Scavenging Oxygen

This invention relates to scavenging oxygen and particularly, although not exclusively, relates to scavenging oxygen in packaging, for example bottles. Preferred embodiments relate to a formulation for scavenging oxygen, its incorporation into a composition and its use.

Demand exists for packaging that can preserve or extend the shelf life of foods, beverages, and other products that can be susceptible to degradation or spoilage by oxidation between production and consumption at a later time. However, neat PET does not possess the level of oxygen barrier properties required for some packaging for foods or beverages. Thus, it is known to use oxygen scavengers to enhance the oxygen barrier properties of PET packaging.

There is a trade-off between enhancing oxygen barrier properties and negatively impacting the high transparency of neat PET. Undesirably, increasing the loading level of oxygen scavengers in PET, in order to enhance the oxygen barrier properties, tends to decrease transparency (i.e. increase haze) of the PET.

It is known to enhance oxygen barrier properties of PET by addition of a polyamide, especially polyxylylene adipamide (MXD-6). However, because PET and MXD-6 are such dissimilar materials, it is undesirable to directly recycle a monolayer container comprising PET/MXD-6 with substantially pure PET since it would detrimentally affect the optical properties of the recycle stream. Consequently, containers comprising PET/MXD-6 may be segregated from other containers and may then be recycled to produce lower quality recycled PET.

There is a need for an oxygen scavenging formulation which can be used to produce very high levels of oxygen scavenging in a container, whilst not significantly affecting optical properties. In this case, bottles incorporating such a formulation could be directly recycled with substantially pure PET bottles which would be highly advantageous.

It is an object of the present invention to address the above-described problem.

According to a first aspect of the invention, there is provided a formulation for scavenging oxygen, said formulation comprising:

(A) an oxygen-scavenging compound;

(B) an oil, wherein said oil is selected from:

(a) olive oil; (b) macadamia oil;

(c) avocado oil;

(d) bataua oil;

(e) gevuina oil;

(f) an oil PQ comprising:

(i) less than 25 % of linoleic acid; and/or

(ii) less than 10 % of linolenic acid; and/or

(iii) greater than 40 % of oleic acid; and/or

(iv) greater than 40 % of monounsaturated fatty acids; and/or

(v) less than 40 % of polyunsaturated fatty acids; and/or

(vi) at least 0.1 % of squalene;

(g) an oil RS comprising at least 20% of a glycerol oleate.

A reference to “ppm” or “parts-per-million” herein (or cognate expression) refers to the parts per million of a specified material by weight.

In an embodiment, said oil may be selected from any oil in (B)(a) to (f).

The % of components in oils, for example in an oil described in (B), may be assessed by GC- HRMS. Analysis may be as described in, 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 the citations therein. The method involves derivatization of fatty acids to methyl esters as described in W.W. Christie, “Gas Chromatography and Lipids, A Practical Guide”, (1989), The Oily Press, Ayr, Scotland (ISBN 0-9514171 -O-X) and then analysis of the fatty acid methyl esters (FAMEs).

Any grade of olive oil, macadamia oil, avocado oil, bataua oil, gevuina oil and oil PQ, for example virgin, extra virgin or highly refined, may be selected.

Said olive oil may include less than 25 % of linoleic acid, preferably less than 15 %, more preferably less than 10 %. Said olive oil may include at least 1 %, preferably at least 3 %, of linoleic acid.

Said olive oil may include less than 5.0 % of linolenic acid, preferably less than 2.0 %, more preferably less than 1 .0 %. Said olive oil may include at least 0.1 %, preferably at least 0.3 %, of linolenic acid.

Said olive oil may include at least 40 % of oleic acid, preferably at least 50 %, more preferably at least 65 %. Said olive oil may include less than 85 %, preferably less than 82 %, of oleic acid. Said olive oil may include at least 40 % of monounsaturated fatty acids, preferably at least 50 %, more preferably at least 65 %, Said olive oil may include less than 85 %, preferably less than 82 %, of monounsaturated fatty acids.

Said olive oil may include less than 13 %, preferably less than 11 %, of polyunsaturated fatty acids, Said olive oil may include at least 3 % of polyunsaturated fatty acids, for example at least 4 %, of polyunsaturated fatty acids.

Said olive oil may include less than 10 %, preferably less than 5 %, of compounds with more than two, double bonds.

Said olive oil may include at least 0.05 % of squalene, preferably at least 0.1 %. Said olive oil may include less than 2.0 %, preferably less than 1 .0 %, of squalene.

In said olive oil, the sum of the % 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 %.

Said macadamia oil may include less than 25 % of linoleic acid, preferably less than 15 %, more preferably less than 10 %. Said macadamia oil may include at least 0.5 %, preferably at least 1 %, of linoleic acid.

Said macadamia oil may include less than 10 % of linolenic acid, preferably less than 5 %. Said macadamia oil may include at least 0.05 %, preferably at least 0.1 %, of linolenic acid.

Said macadamia oil may include at least 40 % of oleic acid, preferably at least 45 %, more preferably at least 50 %. Said macadamia oil may include less than 80 %, preferably less than 70 %, of oleic acid.

Said macadamia oil may include at least 40 % of monounsaturated fatty acids, preferably at least 50 %, more preferably at least 60 %, Said macadamia oil may include less than 85 %, preferably less than 82 %, of monounsaturated fatty acids.

Said macadamia oil may include less than 13 %, preferably less than 11 %, of polyunsaturated fatty acids. Said macadamia oil may include at least 1 % of polyunsaturated fatty acids.

Said macadamia oil may include less than 10 %, preferably less than 5 %, of compounds with more than two, double bonds. Said macadamia oil may include less than 2.0 %, preferably less than 1.0 %, of squalene.

In said macadamia oil, the sum of the % 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 %.

Said oil PQ may include less than 25 % of linoleic acid, preferably less than 15 %, more preferably less than 10 %. Said oil PQ may include at least 1 %, preferably at least 3 %, of linoleic acid.

Said oil PQ may include less than 10 % of linolenic acid, preferably less than 5 %. Said oil PQ may include at least 0.1 %, preferably at least 0.3 %, of linolenic acid.

Said oil PQ may include at least 40 % of oleic acid, preferably at least 45 %, more preferably at least 50 wt%. Said oil PQ may include less than 80 %, preferably less than 70 %, of oleic acid.

Said oil PQ may include at least 40 % of monounsaturated fatty acids, preferably at least 50 %, more preferably at least 60 %. Said oil PQ may include less than 85 %, preferably less than 80 %, of monounsaturated fatty acids.

Said oil PQ may include less than 50 %, preferably less than 30 %, more preferably less than 15 %, especially less than 10%, of polyunsaturated fatty acids. Said oil PQ may include at least 2 % of polyunsaturated fatty acids.

Said oil PQ may include less than 30 %, preferably less than 20 %, more preferably less than 15 %, especially less than 10%, of compounds with more than two, double bonds.

Said oil PQ may include at least 0.1 % of squalene, preferably at least 0.2 %. Said oil PQ may include less than 2.0 %, preferably less than 1 .0 %, of squalene.

In said oil PQ, the sum of the % of linoleic acid and linolenic acid may be less than 25 %, preferably less than 17 %, more preferably less than 12 %, especially less than 6 %. The sum may be at least 1 % or at least 2 %.

Said oil PQ may include at least two, preferably at least four, preferably each of characteristics (f)(i) to (vi) referred to. Said oil PQ preferably includes at least characteristics (f)(i) to (iii) referred to.

Said oil PQ preferably has the following characteristics: - less than 25 % of linoleic acid;

- less than 10 % of linolenic acid; and

- greater than 40 % of oleic acid.

Said oil PQ preferably has the following characteristics:

- 1 to 15 %, preferably 2 to 10 % of linoleic acid;

- 0.1 to 10 %, preferably 0.1 to 5 %, of linolenic acid; and

- 40 to 80 %, preferably 45 to 70 %, of oleic acid.

Said oil PQ preferably has the following characteristics:

- greater than 40 % of monounsaturated fatty acids;

- less than 40 % of polyunsaturated fatty acids; and

- at least 0.1 % of squalene.

Said oil PQ preferably has the following characteristics:

- 40 to 80 %, preferably 45 to 75 %, of 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.

Said oil RS may include glycerol mono-oleate, glycerol di-oleate and/or glycerol tri-oleate. The sum of the % of glycerol mono-oleate, glycerol di-oleate and glycerol tri-oleate in said oil RS is preferably at least 70%, at least 90%, at least 95% or at least 98%.

In an embodiment (I), said oil RS may include at least 20%, preferably at least 30%, more preferably at least 35% or at least 39% of glycerol mono-oleate. In some cases, said oil RS may include at least 90%, at least 95%, at least 99% or about 100% of glycerol mono-oleate. Suitably, said oil RS may include less than 90%, less than 70%, or less than 50%, of glycerol monooleate. In embodiment (I), said oil RS may be monoolein.

In embodiment (I), oil RS may include glycerol mono-oleate as the oil present in the highest amount. The balance may comprise other glycerol esters, for example, other glycerol oleates. It may include 5 to 45% of glycerol di-oleate and 5 to 45% of glycerol tri-oleate, wherein suitably the sum of the % of di-oleate and tri-oleate is less than 65% or less than 55%.

In an embodiment (II), said oil RS may include at least 20%, preferably at least 30%, more preferably at least 40% or at least 45% of glycerol tri-oleate. In some cases, said oil RS may include at least 90%, at least 95%, at least 99% or about 100% of glycerol tri-oleate. Suitably, said oil RS may include less than 90%, less than 70%, or less than 50%, of glycerol tri-oleate. In embodiment (II), said oil RS may be tri-olein. In embodiment (II), oil RS may include glycerol tri-oleate as the oil present in the highest amount. The balance may comprise other glycerol esters, for example, other glycerol oleates. It may include 5 to 45% of glycerol mono-oleate and 5 to 45% of glycerol di-oleate, wherein suitably the sum of the % of mono-oleate and di-oleate is less than 65% or less than 55%.

Said oxygen-scavenging compound preferably includes oxygen-scavenging segments. Said oxygen-scavenging compound is suitably adapted to be compatible with packaging resins (eg of polyester) so that it can be mixed with standard packaging resins, thus minimizing cost.

Said oxygen-scavenging compound is preferably an oxidisable organic compound. Said oxygen-scavenging compound is preferably an oxygen-scavenging polymer or copolymer.

Said oxygen-scavenging compound may be selected from amide-containing compounds, for example aliphatic or at least partially aromatic polyamides, or a polyester modified by inclusion of ether moieties, for example as in a polyether-polyester. Preferably, said oxygen-scavenging compound is an amide-containing compound, for example an aliphatic or at least partially aromatic polyamide. Said oxygen-scavenging compound is preferably poly(m-xylylene adipamide) (MXD-6).

Said formulation for scavenging preferably includes a catalyst, for example a metal, for example transition metal, catalyst.

In an embodiment E1 , said oxygen-scavenging compound, for example said oxygen-scavenging copolymer, may be a polyamide. A said polyamide may be an aliphatic polyamide or an at least partially aromatic polyamide. The number average molecular weight Mn of the polyamide is preferably from 1000 to 45000, more preferably between 3000 and 25000.

When said polyamide is an aliphatic polyamide, said aliphatic polyamide may be a fully aliphatic polyamide. It may include a moiety — CO(CH2)mCONH(CH2)n2NH — or a moiety

— (CH ₂ )n ₃ CONH — , wherein n1 , n2 and n3 are integers independently from each other in the range 1 to 10, preferably 4 to 6. Preferably, aliphatic polyamides include poly(hexamethylene adipamide), poly(caprolactam) and poly(hexamethylene adipamide)-co-caprolactam. Especially, an aliphatic polyamide is poly(hexamethylene adipamide)-co-caprolactam.

A said partially aromatic polyamide may be polymerized from a mixture of aromatic and nonaromatic monomers or precursors. Preferred partially aromatic polyamides are selected from the group consisting of polyamides formed at least from isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, aliphatic diacids with 6 to 12 carbon atoms together with meta- or para-xylene diamine, 1 ,3- or 1 ,4-cyclohexane(bis)methylamine, aliphatic diamines with 4 to 12 carbon atoms, or aliphatic amino acids with 6 to 12 carbon atoms, or from lactams with 6 to 12 carbon atoms, in all possible combinations, and from other generally known polyamide forming diacids and diamines.

Said partially aromatic polyamide may also contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, pyromellitic dianhydride, or other polyamide forming polyacids and polyamines known in the art.

More preferably, partially aromatic polyamides are selected from the group consisting of poly(m- xylylene adipamide), poly(hexamethylene isophthalamide), poly(hexamethylene adipamide-co- isophthalamide), poly(hexamethylene adipamide-co-terephthalamide) and poly(hexamethylene isophthalamide-co-terephthalamide).

Even more preferably, the polyamide of embodiment E1 is poly(m-xylylene adipamide) (MXD- 6).

In embodiment E1 , said formulation for scavenging preferably includes a catalyst, as described at [0030] - [0033] of US2013089686, the content of which is incorporated by said reference.

In an embodiment E2, said oxygen-scavenging compound, for example, said oxygenscavenging copolymer, may be a polyester modified by inclusion of ether moieties. It is suitably a polyether-polyester, for example as described in WO2018149778, the content of which is incorporated by said reference.

Preferably, a polyether-polyester copolymer comprises:

(i) polyether segments wherein at least one polyether segment contains at least one polytetramethylene oxide segment,

(ii) polyester segments,

(iii) bridging elements of the structure -CO-R ² -CO-, wherein R ² represents an optionally substituted bivalent hydrocarbon residue consisting of 1 to 100 carbon atoms wherein the substituents are preferably C1-C5-alkoxy, nitro, cyano or sulfo or a combination thereof;

(iv) one or two end-caps R ¹ -O-(C2-C4-O-) _e -*, wherein R ¹ is an optionally substituted hydrocarbon residue and e is an integer of from 0 to 1000. The polyether-ester copolymer of Embodiment E2 is preferably a non-branched copolymer, but it may also contain small amounts, i.e. up to 10 mol-%, of trifunctional or tetrafunctional comonomers, such as trimellitic anhydride, trimethylpropane, pyromellitic dianhydride, pentaerythritol and other polyacids polyols generally known in the art.

Beside the polytetramethylene oxide segments, the polyether segments (i) can contain other alkylene oxide segments such as ethylene oxide, propyleneoxide or a combination thereof.

Preferred embodiments of the polyether segments (i) are represented for example by formulae (I), (la), (lb), and (Ic), and optionally (Id) below: wherein k is an integer between 0 and 70, preferably between 0 and 35, particular preferably between 0 and 30; v is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 50; x is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 12; y is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 50; z is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 12; and the sum of k+v+x+y+z is between 0 and 1070, preferably between 0 and 535. For v+x > 2 and for v and x 0, and for y+z> 2 and y and z 0, the resulting polyethylenoxide/polypropylenoxide copolymer part can represent a randomly distributed copolymer or a block-copolymer, wherein both blocks (the polyethylenoxide block alternatively the polypropylenoxide block) can be chemically connected to the polytetramethyleneoxide block. Formula (la): wherein p is an integer between 0 and 35, preferably between 0 and 20, particular preferably between 0 and 15; w is an integer between 0 and 35, preferably between 0 and 20, particular preferably between 0 and 15; q is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 50; r is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 12; and the sum of p+w+q+r is between 0 and 570 , preferably between 0 and 290.

For q+r > 2 and for q and r 0, the resulting polyethylenoxide/polypropylenoxide copolymer part can represent a randomly distributed copolymer or a block- copolymer.

Formula (lb): wherein

K is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 12;

L is an integer between 0 and 35, preferably between 0 and 20, particular preferably between 0 and 15; M is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 50;

N is an integer between 0 and 35, preferably between 0 and 20, particular preferably between 0 and 15;

O is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 12; furthermore L + N cannot be chosen as 0; and the sum of K+L+M+N+O is between 1 and 820, preferably between 2 and 415.

In the case that K+L > 2 and for K, 0, or in the case that N+O > 2 and for N, O and

0, the resulting polypropylene oxide/polytetramethylene oxide- copolymer part can represent a randomly distributed copolymer or a block- copolymer wherein both blocks (the polypropylene oxide block alternatively the polytetramethylene oxide block) can be chemically connected to the polyethylene oxide block.

Formula (lc): wherein

P is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 50;

Q is an integer between 0 and 35, preferably between 0 and 20, particular preferably between 0 and 15;

R is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 12;

S is an integer between 0 and 35, preferably between 0 and 20, particular preferably between 0 and 15;

T is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 50; furthermore Q + S cannot be chosen as 0; and the sum P+Q+R+S+T is between 1 and 820, preferably between 2 and 415.

In the case that P+Q > 2 and for P, Q and R 0, or for the case that S+T > 2 and for S, T and R 0, the resulting polyethylene oxide/polytetramethylene oxide- copolymer part can represent a randomly distributed copolymer or a block- copolymer, wherein both blocks (the polyethylene oxide block alternatively the polytetramethylene oxide block) can be chemically connected to the polypropylene oxide block.

Formute (Id) wherein

U is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 50;

V is an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 12;

W is an integer between 0 and 70, preferably between 0 and 35, particular preferably between 0 and 30; and the sum U+V+W is between 3 and 570, preferably between 5 and 285.

In this embodiment the polyether segment can either be a homopolymer, a randomly distributed copolymer or a block-copolymer.

In all formulae, the asterisk * represents a bond to a bridging element (iii).

Preferably, the polyester segments (ii) are represented by formula (II): wherein

* represents a bond to a bridging element (iii),

R2 and R3 independently of each other 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.

Preferably, R2 and R3 independently of each other represent an aliphatic hydrocarbon residue of 1 to 24 carbon atoms, an olefinic hydrocarbon residue of 2 to 24 carbon atoms or an aromatic hydrocarbon residue of 5 to 14 carbon atoms, wherein said hydrocarbon residues are optionally substituted with C1-C5-alkoxy, nitro, cyano, or a combination thereof.

In a preferred embodiment, R2 and R3 are an aliphatic hydrocarbon residue consisting of 2 to 18 carbon atoms and most particular preferably consisting of 2 to 6 carbon atoms. The aliphatic hydrocarbon residue can be linear, branched or cyclic. Furthermore, the aliphatic hydrocarbon residue can be saturated or unsaturated. Preferably, it is saturated.

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-hexamethylene, 1 ,7- heptamethylene, 1 ,8-octamethylene and 1 ,4-cyclohexylene, and mixtures thereof. Particular 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-hexamethylene, and mixtures thereof. The most particular preferred residues are ethylene, 1 ,2-propylene and 1 ,4-butylene, and mixtures thereof. In a further preferred embodiment, R2 is an aromatic system. The aromatic system can be mono- or polycyclic, such as di- or tricyclic. Preferably, the aromatic system is consisting of 5 to 25 atoms, even more preferably of 5 to 10 atoms. The aromatic system is preferably formed by carbon atoms. In a further embodiment, it consists in addition to carbon atoms of one or more hetero atoms such as nitrogen, oxygen and/or sulfur. Examples of such aromatic systems are benzene, naphthalene, indole, phenanthrene, pyridine, furan, pyrrole, thiophene and thiazole.

Preferred aromatic structure elements for 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-sulphonate, 2,5-furanylene and mixtures thereof. Particularly preferred structure elements for R2 are ethylene, 1 ,2-propylene, 1 ,3-propylene, 2,2'-dimethyl-1 ,3-propylene, 1 ,4- butylene, 2,3-butylene, 1 ,6-hexamethylene, 1 ,4-cyclohexylene, 1 ,3-phenylene, 1 ,4- phenylene, 1 ,8-naphthylene and mixtures thereof. The most particular preferred structure elements for R2 are 1 ,3-phenylene, 1 ,4-phenylene, and mixtures thereof.

In another preferred embodiment R3 can be represented by formula (I la): wherein Z can be an integer number from 0 to 100.

The bridging elements (iii) may link the polyether segments (i), polyester segments (ii) and/or the end caps (iv). The bridging elements are described by formula (III): wherein R2 denotes the meanings given above.

(iv) The end-caps are bonded to a bridging element (iii). The bond is indicated by the asterisk *.

Preferred end-caps can be described by the following general formula wherein R1 is an aliphatic hydrocarbon residue of 1 to 24 carbon atoms, an olefinic hydrocarbon residue of 2 to 24 carbon atoms, an aromatic hydrocarbon residue of 6 to 14 carbon atoms, wherein said hydrocarbon residues are optionally substituted with C1-C5-alkoxy, nitro, cyano, sulfo, or a combination thereof, and e is an integer of from 0 to 1000, preferably an integer between 0 and 500 and most preferably an integer between 0 and 150.

In a preferred embodiment, R1 is an aliphatic hydrocarbon residue consisting of 1 to 18 carbon atoms and more preferably consisting of 1 to 12 carbon atoms. The aliphatic hydrocarbon residue can be linear, branched or cyclic. Furthermore, the hydrocarbon residue can be saturated or unsaturated. Preferably, it is saturated. Particularly preferred aliphatic residues for R1 are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo -pentyl, 1 ,2-dimethylpropyl, iso-amyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, methylphenyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl. Most preferred residues are methyl, ethyl and n-dodecyl. The most particular preferred residue is methyl. In a further preferred embodiment, R1 can be represented by an aromatic system. The aromatic system can be mono- or polycyclic, such as di- or tricyclic.

Preferably, the aromatic system is consisting of 6 to 14 carbon atoms, even more preferably of 6 to 10 atoms. The aromatic system is preferably formed by carbon atoms. In a further embodiment, it consists in addition to carbon atoms of one or more hetero atoms 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 be chemically connected to one, two, three or more identical or different functionalities. Suitable functionalities are for example alkyl- alkenyl-, alkoxy-, poly (alkoxy), cyano-, and I or nitro-functionalities. These functionalities may be bonded to any position of the aromatic system.

Particularly preferred groups R1 -O-(C2-C4-O-) _e -* correspond to the following formulae:

wherein the different monomers are distributed randomly, in blocks or a combination of random and block; b can be chosen as an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 50; a can be chosen as an integer between 0 and 250, preferably between 0 and 125, particular preferably between 0 and 12; c can be chosen as an integer between 0 and 70, preferably between 0 and 35, particular preferably between 0 and 30, and the sum a+b+c is of from 0 to 570; and

R1 is as defined above. The number average of the molecular weight for the copolymers 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.

In embodiment E2, said formulation for scavenging preferably includes a catalyst, as described at page 16 line 8 to page 16 line 32 of WO2018149778, the content of which is incorporated by said reference.

In an embodiment E3, said oxygen-scavenging compound, for example said oxygen-scavenging copolymer, may be a copolyester ether, for example as described in W02009032560, the content of which is incorporated by said reference.

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

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

Poly(tetramethylene-co-alkylene oxide) glycols, for example poly(tetramethylene- co-ethylene oxide) glycols [poly(THF-EO) glycols], can be prepared by methods such as the acid catalyzed copolymerization of the THF and EO, followed by neutralizing the reaction product. An example of this method would be the random copolymerization of THF and EO in an autoclave using 13.4-28.2 weight parts ethylene glycol, 72.7-241 .4 weight parts THF, 236-411 .8 weight parts EO and 15.3-32.3 weight parts boron trifluoride ethyl etherate, at conditions of ordinary pressure and temperature of 30°C. Ethylene glycol is used as the initiation agent and boron trifluoride ethyl etherate is used as the acid catalyst. After completion of the copolymerization, the acid catalyst in the product is neutralized with an alkali. Finally, the precipitates are filtered and dried with nitrogen gas at 100°C. Other poly(alkylene oxide) glycols can be used in combination with the poly(tetramethylene-co- alkylene oxide) glycols described above, for example polyethylene oxide) glycol, poly(trimethylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(pentamethylene oxide) glycol, poly(hexamethylene oxide) glycol, poly(heptamethylene oxide) glycol, poly(octamethylene oxide) glycol or poly(alkylene oxide) glycols derived from cyclic ether monomers, for example poly(2,3- dihydrofurandiyl) .

The total amount of copolyester ether in the final composition is chosen to provide the desired oxygen scavenging performance of the article formed from the composition. Amounts of the copolyester ether can be at least about 0.5 weight % of the total composition, or in the range of from about 0.5 weight % to about 10 weight % of the total composition, for example from about 1 .0 weight % to about 5.0 weight % or from about 1 .5 weight % to about 3.0 weight % of the total composition. The copolyester ether can be physically blended with the polyester. Alternatively, the poly(tetramethylene-co-alkylene oxide) glycol, and the other poly(alkylene oxide) glycols, can be copolymerized with the polyester.

The copolyester ethers can be produced by processes used to prepare polyesters, such as ester interchange with the dialkyl ester of a dicarboxylic acid or direct esterification with the dicarboxylic acid. In the ester interchange process dialkyl esters of dicarboxylic acids undergo transesterification with one or more glycols in the presence of a catalyst such as a compound of manganese, zinc, cobalt, titanium, calcium, magnesium or lithium, in the direct esterification process, one or more dicarboxylic acids are esterified with one or more glycols. The poly(tetramethylene-co~alkylene oxide) glycols and optionally the other poly(alkylene oxide) glycols replace part of these glycols in these esterification processes. The poly(tetramethylene- co-alkylene oxide) glycols and optionally the other poly(alkylene oxide) glycols can be added with the starting raw materials or added after esterification. In either case, the monomer and oligomer mixture can be produced continuously in a series of one or more reactors operating at elevated temperature and pressures at one atmosphere or greater. Alternatively, the monomer and oligomer mixture can be produced in one or more batch reactors. In batch processes, a monomer heel, comprising the monomer bishydroxyethylterephthalate (BHET) can be left in the esterification reactor to aid the esterification of the next batch. Suitable conditions for these reactions are temperatures of from about 180° C to 250°C and pressures of from about 1 bar to 4 bar.

Next, the mixture of copolyester ether monomer and oligomers undergoes melt-phase polycondensation to produce a low molecular weight precursor polymer. The precursor is produced in a series of one or more reactors operating at elevated temperatures. To facilitate removal of excess glycols, water, and other reaction products, the polycondensation reactors are run under a vacuum. Catalysts for the polycondensation reaction include compounds of antimony, germanium, tin, titanium and aluminum. Reaction conditions for polycondensation can include (i) a temperature less than about 290°C, or about 10°C higher than the melting point of the copolyester ether; and (ii) a pressure of less than about 0.01 bar, decreasing as polymerization proceeds. This copolyester ether can be produced continuously in a series of one or more reactors operating at elevated temperature and pressures less than one atmosphere. Alternatively, this copolyester ether can be produced in one or more batch reactors. The intrinsic viscosity after melt phase polymerization can be in the range of from about 0.5 dl/g to about 1 .5 dl/g.

After extruding the molten copolyester ether through a die, the strands are quenched in a bath of cold water and cut into pellets. These pellets can be fed directly into an extruder for forming the article, or solid stated at conventional conditions until the desired molecular weight is attained.

The copolyester ethers can contain the polyether segment in the range of from about 15 weight % to 95 weight % of the copolyester ether, for example from about 25 weight % to about 75 weight % or from about 30 weight % to about 70 weight % of the copolyester ether, using ethane glycol, butane diol or propane diol as the other glycol. The dicarboxylic acid can be terephthalic acid or dimethyl terephthalate. Antioxidants and photo initiators can be added during polymerization to control the initiation of the oxygen scavenging.

In embodiment E3, said formulation for scavenging preferably includes a catalyst, as described at page 5 line 19 to page 6 line 2 of W02009032560, the content of which is incorporated by said reference.

In embodiment E4, said formulation for scavenging preferably includes a polyfarnesene.

In said formulation for scavenging oxygen, the ratio of the wt% of oxygen-scavenging compound divided by the wt% of oil (including each oil referred to in (B) especially the oils referred to in (B)(a) to (f)) may be at least 0.5. It may be less than 30 or less than 15 or less than 11. Said ratio is preferably in the range 0.5 to 30, preferably 0.5 to 15, more preferably 2 to 11 .

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

Preferably, said formulation includes at least 3wt% of oil. Said formulation may include 3 to 35 wt% of said oil, more preferably 4 to 15 wt% of said oil. Preferably, said formulation includes up to 90 wt% of said oxygen-scavenging compound. Said formulation may include 25 to 90 wt% of said oxygen-scavenging compound, more preferably 30 to 86 wt% of said oxygen-scavenging compound.

Preferably, in said formulation, the sum of the wt% of olive oil, macadamia oil, avocado oil, bataua oil and gevuina oil is at least 3 wt% and may be in the range 3 to 35 wt%, preferably in the range 4 to 15 wt%. Preferably, in said formulation the sum of the wt% of oxygen scavenger compound referred to in (A), olive oil, macadamia oil, avocado oil, bataua oil and gevuina oil is at least 35 wt%, preferably at least 40 wt%.

Preferably, in said formulation, the sum of the wt% of olive oil and macadamia oil is at least 3 wt% and may be in the range 3 to 35 wt%, preferably in the range 4 to 15 wt%. Preferably, in said formulation the sum of the wt% of oxygen scavenger compound referred to in (A), olive oil, and macadamia oil is at least 35 wt%, preferably at least 40 wt%.

Preferably, in said formulation the sum of the wt% of oxygen scavenger compound referred to in (A) and is at least 35 wt%, preferably at least 40 wt%.

Said formulation for scavenging oxygen may further include a transition metal, for example a transition metal salt. The transition metal may be cobalt, for example derived from cobalt stearate.

Said formulation may include less than 1 .0wt%, preferably less than 0.6wt%. more preferably less than 0.3wt% of cobalt moieties. Said formulation may include at least 0.05wt%, preferably at least 0.1wt%. more preferably at least 0.15wt% of cobalt moieties. Said formulation may include 0.05 to 0.4 wt% of cobalt moieties.

Said formulation for scavenging may include:

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

- at least 3wt% (preferably 3 to 35wt%) of one or a plurality of oils described in (B) above (especially the oils referred to in (B)(a) to (f)); and, optionally (but preferably),

- at least 0.05wt% (preferably 0.05 to 0.4 wt%) of cobalt moieties.

Said formulation for scavenging may include:

25 to 90 wt% (preferably 30 to 86 wt%) of oxygen-scavenging compound; - olive oil and/or macadamia oil, wherein the sum of the wt% of olive oil and macadamia oil in the formulation is at least 3wt% (preferably 3 to 35wt%); and, optionally (but preferably),

- at least 0.05wt% (preferably 0.05 to 0.4 wt%) of cobalt moieties.

Said formulation for scavenging may include:

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

- at least 3wt% (preferably 3 to 35wt%) olive oil; and, optionally (but preferably),

- at least 0.05wt% (preferably 0.05 to 0.4 wt%) of cobalt moieties.

Said formulation for scavenging oxygen may be provided in a range of different forms. In one embodiment, said formulation may comprise a single mass comprising the components described, wherein the single mass may be a substantially homogenous mixture or a heterogenous mixture. The single mass may be in a solid form, for example in the form of pellets. In this case, an individual pellet may include said oxygen-scavenging compound and said oil; and suitably substantially each pellet in said single mass is as described. In another embodiment, said formulation for scavenging may comprise separate first and second components, wherein said first component may comprise said oxygen-scavenging compound and, optionally, said transition metal (when provided); and said second component comprises said oil. In this case, the first and second components may be brought together when the components are contacted with a packaging resin (eg of polyester) which is arranged to provide the majority of the structure of packaging material in which the formulation for scavenging oxygen is utilised. In a further embodiment, the formulation may comprise a blend which comprises a first component, wherein said first component may comprise said oxygenscavenging compound and, optionally, said transition metal (when provided); and a second component which comprises said oil, optionally in combination with a carrier, for example a solid carrier for said oil. The blend may be a salt and pepper blend. It may comprise a first solid masterbatch which includes said oxygen-scavenging polymer (and optional catalyst); and a second solid masterbatch which includes said oil and a solid carrier (eg polyester such as PET); wherein the first and second masterbatches (e.g. in solid or granular form) are blended to define a salt and pepper blend.

Alternatively, said formulation for scavenging oxygen may comprise a liquid, for example a liquid masterbatch.

Said formulation, for example one or more of the masterbatches referred to, may include additional additives, for example toners. Said formulation may be added to a packaging resin (eg of a polyester, such as PET) to define a composition which may be formed, for example by melt-processing, into a packaging article, for example a preform for a bottle.

The invention extends, in a second aspect, to a composition comprising a packaging resin (eg of a polyester, such as PET); and

(A) an oxygen-scavenging compound as described in the first aspect; and

(B) an oil as described in the first aspect, for example being selected from:

(a) olive oil;

(b) macadamia oil;

(c) avocado oil;

(d) bataua oil;

(e) gevuina oil;

(f) an oil PQ as described in the first aspect; and

(g) an oil RS as described in the first aspect.

Said composition may be formed in a melt-processing apparatus, for example in an injection mouding device. A packaging article, for example a preform for a receptacle (eg a bottle, such as a stretch blow moulded bottle) may be comprised of said composition.

Said composition may comprise:

(I) a packaging resin (eg of a polyester, such as PET);

(II) said oxygen-scavenging compound as described in the first aspect;

(III) a said oil as described in (B) of the first aspect (especially the oils referred to in (B)(a) to (f)).

Said composition may include:

-at least 95wt%, for example at least 97wt%, of packaging resin (eg of a polyester, such as PET); -less than 5.0wt% (preferably less than 2.5wt% or less than 1 ,8wt%) of said oxygen-scavenging compound as described in the first aspect;

-less than 2.0wt% (preferably less than 1 .0wt% or less than 0.6 wt%) of a said oil as described in (B) in the first aspect (especially the oils referred to in (B)(a) to (f)).

Said composition may include at least 0.5wt% (preferably at least 1.0wt%) of said oxygenscavenging compound as described in the first aspect; and at least 0.1 wt% (preferably at least 0.2wt%) of a said oil as described in (B) (especially the oils referred to in (B)(a) to (f)) in the first aspect.

Said composition may include:

-at least 95wt%, for example at least 97wt%, of packaging resin (eg of a polyester, such as PET); -less than 5.0wt% (preferably less than 2.5wt% or less than 1 ,8wt%) of said oxygen-scavenging compound as described in the first aspect;

-olive oil, macadamia oil, avocado oil, bataua oil and/or gevuina oil; wherein the sum of the wt% of olive oil, macadamia oil, avocado oil, bataua oil and gevuina oil in the composition is less than 2.0wt% (preferably less than 1 .0wt% or less than 0.6 wt%.

Said composition may include at least 0.5wt% (preferably at least 1.0wt%) of said oxygenscavenging compound as described in the first aspect; and the sum of the wt% of olive oil, macadamia oil, avocado oil, bataua oil and gevuina oil is at least 0.1 wt% (preferably at least 0.2wt%).

Said composition may include:

-at least 95wt%, for example at least 97wt%, of packaging resin (eg of a polyester, such as PET); -less than 5.0wt% (preferably less than 2.5wt% or less than 1 ,8wt%) of said oxygen-scavenging compound as described in the first aspect;

- less than 2.0wt% (preferably less than 1 .0wt% or less than 0.6 wt%) of olive oil.

Said composition may include at least 0.5wt% (preferably at least 1.0wt%) of said oxygenscavenging compound as described in the first aspect; and at least 0.1wt% (preferably at least 0.2wt%) of olive oil.

Said compositions described preferably includes a transition metal catalyst especially a cobalt catalyst. Said composition preferably include at least 0.001wt%, preferably at least 0.002wt% of cobalt moieties. Said compositions preferably include less than 0.05wt%, preferably less than 0.01 wt% of cobalt moieties. Said composition may include a cobalt compound, for example cobalt stearate. Said composition preferably includes at least 0.01wt%, preferably at least 0.02wt% of said cobalt compound. Said composition preferably include less than 0.5wt%, preferably less than least 0.1 wt% of said cobalt compound.

Said composition of the second aspect may define a packaging material. Said packaging material may define or be a component of a receptacle. A receptacle may comprise an extruded or thermoformed article, such as a tray, for example for food applications. Alternatively, the receptacle may be, for example, a preform for a bottle (a preform suitably being a test-tube shaped article which is stretch blow moulded to define a bottle) or a bottle per se. Preferred receptacles, for example preforms or bottles, are monolayer preforms or bottles. Preferably, a receptacle, for example, a preform or bottle (suitably excluding any closure thereof) comprises at least 90 wt%, more preferably at least 95 wt%, especially at least 99 wt%, of said composition.

According to a third aspect of the invention, there is provided a method of making a packaging article, for example a receptacle such as a preform for a bottle or a bottle per se, the method comprising:

(I) contacting an oxygen-scavenging compound, an oil as described in (B) in the first aspect and a packaging resin (eg of a polyester, such as PET); and

(II) melt-processing the components referred to in (I) to define the packaging article.

Said oxygen-scavenging compound, said oil and said packaging resin may independently be as described in the first or second aspects.

Said packaging article may have a composition as described in the second aspect.

Said receptacle may be as described in the second aspect.

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

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

The method is preferably a method of making a packaging article, for example a receptacle such as a preform for a bottle or a bottle per se which can be directly recycled_with substantially pure PET in accordance with the European PET Bottle Platform (EPBP) protocol.

The invention extends, in a fourth aspect, to a method of recycling a packaging article, the method comprising:

-selecting a packaging article as described in the second aspect and/or made as described in the third aspect; and -contacting the packaging article or fragments thereof with other PET to produce a mixture.

The mixture may include 5 to 50wt% of said packaging article or fragments thereof and 50 to 95wt% of other PET. The other PET may be PET which includes no colorant. It preferably includes no oxygen scavenger compound. It may be virgin PET.

The invention extends, in a fifth aspect, to recycled PET produced as described in the fourth aspect.

In a sixth aspect, there is provided the use of the formulation of the first aspect for scavenging oxygen and for producing a composition which can be recycled with virgin PET to produce a mixture which has a b* less than a predetermined level.

Any aspect of any invention described herein may be combined with any other aspect of any invention described herein mutatis mutandis.

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

Figure 1 which is a graph which provides Pulldown Oxygen Scavenging Test results for Examples 3 and 4;

Figure 2 is a graph which provides Ingress Oxygen Scavenging Test results for Examples 6 to 10; and

Figure 3 is a graph which provides Ingress Oxygen Scavenging Test results for Examples 12 to 21.

The following materials are referred to hereinafter:

MXD-6 - refers to polyxylylene adipamide in pellet form, supplied by Mitsubishi.

Cobalt stearate/PET masterbatch - A masterbatch comprising 12wt% cobalt stearate and 88wt% PET.

PET-X - refers to Equipolymers C93, a polyethylene terephthalate (PET) bottle grade polymer. Valor (Trade Mark) - a scavenger resin being nylon based which is commercially-available from PETnology/tecPET GmbH

Oxyclear (Trade Mark) - a scavenger resin being polyether based which is commercially- available from Invista/lndorama.

Olive oil - a non-refined olive oil purchased from Sigma Aldrich.

Macadamia oil - extra virgin, cold-pressed macadamia oil sold under the brand Pure South Press.

Avocado oil - extra-virgin, cold pressed avocado oil sold under the brand name Mokhado.

Gevuina oil - Organic, cold-pressed, unrefined gevuina oil sold under the brand name Biopurus.

Assessment 1 - “Pulldown” Oxygen Scavenging Testing Procedure

In a “pulldown” test method, oxygen scavenging additives incorporated into bottle walls can be assessed by filling the bottles with oxygen-containing water and monitoring the depletion of dissolved oxygen content over time.

In the method, bottles to be assessed and water (before introduction into the bottles) is stored in a temperature controlled environment (21 °C). Standards of known activity and blank controls (virgin PET) are assessed alongside test samples to verify the test method set-up. Note: If O2 depletion is observed in blank virgin PET bottles over a test period (eg over 14 days of testing) there could be algae/microorganisms in the water and sample testing will have to be repeated. This may occur if insufficient biocide is added.

The method may then comprise the following steps:

(i) A bucket is filled with tap water and biocide (polyhexamethylene biguanide PHMB) (~1 ml biocide in 5 litres water) and covered with a lid. The water is left for about 24 hours in a temperature controlled room for temperature and dissolved oxygen content to equilibrate.

(ii) Stretch-blow moulded bottles, incorporating any oxygen scavenging additives, are made on the same day or day before putting on test. The bottles are stored in sealed aluminum bags purged with N2 before use.

(iii) Before a bottle is filled with the prepared biocide water, an opTech Platinum sensor dot (part of a commercially available oxygen measurement system from Ametek Mocon) is attached onto the inside bottle wall using tweezers or other such tool. Then the following steps are undertaken:

(a) Each bottle is filed to the brim with the prepared water/biocide leaving no headspace.

(b) A bottle closure is placed on each bottle and tightened using a bottle cap torque meter to the recommended Nm, depending on closure specification.

(c) Once all bottles to be assessed had been prepared, an initial reading of dissolved O2 content is taken. This should be ~10 ppm.

(d) Bottles are stored in a temperature controlled room and measurements are taken every 2-3 days for 14 days.

(e) Further measurements may be taken after the specified 14 days if desired.

Assessment 2 - “Ingress” Oxygen Scavenging Testing Procedure

In an “ingress” test method, oxygen scavenging additives incorporated into bottle walls can be assessed by filling the bottles with deoxygenated water and monitoring the dissolved oxygen content of the water as it increases (ingress through bottle wall) over time.

As a standard method for measuring scavenging activity, measurements may be taken at regular intervals every few days up to 14 days and every few weeks thereafter. The frequency of measurements is dependent on the expected shelf life extension the additive can impart. The test is complete when the dissolved oxygen reaches a level of 3 ppm.

The method may then comprise the following steps:

(i) A glove box set-up is required that contains a tank/container for water, a nitrogen supply and a vacuum system. There should be a nitrogen supply to the tanks to bubble through the water. The glove box should also contain weighing scales, bottle lids, torque meter and a dissolved oxygen sensor (probe inserted into water tank).

(ii) Stretch-blow moulded bottles, incorporating any oxygen scavenging additives, are made on the same day or day before putting on test. An appropriate oxygen measurement sensor (such as an OpTech Platinum sensor dot) is attached into the inside of the bottle samples using tweezers or other such tool. The bottles are stored in sealed aluminium bags purged with N2 before use.

(iii) Standards of known activity (e.g 3% 4020G in virgin PET) and blank controls (virgin PET) may be assessed alongside test samples to verify test method set-up. Note: If scavenging is observed in blank virgin PET bottles there could be algae/microorganisms in the water and sample testing will have to be repeated. This can occur if insufficient biocide is added.

(iv) The tank/container in the glove box is filled with tap water and biocide (polyhexamethylene biguanide PHMB) (~1 ml biocide in 5 litres water). (v) All equipment and sample bottles are placed inside the glove box before sealing.

(vi) Nitrogen is bubbled through the water up to the maximum safe pressure, followed by a vacuum up to the lowest maximum safe pressure. This process is repeated multiple times until the oxygen sensor inserted in the water tank reads a dissolved oxygen content below 300 ppb.

(vii) It is ensured there is ambient pressure in the glove box before nominally filling bottles with water/biocide from tank/container (There will be a headspace).

(viii) A bottle closure is placed on each bottle and tightened using a bottle cap torque meter to the recommended Nm, depending on closure specification.

(ix) Once all samples are prepared, the glove box can be opened, samples removed and an initial reading of dissolved O2 content is taken. This should be <300 ppb (parts-per-billion).

(x) Samples are stored in a temperature controlled room and measurements taken every 2- 3 days for 14 days and every few weeks thereafter.

The following examples illustrate preferred embodiments of the invention.

Example 1 - General procedure for preparation of preforms

25g, 38mm neck diameter preforms were manufactured in a Husky GL160 injection moulder, with a two cavity mould installed. PET-X which had been pre-dried to less than 50ppm moisture was premixed manually with components to be tested and manually added into a hopper installed above the feed throat of the injection moulder machine. A standard PET injection moulding process was employed to produce preforms.

Example 2 -Producing bottles from preforms

Preforms made as described in Example 1 were stretch blow moulded using a Sidel SB01 blow moulding machine into a 1 litre cylindrical bottle. A standard blowing process was utilised. The overall power % of the heating ovens was adjusted to achieve a preform temperature of 115°- 120°C as the preform exits the oven and before it enters the blow mould. This is referred to as the blowing temperature.

Examples 3 and 4 - Preparation of bottles to be assessed

Following the general procedure described in Example 1 , preforms were made having the following compositions (which were prepared by tumble blending the specified components before injection moulding):

The preforms were made into bottles as described in Example 2.

Example 5 - Assessment of bottles of Examples 3 and 4.

The bottles of Examples 3 and 4 were assessed as described in Assessment 1 and results are presented in Figure 1 which shows that, when olive oil is included, the oxygen scavenging performance is far superior compared to when no olive oil is included.

The observation in relation to the Example 3 and Example 4 bottles may be exploited in a number of ways. For example, a lower amount of relatively costly MXD-6 may be used in a bottle in favour of cheaper olive oil and a similar level of oxygen scavenging may be achieved. Alternatively, the olive oil may be used to provide increased levels of oxygen scavenging (and therefore improved shelf life) compared to bottles which include the same amount of MXD-6.

Advantageously, it is found that, when relatively low levels of MXD-6 are used in a bottle, the bottle can be recycled with bottles made from pure PET to produce recycled PET which has acceptable colour (eg acceptable L*, a* and b* values) and is acceptable in accordance with an appropriate European PET Bottle Platform (EPBP) test procedure.

Examples 6 to 10 - Preparation of bottles to be assessed to illustrate use of a range of oils together with commercially-available Valor oxygen scavenger.

Following the procedure described for Examples 1 to 4, preforms and subsequently bottles were made having the following compositions:

Example 11 - Assessment of bottles of Examples 6 to 10

The bottles were assessed as described in Assessment 2 and results are provided in Figure 3 which shows that addition of the specified oils improved oxygen scavenging significantly.

Examples 12 to 21 - Preparation of bottles to be assessed to illustrate use of a range of oils together with commercially-available Oxyclear oxygen scavenger.

Following the procedure described for Examples 1 to 4, preforms and subsequently bottles were made having the following compositions:

Example 13 - Assessment of bottles of Examples 12 to 21

The bottles were assessed as described in Assessment 2 and results are provided in Figure 4 which shows that addition of the specified oils improved oxygen scavenging significantly and that the improvement was greater when olive oil was used. The invention is not restricted to the details of the foregoing embodiment(s). The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.