EA042846B1 - OXYGEN ABSORPTING PLASTIC MATERIAL - Google Patents

Description

The field of technology to which the invention belongs

The present invention relates to an oxygen-scavenging polyether-polyester copolymer and its use in compositions and articles capable of scavenging oxygen or functioning as an active oxygen barrier.

State of the art

Thermoplastic resins such as PET (polyethylene terephthalate) are widely used to produce several types of packaging and storage containers. PET is mainly used in the beverage industry because it is as clear as glass but much lighter; it is also resistant to cracking; fully recyclable and has suitable color variability and various designs of PET bottles are possible. The biggest disadvantage of PET is its permeability to gases and, in this case, especially its permeability to oxygen.

It is well known that electronics, personal care, household, industrial, food and beverage packaging require high oxygen barrier properties to maintain the freshness and quality of the contents of the package. In particular, sauces and beverages such as juices, beer and tea require a packaging material with high barrier properties or the ability to block the entry of oxygen and/or remove trapped oxygen to avoid product oxidation and extend product shelf life.

A number of strategies have been used to overcome these limitations and increase the shelf life of oxygen-sensitive products (beer, juice or tomato sauce). In the packaging industry, for example, multilayer structures containing mixed polymer layers have been developed. These multilayer packaging containers offer improved barrier properties similar to but not comparable to those of glass and steel, while losing many of the recycling benefits associated with single layer containers such as PET, polyethylene naphthalate (PEN) or polyolefin bottles. In addition, the transparency of the container is often significantly reduced. Maintaining the right balance of recyclability, barrier properties and clarity is most important for bottling applications.

The use of multilayer bottles, which contain an inner, sometimes interleaved, layer of polymeric material with higher barrier properties compared to the outer polymeric layers, is common. Typically, the center layer is a high barrier polymer that slows down the penetration of oxygen through the container wall. Examples of such high barrier passive polymers include ethylene vinyl alcohol (EVOH) and polyamides, preferably a partially aromatic polyamide containing metaxylylene groups such as poly(m-xylylene adipamide), MXD6. A typical structure for such multilayer structures would include an inner and outer layer of PET with a polyamide core, or an inner and outer layer of polyolefins with an ethylene vinyl alcohol (EVOH) polymer core.

Another strategy that can also be combined with the use of passive barriers is the use of an active oxygen scavenger to reduce or remove oxygen within the package. The method of providing an oxygen barrier when a substance absorbs or reacts with oxygen is known as a (re)active oxygen barrier and is distinct from passive oxygen barriers, which attempt to seal the product from oxygen as a passive approach. Several oxygen scavenging systems are known in the prior art. Among other things, oxygen scavenging compositions comprising an oxidizable substituted or unsubstituted ethylenically unsaturated hydrocarbon and a transition metal catalyst are well known effective solutions.

Containers such as sachets filled with oxygen scavenging compositions are well known examples of the use of such materials. However, these applications are generally limited to solids and solid foods, and special care is required to avoid ingestion.

To solve this problem, oxygen scavengers have also been incorporated into the 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 enhance the oxidation of the scavengers, improving the barrier performance of the container. This method makes it possible to eliminate or reduce the supply of oxygen from outside, as well as unwanted oxygen from the cavity of the package, which could accidentally enter during packaging or filling.

Modified polyesters are also widely used as oxygen scavengers. Various modifications of esters have been found to be active oxygen scavengers. US 6083585A, WO 98/12127 and WO 98/12244 disclose oxygen scavenging polyester compositions in which the oxygen scavenging component is polybutadiene.

Other modifications consist of introducing ester groups using, for example, poly(alkylene oxide)s.

US 6455620 discloses a poly(alkylene glycol) which acts as an oxygen scavenger,

- 1 042846 mixed with various thermoplastic polymers.

Also WO 01/10947 discloses oxygen scavenging compositions comprising an oxidation catalyst and at least one polyether selected from the group consisting of poly(alkylene glycol)ee, poly(alkylene glycol)ee copolymers and mixtures containing poly(alkylene glycol) and suitable for inclusions in products containing oxygen sensitive products.

WO 2009/032560A1 discloses oxygen scavenging compositions comprising an oxidation catalyst and an ether copolyester comprising polyether segments comprising poly(tetramethylene-co-alkylene ether) having a low haze level.

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

The above oxygen scavenging systems aim to reduce the oxygen content of the package to the lowest possible level. This, however, is not always desirable. Not all products have the same requirements for a suitable atmosphere to extend their shelf life. In the case of wine, fruits and vegetables, it is desirable to create a suitable atmosphere, with limited oxygen content, to ensure a pleasant taste. In the case of meat and fish, a certain amount of oxygen in the atmosphere is necessary to avoid the growth of some pathogenic anaerobic bacteria such as Clostridium botulinum.

In order to maintain a certain low oxygen content in the package, it is necessary to match the supply of oxygen to the package with the oxygen uptake rate of the oxygen scavenging composition. This can potentially be achieved by reducing the content of the oxygen scavenging composition in the package. However, this would come at the expense of the overall ability of the packaging to absorb oxygen, thereby reducing the shelf life of the item contained in the product.

Therefore, it is desirable to provide an oxygen scavenging system that is able to precisely control the oxygen scavenging reaction rate to the desired reduced level and maintain this level for the expected shelf life of the product, thus providing a high removal capacity.

It has surprisingly been found that certain polyether-polyester copolymers, as described below, can be effectively used to effect and control oxygen scavenging in a thermoplastic material.

Brief summary of the invention

The subject 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, where the polyester segments (ii) are represented by formula (II):

o o *—o—R3-Po—R2^ o—R ₃ 4^o—* (P) in which * represents the connection with the bridge element (iii),

R2 and R3 independently of each other represent an optionally substituted hydrocarbon residue consisting of 1-100 carbon atoms, where the substituents are C ₁ -C ₅ -alkoxy, nitro, cyano and sulfo, and u is an integer of 1-50;

(iii) -CO-R2-CO- bridging elements in which R2 is an optionally substituted divalent hydrocarbon moiety of 1-100 carbon atoms, where the substituents are C1- _C5 alkoxy, nitro, cyano or sulfo, or their combination;

(iv) one or two end groups R1-O-(C ₂ -C ₄ -O-) _e- *, where R1 represents an aliphatic hydrocarbon residue with 1-24 carbon atoms, an olefinic hydrocarbon residue with 2-24 carbon atoms, aromatic a hydrocarbon residue with 6-14 carbon atoms, wherein said hydrocarbon residues are optionally substituted with C1- _C5 alkoxy, nitro, cyano, sulfo, or combinations thereof, and e is an integer of 0-1000.

The polyether-ester copolymer of the invention is preferably a linear copolymer, but it can also contain small amounts, i.e. up to 10 mole % of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylpropane, pyromellitic dianhydride, pentaerythritol and other polyacids or polyols known in the art.

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

Preferred embodiments of the polyether segments (i) are shown, for example,

- 2 042846 formulas (I), (Ia), (Ib) and (Ic) and optionally (Id) below:

in which k is an integer 0-70, preferably 0-35, more preferably 0-30;

v is an integer 0-250, preferably 0-125, more preferably 0-50;

x is an integer 0-250, preferably 0-125, more preferably 0-12;

y is an integer 0-250, preferably 0-125, more preferably 0-50;

z is an integer 0-250, preferably 0-125, more preferably 0-12;

and the sum of k + v + x + y + z is 0-1070, preferably 0-535.

For v + x > 2 and for v and x # 0, and for y + z > 2 and y and z^0, the resulting portion of the polyethylene oxide/polypropylene oxide copolymer may be a randomly distributed copolymer or block copolymer, where both blocks (polyethylene oxide block or block polypropylene oxide) can be chemically bonded to the polytetramethylene oxide block.

Formula (Ia)

in which p is an integer 0-35, preferably 0-20, more preferably 0-15;

w is an integer 0-35, preferably 0-20, more preferably 0-15;

q is an integer 0-250, preferably 0-125, more preferably 0-50;

r is an integer 0-250, preferably 0-125, more preferably 0-12;

and the sum of p + w + q + r is 0-570, preferably 0-290.

For q + r > 2 and for q and r Ψ 0, the resulting portion of the polyethylene oxide/polypropylene oxide copolymer may be a randomly distributed copolymer or block copolymer.

Formula (IB)

in which K is an integer 0-250, preferably 0-125, more preferably 0-12;

L is an integer 0-35, preferably 0-20, more preferably 0-15;

M is an integer 0-250, preferably 0-125, more preferably 0-50;

N is an integer 0-35, preferably 0-20, more preferably 0-15;

O is an integer 0-250, preferably 0-125, more preferably 0-12;

moreover, L + N cannot be chosen to be 0;

and the sum of K + L + M + N + O is 1-820, preferably 2-415.

In the case where K + L > 2 and for K, L and M # 0, or in the case when N + O > 2 and for N, O and M # 0, the resulting portion of the polypropylene oxide/polytetramethylene oxide copolymer may represent a randomly distributed a copolymer or block copolymer in which both blocks (a polypropylene oxide block or a polytetramethylene oxide block) can be chemically bonded to a polyethylene oxide block.

Formula (Ic)

in which P is an integer 0-250, preferably 0-125, more preferably 0-50;

Q is an integer 0-35, preferably 0-20, more preferably 0-15;

R is an integer 0-250, preferably 0-125, more preferably 0-12;

S is an integer 0-35, preferably 0-20, more preferably 0-15;

T is an integer 0-250, preferably 0-125, more preferably 0-50;

moreover, Q + S cannot be chosen to be 0;

and the sum of P + Q + R+S + T is 1-820, preferably 2-415.

In the case where P + Q > 2 and for P, Q and R > 0, or for the case when S + T > 2 and for S, T and R > 0, the resulting portion of the polyethylene oxide/polytetramethylene oxide copolymer may be a randomly distributed copolymer or block copolymer, wherein both blocks (polyethylene oxide block or polytetramethylene oxide block) can be chemically bonded to the polypropylene oxide block.

Formula (Id)

- 3 042846 in which U represents an integer 0-250, preferably 0-125, more preferably 0-50;

V is an integer 0-250, preferably 0-125, more preferably 0-12;

W is an integer 0-70, preferably 0-35, more preferably 0-30;

and the sum of U + V + W is 3-570, preferably 5-285. In this embodiment, the polyether segment may be a homopolymer, a randomly distributed copolymer, or a block copolymer.

In all formulas, the asterisk * represents the link to the bridging element (iii).

Preferably the polyether segments (ii) are represented by formula (II):

in which * represents the link to the bridging element (iii),

R2 and R3 independently of each other represent an optionally substituted hydrocarbon residue of 1-100 carbon atoms, in which the substituents are preferably C1-C5 alkoxy, nitro, cyano and sulfo.

u represents an integer 1-50, preferably 1-30, in particular 1-25.

Preferably R2 and R3 are independently a C1-C24 aliphatic hydrocarbon residue, a C2-C24 olefinic hydrocarbon residue, or a C5-C14 aromatic hydrocarbon residue, 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 moiety of 2-18 carbon atoms, and most preferably 2-6 carbon atoms. The aliphatic hydrocarbon residue may be linear, branched or cyclic. In addition, the aliphatic hydrocarbon residue may be saturated or unsaturated. Preferably it is saturated.

Preferred aliphatic radicals 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. Particularly preferred radicals 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 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 may be mono- or polycyclic, such as di- or tricyclic. Preferably the aromatic system consists of 5-25 atoms, even more preferably 5-10 atoms. The aromatic system is preferably formed by carbon atoms. In a further embodiment, it consists in addition to the 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.

Preferred aromatic 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-5sulfonate, 2,5-furanylene and mixtures thereof.

Particularly preferred building blocks 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 preferred building blocks for R2 are 1,3-phenylene, 1,4-phenylene and mixtures thereof.

In another preferred embodiment, R3 may be represented by formula (IIa):

where Z can be an integer 0-100.

Bridge elements (iii) may link polyether segments (i), polyester segments (ii) and/or end groups (iv). Bridge elements are described by formula (III):

About 0

Lr2_U _(w): where R2 denotes the values given above.

(iv) The end groups are connected to the bridge element (iii). The relationship is marked with an asterisk *.

Preferred end groups can be described by the following general formula

Rl-O-(C2-C ₄ -O-) _e -*, where R1 represents an aliphatic hydrocarbon residue with 1-24 carbon atoms, an olefinic hydrocarbon residue with 2-24 carbon atoms, an aromatic hydrocarbon residue with 6-14 carbon atoms, moreover, these hydrocarbon residues are optionally substituted with C 1 -C ₅ -alkoxy, nitro, cyano, sulfo, or a combination thereof, and e represents an integer 0-1000, preferably an integer

- 4 042846

0-500 and most preferably an integer of 0-150.

In a preferred embodiment, R1 is an aliphatic hydrocarbon moiety of 1-18 carbon atoms, and more preferably 1-12 carbon atoms. The aliphatic hydrocarbon residue may be linear, branched or cyclic. In addition, the hydrocarbon residue may be saturated or unsaturated. Preferably it is saturated.

Particularly preferred aliphatic residues for R1 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2dimethylpropyl, isoamyl, n -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, methylphenylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl , cyclodecyl. The most preferred residues are methyl, ethyl and n-dodecyl. The most preferred residue is methyl.

In a further preferred embodiment, R1 may be an aromatic system. The aromatic system may be mono- or polycyclic, such as di- or tricyclic. Preferably the aromatic system consists of 6-14 carbon atoms, more preferably 6-10 carbon atoms.

The aromatic system is preferably formed by carbon atoms. In a further embodiment, it consists in addition to the 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. In addition, the aromatic system may be chemically linked to one, two, three or more of the same or different functional groups. Suitable functional groups are, for example, alkyl alkenyl, alkoxy, poly(alkoxy), cyano and/or nitro functional groups. These functional groups can be in any position of the aromatic system.

Particularly preferred R1-O-(C ₂ -C ₄ -O-) _e- * groups correspond to the following formulae

where different monomers are randomly distributed, blocks or a combination of random and block distribution;

b may be selected as an integer 0-250, preferably 0-125, more preferably 050;

a may be selected as an integer 0-250, preferably 0-125, more preferably 012.;

c can be selected as an integer 0-70, preferably 0-35, more preferably 030, and the sum of a + b + c is 0-570; And

R1 is as defined above.

The number average molecular weight of the copolymers of the present invention is preferably 2000-1000000 g/mol, more preferably 3500-100000 g/mol, most preferably 5000-50000 g/mol.

The weight ratio Ω, defined as the weight ratio between the content of poly(tetramethylene oxide) and the total content of all dicarbonyl structural elements, i.e. in (ii) and (iii), of the copolymers of the present invention is preferably 0.1-10, more preferably 0.2 -5 and most preferably 0.5-2.

Mass ratio Θ, defined as the mass ratio between the content of terminal

- 5 042846 groups and the total content of all dicarbonyl structural elements, that is, in (ii) and (iii), the copolymers of the present invention is preferably 0.001-100, more preferably 0.00550 and most preferably 0.01-2.

The copolymers of the present invention can be prepared by polycondensation of at least one polyether segment comprising at least one polytetramethylene oxide segment, at least one polyester segment, at least one bridging element, and at least one end group R1-O-(C ₂ -C ₄ -O-) _e _*.

The parent compounds giving the polyether segments (i) of the invention may be homo- or copolymers, the copolymers may 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)-copoly(tetrahydrofuran)diol, poly(propylene glycol) )-co-poly(tetrahydrofuran)diol; and poly(ethylene glycol)-co-poly(propylene glycol)-co-poly(tetrahydrofuran)diol.

The polyester segment can be synthesized directly during the polycondensation reaction or introduced as a pre-synthesized building block at the start of the reaction. Preferred polyether segments are those resulting from the condensation reaction of dibasic acids, or their esters or anhydrides, and diols.

Examples of starting compounds forming polyether segments (ii) according to the invention are dimethyl terephthalate, terephthalic acid, dimethyl isophthalate, isophthalic acid, dimethyl adipate, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, 1,2 cyclohexane dicarboxylic acid, dimethyl ether 1, 4-cyclohexanedicarboxylic acid and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 2,2-dimethyl-1,3propanediol, 1,6-hexanediol, diethylene glycol , triethylene glycol, poly(ethylene terephthalate), and poly(butylene terephthalate).

Examples of starting compounds forming bridge elements (iii) according to the invention are dimethyl terephthalate, terephthalic acid, dimethyl isophthalate, isophthalic acid, dimethyl adipate, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, 1,2 cyclohexane dicarboxylic acid, dimethyl ether 1,4 -cyclohexane-dicarboxylic acid.

Examples of end group forming parent compounds are monomethoxylated poly(ethylene glycol) monool, monomethoxylated poly(ethylene glycol) copoly(propylene glycol) monool, lauryl alcohol ethoxylate, oleyl alcohol ethoxylate, nonylphenol ethoxylate, n-dodecanol, oleyl alcohol.

To obtain the copolymers of the present invention usually use a two-stage process of either direct esterification of diacids and diols, or interesterification of diesters and diols, followed by a polycondensation reaction under reduced pressure.

A suitable method for preparing the copolymers of the present invention comprises heating suitable starting compounds for segments (i)-(iv) with the addition of a catalyst to a temperature of 160-220°C, preferably starting at atmospheric pressure, and then continuing the reaction at reduced pressure and a temperature of 160-240 °C.

Reduced pressure preferably means a pressure of 0.1-900 mbar, and more preferably a pressure of 0.5-500 mbar.

Conventional transesterification and condensation catalysts known in the art can be used to prepare copolymers, such as those based on antimony, germanium and titanium. Preferably, tetraisopropylorthotitanate (IPT) and sodium acetate (NaOAc) are used as the catalyst system in the process.

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

Accordingly, 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 at a concentration of 0.001-5 wt.%, more preferably 0.01-0. 5% relative to the total weight of the oxygen barrier composition.

Without wishing to be bound by theory, it is believed that the polyether-polyester copolymer is an oxidizable support in which the end groups at the ends of the chains are able to control oxygen permeation and form a controlled active oxygen barrier. The rate of the oxygen uptake reaction can be changed by the number and chemical composition of the end groups.

The transition metal catalyst also initiates and accelerates the oxygen scavenging rate. The mechanism by which this transition metal functions has not been determined. The catalyst may or may not be consumed with oxygen, or, if consumed, may be consumed only temporarily by being converted back to the catalytically active state.

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 degree of oxidation of the metal upon introduction does not necessarily have to correspond to the state 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 metal counterions include, but are not limited to, chloride, acetate, acetylacetonate, propionate, oleate, stearate, palmitate, 2-ethylhexanoate, octanoate, neodecanoate, or naphthenate.

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

Even more preferably, the salt, transition metal, and counterion either comply with country regulations for food contact materials or, if they are part of the packaging article, substantially prevent migration from the oxygen barrier composition into the packaged contents. Particularly preferred salts include cobalt oleate, cobalt propionate, cobalt stearate and cobalt neodecanoate.

Another object of the invention is a plastic material comprising:

component a) which is a thermoplastic polymer, preferably selected from the group consisting of polyesters, polyolefins, polyolefin copolymers and polystyrenes;

component b) which is a polyether-polyester copolymer as described above; and component c) which is a transition metal catalyst as described above.

The plastic material may be a concentrate, a compound, or a molded article.

Depending on its use, the plastic material may contain component b) in an amount of 0.5-99.995 wt.%, or more preferably 1-99.8 wt.%, and component c), in the form of a transition metal element concentration, in an amount of 0.001 -5 wt.%, or more preferably 0.002-4 wt.%, relative to the total weight of the plastic material.

Preferred components a) within the meaning of the invention are polyesters. The intrinsic viscosity values of the polyesters are given in units of dl/g calculated from the intrinsic viscosity measured at 25° C. at 60/40 w/w. phenol/tetrachloroethane. The intrinsic viscosity of the polyesters is preferably in the range of about 0.55-1.14 dl/g.

Preferred polyesters are those obtained from the condensation reaction of dibasic acids and glycols.

Generally, the diacid includes an aromatic diacid or an ester or anhydride thereof and is selected from the group consisting of isophthalic acid, terephthalic acid, naphthalene 1,4-dicarboxylic acid, naphthalene-2,6-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. The diacid may also be an aliphatic dibasic acid or an anhydride such as adipic acid, sebacic acid, decane-1,10-dicarboxylic acid, fumaric acid, succinic anhydride, succinic acid, cyclohexanedioacetic acid, glutaric acid, azelaic acid, and mixtures thereof. Other aromatic and aliphatic dibasic acids known to those skilled in the art may also be used. More preferably, the diacid includes an aromatic dibasic acid, optionally further comprising up to about 20% by weight of the dibasic acid component of the aliphatic dibasic acid.

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, polyethylene glycol, polypropylene glycol, neopentyl glycol, polytetramethylene glycol, 1,6-hexylene glycol, pentane-1,5-diol, 3-methylpentanediol -(2,4), 2-methylpentane-(1,4)diol, 2,2,4-trimethylpentane-(1,3)diol, 2ethylhexane-(1,3)diol, 2,2-diethylpropane(1, 3) diol, hexane(1,3) diol, 1,4-di-(hydroxyethoxy)benzene, 2,2-bis-(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3- tetramethylcyclobutane, 2,2-bis-(3hydroxyethoxyphenyl)propane, 2,2-bis-(4-hydroxypropoxyphenyl)propane, 1,4-dihydroxymethylcyclohexane and mixtures thereof. Additional glycols known to those skilled in the art may also be used as the glycol component of the polyester.

Two preferred polyesters are polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). PET and PEN may be homopolymers or copolymers further comprising up to 10 mole percent dibasic acid other than terephthalic acid or naphthalenedicarboxylic acid and/or up to 10 mole percent glycol other than ethylene glycol.

- 7 042846

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

More preferably, the plastic material is selected from the group consisting of PET, such as virgin bottle PET and waste PET (PC-PET), cyclohexanedimethanol/PET copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PB), and mixtures thereof.

Also preferred plastic materials are biobased polymers, preferably polyethylene furanoate (PEF), as well as a biodegradable polyester, preferably selected from the group consisting of PLAs (polylactic acid), polycaprolactones (PCL) and polyhydroxybutyrates (PHB); and bio-based polyesters, which are derived from renewable resources such as corn and sugar cane, and non-biodegradable by-products associated with their collection and processing.

Preferred polyolefins and polyolefin copolymers, i.e. 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 of high density polyethylene (HDPE) , medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), metallocene low density polyethylene (mLDPE) and metallocene linear low density polyethylene (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), PE copolymers, preferably selected from the group consisting of ethylene vinyl acetate copolymers (EVA), ethylene-methyl acrylate copolymers ( EMA), copolymers of ethylene and butyl acrylate (EBA), copolymers of ethylene and ethyl acrylate (EEA), and cycloolefin copolymers (COC), general purpose polystyrene (GPPS) and high impact polystyrene (HIPS); more preferably high density polyethylene (HDPE) and low density polyethylene (LDPE) polypropylene homopolymer (PPH), general purpose polystyrene (GPPS).

Preferred polystyrenes, ie component a) within the meaning of the invention, can be a styrene homopolymer, an alkylstyrene homopolymer, preferably a C ₁ -C ₄ alkylstyrene homopolymer, for example an α-methylstyrene homopolymer; a styrene copolymer, in particular high impact polystyrene (HIPS).

High-impact polystyrenes (HIPS) are usually 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 an elastic polymer backbone comprising copolymers selected from polybutadiene, polyisoprene, rubber-like styrene-diene copolymers, acrylic rubber, nitrile rubber, and olefin rubbers such as propylene diene monomer rubber (PDM) and propylene rubber (PR). In high impact polystyrene, the elastic polymeric backbone typically makes up 5-80% by weight, preferably 5-50% by weight, of the total weight of the grafted polymer.

Optionally, the composition of the active oxygen barrier and the plastic material of the present invention contain one or more additional substances (component d) which are selected from the group consisting of natural dyes derived from plants or animals and synthetic dyes, the preferred synthetic dyes are synthetic organic and inorganic dyes and pigments, the preferred synthetic organic pigments are azo or disazo pigments, azo or disazo lacquer pigments or polycyclic pigments, more preferably phthalocyanine, diketopyrrolopyrrole, quinacridone, perylene, dioxazine, anthraquinone, thioindigo, diaryl or quinophthalone pigments;

preferred synthetic inorganic pigments are metal oxides, mixed oxides, aluminum sulfates, chromates, metal powders, pearlescent pigments (mica), fluorescent paints, titanium oxides, cadmium and lead based pigments, iron oxides, carbon black, silicates, nickel titanates, pigments based on cobalt or chromium oxides;

surfactants;

excipients, preferably acid scavengers, processing aids, binders, 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 blends;

UV absorbers, slip agents, anti-fogging agents, anti-condensation agents, suspension stabilizers, anti-blocking agents, waxes and mixtures of these substances.

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More preferably component d) is selected from the group consisting of compatibilizers, UV absorbers, antioxidants and colorants.

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

The plastic material of the present invention is expediently molded into a plastic article, for example by blow molding.

Accordingly, another object of the present invention is a molded plastic article comprising said plastic material.

The molded plastic article according to the invention may be a packaging material, preferably a container, film or sheet, especially for use in personal care, cosmetics, household, industrial, food and beverage packaging where a high oxygen barrier is required.

Packaging materials can be flexible, rigid, semi-rigid, or combinations thereof. Rigid packaging products typically have a wall thickness of 100-1000 micrometers. Conventional flexible packaging typically has a thickness of 5-250 micrometers.

Rigid packaging products or flexible films according to the invention may consist of a single layer or may contain several layers.

When the packaging article or film contains an oxygen scavenging layer, it may further include one or more additional layers, one or more additional layers including an oxygen barrier or oxygen permeable layer. Other additional layers, such as adhesive layers, can also be used in a multilayer packaging product or film.

Another object of the invention is a method for manufacturing a plastic product as defined above, characterized in that the components a), b), c) and optionally d) are physically mixed with each other and subjected to a molding process.

For physical mixing, a mixing device common in the plastics industry can be used. Preferably, the mixing device may be one used to prepare a liquid concentrate or a solid concentrate, or may be a combination of these devices.

The liquid concentrate mixing device can be a high speed disperser (eg Cowles™ type), a mill, a three roll mill, an auxiliary mill, or a rotary stator disperser.

The mixing device used to make MB solid concentrates or CO compounds can be a mixer, an extruder, a kneader, a press, a mill, a calender, a blender, an injection molding machine, an ISBM, an extrusion machine with blow molding machine (EBM), compression molding machine, compression blow molding machine; more preferably a mixer, an extruder, an injection molding machine, a stretch blow molding machine, an injection molding machine; even more preferably a mixer, an extruder, a stretch blow molding machine and a blow molding machine.

The process of molding the product depends on the desired shape of the manufactured product.

The containers are preferably manufactured by blow molding, injection molding, stretch blow molding, stretch blow molding, injection molding, compression stretch blow molding.

Films and sheets are preferably made using cast or blown or co-extrusion processes, depending on the required thickness and the number of layers required to obtain certain properties, which are ultimately followed by post-extrusion molding processes such as thermoforming or stretching. In the thermoforming process, a plastic sheet is heated to a suitable forming temperature, molded into a predetermined shape in a mold, and cut to create the final product. If vacuum is used, this process is usually referred to as vacuum forming. In post-extrusion stretching processes, the extruded film can, for example, be oriented in two directions by stretching. All of the above processes are well known in the art.

The mixing of the components can take place in one step, two steps, or multiple steps.

Mixing can take place in one step when components a), b), c) and optionally component d) or only b), c) and optionally component d) are directly dosed and/or introduced in the form of liquid or solid concentrates, or in the form clean components, for example in a stretch blow molding machine.

Mixing can also take place in two or three stages, wherein in the first stage components b), c) and optionally d) are pre-dispersed in component a), and in one or more successive stages are added to component a).

Mixing can also take place in two or three stages, and in the first stage the components

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c) and optionally component d) is pre-dispersed in component a) and component b) is directly dosed and/or injected as a pure component, for example into a stretch blow molding machine.

Preferably, component b) and component c) are pre-dispersed in component a) to form two separate concentrates and then these concentrates are combined with components a) and optionally d). In one preferred embodiment, in the first step, component b) and optionally component d) are dispersed in component a), while component c) is dispersed in component a) to obtain two separate concentrates. After melt compounding, for example in a single screw or twin screw extruder, the extrudates are obtained in the form of strands and are recovered in the form of tablets in accordance with a conventional method such as cutting. In the second stage, the obtained concentrates are dosed and fed by a converter/compounder into the main stream of component A granules, for example, in a stretch blow molding machine. These extrudates can be dosed and introduced into the main stream of component a) directly into the injection process, avoiding the mixing process.

In another embodiment, in the first step, component b), c) and optionally component d) are dispersed in component a) to obtain a concentrate. After melt compounding, for example in a single screw or twin screw extruder, the extrudate is obtained in the form of strands and recovered in the form of pellets in accordance with a conventional method such as cutting. In the second stage, the resulting solid concentrate is dosed and fed by a converter/compounder into the main stream of component a), for example, into a stretch blow molding machine at a speed corresponding to the final required concentration of components b) and c) in the product.

The mixing preferably takes place continuously or intermittently, more preferably continuously; in the case of a solid MB concentrate, preferably by extrusion, mixing, grinding or calendering, more preferably by extrusion; in the case of liquid MB concentrate, preferably by mixing or grinding; in the case of CO compound, preferably by extrusion or calendering, more preferably by extrusion.

Mixing is preferably carried out at a temperature of 0-330°C.

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

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

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

In the case of the MB liquid concentrate, the mixing is preferably carried out at a temperature of 0150° C. with a mixing time of 0.5-60 minutes.

In the case of an MB solid concentrate or a CO compound, the mixing is preferably carried out at a temperature of 80-330° C. with a mixing time of 5 seconds to 1 hour.

Particular articles of the present invention include preforms, containers, films and sheets for food, beverage, cosmetics and personal care applications where a high oxygen barrier is required. Examples of beverage containers are: bottles for juices, sports drinks, beer, or any other beverage in which oxygen adversely affects the taste, aroma, characteristics (prevents vitamin degradation), or color of the beverage. The compositions of the present invention are also particularly useful as a sheet for thermoforming into rigid bags and films for flexible structures. Rigid bags include food trays and lids. Examples of applications for food trays include heat-resistant food trays or cold storage trays, both in the main container and in the lid (whether thermoformed lid or film), where the freshness of the food contents may be impaired by the ingress of oxygen.

Preferred products of the present invention are rigid packaging products such as bottles and thermoformed sheets and flexible films.

An additional aspect of the present invention relates to single layer films. The term "single layer film or monolayer cast film or single layer sheet" means a semi-finished product consisting of a sheet (blank), usually obtained by extrusion of films forming a layer. The resulting sheet has not been subjected to the preferred orientation process and is therefore not oriented. The sheet may subsequently be formed into a finished product, such as a container, by known processes that do not cause orientation, typically by thermoforming. The term "container" refers to any article having an opening for the introduction of a product, in particular foodstuffs.

To determine the oxygen scavenging capacity of the copolymers of the invention, the oxygen scavenging rate can be calculated by measuring the time elapsed before a certain reduction in oxygen content in a sealed container.

Another definition of acceptable oxygen uptake comes from testing actual packages.

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The oxygen scavenging capacity of an article according to the invention can be measured by determining the amount of oxygen consumed before the article's absorption efficiency is exhausted.

The plastic material of the present invention provides an oxygen scavenging system with high oxygen scavenging capacity, fine adjustment of the rate of oxygen transmission to the interior of the package, and suitable transparency of the final plastic products.

Test methods.

Product properties are determined by the following methods, unless otherwise indicated:

Density values are determined in accordance with ASTM D792 (g/cm ³ ).

Melt flow rate (MFR) values are determined according to ASTM D1238 (g/10 min at specified temperature and weight).

Method for measuring the absorbing capacity of oxygen.

The cast film, including a suitable absorbent composition, is introduced into a glass container equipped with an optical sensor and a rubber lid.

The measurement of the oxygen content in the headspace of the vessel is then carried out using two different methods. One of them is the non-penetrating measurement with an oxygen sensor and a Fibox® transmitter. The other is CheckMate 3 O ₂ (Zr) CO ₂ -100%.

For both of these, data are collected in parallel for at least two samples of the same composition at regular intervals. For each sample, the oxygen uptake at a certain time is calculated as the difference between the oxygen content measured at a given time and the oxygen content measured at time 0, which is close to 21%. The oxygen uptake is then averaged over the number of samples measured for each formulation and plotted against time.

Implementation of the invention

Examples wt.% indicated in the following examples, are given relative to the total weight of the mixture, composition or product; parts are mass parts;

ex means example; seh means comparative example; MB stands for concentrate; CO stands for compound, D stands for direct dosing of the respective additives.

Used equipment.

The equipment used to perform the PET cast film production test described below consists of a single screw extruder, a screw diameter of 25mm, a filter changer with a 40 micron filter mesh, a 350mm wide flat die for making a single layer film, a horizontal calender with 3 rollers.

Substances used.

Component A: A1:

Polyethylene terephthalate (PET) having a density of 1.35-1.45 g/cm ³ and an intrinsic viscosity of 0.74-0.78 dl/g (ASTM D3236-88).

Component a: A2:

Polybutylene terephthalate (PBT) having a density of 1.28-1.32 g/cm ³ and an intrinsic viscosity of 0.90-1.00 dl/g (ASTM D3236-88).

Component b: B1 - B 13:

Polyester-Ethers are prepared using the following general procedure:

In a 500 ml multi-neck flask equipped with a KPG stirrer, Christmas tree reflux condenser, vacuum source and nozzle, chemicals in accordance with Table. 1 is placed in a reactor in a nitrogen atmosphere and in the amount indicated in table. 1.

The mixture is heated to an internal temperature of 60° C., followed by the addition of 200 µl of tetraisopropyl orthotitanate.

Within 2 h, the temperature of the reaction mixture is continuously raised to 230° C. under a low flow of nitrogen (5 l/h) and maintained at this temperature for 2 hours. After reaching 70° C., methanol begins to distill off. After reaching 190°C, ethylene glycol continuously starts distilling off. Thereafter, the N2 flow was stopped and the pressure of the reaction mixture was continuously reduced to 400 mbar at 230° C. for 165 min, followed by further continuous pressure reduction to 1 mbar over 90 min. In the next step, the reaction mixture is stirred at a pressure of 1 mbar and an internal temperature of 230°C for an additional 4 hours. After this period of time, the internal pressure in the reaction flask is brought back to 1 bar using N2, and then the polymer melt is removed from the reactor and given him to harden.

To determine the molecular weight of polyester-ether, measurements are made using GPC under the following conditions:

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Columns: 1 x PSS SDV Guard, 5 µm, 50 mm x 8.0 mm ID;

x PSS SDV 100 A, 5 µm, 300 mm x 8.0 mm ID;

x PSS SDV 1000 A, 5 µm, 300 mm x 8.0 mm ID;

x PSS SDV 100000 A, 5 µm, 300 mm x 8.0 mm ID;

Detector: RI;

Furnace temperature: 40°C;

Flow rate: 1 ml/min;

Injection volume: 50 µl;

Eluent: THF;

Calculation: PSS-WinGPC Version 8.2;

Calibration: polystyrene standards in the range 682-1 670 000 Da;

Internal standard: toluene;

Injection concentration: 4 g/l in THF.

Table 1

Sample DMT/r DMI/r Poly-THF 1000/g Poly-THF 2000/y PEG 1000/g PR-1000/g MPEG 750/g M41/g ε-Carolactone/g 1,4-Butavdiol/g EG/r PG/g Na-acetate/g Θ Ω McL^mol ¹ Md/^mol' ¹ IN 1 48.5 50.0 25.0 25.0 125.0 0.3 0.8 1 5 17311 8073 AT 2 48.5 50.0 37.5 12.5 125.0 0.3 0.4 1 5 28398 12019 VZ 48.5 50.0 43.8 6.3 125.0 0.3 0.2 1 5 35318 16430 AT 4* 48.5 50.0 50.0 125.0 0.3 ο, ο 1 5 39852 18412 AT 5 43.7 4.9 50.0 37.5 12.5 125.0 0.3 0.4 1 5 27623 11793 wb 48.5 4.9 50.0 43.8 6.3 125.0 0.3 0.2 1 5 36165 15054 AT 7 48.5 4.9 50.0 46.9 3.1 125.0 0.3 0.1 1 5 24979 10948 AT 8 48.5 50.0 37.5 12.5 125.0 0.3 0.4 1 5 27986 13604 AT 9 48.5 50.0 37.5 12.5 125.0 0.3 0.4 1 5 26281 11626 AT 10 48.5 50.0 37.5 12.5 125.0 0.3 0.4 1 5 38476 17954 AT 11 48.5 50.0 12.5 37.5 37.5 0.3 0.4 1 5 32345 11953 AT 12 48.5 50.0 37.5 12.5 29.3 24.7 0.3 0.4 1 5 29894 13465 B13 48.5 50.0 18.8 31.3 37.5 0.3 0.6 1 5 25310 10501

* B4 Comparative - no end group was used for the synthesis of this polymer.

DMT = dimethyl terephthalate.

MPEG 750 = monomethoxylated poly(ethylene glycol) - monol.

DMI = dimethyl isophthalate (average molecular weight (Mn) = 0.75 kDa).

Poly-THF 1000 = Poly-THF-diol (average molecular weight (Mn) = 1 kDa).

M41 = Monomethoxylated poly(ethylene glycol)-co-poly(propylene glycol)-monool (average molecular weight (Mn) = 2 kDa).

Poly-THF 2000 = Poly-THF-diol (average molecular weight (Mn) = 2000 kDa).

EG = ethylene glycol.

PEG 1000 = Poly(ethylene glycol) diol (average molecular weight (Mn) = 1 kDa).

PG = propylene glycol.

PR 1000 = Poly(ethylene glycol)-co-poly(propylene glycol) diol (average molecular weight (Mn) = 1 kDa).

Component c: C1:

Solid form of cobalt stearate (concentration of elemental cobalt 9.5%).

Component d: D1:

Surface-active substance.

Concentrates MB1 -MB 10.

The components are co-homogenized using a Leistritz® ZSE18HP extruder at 260° C. to obtain a MB solid concentrate; tab. 2 gives detailed information.

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table 2

concentrates Used components [parts] A1 A2 IN 1 AT 4 AT 5 AT 8 AT 9 AT 10 AT 11 AT 12 B13 C1 D1 MV1 83 17 MV2 (Compound) 97.8 2.2 cost center 90 10 MV4 90 10 MV5 90 10 MV6 90 10 MV7 90 10 MV8 90 10 MV9 90 10 MV10 86 6 8

Production of cast films.

As an example of an operating mode, cast films with a thickness of 200 μm are obtained by extrusion using Colling E 25 PK by introducing component A1, previously dried for 18 hours at 120 ° C, into the main hopper of the apparatus and by adding other components (directly dosed MB and / or pure additives) through dosing devices supplied to the main flow of component A1 before entering the cylinder of the injection unit. The extruder temperature can be maintained at 260°C and the flat head temperature is 270°C.

The operating conditions during the test are as follows: T1 = 60°C / T2 = 240°C / T3 = 260°C / T4 = 260°C / T5 = 260°C / _Head T = 270°C / _Calender T = 70°C / screw speed 80 rpm.

Table 3

ex-sreh Material type Composition (%) cpexl 100 PET sreh2 MV 86.3 PET + 12MV1+ 1.7 MV10 ex2 SO 7.3 PET+ 91 MV2+ ex3 D 96.3 PET + 2in1+ ex4 D 2B2+ ex5 D 2VZ + srehb D 2B4+ ex7 MV 78.3 PET + 20 cost centers + ex8 MV 20 MV4+ ex9 MV 20 MV5+ exju MV 20 MV6+ exll MV 20 MV7+ ex12 MV 20 MV8+ ex13 MV 20 MV9+

The oxygen uptake capacity (in ml O ₂ , per gram of composition) corresponding to the cast films is measured by the methods described above. In table. Figure 4 shows data on oxygen uptake by compositions with different copolymer structures and different numbers of end groups.

Table 4

Θ OD 0.2 0.4 0.8 0.4 0.6 Sample Day srehb ex5 ex4 ex3 exll ex13 0 0.0 oh oh oh oh 0.0 0.0 oh oh 2 6.2 6.2 4.7 2.0

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Claims (13)

3 0.8 0.6 6 24.0 20.8 17.9 6.4 7 29.1 24.8 21.8 7.8 4.5 3.1 9 37.5 32.1 27.4 9.2 10 13.0 6.5 12 44.7 42.2 36.0 11.8 14 52.0 50.6 42.2 14.8 28.2 13.2 17 39.4 19.7 19 68.3 64.4 55.6 23.0 21 71.9 70.5 60.1 27.2 50.7 26.4 23 76.8 70.5 64.5 31.4 26 82.2 76.5 68.1 36.9 28 91.8 78.8 71.6 40.9 When compared between ex3, ex4, ex5 and cpexb, there is a significant dependence of the oxygen uptake rate on the amount of end groups present. Generally, the amount of oxygen uptake decreases as more groups are introduced. The oxygen uptake rate greatly depends on the amount of end groups contained in the polyester-copolyester, so the amount of oxygen uptake can be finely adjusted and controlled by increasing or decreasing the amount of end groups. This effect is observed when polyester-copolyester additives are dosed together with the resin directly into the extruder feed mechanism, and also during the preparation of MB. Ex11 and ex13, which are polyesters with different end groups than ex3-ex5 and cpexb polyesters, show exactly the same behavior: higher end groups reflect a reduction in oxygen uptake. CLAIM 1. Polyether-polyester copolymer, comprising: (i) polyether segments, in which at least one polyether segment contains at least one polytetramethylene oxide segment, (ii) polyester segments, where the polyester segments (ii) are represented by the formula (II) o o *—o—R3 -l o—R2o—o—* (P) in which * represents the connection with the bridge element (iii), R2 and R3 independently of each other represent an optionally substituted hydrocarbon residue consisting of 1-100 carbon atoms, where the substituents are C ₁ -C ₃ -alkoxy, nitro, cyano and sulfo, and u is an integer of 1-50; (iii) -CO-R2-CO- bridging elements in which R2 is an optionally substituted divalent hydrocarbon moiety of 1-100 carbon atoms, where the substituents are C1- _C5 alkoxy, nitro, cyano or sulfo, or their combination; (iv) one or two end groups R1-O-(C ₂ -C ₄ -O-)e-*, where R1 represents an aliphatic hydrocarbon residue with 1-24 carbon atoms, an olefinic hydrocarbon residue with 2-24 carbon atoms, aromatic a hydrocarbon residue with 6-14 carbon atoms, wherein said hydrocarbon residues are optionally substituted with C ₁ -C ₅ alkoxy, nitro, cyano, sulfo, or combinations thereof, and e is an integer of 0-1000. 2. The polyether-polyester copolymer of claim 1, wherein the polyether segments (i) comprise ethylene oxide segments, propylene oxide segments, or a combination thereof. 3. Polyether-polyester copolymer according to any one of the preceding claims 1, 2, wherein the bridge elements are described by formula (III) 10 about U-R2-U (u) wherein R2 is an optionally substituted divalent hydrocarbon residue of 1-100 carbon atoms, where the substituents are C1- _C5 alkoxy, nitro, cyano or sulfo, or a combination thereof. 4. The polyether-polyester copolymer according to any of the preceding claims 1 to 3, wherein the end groups are described by the following general formula Rl-O-(C ₂ -C ₄ -O-)e-*, in which R1 is as defined in claim 1, e is an integer 0-500. 5. Polyether-polyester copolymer according to any one of the preceding claims 1 to 3, wherein R1-O-(C ₂ -C ₄ -O-) _e- * corresponds to the following formulae: - 14 042846 in which the various monomers are randomly distributed, in blocks, or by a combination of random and block distribution, and b represents an integer of 0-250, a is an integer of 0-250, c represents an integer of 0-70, and the sum of a + b + c is 0 -570; And R1 is as defined in claim 1. 6. Polyether-polyester copolymer according to any of the preceding claims 1 to 5, wherein R1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, npentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, sec-hexyl, ngeptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, methylphenylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl. 7. The polyether-polyester copolymer according to any of the preceding claims 1 to 6, wherein the number average molecular weight is 2000-1000000 g/mol. 8. Polyether-polyester copolymer according to any of the preceding claims 1 to 7, wherein the weight ratio Ω, defined as the weight ratio between the content of poly(tetramethylene oxide) and the total content of all elements of the dicarbonyl structure (p) and (iii), is 0.1-10. 9. The polyether-polyester copolymer according to any of the preceding claims 1 to 8, wherein the weight ratio Θ, defined as the weight ratio between the content of the end group and the total content of all elements of the dicarbonyl structure (i) and (iii), is between 0.001 and 100. 10. A process for producing a polyether-polyester copolymer according to any of the preceding claims 1 to 9, comprising polycondensing polyether segments comprising at least one polytetramethylene oxide segment as defined in claim 1, polyester segments as defined in π. 1, bridging elements and end groups as defined in π. 1. I. The active composition of the oxygen barrier, comprising a copolymer simple polyethercomplex polyester according to any one of paragraphs. 1-9 and a transition metal catalyst in the form of a salt, wherein the salts include cobalt oleate, cobalt propionate, cobalt stearate and cobalt neodecanoate. 12. Oxygen-absorbing plastic material, including component a), which is a PET thermoplastic polymer; component b), which is a polyether-polyester copolymer according to any one of claims 1 to 9; and component c) which is a transition metal catalyst in the form of a salt, wherein the salts include cobalt oleate, cobalt propionate, cobalt stearate and cobalt neodecanoate. 13. The plastic material according to claim 12, which is a concentrate, a compound, or a molded article. 14. Plastic material according to claim 12 or 13, which is a container or film or part thereof. Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky per., 2 -