BR112019015421B1 - POLYETHER-POLYESTER COPOLYMER, ITS PREPARATION METHOD, COMPOSITION OF ACTIVE OXYGEN BARRIER AND OXYGEN ABSORBING PLASTIC MATERIAL - Google Patents

Abstract

The invention relates to a polyether-polyester copolymer comprising (i) polyether segments in which at least one polyether segment contains at least one polytetramethylene oxide segment, (ii) polyester segments, (iii) bonding elements of the -CO-R2-CO- structure, wherein R2 represents an optionally substituted divalent hydrocarbon residue consisting of 1 to 100 carbon atoms; (iv) one or more caps R1-O-(C2-C4-O-)e-*, wherein R1 is an optionally substituted hydrocarbon residue and is an integer from 0 to 1000.

Description

[0001] The present invention relates to an end-capped polyether-polyester copolymer capable of absorbing oxygen and its use in combinations and articles capable of removing oxygen or functioning as an active oxygen barrier.

[0002] Thermoplastic resins such as PET (polyethylene terephthalate) have been widely used to produce various types of storage and packaging containers. PET is mainly involved in the beverage industry because it is as transparent as glass but much lighter; it is also resistant to fractures; completely recyclable and has good color flexibility and a variety of PET bottle designs are also made possible. The biggest disadvantage of PET is its permeability to gases and in this case, specifically, its permeability to oxygen.

[0003] It is well known that packaging for electronics, personal care, household, industrial, food and beverage requires high oxygen barrier properties to preserve the freshness and quality of the packaging contents. Especially, sauces and beverage products such as juices, beer and tea require packaging material with high barrier properties or the ability to block oxygen entry and/or remove captured oxygen to prevent product oxidation and extend shelf life. merchandise shelf.

[0004] To resolve these limitations and improve the shelf life of oxygen-sensitive products (beer, juices or tomato sauce), several strategies have been used.

[0005] The packaging industry has developed, for example, +9854 comprising mixed polymer layers. These laminated packaging containers provide improved barrier properties that approach, but are not comparable to, those of glass and steel, while sacrificing many of the recycling benefits associated with single-layer containers such as PET, polyethylene naphthalate (PEN) or polyolefin bottles. Furthermore, the clarity of the container is often substantially diminished. Maintaining the proper balance of recyclability, barrier properties and clarity is most critical in bottling applications.

[0006] The use of multi-layer bottles that contain an inner layer, sometimes interspersed, of a higher barrier polymer material compared to the other polymer layers is common. Typically, the core layer is a high barrier polymer that shows oxygen permeability through the container wall. Examples of such passive high-barrier polymers include ethylene vinyl alcohol (EVOH) and polyamides, preferably a partially aromatic polyamide containing meta-xylylene groups, such as poly(m-xyllylene adipomide), MXD6. A common construction for such multilayer structures would comprise inner and outer layers of PET with a core layer of a polyamide, or inner and outer layers of polyolefins with a core layer of ethylene vinyl alcohol (EVOH) polymer.

[0007] A different strategy that can also be combined with the use of passive barriers is the use of an active oxygen absorber to reduce or remove oxygen ingress from the packaging. The method of providing oxygen barrier properties in which a substance consumes or reacts with oxygen is known as a (re)active oxygen barrier and differs from passive oxygen barriers which attempt to hermetically seal a product away from oxygen by through the passive method. Various systems of oxygen scavenging systems are known in the art. Among others, oxygen scavenging compositions comprising an oxidizable substituted or unsubstituted ethylenically unsaturated hydrocarbon and a transition metal catalyst are well-known viable solutions.

[0008] Containers, such as sachets, loaded with oxygen scavenging compositions are well-known examples of applications of such materials. However, these applications are generally limited to solid substances and solid foods, and special care is required to avoid ingestion.

[0009] To solve this problem, the oxygen absorbers were also embedded in a polymer resin that forms at least one layer of the container and small amounts of transition metal salts can be added to catalyze and actively promote the oxidation of the absorbers, enhancing the oxygen barrier characteristics of the packaging.

[0010] This method provided the opportunity to absorb or reduce oxygen from outside, but also unwanted oxygen from the packaging cavity that may have been inadvertently introduced during packaging or loading.

[0011] Modified polyesters were also widely used as oxygen absorbers. Modifications other than esters have been discovered to be active as oxygen absorbers. US 6083585A, WO 98/12127 and WO 98/12244 describe oxygen absorbing polyester compositions in which the absorber component is polybutadiene.

[0012] Other modifications consist of introducing ether groups using poly(alkylene oxide)s, for example. US 6455620 describes poly(alkylene glycol)s that act as oxygen absorbers mixed with different thermoplastic polymers.

[0013] Furthermore, WO 01/10947 describes oxygen absorbing compositions comprising an oxidation catalyst and at least one polyether selected from the group consisting of poly(alkylene glycol)s, copolymers of poly(alkylene glycol)s and mixtures containing poly (alkylene glycol)s suitable for incorporation into articles containing oxygen-sensitive products.

[0014] WO 2009/032560A1 describes oxygen absorbing compositions comprising an oxidation catalyst and a copolyester ether comprising a polyether segment comprising poly(tetramethylene-co-alkylene ether) having a low level of haze.

[0015] WO 2005/059019 A1 and WO 2005/059020 A2 describe a composition comprising a copolymer comprising polypropylene oxide segments and a polymer with improved active oxygen barrier properties compared to previously known compositions.

[0016] The aforementioned oxygen absorbing systems aim to reduce the oxygen level in the packaging to as low a degree as possible. This, however, is not always desirable. Not all products have the same needs for a suitable atmosphere for extended shelf life. In the case of wines, fruits and vegetables, creating a suitable atmosphere containing a limited level of oxygen is desirable to mitigate the development of an unpleasant taste. In the case of meat and fish, a certain low level of oxygen in the atmosphere is necessary to prevent development of certain pathogen anaerobic bacteria, type Clostridium botulinum.

[0017] To maintain a certain low level of oxygen in the packaging, it is necessary to match the ingress of oxygen into the packaging with the rate of oxygen consumption by the oxygen absorbing composition. This could potentially be achieved by reducing the content of the oxygen absorbing composition in the packaging. However, this would come at the expense of the overall oxygen-absorbing capacity of the packaging, thereby reducing the shelf life of the contained product article.

[0018] Consequently, it is desirable to provide an oxygen absorption system, which is capable of finely adjusting the oxygen absorption reaction rate to a desired reduced level and maintaining this level over the intended shelf life of the product, thereby providing high absorption capacity.

[0019] It has surprisingly been discovered that certain polyether-polyester polymers as described hereinafter can be effectively used to effect and control oxygen absorption in a thermoplastic material.

SUMMARY OF THE INVENTION

[0020] An object of the present invention is a polyether-polyester copolymer comprising (i) polyether segments in which at least one polyether segment contains at least one polytetramethylene oxide segment, (ii) polyester segments, ( iii) linkers of the -CO-R2-CO- structure, wherein R2 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 more caps at the R1-O-(C2-C4-O-)e-* end, wherein R1 is an optionally substituted hydrocarbon residue and is an integer from 0 to 1000.

[0021] The polyether-ester copolymer of the invention is preferably an unbranched copolymer, it may also contain small amounts, that is, up to 10 mol%, of trifunctional and tetrafunctional comonomers, such as trimellitic anhydride, trimethylpropane, priomelytic dianhydride, pentaerythritol and other polyacids and polyacids generally known in the art.

[0022] In addition to the polytetramethylene oxide segments, the polyether segments (i) may contain other alkylene oxide segments such as ethylene oxide, propylene oxide or a combination thereof.

[0023] Preferred embodiments of polyether segments (i) are represented, for example, by formulas (I), (Ia), (Ib), and (Ic), and, optionally, (Id) below: wherein k is an integer between 0 and 70, preferably between 0 and 35, particularly preferably between 0 and 30; v is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50; x is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12; y is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50; z is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12; and the sum of k+v+x+y+z is between 0 and 1070, preferably between 0 and 535.

[0024] For v+x > 2 and for vex # 0, and for y+z > 2 and z # 0, the polyethyleneoxide/polypropylenoxide copolymer part may represent a randomly distributed copolymer or a blocking copolymer, in which both locks (the polyethylene oxide lock and alternatively the polypropylene oxide lock) can be chemically connected to the polytetramethylene oxide lock. Formula (Ia): wherein p is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15; w is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15; q is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50; r is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12; and the sum of p+w+q+r is between 0 and 570, preferably between 0 and 290.

[0025] For q+r > 2 and for qer # 0, the polyethyleneoxide/polypropyleneoxide copolymer part may represent a randomly distributed copolymer or a blocking copolymer. Formula (Ib): wherein K is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12; L is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15; M is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50; N is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15; O is an integer between 0 and 250, preferably between 0 and 125, particularly 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.

[0026] In the case where K+L > 2 and for K, L and M # 0, or in the case where N+O > 2 and for N, O and M # 0, the polypropylene oxide copolymer part /polytetramethylene oxide may represent a randomly distributed copolymer or a block copolymer in which both blocks (the polypropylene oxide block and alternatively the polytetramethylene oxide block) can be chemically connected to the polyethylene oxide block . Formula (Ic): wherein P is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50; Q is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15; R is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12; s is an integer between 0 and 35, preferably between 0 and 20, particularly preferably between 0 and 15; T is an integer between 0 and 250, preferably between 0 and 125, particularly 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.

[0027] In the case where P+Q > 2 and for P, qer # 0, or for the case where S+T > 2 and for S, T and R # 0, the polyethylene oxide / oxide copolymer part The resulting polytetramethylene block may represent a randomly distributed copolymer or a block copolymer, in which both blocks (polyethylene oxide block and alternatively polytetramethylene oxide block) may be chemically connected to the polypropylene oxide block. Formula (Id): wherein U is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50; V is an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12; W is an integer between 0 and 70, preferably between 0 and 35, particularly preferably between 0 and 30; and the sum U+V+W is between 3 and 570, preferably between 5 and 285.

[0028] In this embodiment, the polyether segment can be a homopolymer, a randomly distributed copolymer or a block copolymer.

[0029] In the formulas, the asterisk * represents a connection to a connection element (iii).

[0030] Preferably, the polyester segments (ii) are represented by formula (II): wherein * represents a bond to a linker (iii), R2 and R3 independently of each other represent an optionally substituted hydrocarbon residue consisting of 1 to 100 carbon atoms in which 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.

[0031] 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. carbon, wherein said hydrocarbon residues are optionally substituted with C1-C5-alkoxy, nitro, cyano, or a combination thereof.

[0032] In a preferred embodiment, R2 and R3 are an aliphatic hydrocarbon residue consisting of 2 to 18 carbon atoms and more particularly preferably consisting of 2 to 6 carbon atoms. The aliphatic hydrocarbon residue may be linear, branched or cyclic. Furthermore, the aliphatic hydrocarbon residue can be saturated or unsaturated. Preferably, it is saturated.

[0033] 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. of the same. More particular preferred residues are ethylene, 1,2-propylene and 1,4-butylene, and mixtures thereof.

[0034] In another preferred embodiment, R2 is an aromatic system. The aromatic system may be mono- or polycyclic, such as d- or tricyclic. Preferably, the aromatic system consists of 5 to 25 atoms, even more preferably 5 to 10 atoms. The aromatic system is preferably formed by carbon atoms. In another embodiment, it further consists of carbon atoms of 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.

[0035] Preferred aromatic structural elements for R2 are 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,8-naphthalene, 1,4-naphthalene, 2,2'-biphenylene, 4, 4'-biphenylene, 1,3-phenylene-5-sulfonate, 2,5-furanylene and mixtures thereof.

[0036] Particularly preferred structural 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-naphthalene and mixtures thereof. More particular preferred structural elements for R2 are 1,3-phenylene, 1,4-phenylene, and mixtures thereof.

[0037] In another preferred embodiment R3 can be represented by formula (IIa): where Z can be an integer from 0 to 100.

[0038] The connecting elements (iii) can connect the polyether segments (i), polyester segments (ii) and/or the end caps (iv). The connecting elements are described by formula (III): where R2 indicates the meanings given above. (iv) The end steps are connected to a connection element (iii). The connection is indicated by the asterisk *.

[0039] Preferred end caps can be described by the following general formula R1-O-(C2-C4-O-)e-*, where R1 is an aliphatic hydrocarbon residue of 1 to 24 carbon atoms, a residue of olefinic hydrocarbon 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 is an integer from 0 to 1000, preferably an integer between 0 and 500 and more preferably an integer between 0 and 150.

[0040] 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 may be linear, branched or cyclic. Furthermore, the hydrocarbon residue can be saturated or unsaturated. Preferably, it is saturated.

[0041] 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-dimethyl-propyl, iso-amyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, tridecyl, isotridecyl , tetradecyl, hexadecyl, octadecyl, methylphenyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl. The most preferred residues are methyl, ethyl and n-dodecyl. The most particular preferred residue is methyl.

[0042] In another preferred embodiment, R1 can be represented by an aromatic system. The aromatic system may be mono- or polycyclic, such as d- or tricyclic. 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, it further consists of carbon atoms of 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. Furthermore, 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/or nitro functionalities. These functionalities can be connected to any position in the aromatic system.

[0043] The particularly preferred groups R1-O-(C2-C4-O-)e-* correspond to the following formulas wherein the different monomers are distributed randomly, in blocks or a combination of random and block b may be chosen as an integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 50 a may be chosen as a number integer between 0 and 250, preferably between 0 and 125, particularly preferably between 0 and 12. c may be chosen as an integer between 0 and 70, preferably between 0 and 35, particularly preferably between 0 and 30, and the sum a+ b+c is from 0 to 570; and R1 is as defined above.

[0044] The number average molecular weight for the copolymers of the present invention is preferably between 2000 and 1000000 g/mol, more preferably between 3500 and 100000 g/mol, more preferably between 5000 and 50000 g/mol.

[0045] The mass ratio Q defined as the mass ratio between the poly(tetramethylene-oxide) content and the global content of all dicarbonyl structure elements, that is, in (ii) and (iii), of the copolymers of the present invention is preferably between 0.1 and 10, more preferably between 0.2 and 5 and most preferably between 0.5 and 2.

[0046] The mass ratio Q defined as the mass ratio between capping content at the end and the overall content of all dicarbonyl structure elements, that is, in (ii) and (iii), of the copolymers of the present invention is preferably between 0.001 and 100, more preferably between 0.005 and 50 and most preferably between 0.01 and 2.

[0047] The copolymers of the present invention can be prepared by polycondensation of at least one polyether segment containing at least one polytetramethylenoxide segment, at least one polyester segment, at least one bridging element and at least one capping at the R1-O- (C2-C4-O-)e-* end.

[0048] The starting compounds that provide polyether segments (i) according to the invention can be homo- or copolymers, the copolymers can be block, random or segmented. Examples of starting compounds are: poly(tetrahydrofuran)-diol, poly(propylene glycol)-diol, poly(ethylene glycol)-diol, poly(ethylene glycol)-co-poly(propylene glycol)-diol, poly(ethylene glycol)-co - poly(tetrahydrofuran)-diol, poly(propylene glycol)-co-poly(tetrahydrofuran)-diol and poly(ethylene glycol)-co-poly(propylene glycol)-co-poly(tetrahydrofuran)-diol.

[0049] The polyester segment can be synthesized in situ during the polycondensation reaction or introduced as a pre-synthesized building block at the beginning of the reaction. Preferred polyester segments are those resulting from the condensation reaction of dibasic acids, or esters or anhydrides thereof, and diols.

[0050] Examples for starting compounds that provide polyester segments (ii) according to the invention are dimethyl terephthalate, terephthalic acid, dimethyl isophthalate, isophthalic acid, dimethyl adipate, adipic acid, azelaic acid, sebacic acid, diacid dodecanoic acid, 1,2-cyclohexane dicarboxylic acid, dimethyl-1,4-cyclohexane ester dicarboxylate, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclo - hexanedimethanol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, poly(ethylene terephthalate) and poly(butylene terephthalate).

[0051] Examples for starting compounds that provide binding elements (iii) according to the invention are dimethyl terephthalate, terephthalic acid, dimethyl isophthalate, isophthalic acid, dimethyl adipate, adipic acid, azelaic acid, sebacic acid, diacid dodecanoic acid, 1,2-cyclohexane dicarboxylic acid, dimethyl-1,4-cyclohexane dicarboxylate ester.

[0052] Examples for starting compounds that provide end caps are monomethoxylated poly(ethylene glycol)-monool, monomethoxylated poly(ethylene glycol)-co-poly(propylene glycol)-monool, lauryl alcohol ethoxylate, oleic alcohol ethoxylate, nonyl ethoxylate -phenol, n-dodecanol, oleyl alcohol.

[0053] For the preparation of the copolymers of the present invention, typically, a two-stage process is used in direct esterification of diacids and diols or transesterification and diols, followed by a polycondensation reaction under reduced pressure.

[0054] A suitable process for preparing the copolymers of the present invention comprises heating the starting compounds suitable for segments (i) to (iv) with the addition of a catalyst, to temperatures of 160 to 220°C, expediently starting at atmospheric pressure, and then continuing the reaction under reduced pressure at temperatures of 160 to 240°C.

[0055] Reduced pressure preferably means a pressure of 0.1 to 900 mbar and more preferably a pressure of 0.5 to 500 mbar.

[0056] Typical transesterification and condensation catalysts known in the art can be used for the preparation of copolymers, such as catalysts based on antimony, germanium and titanium. Preferably, tetraisopropyl orthotitanate (IPT) and sodium acetate (NaOAc) are used as the catalyst system in the process.

[0057] The present invention also provides a method of providing an active oxygen barrier in a plastic material of a packaging article comprising incorporating an effective amount of the polyether-polyester copolymer and a transition metal catalyst into a thermoplastic polymer material. which is preferably a polyester, a polyolefin, a polyolefin copolymer or a polystyrene.

[0058] Therefore, another object of the present invention is an active oxygen barrier composition comprising a polyether-polyester copolymer as described above and a transition metal catalyst, preferably in a concentration of 0.001 to 5% by weight, more preferably 0.01 to 0.5%, based on the total weight of the oxygen barrier composition.

[0059] Without wishing to be bound by theory, it is believed that the polyether-polyester copolymer is an oxidizable substrate in which end-to-end steps of the chains are capable of controlling oxygen entry and providing a controlled active oxygen barrier . The speed of the oxygen absorption reaction can be modified by the quantity and chemical constitution of the caps at the end.

[0060] The transition metal catalyst also initiates and accelerates the rate of oxygen consumption. The mechanism by which this transition metal works is not certain. The catalyst may or may not be consumed with oxygen, or, if consumed, may only be consumed temporarily by converting back into a catalytically active state.

[0061] More preferably, the transition metal catalyst is in the form of a salt, with the transition metal selected from the first, second or third transition series of the Periodic Table of the elements. Suitable metals and their oxidation states include, but are not limited to, manganese II or III, iron II or III, cobalt II or III, nickel II or III, copper I or II, rhodium II, III or IV, and ruthenium . The oxidation state of the metal when introduced does not need to be that of the active form. The metal is preferably iron, nickel, manganese, cobalt or copper; more preferably manganese or cobalt; and even more preferably cobalt. Suitable counterions for the metal include, but are not limited to, chloride acetate acetylacetonate, propionate, oleate, stearate, palmitate, 2-ethylexanoate, octanoate, neodecanoate or naphthenate.

[0062] The metal salt can also be an ionomer, in which case a polymeric counterion is used. Such monomers are well known in the art.

[0063] Even more preferably, the salt, transition metal, and counterion are compatible with country regulations relating to the subject of contact materials or, if part of a packaging article, exhibit substantially no migration of the composition. oxygen barrier for packaged contents. Particularly preferred salts include cobalt oleate, cobalt propionate, cobalt stearate, and cobalt neodecanoate.

[0064] Another subject of the invention is a plastic material comprising: a component a) which is a thermoplastic polymer, preferably selected from the group consisting of polyesters, polyolefins, polyolefin copolymers and polystyrenes; a component b) which is a polyether-polyester copolymer as described above; and a component c) which is a transition metal catalyst as described above.

[0065] The plastic material can be a masterbatch, a compound or a formed article.

[0066] Depending on its use, the plastic material may contain component b) in an amount of 0.5 to 99.995 -% by weight or more preferably 1 to 99.8 -% by weight, and component c) expressed as a concentration of transition target element, in an amount of 0.001 to 5 wt% or more preferably 0.002 to 4 wt%, based on the total weight of the plastic material.

[0067] The preferred components a) within the meaning of the invention are polyesters. The intrinsic viscosity values of polyesters are stated in units of dL/g as calculated from the inherent viscosity measured at 25°C in 60/40 wt/wt phenol/tetrachlorethane. The intrinsic viscosity of polyesters preferably ranges from about 0.55 to about 1.14 dL/g.

[0068] The preferred polyesters are those that result from the condensation reaction of dibasic acids and glycols.

[0069] Typically, dibasic acid comprises an aromatic dibasic acid, or ester or anhydride thereof, and is selected from the group consisting of isophthalic acid, terephthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6 acid ,-dicarboxylic acid, phthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, diphenoxyethane-4,4'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, 2,5-furandicarboxylic acid and mixtures thereof. Dibasic acid can also be an aliphatic dibasic acid or anhydride, such as adipic acid, sebacic acid, decan-1,10-dicarboxylic acid, fumaric acid, succinic acid, succinic acid, cyclohexanediacetic acid, glutaric acid, azeleic acid, and mixtures thereof. Other aromatic and aliphatic dibasic acids known to those skilled in the art can also be used. More preferably, the dibasic acid comprises an aromatic dibasic acid, optionally also comprising up to about 20% by weight of the dibasic acid component of an aliphatic dibasic acid.

[0070] Preferably, the glycol or diol component of the polyester is selected from the group consisting of ethylene glycol, propylene glycol, butane-1,4-diol, diethylene glycol, a polyethylene glycol, a polypropylene glycol, neopentyl glycol, a poly -tetramethylene glycol, 1,6-hexylene glycol, pentane-1,5-diol, 3-methylpentanediol-(2,4), 2-methylpentanediol-(1,4), 2,2,4-trimethylpentane-diol-( 1,3), 2-ethylhexanediol-(1,3),2,2-diethylpropanediol-(1,3), hexanediol-(1,3), 1,4-di-(hydroxyethoxy)benzene, 2,2-bis-(4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl) propane, 2,2-bis- (4-hydroxypropoxyphenyl) propane, 1,4-dihydroxymethyl-cyclohexane, and mixtures thereof. Additional glycols known to those skilled in the art can also be used as the glycol component of the polyester.

[0071] Two preferred polyesters are polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). PET and PEN may be homopolymers, or copolymers also containing up to 10 mole percent of a dibasic acid other than terephthalic acid or a dicarboxylic acid of naphthalene, and/or up to 10 mole percent of a glycol other than ethylene glycol.

[0072] PEN is preferably selected from the group consisting of polyethylene naphthalene 2,6-dicarboxylate, polyethylene naphthalene 1,4-dicarboxylate, polyethylene naphthalene 1,6-dicarboxylate, polyethylene naphthalene 1,8-dicarboxylate, and 2, Naphthalene polyethylene 3-dicarboxylate. More preferably, PEN is polyethylene naphthalene 2,3-dicarboxylate.

[0073] More preferably, the plastic material is selected from the group consisting of PET, for example, virgin bottle grade PET and post-consumer PET (PC-PET), cyclohexane dimethanol copolymer/PET copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and mixtures thereof.

[0074] Furthermore, preferred plastic materials are biobasic polymers, preferably polyethylene furanoate (PEF) and also biodegradable polyester, preferably selected from the group consisting of PLAs (polylactic acid), polycaprolactones (PCL) and polyhydroxybutyrates (PHB); and biobasic polyesters, which are derived from renewable sources such as corn and sugar cane and the byproducts associated with their harvesting and processing, but are not biodegradable.

[0075] The preferred polyolefins and polyolefin copolymers, that is, component a) within the meaning of the Invention, are thermoplastic polyolefins known in the art and are selected from the group consisting of - polyethylene (PE), preferably selected from the group consisting in high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), metallocene low-density polyethylene (mLDPE) and metallocene low-density polyethylene linear (mLLDPE), - polypropylene (PP), preferably selected from the group consisting of polypropylene homopolymer (PPH), polypropylene random copolymer (PP-R) and polypropylene block copolymers (PP-block-COPO), - copolymers of PE, preferably selected from the group consisting of ethylene-vinyl acetate (EVA) copolymers, ethylene and methyl acrylate (EMA) copolymers, ethylene and butyl acrylate (EBA) copolymers, ethylene and ethyl acrylate copolymers (EEA), and cycloolefin copolymers (COC), - general purpose polystyrene (GPPS) and high impact polystyrene (HIPS); more preferably of - high density polyethylene (HDPE) and low density polyethylene (LDPE) - polypropylene homopolymer (PPH), - general purpose polystyrene (GPPS).

[0076] Preferred polystyrenes, that is, component a) within the meaning of the invention, may be a styrene homopolymer, an alkylstyrene homopolymer, preferably a C1-C4-alkystyrene homopolymer, for example, α-methylstyrene homopolymer; a styrene copolymer, especially a high impact polystyrene (HIPS).

[0077] High impact polystyrenes (HIPS) are generally prepared by graft polymerization of mixtures of styrene and, optionally, one or more copolymerizable vinyl monomers, preferably mixtures of styrene, methylstyrene, ethylstyrene, butylstyrene, halostyrenes, vinylalkylbenzenes, such as vinyltoluene, vinylxylene, acrylonitrile, methacrylonitrile, lower alkyl esters of methacrylic acid, in the presence of a rubber polymer stem comprising copolymers chosen from polybutadiene, polyisoprene, styrene-diene rubber copolymers, acrylic rubber, olefin rubber and rubber nitrile rubber, such as propylene diene monomer (PDM) rubber and propylene rubber (PR). In high-impact polystyrene, the rubber polymer stem typically constitutes 5 to 80% by weight, preferably 5 to 50% by weight, of the total weight of the grafted polymer.

[0078] Optionally, the active oxygen barrier composition and plastic material of the present invention comprise one or more other substances (component d), which are selected from the group consisting of - natural dyes derived from plants or animals and synthetic dyes, preferred synthetic dyes being synthetic inorganic and organic dyes or pigments, • preferred synthetic organic pigments being azo or diazo pigments, azo or diazo pigmented pigments or polycyclic pigments, particularly pigments of preferably phthalocyanine, diketopyrrolopyrrole, quinacridone, perylene, dioxazine, anthraquinone , thioindigo, diaryl or quinophthalone; • preferred synthetic inorganic pigments being metal oxides, mixed oxides, aluminum sulfates, chromates, metal powders, pearlescent pigments (mica), luminescent colors, titanium oxides, cadmium lead pigments, iron oxides, carbon black, silicates, nickel titanates, cobalt pigments or chromium oxides; - surfactants; - auxiliaries, preferably acid absorbers, processing aids, coupling agents, lubricants, stearates, blowing agents, polyhydric alcohols, nucleating agents, or antioxidants, for example stearates, or oxides such as magnesium oxide; - antioxidants, preferably primary or secondary antioxidants; - antistatic agents; - compatibilizers for polyester/polyamide mixtures; - UV absorbers, slip agents, anti-darkening agents, anti-condensation agents, suspension stabilizers, anti-blocking agents, waxes, and a mixture of these substances.

[0079] More preferably, component d) is selected from the group consisting of compatibilizers, UV absorbers, antioxidants and dyes.

[0080] Component d) may be present in an amount of 0 to 60 -% by weight, preferably 0.001 to 50 -% by weight, more preferably 0.1 to 30 -% by weight, more preferably 1 to 25 -% by weight, based on the total weight of the plastic material.

[0081] The plastic material of the present invention is conveniently formed, for example, molded by blowing, into a plastic article.

[0082] Accordingly, another subject of the present invention is a plastic article formed comprising said plastic material.

[0083] The plastic article formed in accordance with the invention may be a packaging material, preferably a container, a film or a sheet, especially for use in the packaging of personal care, cosmetics, household, industry, food and beverages in that a high oxygen barrier is necessary.

[0084] Packaging materials can be flexible, rigid, semi-rigid or combinations thereof.

[0085] Rigid packaging articles typically have wall thicknesses in the range of 100 to 1000 micrometers. Typical flexible packaging typically ranges in thickness from 5 to 250 micrometers.

[0086] The rigid packaging articles or flexible films of the invention may consist of a single layer or may comprise multiple layers.

[0087] When an article or packaging film comprises an oxygen absorption layer, it may also comprise one or more additional layers, one or more of the additional layers comprising an oxygen barrier layer or being permeable to oxygen. Furthermore, additional layers, such as adhesive layers, can also be used in a multilayer packaging article or film.

[0088] Another object of the invention is a method for manufacturing a plastic article as defined above, characterized by the fact that components a), b), c), and, optionally, d), are physically mixed with each other. the other and subjected to a modeling process.

[0089] For physical mixing, it is possible to use a mixing apparatus customary in the plastics industry. Preferably, the mixing apparatus may be that used to prepare a liquid masterbatch or a solid masterbatch or may be a combination of those apparatus.

[0090] A mixing apparatus for a liquid masterbatch may be a high-speed disperser (for example, of the CowlesTM type), a media mill, a three-roll mill, a rotor-stator type disperser or submill.

[0091] A mixing apparatus used to make solid MB or CO compound masterbatches may be a mixer, extruder, kneader, press, mill, calender, blender, injection molding machine, injection stretch blow molding machine (ISBM ), extrusion blow molding machine (EBM), compression molding machine, stretch and compression blow molding machine; more preferably a mixer, extruder, injection molding machine, stretch and injection blow molding machine, compression molding machine, stretch and compression blow molding machine; even more preferably a mixer, extruder, stretch or injection blow molding machine and extrusion blow molding machine.

[0092] The modeling process for the article is dependent on the desired model of article to be manufactured.

[0093] Containers are preferably made by blow molding, injection molding, stretch and injection blow molding, extrusion blow molding, compression molding, stretch and compression blow molding.

[0094] Films and sheets are preferably made by melt or blown film extrusion or coextrusion processes, depending on the thickness required and the number of layers necessary to obtain specific properties, eventually followed by post-extrusion modeling processes such as thermoforming or stretching. . In the thermoforming process, plastic sheet is heated to a flexible forming temperature, formed to a specific pattern in a mold, and trimmed to create a final article. If vacuum is used, this process is generally called vacuum formation. In post-extrusion stretching processes, an extruded film can be, for example, biaxially oriented by the design. All of the processes listed above are well known in the art.

[0095] The mixing of the components can occur in one step, two steps or in a plurality of steps.

[0096] Mixing can occur in one step when components a), b), c), and, optionally, component d) or just b), c) and, optionally, component d), are directly measured and /or reduced in the form of liquid and solid concentrates or as pure components, for example, in a stretch molding and injection molding machine.

[0097] Mixing can also occur in two or three stages, in which, in a first stage, components b), c) and, optionally, d) are pre-dispersed in component a), and in one or more stages consecutive lines are added to component a).

[0098] Mixing can occur in two or three steps, in which, in a first step, components c) and, optionally, component d) are pre-dispersed in component a) and component b) is directly measured and / or reduced as a pure component, for example in an injection stretch blow molding machine.

[0099] Preferably, component b) and component c) are pre-dispersed in component a) to form two separate masterbatches, and then these masterbatches are combined with components a) and, optionally, d).

[00100] In a preferred embodiment, in a first step, component b) and, optionally, component d) are dispersed in component a) at the same time that component c) is dispersed in component a) to provide two masterbatches separated. After being melt compounded, for example in a single or twin screw extruder, the extrudates are withdrawn in filament form, and absorbed as pellets according to the usual means, such as cutting. In a second step, the obtained masterbatches are measured and reduced by a converter/computer into the main flow of component A pellets, for example in an injection stretch blow molding machine. These extrudates can be measured and reduced in the main component flow a) directly in an injection process avoiding the compounding process.

[00101] In another embodiment, in a first step, component b), c) and, optionally, component d) are dispersed in component a) to provide a masterbatch. After being melt compounded, for example in a single or twin screw extruder, the extrudate is withdrawn in filament form, and absorbed as pellets according to the usual means such as cutting. In a second step, an obtained solid masterbatch is measured and reduced by a converter/computer in the main flow of component a) of, for example, an injection stretch blow molding machine, at a rate that corresponds to the final desired concentration of component b) and c) in the article.

[00102] Mixing preferably occurs continuously or in batches, more preferably continuously; in the case of a solid MB masterbatch, preferably by extrusion, mixing, grinding or calendering, more preferably by extrusion; in the case of an MB liquid masterbatch, preferably by mixing or grinding; in the case of a CO compound, preferably by extrusion or calendering, more preferably by extrusion.

[00103] Mixing is preferably carried out at a temperature of 0 to 330°C.

[00104] The mixing time is preferably 5 seconds to 36 hours, preferably 5 seconds to 24 hours.

[00105] The mixing time in the case of continuous mixing is preferably 5 seconds to 1 hour.

[00106] The mixing time in the case of batch mixing is preferably from 1 second to 36 hours.

[00107] In the case of an MB liquid masterbatch, mixing is preferably carried out at a temperature of 0 to 150°C with a mixing time of 0.5 minutes to 60 minutes.

[00108] In the case of a solid masterbatchMB or a CO compound, mixing is preferably carried out at a temperature of 80 to 330°C with a mixing time of 5 seconds to 1 hour.

[00109] Specific articles of the present invention include preforms, containers, films and foils for packaging food, beverages, cosmetics, and personal care products in which a high oxygen barrier is required. Examples of beverage containers are: groove bottles, sports drinks, beer, or any other beverage in which oxygen detrimentally affects the flavor, fragrance, performance (prevents vitamin degradation), or color of the beverage. The compositions of the present invention are also particularly useful as a sheet for thermoforming rigid packaging and films for flexible structures. Rigid packaging includes trays and covers at the food end. Examples of food tray applications include dual oven food trays, or cold storage food trays, both in the base container and in the covering (either a thermoformed end cap or a film), where the freshness of the contents food can decay with the entry of oxygen.

[00110] Preferred articles of the present invention are rigid packaging articles, such as thermoformed bottles and sheets and flexible films.

[00111] Another aspect of the present invention relates to monolayer films. The term monolayer film or monolayer cast film or monolayer sheet indicates the semi-finished product consisting of the sheet (preform) generally obtained by extrusion of the films forming the layer. The sheet obtained has not been subjected to any preferential orientation process and is, consequently, disoriented. The sheet can be further formed into a finished article such as a container by known processes that do not include orientation, generally by thermoforming. The term "container" refers to any article having an opening for the introduction of a product, particularly food products.

[00112] To determine the oxygen absorption capabilities of the copolymers of the invention, the oxygen absorption rate can be calculated by measuring the time elapsed until the article has exhausted a certain amount of oxygen from a sealed container.

[00113] Another definition of acceptable oxygen absorption is derived from testing actual packaging.

[00114] The oxygen absorption capacity of an article comprising the invention can be measured by determining the amount of oxygen consumed until the article becomes ineffective as an absorber.

[00115] The plastic material of the present invention provides an oxygen absorption system with high oxygen absorption capacity, accurate adjustment of oxygen transmission rate inside the packaging and satisfactory transparency of the final plastic articles.

TEST METHODS

[00116] Product properties are determined by the following methods, unless otherwise indicated: density values are determined in accordance with ASTM D792 (g/cm3).

[00117] Melt flow rate (MFR) values are determined in accordance with ASTM D1238 (g/10 minutes at specified temperature and weight).

[00118] Measuring method for oxygen absorption activity A cast film containing suitable absorption composition is introduced into a glass bottle equipped with an optical sensor and a cap at the rubber end.

[00119] Measurement of the oxygen level in the headspace at the top of the bottle is then carried out using two different techniques. One of them is a non-invasive oxygen measurement sensor and Fibox® transmitter. The other is CheckMate 3 O2 (Zr) CO2-100%.

[00120] For both, data collected in parallel for at least two samples of the same composition, at regular time intervals. For each sample, the oxygen consumption at a certain time is calculated as the difference between the oxygen content measured at that time and the oxygen measured at time 0, which was close to 21%. Oxygen consumption is then measured over the number of samples measured for each consumption and plotted against time.

EXAMPLES

[00121] The weight % mentioned in the following examples is based on the total weight of the mixture, composition or article; parts are parts by weight; "ex" means example; "cpex" means comparative example; MB means masterbatch; CO means compound, "D" means direct measurement on the respective additives.

Used equipment

[00122] The equipment used to carry out the PET cast film production tests described below consists of - single screw extruder, 25 mm screw diameter - 1 filter chamber with 40 micron filter mesh - 1 die and head flat with a width of 350 mm for producing a monolayer film - 1 horizontal calender with 3 winders Substances used Component a: A1: Polyethylene terephthalate (PET) having a density of 1.35 to 1.45 g/cm3 and intrinsic viscosity from 0.74 to 0.78 dl/g (ASTM D3236-88). Component a: A2: Polybutylene terephthalate (PBT) having a density of 1.28 to 1.32 g/cm3 and intrinsic viscosity of 0.90 to 1.00 dl/g (ASTM D3236-88).

Component b: B1 - B13:

[00123] Polyester ethers were prepared using the following general procedures:

[00124] In a 500 ml multi-neck flask equipped with a KPG stirrer, a vigreux column, a vacuum supply and a distillation bridge, the chemical materials according to Table 1 are placed in the reactor under an atmosphere of nitrogen and in an amount as given in Table 1. The mixture is heated to an internal temperature of 60 ° C, followed by the addition of 200 μl of tetraisopropyl orthotitanate.

[00125] Within 2 hours, the temperature of the reaction mixture is continuously increased to 230°C under a weak nitrogen flow (5 l/h) and maintained at this temperature for 2 hours. After reaching 70°C, the methanol begins to distill. After reaching 190°C, ethylene glycol continually begins to distill. Subsequently, the flow of N2 is stopped and the pressure of the reaction mixture is continuously decreased to 400 mbar at 230 ° C within 165 minutes, followed by another continuous pressure decrease to 1 mbar within 90 minutes. In the next step, the reaction mixture is stirred at a pressure of 1 mbar and an internal temperature of 230°C for another 4 hours. After the end of this time period, the internal pressure of the reaction flask is set again at 1 bar using N2 and the molten polymer is subsequently removed from the reactor and allowed to solidify.

[00126] To determine the molecular weight of the polyester ether, GPC measurements were made under the following conditions: Columns: 1 x PSS SDV Guard, 5μm, 50 mm x 8.0 mm ID 1 x PSS SDV 100 A, 5 μm, 300 mm x 8.0 mm ID 1 x PSS SDV 1000 A, 5 μm, 300 mm x 8.0 mm ID 1 x PSS SDV 100000 A, 5 μm, 300 mm x 8.0 mm ID Detector: RI Temperature oven: 40°C Flow: 1 ml/minute Injection volume: 50 μl Eluent: THF Assessment: PSS-WinGPC Version 8.2 Calibration: Polystyrene standards in the range of 682 - 1,670,000 Dalton Internal Standard: Toluene Convention of injection: 4 g/l in THF Table 1 Table 1 -continued- Component c: C1: Solid form of cobalt stearate (9.5% concentration of elemental cobalt).

Component d: D1: Surfactant Masterbatches MB1 to MB10

[00127] The components were homogenized together in a Leistritz® ZSE18HP extruder at a temperature of 260°C to obtain solid MB masterbatches; Table 2 provides the details. Table 2

Preparation of cast films:

[00128] As an example of operational mode, 200 μm of cast films were obtained through extrusion using the Colling E 25 PK by inserting component A1, pre-dried for 18 hours at 120°C, into the main funnel of the machine. , and adding the other components (MB and/or pure dosed additives) through dosing units applied to the main flow of component A1 before entering the injection unit barrel. The extruder temperatures can be maintained at 260°C and the flat die temperature is 270°C.

[00129] The operating conditions during the test were: T1 = 60°C / T2 = 240°C / T3 = 260°C / T4 = 260°C / T5 = 260°C / Tmatrix = 270°C / Tcalenderwinders = 70°C/screw revolutions at 80 rpm Table 3

[00130] The oxygen absorption activity (in ml O2 consumed per gram of absorption composition) corresponding to the cast films was measured by the methods described above. Table 4 describes the oxygen consumption of compositions with different copolymer structures and different amounts of end caps. Table 4

[00131] By comparing ex3 and ex5 and cpex6, a significant dependence of the oxygen consumption rate on the amount of capping at the present end is observed. In general, the amount of oxygen consumed decreases when a greater amount of tip caps are introduced. The rate of oxygen consumption is strongly dependent on the amount of end caps contained in the polyester-copolyether, so one can adjust and control the amount of oxygen being absorbed by increasing or reducing the amount of end caps.

[00132] This effect is observed when polyester-copolyether additives are dosed together with the resin directly at the end of the extruder, as well as when a MB is prepared.

[00133] Ex11 and ex13, which refer to polyesters with end caps that are different from those of ex3 to ex5 and cpex6, show exactly the same behavior: the greater amounts of end caps reflect a reduction in oxygen consumption.

Claims (15)

1. Polyether-polyester copolymer, characterized in that it comprises: (i) polyether segments, wherein at least one polyether segment contains at least one polytetramethylene oxide segment, (ii) polyester segments, ( iii) linkers of the -CO-R2-CO- structure, wherein R2 represents an optionally substituted divalent hydrocarbon residue consisting of 1 to 100 carbon atoms; (iv) one or more caps at the R1-O-(C2-C4-O-)e-* end, wherein R1 is an optionally substituted hydrocarbon residue and is an integer from 0 to 1000. 2. Polyether-polyester copolymer according to claim 1, characterized in that the polyether segments (i) contain ethylene oxide segments, propylene oxide segments or a combination thereof. 3. Polyether-polyester copolymer according to claim 1 or 2, characterized by the fact that the polyester segments (ii) are represented by formula (II): wherein * represents a bond to a linker (iii), R2 and R3 independently of each other represent an optionally substituted hydrocarbon residue consisting of 1 to 100 carbon atoms, I is an integer between 1 and 50. 4. Polyether-polyester copolymer according to any one of claims 1 to 3, characterized in that the binding elements are described by formula (III) wherein R2 represents an optionally substituted hydrocarbon residue consisting of 1 to 100 carbon atoms. 5. Polyether-polyester copolymer according to any one of claims 1 to 4, characterized in that the end caps are described by the following general formula R1-O-(C2-C4-O-)e-*, 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 is an integer between 0 and 500. 6. Polyether-polyester copolymer according to any one of claims 1 to 5, characterized by the fact that R1-(C2- C4-O-)e-* corresponds to the following formulas wherein the different monomers are distributed randomly, in blocks or in a combination of random and blocks, and b is an integer between 0 and 250, a is an integer between 0 and 250, c is an integer between 0 and 70, and the sum a+b+c is from 0 to 570; and R1 is as defined in claim 5. 7. Polyether-polyester copolymer according to any one of claims 1 to 6, characterized in that R1 indicates 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, or cyclodecyl. 8. Polyether-polyester copolymer according to any one of claims 1 to 7, characterized in that the number average molecular weight is between 2000 and 1000000 g/mol. 9. Polyether-polyester copolymer according to any one of claims 1 to 8, characterized by the fact that the mass ratio Q defined as the mass ratio between the content of poly(tetramethylene-oxide) and the overall content of all dicarbonyl backbone elements (ii) and (iii) is between 0.1 and 10. 10. Polyether-polyester copolymer according to any one of claims 1 to 9, characterized in that the mass ratio Q defined as the mass ratio between the capping content at the end and the overall content of all elements of dicarbonyl structure (ii) and (iii) is between 0.001 and 100. 11. Method of preparing a polyether-polyester copolymer as defined in any one of claims 1 to 10, characterized in that it comprises a polyconsensus of polyether segments containing at least one polytetramethylenoxide segment, the polyester segments, the connecting elements and the end caps. 12. Active oxygen barrier composition, characterized in that it comprises a polyether-polyester copolymer, as defined in any one of claims 1 to 10, and a transition metal catalyst. 13. Plastic material, characterized by the fact that it comprises: a component (a) which is a thermoplastic polymer; a component (b) which is a polyether-polyester copolymer as defined in any one of claims 1 to 10; and a component (c) which is a transition metal catalyst. 14. Plastic material according to claim 13, characterized in that it is a masterbatch, a compound or a formed article. 15. Plastic material according to claim 13 or 14, characterized in that it is part of a container or a film.