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 scavenging oxygen, particularly but not exclusively to scavenging oxygen from packaging such as bottles. Preferred embodiments relate to formulations for scavenging oxygen, their incorporation into compositions and their use. Background Art

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

[0003] There is a trade-off between enhancing oxygen barrier properties and negatively affecting the high clarity of neat PET. Undesirably, increasing the loading level of oxygen scavengers in PET to improve oxygen barrier properties tends to reduce the clarity 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, it is not desirable to directly recycle a monolayer container comprising PET / MXD-6 and substantially pure PET, since it would adversely affect the optical properties of the recycling stream. Therefore, containers comprising PET / MXD-6 can be separated from other containers and can then be recycled to produce lower quality recycled PET.

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

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

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

[0008] (A) oxygen scavenging compounds;

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

[0010] (a) Olive oil;

[0011] (b) macadamia oil;

[0012] (c) avocado oil;

[0013] (d) bataua oil;

[0014] (e) Chilean hazelnut oil (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% glycerol oleate.

[0023] Reference herein to "ppm" or "parts per million" (or similar expressions) refers to parts per million by weight of a particular material.

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

[0025] The percentage of components in the oil (e.g., components in the oil described in (B)) can be evaluated by GC-HRMS. The analysis can be as described in, for example, "Column Selection for the Analysis of Fatty Acid Methyl Esters"; Authors: Frank David, Pat Sandra, Allen KVickers, Agilent Technologies 5989-3760EN and references thereto. The method involves derivatizing fatty acids into methyl esters and then analyzing fatty acid methyl esters (FAMEs) as described in WW Christie, "Gas Chromatography and Lipids, APractical Guide" (1989), The Oily Press, Ayr, Scotland (ISBN 0-951417-OX).

[0026] You can choose any grade of olive oil, macadamia oil, avocado oil, patava oil, chilean oil, and PQ oil, such as virgin, extra virgin, or highly refined.

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

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

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

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

[0031] The olive oil may comprise less than 13%, preferably less than 11% polyunsaturated fatty acids. The olive oil may comprise at least 3% polyunsaturated fatty acids, such as at least 4% 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% squalene. The olive oil may contain less than 2.0%, preferably less than 1.0% squalene.

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

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

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

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

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

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

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

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

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

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

[0046] The PQ oil may comprise at least 40%, preferably at least 50%, more preferably at least 60% monounsaturated fatty acids. The PQ oil may comprise less than 85%, preferably less than 80% 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% polyunsaturated fatty acids. The PQ oil may contain at least 2% 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% squalene. The PQ oil may contain less than 2.0%, preferably less than 1.0% squalene.

[0050] In the PQ oil, the sum of the percentages of linoleic acid and linolenic acid may be less than 25%, preferably less than 17%, more preferably less than 12%, in particular less than 6%. The sum may be at least 1% or at least 2%.

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

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

[0053] - Less than 25% linoleic acid;

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

[0055] - Greater than 40% oleic acid.

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

[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 characteristics:

[0061] - greater 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 characteristics:

[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% of squalene.

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

[0069] In embodiment (I), described RS oil can comprise at least 20%, preferably at least 30%, more preferably at least 35% or at least 39% glyceryl monooleate.In some cases, described RS oil can comprise at least 90%, at least 95%, at least 99% or about 100% glyceryl monooleate.Suitably, described RS oil can comprise less than 90%, less than 70% or less than 50% glyceryl monooleate.In embodiment (I), described RS oil can be glyceryl monooleate.

[0070] In embodiment (I), RS oil can comprise glyceryl monooleate as the highest oil. The remainder can comprise other glycerides, for example other glyceryl oleates. It can comprise 5% to 45% glyceryl dioleate and 5% to 45% glyceryl trioleate, wherein suitably, the percentage sum of dioleate and trioleate is less than 65% or less than 55%.

[0071] In embodiment (II), described RS oil can comprise at least 20%, preferably at least 30%, more preferably at least 40% or at least 45% triolein.In some cases, described RS oil can comprise at least 90%, at least 95%, at least 99% or about 100% triolein.Suitably, described RS oil can comprise less than 90%, less than 70% or less than 50% triolein.In embodiment (II), described RS oil can be triolein.

[0072] In embodiment (II), RS oil can comprise glyceryl trioleate as the highest oil. The remainder can comprise other glycerides, for example other glyceryl oleates. It can comprise 5% to 45% glyceryl monooleate and 5% to 45% glyceryl dioleate, wherein suitably, the percentage sum of glyceryl monooleate and glyceryl dioleate is less than 65% or less than 55%.

[0073] The oxygen scavenging compound preferably comprises an oxygen scavenging segment. Suitably, the oxygen scavenging compound is adapted to be compatible with packaging resins (eg polyesters) so that it can be blended with standard packaging resins, thereby minimising cost.

[0074] The oxygen scavenging compound is preferably an oxidizable organic compound.The oxygen scavenging compound is preferably an oxygen scavenging polymer or copolymer.

[0075] The oxygen scavenging compound may be selected from amide containing compounds, such as aliphatic polyamides or at least partially aromatic polyamides, or polyesters modified by including ether moieties, such as polyether-polyesters. Preferably, the oxygen scavenging compound is an amide containing compound, such as aliphatic polyamides or at least partially aromatic polyamides. The oxygen scavenging compound is preferably poly(m-xylylene adipamide) (MXD-6).

[0076] The agent for scavenging oxygen preferably comprises a catalyst, such as a metal catalyst, such as a transition metal catalyst.

[0077] In embodiment E1, the oxygen scavenging compound, such as the oxygen scavenging copolymer, may be a polyamide. The polyamide may be an aliphatic polyamide or an at least partially aromatic polyamide. The number average molecular weight Mn of the polyamide is preferably 1000 to 45000, more preferably 3000 to 25000.

[0078] When the polyamide is an aliphatic polyamide, the aliphatic polyamide may be a fully aliphatic polyamide. It may contain a portion -CO(CH 2 ) n1 CONH(CH 2 ) n2 NH- or part of -(CH 2 ) n3 CONH-, wherein n1, n2 and n3 are independently integers in the range of 1 to 10, preferably 4 to 6. Preferably, the aliphatic polyamide includes polyhexamethylene adipamide, polycaprolactam and polyhexamethylene adipamide-co-caprolactam. In particular, the aliphatic polyamide is polyhexamethylene adipamide-co-caprolactam.

[0079] The partially aromatic polyamide can be polymerized from a mixture of aromatic and non-aromatic monomers or precursors. Preferred partially aromatic polyamides are selected from polyamides formed from at least isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, aliphatic dibasic acids having 6 to 12 carbon atoms and m-xylenediamine or p-xylenediamine, 1,3- or 1,4-cyclohexane (bis)methylamine, aliphatic diamines having 4 to 12 carbon atoms or fatty amino acids having 6 to 12 carbon atoms, or polyamides formed from lactams having 6 to 12 carbon atoms in all possible combinations, and other known polyamides formed from dibasic acids and diamines.

[0080] The partially aromatic polyamide may also contain a small amount of trifunctional or tetrafunctional comonomers, such as trimellitic anhydride, pyromellitic dianhydride, or other polyamide-forming polyacids and polyamines known in the art.

[0081] More preferably, the partially aromatic polyamide is selected from poly(meta-xylylene adipamide), poly(hexamethylene isophthalamide), poly(hexamethylene adipamide-hexamethylene isophthalamide) copolymers, poly(hexamethylene adipamide-hexamethylene terephthalamide) copolymers and poly(hexamethylene isophthalamide-hexamethylene terephthalamide) copolymers.

[0082] Even more preferably, the polyamide of embodiment El is poly(meta-xylylene adipamide) (MXD-6).

[0083] In embodiment E1, the formulation for oxygen scavenging preferably comprises a catalyst, as described in paragraphs

[0030] to

[0033] of US2013089686, the relevant contents of which are incorporated herein by said reference.

[0084] In embodiment E2, the oxygen scavenging compound, for example the oxygen scavenging copolymer, may be a polyester modified by containing an ether moiety. Suitably, it is a polyether-polyester, for example as described in WO2018149778, the contents of which are incorporated herein by reference.

[0085] Preferably, the polyether-polyester copolymer comprises:

[0086] (i) polyether segments, wherein at least one polyether segment comprises at least one polytetramethylene oxide segment,

[0087] (ii) polyester segments,

[0088] (iii) Structure -CO-R 2 -CO- bridging unit, where R 2 represents an optionally substituted divalent hydrocarbon residue consisting of 1 to 100 carbon atoms, wherein the substituent is preferably a C1-C5 alkoxy group, a nitro group, a cyano group or a sulfo group or a combination thereof;

[0089] (iv) one or two terminal groups R 1 -O-(C 2 -C 4 -O-) e -*, where R 1 is an optionally substituted hydrocarbon residue, and e is an integer from 0 to 1000. The polyether-polyester copolymer of embodiment E2 is preferably an unbranched copolymer, but it may also contain a small amount (i.e., up to 10 mol%) of a trifunctional or tetrafunctional comonomer, such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyacid polyols known in the art.

[0090] In addition to the polytetramethylene oxide segments, the polyether segment (i) may also contain other alkylene oxide segments, such as ethylene oxide, propylene oxide or a combination thereof.

[0091] Preferred embodiments of the polyether segment (i) are represented, for example, by the general formulae (I), (Ia), (Ib) and (Ic), and optionally by the following general formula (Id):

[0092]

[0093] in:

[0094] k is an integer between 0 and 70, preferably between 0 and 35, particularly preferably between 0 and 30;

[0095] v is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50;

[0096] x is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12;

[0097] y is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50;

[0098] z is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12;

[0099] And the sum of k+v+x+y+z is between 0 and 1070, preferably between 0 and 535. For the case where v+x>2 and v and x≠0, and y+z>2 and y and z≠0, the resulting polyethylene oxide / polypropylene oxide copolymer portion may represent a random copolymer or a block copolymer, wherein two blocks (polyethylene oxide blocks or polypropylene oxide blocks) may be chemically linked to a polytetramethylene oxide block.

[0100] General formula (Ia)

[0101]

[0102] in:

[0103] p is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15;

[0104] w is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15;

[0105] q is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50;

[0106] r is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12;

[0107] And the sum of p+w+q+r is between 0 and 570, preferably between 0 and 290.

[0108] For q+r>2 and q and r≠0, the resulting polyethylene oxide / polypropylene oxide copolymer portion may represent a random copolymer or a block copolymer.

[0109] General formula (Ib)

[0110]

[0111] in:

[0112] K is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12;

[0113] L is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15;

[0114] M is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50;

[0115] N is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15;

[0116] O is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12;

[0117] In addition, L+N cannot be selected as 0;

[0118] The sum of K+L+M+N+O is between 1 and 820, preferably between 2 and 415.

[0119] In the case where K+L>2 and K, L and M≠0, or in the case where N+O>2 and N, O and M≠0, the resulting polyethylene oxide / polytetramethylene oxide copolymer portion can represent a random copolymer or a block copolymer, in which two blocks (polypropylene oxide blocks or polytetramethylene oxide blocks) can be chemically linked to the polyethylene oxide block.

[0120] General formula (Ic)

[0121]

[0122] in:

[0123] P is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50;

[0124] Q is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15;

[0125] R is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12;

[0126] S is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15;

[0127] T is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50; in addition, Q+S cannot be selected to be 0;

[0128] And the sum of P+Q+R+S+T is between 1 and 820, preferably between 2 and 415.

[0129] In the case where P+Q>2 and P, Q and R≠0, or in the case where S+T>2 and S, T and R≠0, the resulting polyethylene oxide / polytetramethylene oxide copolymer portion can represent a random copolymer or a block copolymer, in which two blocks (polyethylene oxide blocks or polytetramethylene oxide blocks) can be chemically linked to the polypropylene oxide block.

[0130] General formula (Id)

[0131]

[0132] in:

[0133] U is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50;

[0134] V is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12;

[0135] W is an integer between 0 and 70, preferably between 0 and 35, particularly preferably between 0 and 30;

[0136] And the sum of U+V+W is between 3 and 570, preferably between 5 and 285.

[0137] In this embodiment, the polyether segment may be a homopolymer, a random copolymer, or a block copolymer.

[0138] In all formulae, the asterisk * denotes a bond to the bridging unit (iii).

[0139] Preferably, the polyester segment (ii) is represented by the general formula (II):

[0140]

[0141] in:

[0142] * represents a bond connected to the bridging unit (iii),

[0143] R2 and R3 independently represent an optionally substituted hydrocarbon residue consisting of 1 to 100 carbon atoms, wherein the substituents are preferably C1-C5 alkoxy, nitro, cyano and sulfo. u is an integer between 1 and 50, preferably between 1 and 30, in particular between 1 and 25.

[0144] Preferably, R2 and R3 independently represent an aliphatic hydrocarbon residue of 1 to 24 carbon atoms, an olefin residue of 2 to 24 carbon atoms or an aromatic hydrocarbon residue of 5 to 14 carbon atoms, wherein the hydrocarbon residue is optionally substituted by a C1-C5 alkoxy group, a nitro group, a cyano group or a combination thereof.

[0145] In a preferred embodiment, R2 and R3 are aliphatic hydrocarbon residues consisting of 2 to 18 carbon atoms, most preferably aliphatic hydrocarbon residues consisting of 2 to 6 carbon atoms. The aliphatic hydrocarbon residues may be straight-chain, branched or cyclic. In addition, the aliphatic hydrocarbon residues may be saturated or unsaturated. Preferably, they are saturated.

[0146] Preferred aliphatic residues are ethylene, 1,2-propylene, 1,3-propylene, 2,2'-dimethyl-1,3-propylene, 1,4-butylene, 2,3-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene and 1,4-cyclohexylene, and mixtures thereof. Particularly preferred residues are ethylene, 1,2-propylene, 1,3-propylene, 2,2'-dimethyl-1,3-propylene, 1,4-butylene, 2,3-butylene and 1,6-hexylene, and mixtures thereof. Most particularly preferred residues are ethylene, 1,2-propylene and 1,4-butylene, and mixtures thereof. In another preferred embodiment, R2 is an aromatic system. The aromatic system may be monocyclic or polycyclic, such as bicyclic or tricyclic. Preferably, the aromatic system consists of 5 to 25 atoms, even more preferably of 5 to 10 atoms. The aromatic system is preferably formed by carbon atoms. In another embodiment, in addition to carbon atoms, it also includes one or more heteroatoms, such as nitrogen, oxygen and / or sulfur. Examples of such aromatic systems are benzene, naphthalene, indole, phenanthrene, pyridine, furan, pyrrole, thiophene and thiazole.

[0147] Preferred aromatic structural units of R2 are 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2'-biphenylene, 4,4'-biphenylene, 1,3-phenylene-5-sulfonate, 2,5-furandiyl, and mixtures thereof. Particularly preferred structural elements of R2 are ethylene, 1,2-propylene, 1,3-propylene, 2,2'-dimethyl-1,3-propylene, 1,4-butylene, 2,3-butylene, 1,6-hexylene, 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, 1,8-naphthylene, and mixtures thereof. The most particularly preferred structural units of R2 are 1,3-phenylene, 1,4-phenylene, and mixtures thereof.

[0148] In another preferred embodiment, R3 can be represented by formula (Ia):

[0149]

[0150] Where Z can be an integer from 0 to 100.

[0151] The bridging unit (iii) can connect the polyether segment (i), the polyester segment (ii) and / or the terminal group (iv). The bridging unit is described by the general formula (III):

[0152]

[0153] wherein R2 represents the meaning as described above.

[0154] (iv) The terminal group is bonded to the bridging unit (iii). This bond is indicated by an asterisk *.

[0155] Preferred end groups can be described by the following general formula:

[0156] R1-O-(C2-C4-O-)e-*,

[0157] wherein R1 is an aliphatic hydrocarbon residue of 1 to 24 carbon atoms, an olefin residue of 2 to 24 carbon atoms, or an aromatic hydrocarbon residue of 6 to 14 carbon atoms, wherein the hydrocarbon residue is optionally substituted by a C1-C5 alkoxy group, a nitro group, a cyano group, a sulfo group, or a combination thereof, and e is an integer between 0 and 1000, preferably an integer between 0 and 500, and most preferably an integer between 0 and 150.

[0158] In a preferred embodiment, R1 is an aliphatic hydrocarbon residue consisting of 1 to 18 carbon atoms, more preferably an aliphatic hydrocarbon residue consisting of 1 to 12 carbon atoms. The aliphatic hydrocarbon residue may be straight chain, branched or cyclic. In addition, the hydrocarbon residue may be saturated or unsaturated. Preferably, it is saturated.

[0159] Particularly preferred aliphatic residues of R1 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, methylphenylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl. The most preferred residues are methyl, ethyl and n-dodecyl. The most particularly preferred residue is methyl. In another preferred embodiment, R1 can be represented by an aromatic system. The aromatic system can be monocyclic or polycyclic, such as bicyclic or tricyclic.

[0160] Preferably, the aromatic system consists of 6 to 14 carbon atoms, even more preferably 6 to 10 atoms. The aromatic system is preferably formed by carbon atoms. In another embodiment, in addition to carbon atoms, it also includes one or more heteroatoms, such as nitrogen, oxygen and / or sulfur. Examples of such aromatic systems are benzene, naphthalene, indole, phenanthrene, pyridine, furan, pyrrole, thiophene and thiazole. In addition, the aromatic system can chemically link one, two, three or more identical or different functional groups. Suitable functional groups are, for example, alkyl-, alkenyl-, alkoxy-, poly (alkoxy), cyano- and / or nitro-functional groups. These functional groups can be bonded to any position of the aromatic system.

[0161] Particularly preferred groups are R1-O-(C 2 -C 4 -O-) e -* corresponds to the following formula:

[0162]

[0163]

[0164] wherein the different monomers are randomly distributed in the form of random, block, or a combination of random and block;

[0165] b can be selected as an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50;

[0166] a can be selected as an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12;

[0167] c can be selected as an integer between 0 and 70, preferably between 0 and 35, particularly preferably between 0 and 30, and the sum of a+b+c is between 0 and 570; and

[0168] R1 is as described above. The number average molecular weight of the copolymer of embodiment E2 is preferably between 2000 and 1000000 g / mol, more preferably between 3500 and 100000 g / mol, most preferably between 5000 and 50000 g / mol.

[0169] In embodiment E2, the formulation for scavenging oxygen preferably includes a catalyst, as described on page 16, lines 8 to 32 of WO2018149778, the contents of which are incorporated herein by reference.

[0170] In embodiment E3, the oxygen scavenging compound, for example the oxygen scavenging copolymer, may be a copolyester ether, for example as described in WO2009032560, the contents of which are incorporated herein by said reference.

[0171] In embodiment E3, the copolyester ether may include a polyether segment comprising a poly(tetramethylene-co-alkylene ether).

[0172] The copolyester ether of embodiment E3 may comprise at least one polyether segment comprising poly(tetramethylene-co-alkylene ether), wherein the alkylene group may be C2 to C4, such as poly(tetramethylene-co-ethylene ether). The molecular weight of the polyether segment may be in the range of about 200 g / mol to about 5000 g / mol, such as in the range of about 1000 g / mol to about 3000 g / mol. The mole % of alkylene oxide in the polyether segment may be in the range of about 10 mole % to about 90 mole %, such as in the range of about 25 mole % to about 75 mole % or about 40 mole % to 60 mole %. For use in preparing the copolyester ether, the end groups of the polyether segment may be hydroxyl groups, such as poly(tetramethylene-co-alkylene oxide) glycol, which may be, for example, poly(tetramethylene-co-ethylene oxide) glycol or poly(tetramethylene-co-propylene oxide) glycol.

[0173] Poly(tetramethylene-co-alkylene oxide) glycols, such as poly(tetramethylene-co-ethylene oxide) glycol [poly(THF-EO) glycol], can be prepared by methods such as acid-catalyzed copolymerization of THF and EO, followed by neutralization of the reaction product. An example of such a method is the random copolymerization of THF and EO using 13.4-28.2 parts by weight of ethylene glycol, 72.7-241.4 parts by weight of THF, 236-411.8 parts by weight of EO, and 15.3-32.3 parts by weight of boron trifluoride etherate in an autoclave at atmospheric pressure and a temperature of 30°C. Ethylene glycol is used as an initiator and boron trifluoride etherate is used as an acid catalyst. After the copolymerization is completed, the acid catalyst in the product is neutralized with a base. Finally, the precipitate is filtered and dried with nitrogen at 100°C.

[0174] Other poly(alkylene oxide) glycols may be used in combination with the above poly(tetramethylene-co-alkylene oxide) glycols, such as poly(ethylene oxide) glycol, poly(trimethylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(pentamethylene oxide) glycol, poly(hexamethylene oxide) glycol, poly(heptamethylene oxide) glycol, polymethyl methacrylate, or poly(alkylene oxide) glycols derived from cyclic ether monomers, such as poly(2,3-dihydrofurandiyl).

[0175] The total amount of the copolyester ether in the final composition is selected to provide the desired oxygen scavenging effect for the article formed from the composition. The amount of the copolyester ether can be at least about 0.5% by weight of the total composition, or about 0.5% to about 10% by weight of the total composition, such as about 1.0% to about 5.0% by weight of the total composition or about 1.5% to about 3.0% by weight of the total composition. The copolyester ether can be physically blended with the polyester. Alternatively, poly(tetramethylene-co-alkylene oxide) glycol and other poly(alkylene oxide) glycols can be copolymerized with the polyester.

[0176] Copolyester ethers can be produced by methods for preparing polyesters, such as transesterification with dialkyl esters of dicarboxylic acids or direct esterification with dicarboxylic acids. In transesterification, dialkyl esters of dicarboxylic acids are transesterified with one or more diols in the presence of a catalyst (e.g., a compound of manganese, zinc, cobalt, titanium, calcium, magnesium or lithium); in direct esterification, one or more dicarboxylic acids are esterified with one or more diols. In these esterification processes, poly(tetramethylene-co-alkylene oxide) glycols and optional other poly(alkylene oxide) glycols replace a portion of these diols. Poly(tetramethylene-co-alkylene oxide) glycols and optional other poly(alkylene oxide) glycols can be added with the starting materials or after esterification. In either case, the monomer and oligomer mixture can be produced continuously in a series of one or more reactors, which are operated at high temperature at a pressure above one atmosphere. Alternatively, the monomer and oligomer mixture can be produced in one or more batch reactors. In a batch process, monomer residues including the monomer dihydroxyethyl terephthalate (BHET) may be left in the esterification reactor to aid in the esterification of the next batch. Suitable conditions for these reactions are temperatures of about 180°C to 250°C and pressures of about 1 bar to 4 bar.

[0177] Next, the mixture of the copolyester ether monomers and oligomers undergoes melt phase polycondensation to produce a low molecular weight precursor polymer. The precursor is prepared in a series of one or more reactors operating at elevated temperatures. To facilitate removal of excess glycol, water and other reaction products, the polycondensation reactor is operated under vacuum. Catalysts for the polycondensation reaction include compounds of antimony, germanium, tin, titanium and aluminum. The conditions for the polycondensation reaction may include (i) a temperature below about 290°C, or about 10°C above the melting point of the copolyester ether; and (ii) a pressure below about 0.01 bar, which decreases as the polymerization reaction proceeds. The copolyester ether may be produced continuously in a series of one or more reactors operating at less than one atmosphere and elevated temperature. Alternatively, the copolyester ether may be produced in one or more batch reactors. The intrinsic viscosity after melt phase polymerization may be in the range of about 0.5 dl / g to about 1.5 dl / g.

[0178] After the molten copolyester ether is extruded through a die, the strands are quenched in a cold water bath and cut into pellets. These pellets can be fed directly into an extruder to form articles, or made into solids under conventional conditions until the desired molecular weight is reached.

[0179] Using ethylene glycol, butanediol or propylene glycol as another diol, the content of the polyether segment in the copolyester ether is about 15 wt % to 95 wt %, for example, about 25 wt % to about 75 wt % or about 30 wt % to about 70 wt %. The dicarboxylic acid can be terephthalic acid or dimethyl terephthalate. Antioxidants and photoinitiators can be added during the polymerization process to control the start of oxygen scavenging.

[0180] In embodiment E3, the formulation for scavenging oxygen preferably comprises a catalyst as described in WO2009032560, page 5, line 19 to page 6, line 2, the contents of which are incorporated herein by said reference.

[0181] In embodiment E4, the agent for scavenging oxygen preferably comprises polyfarnesene.

[0182] In the formulation for scavenging oxygen, the ratio of the weight % of oxygen scavenging compound divided by the weight % of oil (including each oil mentioned in (B), especially the oils mentioned in (a) to (f) in (B)) may be at least 0.5. It may be less than 30 or less than 15 or less than 11. The ratio is preferably in the range of 0.5 to 30, preferably 0.5 to 15, more preferably 2 to 11.

[0183] In the formulation for scavenging oxygen, the sum of the wt% of oxygen scavenging compound and the wt% of oil (including each oil mentioned in (B), especially the oils mentioned in (a) to (f) in (B)) is suitably at least 30 wt%, preferably at least 35 wt%, more preferably at least 40 wt%.

[0184] Preferably, the formulation comprises at least 3 wt% of oil. The formulation may comprise 3 to 35 wt% of the oil, more preferably 4 to 15 wt% of the oil. Preferably, the formulation comprises up to 90 wt% of the oxygen scavenging compound. The formulation may comprise 25 to 90 wt% of the oxygen scavenging compound, more preferably 30 to 86 wt% of the oxygen scavenging compound.

[0185] Preferably, in the formulation, the sum of the weight percentages of olive oil, macadamia oil, avocado oil, patava oil and Chilean hazelnut oil is at least 3 weight %, may be in the range of 3 weight % to 35 weight %, preferably in the range of 4 weight % to 15 weight %. Preferably, in the formulation, the sum of the weight percentages of the oxygen scavenger compound mentioned in (A), olive oil, macadamia oil, avocado oil, patava oil and Chilean hazelnut oil is at least 35 weight %, preferably at least 40 weight %.

[0186] Preferably, in the formulation, the sum of the weight percentages of olive oil and macadamia oil is at least 3 weight %, may be in the range of 3 weight % to 35 weight %, preferably in the range of 4 weight % to 15 weight %. Preferably, in the formulation, the sum of the weight percentages of the oxygen scavenging compound, olive oil and macadamia oil mentioned in (A) is at least 35 weight %, preferably at least 40 weight %.

[0187] Preferably, in the formulation, the sum of the weight percentages of the oxygen scavenger compounds mentioned in (A) is at least 35 weight %, preferably at least 40 weight %.

[0188] The oxygen scavenging agent may further comprise a transition metal, such as a transition metal salt. The transition metal may be cobalt, such as cobalt derived from cobalt stearate.

[0189] The formulation may include less than 1.0 wt%, preferably less than 0.6 wt%. More preferably less than 0.3 wt% of the cobalt portion. The formulation may include at least 0.05 wt%, preferably at least 0.1 wt%. More preferably at least 0.15 wt% of the cobalt portion. The formulation may include 0.05 wt% to 0.4 wt% of the cobalt portion.

[0190] The oxygen scavenging formulation may include:

[0191] - 25 wt% to 90 wt% (preferably 30 wt% to 86 wt%) of an oxygen scavenging compound;

[0192] - at least 3 wt% (preferably 3 to 35 wt%) of one or more oils mentioned in (B) above (particularly the oils mentioned in (a) to (f) in (B)); and optionally (but preferably),

[0193] - A cobalt fraction of at least 0.05 wt% (preferably 0.05 to 0.4 wt%).

[0194] The oxygen scavenging formulation may include:

[0195] - 25 wt% to 90 wt% (preferably 30 wt% to 86 wt%) of an oxygen scavenging compound;

[0196] - olive oil and / or macadamia oil, wherein the sum of the weight percentages of olive oil and macadamia oil in the formulation is at least 3 wt% (preferably 3 wt% to 35 wt%); and optionally (but preferably),

[0197] - A cobalt fraction of at least 0.05 wt% (preferably 0.05 to 0.4 wt%).

[0198] The oxygen scavenging formulation may include:

[0199] - 25 wt% to 90 wt% (preferably 30 wt% to 86 wt%) of an oxygen scavenging compound;

[0200] - at least 3 wt% (preferably 3 wt%-35 wt%) of olive oil; and optionally (but preferably),

[0201] - A cobalt fraction of at least 0.05 wt% (preferably 0.05 to 0.4 wt%).

[0202] The formulation for scavenging oxygen can be provided in a range of different forms. In one embodiment, the formulation can include a single substance comprising the above-mentioned components, wherein the single substance can be a substantially uniform mixture or a non-uniform mixture. The single substance can be in solid form, such as in particulate form. In this case, a single particle can include the oxygen scavenging compound and the oil; and suitably, each particle in the single substance is substantially as described. In another embodiment, the formulation for scavenging oxygen can include a separate first component and a second component, wherein the first component can include the oxygen scavenging compound and optionally the transition metal (if provided); and the second component includes the oil. In this case, when the first component and the second component are in contact with a packaging resin (e.g., a packaging resin of polyester), they can be combined together, and the packaging resin is designed to provide most of the structure of the packaging material, wherein the packaging material uses the formulation for scavenging oxygen. In another embodiment, the formulation may include a blend, which includes a first component, wherein the first component can include the oxygen scavenging compound and optionally the transition metal (if provided); and a second component, which includes the oil, the oil is optionally combined with a carrier (e.g., a solid carrier for the oil). The blend may be a salt and pepper blend. It may comprise a first solid masterbatch comprising the oxygen scavenging polymer (and optionally a catalyst); and a second solid masterbatch comprising the oil and a solid carrier (e.g., a polyester such as PET); wherein the first masterbatch and the second masterbatch (e.g., in solid or granular form) are blended to define a salt and pepper blend.

[0203] Alternatively, the formulation for scavenging oxygen may comprise a liquid, such as a liquid concentrate.

[0204] The formulations, such as one or more of the masterbatches mentioned, may contain additional additives, such as colorants.

[0205] The formulation may be added to a packaging resin (eg a polyester such as PET) to define a composition which may be formed (eg by melt processing) into a preform for a packaging article, such as a bottle.

[0206] In a second aspect, the invention extends to a composition comprising a packaging resin (e.g. a polyester such as PET); and

[0207] (A) an oxygen scavenging compound as described in the first aspect; and

[0208] (B) The oil as described in the first aspect, which is for example selected from:

[0209] (a) Olive oil;

[0210] (b) macadamia oil;

[0211] (c) avocado oil;

[0212] (d) Patava oil;

[0213] (e) Chilean hazelnut oil;

[0214] (f) PQ oil as described in the first aspect; and

[0215] (g) The RS oil as described in the first aspect.

[0216] The composition may be formed in a melt processing apparatus, such as an injection molding apparatus.Packaging articles, such as preforms of containers (eg, bottles, such as stretch blow molded bottles) may be formed from the composition.

[0217] The composition may comprise:

[0218] (I) packaging resin (e.g. polyester, such as PET);

[0219] (II) an oxygen scavenging compound as described in the first aspect;

[0220] (III) The oil as described in the first aspect (B) (particularly the oils mentioned in (a) to (f) in (B)).

[0221] The composition may comprise:

[0222] - at least 95 wt%, for example at least 97 wt%, of a packaging resin (for example a polyester, such as PET);

[0223] - less than 5.0 wt% (preferably less than 2.5 wt% or less than 1.8 wt%) of an oxygen scavenging compound as described in the first aspect;

[0224] - Less than 2.0 wt% (preferably less than 1.0 wt% or less than 0.6 wt%) of the oil as described in the first aspect (B) (especially the oils mentioned in (a) to (f) in (B)).

[0225] The composition may comprise at least 0.5 wt% (preferably at least 1.0 wt%) of an oxygen scavenging compound 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) in (B)).

[0226] The composition may include:

[0227] - at least 95 wt%, for example at least 97 wt%, of a packaging resin (for example a polyester, such as PET);

[0228] - less than 5.0 wt% (preferably less than 2.5 wt% or less than 1.8 wt%) of an oxygen scavenging compound as described in the first aspect;

[0229] - olive oil, macadamia oil, avocado oil, patava oil and / or hazelnut oil;

[0230] The total weight percentage of olive oil, macadamia oil, avocado oil, patava oil and Chilean hazelnut oil in the composition is less than 2.0wt% (preferably less than 1.0wt% or less than 0.6wt%).

[0231] The composition may comprise at least 0.5 wt% (preferably at least 1.0 wt%) of an oxygen scavenging compound as described in the first aspect; the sum of the weight percentages of olive oil, macadamia oil, avocado oil, patawa oil and Chilean hazelnut oil is at least 0.1 wt% (preferably at least 0.2 wt%).

[0232] The composition may comprise:

[0233] - at least 95 wt%, for example at least 97 wt%, of a packaging resin (for example a polyester, such as PET);

[0234] - less than 5.0 wt% (preferably less than 2.5 wt% or less than 1.8 wt%) of an oxygen scavenging compound as described in the first aspect;

[0235] - Less than 2.0 wt% (preferably less than 1.0 wt% or less than 0.6 wt%) olive oil.

[0236] The composition may comprise at least 0.5 wt% (preferably at least 1.0 wt%) of an oxygen scavenging compound as described in the first aspect; and at least 0.1 wt% (preferably at least 0.2 wt%) of olive oil.

[0237] The composition preferably comprises a transition metal catalyst, in particular a cobalt catalyst. The composition preferably comprises at least 0.001 wt%, preferably at least 0.002 wt% of a cobalt portion. The composition preferably comprises less than 0.05 wt%, preferably less than 0.01 wt% of a cobalt portion. 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.

[0238] The composition of the second aspect may define a packaging material. The packaging material may define a component of a container or be a component of a container. The container may include an extruded or thermoformed article, such as a tray, such as a tray for food applications. Alternatively, the container may be a preform such as a bottle (the preform is suitably a test tube-shaped article, which is stretch blow molded to define a bottle) or a bottle itself. Preferred containers, such as preforms or bottles, are single-layer preforms or bottles. Preferably, the container, such as a preform or bottle (suitably excluding any closure thereof) comprises at least 90% by weight, more preferably at least 95% by weight, and especially at least 99% by weight of the composition.

[0239] 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:

[0240] (I) contacting an oxygen scavenging compound, such as the oil described in the first aspect (B), with a packaging resin (e.g., polyester such as PET); and

[0241] (II) melt processing the components mentioned in (I) to define a packaging article.

[0242] The oxygen scavenging compound, the oil and the packaging resin may independently be as described in the first aspect or the second aspect.

[0243] The packaging article may have a composition as described in the second aspect.

[0244] The container may be as described in the second aspect.

[0245] The method may comprise contacting a formulation as described in the first aspect with a packaging resin (eg a polyester such as PET); and suitably melt processing the mixture as described in (II).

[0246] The method may comprise selecting at least 95 wt %, preferably at least 97 wt %, of a packaging resin (e.g. a polyester such as PET) relative to the wt % of the packaging article (excluding any closure thereof, defined as 100 wt %). The remainder of the packaging article (up to 100 wt %) may be defined by the formulation of the first aspect.

[0247] The method is preferably a method of making a packaging article, such as a container, such as a preform for a bottle or the bottle itself, which can be directly recycled with essentially pure PET according to the European PET Bottle Platform (EPBP) protocol.

[0248] In a fourth aspect, the present invention extends to a method of recycling a packaging article, the method comprising:

[0249] - selecting a packaging product as described in the second aspect and / or a packaging product made as described in the third aspect; and

[0250] - contacting the packaging article or its fragments with other PET to prepare a mixture.

[0251] The mixture may comprise 5 to 50 wt% of the packaging article or fragments thereof and 50 to 95 wt% of other PET. The other PET may be a PET without colorant. It preferably does not comprise an oxygen scavenger compound. It may be virgin PET.

[0252] In a fifth aspect, the invention extends to recycled PET prepared as described in the fourth aspect.

[0253] In a sixth aspect, there is provided use of the formulation of 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.

[0254] Any aspect of any invention described herein may be combined with any other aspect of any invention described herein, with corresponding modifications as necessary. BRIEF DESCRIPTION OF THE DRAWINGS

[0255] Specific embodiments of the present invention will now be described by way of example with reference to the accompanying drawings, in which:

[0256] Figure 1 Shown are the pulldown oxygen scavenging test results for Examples 3 and 4;

[0257] Figure 2 The results of the ingress oxygen scavenging tests of Examples 6 to 10 are shown;

[0258] Figure 3 The results of the infiltrated oxygen scavenging tests of Examples 12 to 21 are shown; DETAILED DESCRIPTION

[0259] The following materials are mentioned below:

[0260] MXD-6—refers to granular poly(m-xylylene adipamide) supplied by Mitsubishi.

[0261] Cobalt Stearate / PET Masterbatch—A masterbatch containing 12 wt% cobalt stearate and 88 wt% PET.

[0262] PET-X—refers to Equippolymers C93, a polyethylene terephthalate (PET) bottle-grade polymer.

[0263] Valor (trademark) - a nylon-based scavenger resin available from PETnology / tecPET GmbH

[0264] Oxyclear (Trademark) - a polyether based scavenger resin available from Invista / Indorama.

[0265] Olive oil—Unrefined olive oil was purchased from Sigma-Aldrich.

[0266] Macadamia Oil – Extra virgin cold-pressed macadamia oil sold under the Pure South Press brand.

[0267] Avocado Oil — Extra virgin cold-pressed avocado oil sold under the Mokhado brand.

[0268] Chilean Hazelnut Oil - Organic cold pressed unrefined Chilean hazelnut oil sold under the Biopurus brand. Assessment 1 - "Pulldown" Oxygen Scavenging Test Procedure

[0269] In the "pull-down" test method, oxygen scavenging additives incorporated into the bottle wall can be evaluated by filling the bottle with oxygenated water and monitoring the depletion of dissolved oxygen content over time.

[0270] In this method, the bottles to be evaluated and the water (prior to introduction into the bottles) are stored in a temperature controlled environment (21°C). A known active standard and a blank control (virgin PET) are evaluated along with the test samples to validate the test method setup. NOTE: If O is observed in the blank virgin PET bottles during the testing period (e.g., testing longer than 14 days), the test results may be negative. 2 If the water is not depleted, there may be algae / microorganisms in the water and the sample test must be repeated. This may occur if not enough biocide is added.

[0271] The method may then include the following steps:

[0272] (i) Fill a bucket with tap water and biocide (polyhexamethylene biguanide PHMB) (approximately 1 ml of biocide dissolved in 5 liters of water) and cover it. Place the water in a temperature-controlled chamber for approximately 24 hours to allow the temperature and dissolved oxygen content to reach equilibrium.

[0273] (ii) Stretch blow molded bottles containing any oxygen scavenging additives were made the day before or on the day of testing. The bottles were stored in sealed aluminum bags and purged with nitrogen before use.

[0274] (iii) Before filling the bottle with the prepared sterilant water, attach the opTechPlatinum sensor point (part of the oxygen measurement system of Ametek Mocon) to the inner wall of the bottle using tweezers or other such tool. Then take the following steps:

[0275] (a) Each bottle is filled with the prepared water / biocides without leaving head space.

[0276] (b) Place a cap on each bottle and tighten it using a cap torque gauge to the recommended torque (Nm), depending on the cap specification.

[0277] (c) Once all bottles to be evaluated are ready, an initial reading of the dissolved oxygen content is taken. This should be approximately 10 ppm.

[0278] (d) The bottles were stored in a temperature-controlled room and measurements were taken every 2-3 days for 14 days.

[0279] (e) If necessary, further measurements may be taken after a specified period of 14 days.

[0280] Assessment 2—“Ingress” Oxygen Scavenging Test Procedure

[0281] In the "penetration" test method, oxygen scavenging additives in the bottle wall can be evaluated by filling the bottle with deoxygenated water and monitoring the increase in dissolved oxygen content in the water over time (entry through the bottle wall).

[0282] As a standard method for measuring scavenging activity, measurements can be taken every few days (up to 14 days) and every few weeks thereafter. The frequency of measurement depends on the expected shelf life that the additive can extend. The test is complete when the dissolved oxygen reaches 3 ppm.

[0283] The method may then include the following steps:

[0284] (i) A glove box set-up is required, which contains a water tank / container, a nitrogen supply, and a vacuum system. Nitrogen should be supplied to the water tank so that it bubbles through the water. The glove box should also contain a scale, bottle cap, torque meter, and a dissolved oxygen sensor (probe inserted into the water tank).

[0285] (ii) Stretch blow molded bottles containing any oxygen scavenging additives are made the day before or on the same day as the test. An appropriate oxygen measuring sensor (such as the OpTech Platinum sensor point) is attached to the interior of the bottle sample using tweezers or other similar tools. The bottles are stored in sealed aluminum bags and purged with nitrogen before use.

[0286] (iii) A known active standard (e.g. 3% 4020G in virgin PET) and a blank control (virgin PET) can be evaluated along with the test samples to validate the test method setup. Note: If purge is observed in the blank virgin PET bottle, there may be algae / microorganisms in the water and the sample test must be repeated. This may occur if insufficient biocide was added.

[0287] (iv) The water tank / container inside the glove box is filled with tap water and fungicide (polyhexamethylene biguanide PHMB) (approximately 1 ml of fungicide is dissolved in 5 liters of water).

[0288] (v) All equipment and sample bottles were placed in the glove box before sealing.

[0289] (vi) Nitrogen is bubbled through the water to the maximum safe pressure, then vacuumed to the lowest maximum safe pressure. This process is repeated multiple times until the oxygen sensor inserted into the water tank reads a dissolved oxygen level of less than 300 ppb.

[0290] (vii) Ensure that there is ambient pressure in the glove box (there will be headspace) before nominally filling the bottles with water / sterilizer from the tank / container.

[0291] (viii) Place a cap on each bottle and tighten it using a cap torque gauge to the recommended torque (Nm), depending on the cap specification.

[0292] (ix) After all samples are prepared, the glove box can be opened, the samples can be taken out, and the dissolved O 2 Take an initial reading of the concentration. This should be less than 300 ppb (parts per billion).

[0293] (x) Samples were stored in a temperature-controlled room and measured every 2-3 days for 14 days and every few weeks thereafter.

[0294] The following examples illustrate preferred embodiments of the invention.

[0295] Example 1 - General Procedure for Preparing Preforms

[0296] Preforms of 25 g and 38 mm neck diameter were manufactured in a Husky GL160 injection molding machine equipped with a dual-cavity mold. PET-X, which had been previously dried to less than 50 ppm of moisture, was manually premixed with the components to be tested and manually added to a hopper mounted above the injection molding machine feed port. Standard PET injection molding processes were used to produce the preforms.

[0297] Example 2 - Bottle production from preforms

[0298] 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 used. Before the preforms left the oven and entered the blow mold, the total power percentage of the heating oven was adjusted to achieve a preform temperature of 115°C-120°C. This is referred to as the blowing temperature.

[0299] Examples 3 and 4—Preparation of Bottles to be Evaluated

[0300] Following the general procedure described in Example 1, preforms were prepared having the following composition (prepared by tumble mixing the indicated components prior to injection molding):

[0301]

[0302] The preforms were formed into bottles as described in Example 2.

[0303] Example 5 - Evaluation of the bottles of Examples 3 and 4

[0304] The bottles of Examples 3 and 4 were evaluated as described in Evaluation 1. Figure 1 As shown, Figure 1 It was shown that when olive oil was present, the oxygen scavenging effect was much better than when it was not present.

[0305] The observations regarding the Example 3 and Example 4 bottles can be exploited in a variety of ways. For example, lower amounts of the relatively expensive MXD-6 can be used in the bottle to support the use of cheaper olive oil and achieve a similar level of oxygen scavenging effect. Alternatively, olive oil can be used to provide a higher level of oxygen scavenging (thereby extending shelf life) than a bottle containing the same amount of MXD-6.

[0306] Advantageously, it has been found that when relatively low levels of MXD-6 are used in bottles, the bottles can be recycled together with bottles made from virgin PET to produce recycled PET that has acceptable color (e.g., acceptable L*, a*, and b* values) and is acceptable according to the appropriate European PET Bottle Platform (EPBP) testing procedures.

[0307] Examples 6 to 10 - Preparation of bottles for evaluation to illustrate the use of a range of oils with the commercially available Valor oxygen scavenger

[0308] Following the procedure described in Examples 1 to 4, preforms and subsequently bottles having the following composition were prepared:

[0309]

[0310]

[0311] Example 11 - Evaluation of the bottles of Examples 6 to 10

[0312] The bottles were evaluated as described in Evaluation 2 and the results were Figure 3 As shown, it is shown that the addition of the specified oil significantly improves the oxygen scavenging effect.

[0313] Examples 12 to 21 - Preparation of bottles for evaluation to illustrate the use of a range of oils with the commercially available Oxyclear oxygen scavenger

[0314] Following the procedure described in Examples 1 to 4, preforms and subsequently bottles having the following composition were prepared:

[0315]

[0316] Example 13 - Evaluation of Bottles of Examples 12 to 21

[0317] The bottles were evaluated as described in Evaluation 2 and the results are shown in Figure 4, which shows that the addition of the specified oils significantly improved oxygen scavenging, and the improvement was even greater when olive oil was used.

[0318] 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 disclosed in this specification (including any accompanying claims, abstract and drawings), or any innovative step or any combination of innovative steps in the steps of any disclosed method or process.

Claims

1. A preparation for scavenging oxygen, the preparation comprising: (A) oxygen scavenging copolymer; (B) oil, wherein the oil is selected from: (a) Olive oil; (b) macadamia oil; (c) avocado oil; (d) Patava oil; (e) Chilean hazelnut oil; (f) PQ oil comprising: (i) less than 25% linoleic acid, and / or (ii) less than 10% linolenic acid, and / or (iii) greater than 40% oleic acid, and / or (iv) greater than 40% monounsaturated fatty acids, and / or (v) less than 40% polyunsaturated fatty acids, and / or (vi) at least 0.1% squalene; and / or (g) RS oil comprising at least 20% glycerol 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. A formulation according to any preceding claim, wherein: The PQ oil comprises at least 40%, preferably at least 45%, more preferably at least 50% by weight oleic acid; and the PQ oil comprises less than 80%, preferably less than 70% oleic acid.

5. A formulation according to any preceding claim, 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. A formulation according to any preceding claim, 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. A formulation according to any preceding claim, wherein: The PQ oil comprises less than 30%, preferably less than 20%, more preferably less than 15%, in particular less than 10% of compounds having more than two double bonds.

8. A formulation according to any preceding claim, wherein: In the PQ oil, the sum of the percentages 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 sum is at least 1% or at least 2%.

9. A formulation according to any preceding claim, 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% of linolenic acid; as well as - 40 to 80%, preferably 45 to 70% oleic acid.

10. A formulation according to any preceding claim, 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% polyunsaturated fatty acids; and - 0.1% to 5.0%, preferably 0.1% to 4.0% of squalene.

11. A formulation according to any preceding claim, wherein the oxygen scavenging compound is an oxidisable organic compound, such as an oxygen scavenging polymer or copolymer.

12. A formulation according to any preceding claim, wherein the oxygen scavenging compound is selected from amide containing compounds, such as aliphatic polyamides or at least partially aromatic polyamides; and polyesters modified by containing ether moieties, such as polyether-polyesters.

13. A formulation according to any preceding claim, wherein the oxygen scavenging compound is an amide-containing compound, such as an aliphatic polyamide or an at least partially aromatic polyamide.

14. A formulation according to any preceding claim, wherein the oxygen scavenging compound is poly(m-xylylene adipamide) (MXD-6).

15. A formulation according to any preceding claim, wherein the formulation for scavenging oxygen comprises a catalyst, such as a metal catalyst, such as a transition metal catalyst.

16. The formulation of any one of claims 1 to 12, wherein the oxygen scavenging compound is a polyether-polyester copolymer comprising: (i) polyether segments, wherein at least one polyether segment comprises at least one polytetramethylene oxide segment, (ii) polyester segments, (iii) Structure -CO-R 2 -CO- bridging unit, where R 2 represents an optionally substituted divalent hydrocarbon residue consisting of 1 to 100 carbon atoms; (iv) one or two terminal groups R 1 -O-(C2-C4-O-) e -*, where R 1 is an optionally substituted hydrocarbon residue, and e is an integer from 0 to 1,000.

17. The formulation of any one of claims 1 to 12 or claim 16, wherein the oxygen scavenging compound is a copolyester ether comprising a polyether segment; the polyether segment comprising a poly(tetramethylene-co-alkylene ether).

18. A formulation according to any preceding claim, wherein In the formulation for scavenging oxygen, the ratio of the weight % of oxygen scavenging compound divided by the weight % of oil is in the range of 0.5 to 30, preferably 2 to 11.

19. A formulation according to any preceding claim, wherein the formulation for scavenging oxygen comprises: - 25 wt% to 90 wt% (preferably 30 wt% to 86 wt%) of an oxygen scavenging compound; - olive oil and / or macadamia oil, wherein the sum of the weight percentages of olive oil and macadamia oil in the formulation is at least 3 wt% (preferably 3 wt% to 35 wt%); and optionally (but preferably), - A cobalt fraction of at least 0.05 wt% (preferably 0.05 to 0.4 wt%).

20. A formulation according to any preceding claim, wherein the formulation comprises the RS oil, the RS oil comprising glyceryl monooleate, glyceryl dioleate and / or glyceryl trioleate, wherein preferably the sum of the percentages of glyceryl monooleate, glyceryl dioleate and glyceryl trioleate in the RS oil is at least 70% or at least 95%.

21. A composition comprising a packaging resin (e.g. a polyester such as PET); and (A) an oxygen scavenging compound as claimed in any preceding claim; and (B) An oil as claimed in any preceding claim, for example selected from: (a) Olive oil; (b) macadamia oil; (c) avocado oil; (d) Patava oil; (e) Chilean hazelnut oil; and (f) A PQ oil as claimed in any preceding claim.

22. The composition according to claim 21, comprising: - at least 95 wt % (e.g. at least 97 wt %) of packaging resin (e.g. polyester, such as PET); - less than 5.0 wt% (preferably less than 2.5 wt% or less than 1.8 wt%) of an oxygen scavenging compound as claimed in any one of claims 1 to 20; - less than 2.0 wt% (preferably less than 1.0 wt% or less than 0.6 wt%) of the oil of any one of claims 1 to 20; in, Optionally, the composition comprises at least 0.5 wt % (preferably at least 1.0 wt %) of the oxygen scavenging compound; and at least 0.1 wt % (preferably at least 0.2 wt %) of the oil.

23. A composition according to claim 21 or 22, wherein the composition comprises at least 0.5 wt% (preferably at least 1.0 wt%) of an oxygen scavenging compound according to any one of claims 1 to 20; and the sum of the weight percentages of olive oil, macadamia oil, avocado oil, patawa oil and Chilean hazelnut oil is at least 0.1 wt% (preferably at least 0.2 wt%).

24. A composition according to any one of claims 21 to 23, wherein the composition defines or is a component of a container, such as a preform for a bottle (eg a monolayer preform) or a bottle.

25. A method for making a packaging article such as a container, such as a preform for a bottle or the bottle itself, the method comprising: (I) contacting an oxygen scavenging compound as claimed in any one of claims 1 to 20, an oil as claimed in any one of claims 1 to 20 and a packaging resin (e.g. polyester such as PET); and (II) melt processing the components mentioned in (I) to define the packaging article.

26. A method for recycling a packaging product, the method comprising: -Select the packaging product according to claim 24 or 25; as well as - contacting the packaging article or its fragments with other PET to prepare a mixture.

27. The method of claim 26, wherein the mixture comprises 5 to 50 wt% of the packaging article or fragments thereof and 50 to 95 wt% of virgin PET.

28. A recycled PET prepared according to claim 26 or 27.

29. Use of a formulation according to any one of claims 1 to 20 for scavenging oxygen and preparing a composition that can be recycled with virgin PET to prepare a mixture having a b* less than a predetermined level.

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