In the "Pulldown" test method, the oxygen scavenging additives incorporated in the bottle wall can be evaluated by filling the bottle with oxygenated water and monitoring the consumption of the dissolved oxygen content over time.

[0184] In this method, the bottles to be evaluated and the water (before introduction into the bottles) are stored in a temperature-controlled environment (21 °C). Known active standards and blank controls (native PET) are evaluated together with the test samples to verify the test method setup. Note: If oxygen consumption is observed in the blank native PET bottles during the test (e.g., for a test exceeding 14 days), there may be algae / microorganisms in the water, and the sample test must be repeated. This may occur if the added bactericide is insufficient. 2 Consumption, there may be algae / microorganisms in the water, and the sample test must be repeated. This may occur if the added bactericide is insufficient.

[0185] Then, the method may include the following steps:

[0186] (i) Fill a water bucket with tap water and a bactericide (polyhexamethylene biguanide PHMB) (about 1 ml of bactericide dissolved in 5 liters of water), and cover the lid. Place the water in the temperature control room for about 24 hours to allow the temperature and the dissolved oxygen content to reach equilibrium.

[0187] (ii) Make stretch blow molded bottles containing any oxygen scavenging additives one day before or on the day of the test. The bottles are stored in sealed aluminum bags and purged with nitrogen before use.

[0188] (iii) Before filling the bottle with the prepared biocide water, use tweezers or other such tools to attach the opTech Platinum sensor point (part of the oxygen measurement system from Ametek Mocon) to the inner wall of the bottle. Then the following steps are taken:

[0189] (a) Each bottle is filled with the prepared water / biocide, leaving no headspace.

[0190] (b) Place a bottle cap on each bottle and use a cap torque meter to tighten it to the recommended torque (Nm), depending on the cap specification.

[0191] (c) Once all the bottles to be evaluated are ready, an initial reading of the dissolved oxygen content is taken. This should be approximately 10 ppm.

[0192] (d) The bottles are stored in a temperature control room and measurements are taken every 2 - 3 days for 14 days.

[0193] (e) Further measurements can be taken after the specified 14 days if required.

[0194] Evaluation 2 - “Ingress” Oxygen Scavenging Test Procedure

[0195] In the “Ingress” test method, the oxygen scavenging additive in the bottle wall can be evaluated by filling the bottle with deoxygenated water and monitoring the increase in the dissolved oxygen content in the water over time (entering through the bottle wall).

[0196] As a standard method for measuring scavenging activity, measurements can be taken periodically every few days (up to 14 days) and then every few weeks thereafter. The measurement frequency depends on the expected shelf life that the additive can extend. The test is complete when the dissolved oxygen reaches 3 ppm.

[0197] Then, the method can include the following steps:

[0198] (i) A glove box apparatus is required, which includes a water tank / container, a nitrogen supply, and a vacuum system. Nitrogen should be supplied to the water tank to bubble through the water. The glove box should also include a weighing scale, bottle caps, a torque meter, and a dissolved oxygen sensor (with the probe inserted into the water tank).

[0199] (ii) Stretch blow molded bottles containing any deoxygenating additive are made one day before or on the same day as the test. Use tweezers or other similar tools to attach an appropriate oxygen measurement sensor (such as the OpTech Platinum sensor point) to the inside of the bottle sample. The bottles are stored in sealed aluminum bags and purged with nitrogen before use.

[0200] (iii) Known active standards (e.g., 3% 4020G in virgin PET) and blank controls (virgin PET) can be evaluated with the test samples to verify the test method setup. Note: If scavengers are observed in the blank virgin PET bottles, there may be algae / microorganisms in the water and the sample test must be repeated. This can occur if insufficient biocide is added.

[0201] (iv) The water tank / container inside the glove box is filled with tap water and biocide (polyhexamethylene biguanide PHMB) (approx. 1 mL of biocide dissolved in 5 L of water).

[0202] (v) All equipment and sample bottles are placed inside the glove box before sealing.

[0203] (vi) Nitrogen is bubbled through the water to the maximum safe pressure and then evacuated to the minimum maximum safe pressure. This process is repeated several times until the dissolved oxygen content read by the oxygen sensor inserted into the water tank is below 300 ppb.

[0204] (vii) Ensure there is ambient pressure inside the glove box (there will be a headspace) before nominally filling the bottles with water / biocide from the tank / container.

[0205] (viii) Place a bottle cap on each bottle and tighten it to the recommended torque (Nm) using a cap torque meter, depending on the cap specification.

[0206] (ix) After all samples are prepared, the glove box can be opened, the samples removed, and an initial reading of the dissolved O 2 content taken. This should be less than 300 ppb (parts per billion).

[0207] (x) The samples are stored in a temperature-controlled chamber and measured every 2 - 3 days for 14 days and then every few weeks thereafter.

[0208] Evaluation 3 - Recyclability Evaluation

[0209] A test has been developed to replicate the European PET Bottle Platform (EPBP) test procedure. The test consists of the following steps:

[0210] (i) The preforms to be evaluated for recyclability are ground and the ground samples (referred to as "additive flakes" as it typically includes oxygen scavenging additives) are crystallized in a convection oven at 155 °C for 60 minutes.

[0211] (ii) The additive flakes are placed in an adsorption oven dryer for at least 4 hours until the moisture content of the sample is below 50 ppm.

[0212] (iii) Grind the preform made of virgin PET-X. The ground sample (referred to as "virgin flakes") is crystallized in a convection oven at 155 °C for 60 minutes.

[0213] (iv) Place the virgin flakes in an adsorption oven dryer for at least 4 hours until the moisture content of the sample is below 50 ppm.

[0214] (v) Mix the additive flakes (25 wt%) and the virgin flakes (75 wt%), extrude and pelletize them on a single-screw extruder at 285 °C (referred to as "mixed pellets").

[0215] (vi) Crystallize the mixed pellets in a convection oven at 155 °C for 60 minutes. Place the pellets in an adsorption oven dryer for at least 4 hours until the moisture content of the sample is below 50 ppm.

[0216] (vii) Mold the crystallized mixed pellets together with virgin PET-X (50 wt%) into a 3-mm substrate on an injection molding machine (referred to as "additive substrate").

[0217] (viii) Measure the color values of the additive substrate.

[0218] (ix) Produce separate pellets by extruding virgin flakes (100 wt%) on a single-screw extruder at 285 °C and then pelletizing. Crystallize and dry the pellets as described above, and then mold them into a 3-mm substrate on an injection molding machine (referred to as "virgin substrate").

[0219] (x) Calculate ΔL*, Δa*, and Δb* between the additive substrate and the virgin substrate. If Δb* is less than 1.5 units, the preform is considered suitable for recycling with virgin PET.

[0220] The following examples illustrate the preferred embodiments of the present invention.

[0221] Example 1 - General procedure for preparing preforms

[0222] Preforms with a neck diameter of 38 mm and a weight of 25 g were manufactured in a Husky GL160 injection molding machine equipped with a two-cavity mold. PET-X pre-dried to a moisture content below 50 ppm was manually pre-mixed with the test component and manually added to the hopper installed above the feed inlet of the injection molding machine. Standard PET injection molding process was used to produce the preforms.

[0223] Example 2 - Producing bottles from preforms

[0224] The preforms prepared as described in Example 1 were stretch blow molded into 1-liter cylindrical bottles using a Sidel SB01 blow molding machine. A standard blowing process was employed. Before the preforms left the oven and entered the blow mold, the total power percentage of the heating oven was adjusted to bring the preform temperature to 115 °C - 120 °C. This is referred to as the blow molding temperature.

[0225] Examples 3 to 6 - Preparation of bottles to be evaluated

[0226] Following the general procedure described in Example 1, preforms with the following composition were prepared (prepared by tumbling and mixing the specified components):

[0227]

[0228] As in Example 2, the preforms were made into bottles.

[0229] Example 7 - Evaluation of the bottles of Examples 3 to 6

[0230] The bottles of Examples 3 to 6 were evaluated as described in Evaluation 2, and the results are as Figure 1 shown:

[0231] (i) The bottles of Example 3 without any oxygen scavenger showed a substantially linear increase in dissolved oxygen and can be used as a benchmark for evaluating other examples.

[0232] (ii) Compared to the bottles of Example 3, the bottles of Example 4 showed a significant scavenging effect, which was expected due to the addition of a commercially available oxygen scavenger.

[0233] (iii) Compared to the bottles of Example 4, the bottles of Example 5 showed a significant improvement in oxygen scavenging.

[0234] (iv) Compared to the bottles of Example 5, the bottles of Example 6 contained a higher level of olive oil, providing excellent oxygen scavenging effects, with surprisingly little dissolved oxygen observed in the first 180 days and very low dissolved oxygen levels thereafter.

[0235] The observations regarding the bottles of Example 5 and Example 6 can be utilized in various ways. For example, a lower amount of the relatively expensive AMOSORB 4020G can be used in the bottles to support the use of the cheaper olive oil, and a similar level of oxygen scavenging effect can be achieved, as shown in Examples 8 to 10. Alternatively, compared to bottles containing the same amount of AMOSORB 4020G, olive oil can be used to provide a higher level of oxygen scavenging (thus extending the shelf life).

[0236] Examples 8 to 10 - Preparation of bottles to be evaluated to illustrate the incorporation of olive oil.

[0237] Following the general procedure described in Example 1, a preform having the following composition was prepared:

[0238]

[0239] As described in Example 2, the preform was made into a bottle.

[0240] Example 11 - Evaluation of the bottles of Examples 8 to 10.

[0241] The bottles of Examples 8 to 10 were evaluated as described in Evaluation 2, and the results are as Figure 2 shown. The results indicate that when olive oil is included, the amount of AMOSORB 4020G can be halved (see Example 10), and the oxygen scavenging effect is still superior to that of Example 9 which does not contain olive oil.

[0242] Examples 12 to 15 - Preparation of bottles to be evaluated to further illustrate the effect of adding olive oil.

[0243] Following the general procedure described in Example 1, a preform having the following composition was prepared:

[0244]

[0245] As described in Example 2, the preform was made into a bottle.

[0246] Example 16 - Evaluation of the bottles of Examples 12 to 15

[0247] The bottles were evaluated as described in Evaluation 1, and the results are as Figure 3 shown. These results indicate that the incorporation of olive oil alone (Example 13a) does not result in significant scavenging activity (compare Examples 12 and 13a, but note that Figure 3 the dashed line representing Example 13a is obscured. For the avoidance of doubt, the line would normally extend at the zero value on the y-axis). Further, the addition of olive oil and 45 ppm cobalt catalyst (Example 13b) does not result in significant scavenging activity (compare Examples 12 and 13b). However, comparison of Examples 14 and 15 shows that the combination of AMOSORB 4020R and olive oil has a synergistic effect. When olive oil is added, the scavenging effect is significantly enhanced, even greater than the enhancement between Examples 12 and 14.

[0248] Examples 17 to 19 - Preparation of bottles to be evaluated to illustrate the incorporation of macadamia nut oil.

[0249] Following the procedure described in Examples 3 to 6, a preform having the following composition was prepared:

[0250]

[0251] As described in Example 2, the preform is made into a bottle.

[0252] Example 20 - Evaluation of the bottles of Examples 17 to 19

[0253] The bottles were evaluated as described in Evaluation 2, and the results are as Figure 4 shown:

[0254] (i) The bottle of Example 17 without any oxygen scavenger can be used as a reference.

[0255] (ii) Compared with the bottle of Example 17, the bottle of Example 18 showed a significant scavenging effect because it contained a commercially available oxygen scavenger.

[0256] (iii) Compared with the bottle of Example 18, the bottle of Example 19 showed a significant improvement in oxygen scavenging.

[0257] Examples 21 and 22 - Evaluation of the recyclability of formulations containing olive oil

[0258] According to the general procedure described in Evaluation 3, as described in (vii) of Evaluation 3, a substrate was prepared from 75 wt% PET-X using a preform (the recyclability of which was to be evaluated) having the components shown in the following table.

[0259]

[0260] The substrates prepared from Examples 21 and 22 will be referred to as Example 21 (substrate) and 22 (substrate) to distinguish the bottle flakes themselves.

[0261] The oxygen scavenging ability and recyclability of the substrates were evaluated. It was found that the formulations of Examples 21 and 22 had comparable oxygen scavenging abilities.

[0262] Figure 5 The color evaluation of the substrates of Example 21 (substrate) and Example 22 (substrate) described in Evaluation 3 is shown. In the figure, it can be noted that the Δb* of Example 21 (substrate) did not pass the EPBP test, so the flakes of Example 21 are not suitable for recycling with virgin PET. In contrast, for Example 22 (substrate), the flakes of Example 22 passed all EPBP tests and are therefore suitable for recycling with virgin PET.

[0263] Example 23 - Evaluation of the recyclability of a formulation containing macadamia nut oil

[0264] According to the procedure described in Example 20, the formulation containing macadamia nut oil was evaluated and found that the formulation not only provided a high level of oxygen scavenging but also had improved recyclability compared to a formulation having an equivalent oxygen scavenging ability obtained by using AMOSORB 4020G alone.

[0265] Examples 24 to 27 - Evaluation of other oils

[0266] Following the general procedure described in Example 1, preforms and bottles having the following compositions were prepared:

[0267]

[0268] The bottles were evaluated as described in Evaluation 1, and the results are as Figure 6 shown Figure 6 showing an enhanced oxygen scavenging effect when the specified oil is combined with AMOSORB 4020R.

[0269] Examples 28 to 35 - Preparation of bottles to be evaluated to illustrate the addition of monoolein or triolein.

[0270] Following the procedure described in Examples 3 to 6, preforms having the following compositions were prepared:

[0271]

[0272] The preforms were formed into bottles as described in Example 2.

[0273] Example 35 - Evaluation of the bottles of Examples 28 to 35

[0274] The bottles were evaluated as described in Evaluations 1 and 2, and the results are as shown in Figure 7 and Figure 8 respectively.

[0275] Figure 7 It was shown that:

[0276] (i) The bottle of Example 28 having only the oxygen scavenger can be used as a reference.

[0277] (ii) The bottle of Example 29 containing monoolein in addition to the oxygen scavenger of Example 28 showed improved oxygen scavenging compared to Example 28.

[0278] (iii) The bottle of Example 30 containing triolein in addition to the oxygen scavenger of Example 28 showed significantly improved oxygen scavenging compared to Example 28.

[0279] (iv) The bottle of Example 33 having only the oxygen scavenger can be used as a reference.

[0280] (v) The bottle of Example 34 containing monoolein in addition to the oxygen scavenger of Example 33 showed improved oxygen scavenging compared to Example 33.

[0281] (vi) Example 35 bottles containing triolein in addition to the oxygen scavenger of Example 33 showed significantly improved oxygen scavenging compared to Example 33.

[0282] Figure 8 showed improvements similar to Figure 7 the oxygen scavenging effect described, and in addition, when the amount of monoolein or triolein was increased from 0.3 wt% to 0.6 wt%, the scavenging effect was also improved (compare Example 31 with Example 29; compare Example 32 with Example 30).

[0283] The present invention is not limited to the details of the above embodiments. The present invention extends to any novel feature or any combination of novel features among the features disclosed in this specification (including any accompanying claims, abstract, and drawings), or to any inventive step among the steps of any method or process disclosed, or to any combination of inventive steps.

Claims

1. An oxygen-scavenging preparation, the preparation comprising: (A) an oxygen-scavenging copolymer; and (B) an oil, wherein the oil is selected from: (a) olive oil; (b) macadamia nut oil; (c) avocado oil; (d) patawa oil; (e) Chilean hazelnut oil; (f) PQ oil, which comprises: (i) less than 25% linoleic acid, and / or (ii) less than 10% linolenic acid, and / or (iii) more than 40% oleic acid, and / or (iv) more than 40% monounsaturated fatty acids, and / or (v) less than 40% polyunsaturated fatty acids, and / or (vi) at least 0.1% squalene; (g) RS oil, which comprises at least 20% glyceryl oleate.

2. The preparation according to claim 1, wherein the oil is selected from any of the oils (a) to (f) in (B).

3. The preparation according to claim 1 or 2, wherein: the PQ oil comprises less than 25%, preferably less than 15%, more preferably less than 10% linoleic acid; and the PQ oil comprises at least 1%, preferably at least 3% linoleic acid; and / or the PQ oil comprises less than 10%, preferably less than 5% linolenic acid; and the PQ oil comprises at least 0.1%, preferably at least 0.3% linolenic acid.

4. The preparation according to any one of the preceding claims, wherein: the PQ oil comprises at least 40%, preferably at least 45%, more preferably at least 50 wt% oleic acid; and the PQ oil comprises less than 80%, preferably less than 70% oleic acid.

5. The preparation according to any one of the preceding claims, wherein: the PQ oil comprises at least 40%, preferably at least 50%, more preferably at least 60% monounsaturated fatty acids; and the PQ oil comprises less than 85%, preferably less than 80% monounsaturated fatty acids.

6. The preparation according to any one of the preceding claims, wherein: the PQ oil comprises less than 50%, preferably less than 30%, more preferably less than 15%, especially less than 10% polyunsaturated fatty acids; and the PQ oil comprises at least 2% polyunsaturated fatty acids.

7. The preparation according to any one of the preceding claims, wherein: the PQ oil comprises less than 30%, preferably less than 20%, more preferably less than 15%, especially less than 10% compounds having more than two double bonds.

8. The preparation according to any one of the preceding claims, wherein: in the PQ oil, the total percentage of linoleic acid and linolenic acid is less than 25%, preferably less than 17%, more preferably less than 12%, especially less than 6%; and the total is at least 1% or at least 2%.

9. The preparation according to any one of the preceding claims, wherein the PQ oil has the following characteristics: - 1% to 15%, preferably 2% to 10% linoleic acid; - 0.1% to 10%, preferably 0.1% to 5% linolenic acid; and - 40% to 80%, preferably 45% to 70% oleic acid.

10. The preparation according to any one of the preceding claims, wherein the PQ oil has the following characteristics: - 40% to 80%, preferably 45% to 75% monounsaturated fatty acids; - 3% to 30%, preferably 4% to 15% of polyunsaturated fatty acids; and - 0.1% to 5.0%, preferably 0.1% to 4.0% of squalene.

11. The preparation according to any one of the preceding claims, wherein the oxygen scavenging copolymer comprises a polycondensate chain segment and an oxygen scavenging moiety (OSM) chain segment, wherein the OSM chain segment is composed of polyolefin oligomer chain segments incorporated into the oxygen scavenging copolymer, wherein, optionally, based on the weight of the oxygen scavenging copolymer, the oxygen scavenging copolymer comprises at least 80 wt% of polyester chain segments, and based on the weight of the oxygen scavenging copolymer, the oxygen scavenging copolymer comprises 0.5 wt% to 20 wt%, preferably 2 wt% to 15 wt%, more preferably 5 wt% to 10 wt% of OSM chain segments.

12. The preparation according to any one of the preceding claims, wherein the oxygen scavenging copolymer comprises an OSM chain segment derived from polybutadiene oligomers and / or it comprises polybutadiene oligomer chains.

13. The preparation according to any one of the preceding claims, wherein the oxygen scavenging copolymer comprises about 80 wt% to 90 wt% of PET chain segments, about 5 wt% - 12 wt% of polybutadiene chain segments and 0.1 wt% - 2.0 wt% of PMDA-derived moieties.

14. The preparation according to any one of the preceding claims, wherein, in the preparation for scavenging oxygen, the ratio of the weight percentage of the oxygen scavenging copolymer to the weight percentage of the oil is in the range of 1 to 30, preferably 2 to 11.

15. The preparation according to any one of the preceding claims, wherein the preparation for scavenging oxygen comprises: - 25 wt% to 90 wt% (preferably 30 wt% to 86 wt%) of an oxygen scavenging copolymer, which comprises polybutadiene chain segments; - olive oil and / or macadamia nut oil, wherein the total weight percentage of olive oil and macadamia nut oil in the preparation is at least 3 wt% (preferably 3 wt% to 20 wt%); and optionally (but preferably), - at least 0.05 wt% (preferably 0.05 wt% to 0.4 wt%) of a cobalt moiety.

16. The preparation according to any one of the preceding claims, wherein the preparation comprises the RS oil, and the RS oil comprises glycerol monooleate, glycerol dioleate and / or glycerol trioleate, wherein preferably, the total percentage of glycerol monooleate, glycerol dioleate and glycerol trioleate in the RS oil is at least 70% or at least 95%.

17. A composition, which comprises a packaging resin (such as polyester, such as PET); and (A) an oxygen scavenging copolymer as described in any one of the preceding claims; and (B) an oil as described in any one of the preceding claims, for example, the oil is selected from: (a) olive oil; (b) macadamia nut oil; (c) avocado oil; (d) patawa oil; (e) Chilean hazelnut oil; and (f) PQ oil as described in any one of the preceding claims.

18. The composition according to claim 17, which comprises: - at least 93 wt% (such as at least 94 wt%) of a packaging resin (such as polyester, such as PET); - An oxygen scavenging copolymer as described in any one of claims 1 to 15, less than 7 wt% (preferably less than 5 wt% or less than 4 wt%); - An oil as described in any one of claims 1 to 15, less than 2.0 wt% (preferably less than 1.0 wt% or less than 0.6 wt%); wherein, Optionally, the composition comprises at least 0.5 wt% (preferably at least 1.0 wt%) of the oxygen scavenging copolymer; and at least 0.1 wt% (preferably at least 0.2 wt%) of the oil.

19. The composition according to claim 17 or 18, wherein the composition comprises at least 0.5 wt% (preferably at least 1.0 wt%) of an oxygen scavenging copolymer as described in any one of claims 1 to 15; and the total weight percentage of olive oil, macadamia nut oil, avocado oil, patawa oil and Chilean hazelnut oil is at least 0.1 wt% (preferably at least 0.2 wt%).

20. The composition according to any one of claims 17 to 19, wherein the composition comprises less than 1 wt%, more preferably about 0 wt% of polyamide; and / or comprises less than 1 wt%, more preferably about 0 wt% of MXD6.

21. The composition according to any one of claims 17 to 20, wherein the composition defines or is a component of a container, such as a preform of a bottle (e.g., a monolayer preform) or a bottle.

22. A method for manufacturing a packaging article such as a container, such as a preform of a bottle or the bottle itself, the method comprises: (I) contacting an oxygen scavenging copolymer as described in any one of claims 1 to 16, an oil as described in any one of claims 1 to 16 with a packaging resin (e.g., a polyester, such as PET); and (II) melt-processing the components mentioned in (I) to define the packaging article.

23. A method for recycling a packaging article, the method comprises: - selecting a packaging article as described in any one of claims 17 to 21 and / or a packaging article made as described in claim 22; and - contacting the packaging article or its fragments with other PET to prepare a mixture.

24. The method according to claim 23, wherein the mixture comprises 5 wt% to 50 wt% of the packaging article or its fragments and 50 wt% to 95 wt% of virgin PET.

25. A recycled PET prepared according to claim 23 or 24.

26. Use of a formulation as described in any one of claims 1 to 16 for scavenging oxygen and preparing a composition that can be recycled with virgin PET to prepare a mixture with b* less than a predetermined level.

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