A laminate that protects from oxygen, the method of protection of product and packaging the product with its use, the material absorbing oxygen

 

(57) Abstract:

The invention relates to materials, products and packaging of substances that are sensitive to oxygen, especially food. Materials include copolyamids containing more than 50 wt.% the polyamide segments and the segments oligomeric polyolefin in an amount to provide the ability to absorb oxygen. Segments of polyamide obtained from conventional polyamides used for the manufacture of bottles and packaging products, such as polyhexamethylenediamine and polyphthalamide. The copolymers preferably receive the transesterification process of reactive extrusion and they usually contain about 0.5-12 wt.% segments oligomeric polyolefin. Compared to the same polyester and similar materials polyamide materials copolyamids used in layered materials have improved active and passive protective properties with respect to oxygen. In some preferred examples of the produced multilayer bottles of polyamides, absorbing oxygen, which consisted of about 99,8% wt. polyamide and recyclable together with other polyamide bottles, 4 C. and 10 C.p. f-crystals, 2 ill., 3 table.

Background of invention.

Polymeric materials continue to find increasing application in the packaging industry due to the original flexibility of these materials and their ability to be processed into products of various sizes and shapes commonly used in the packaging industry. Processing of polymeric materials in packaging articles, such as films, trays, bottles, glasses, cups, coatings and linings, already widely used in the packaging industry. Although polymer materials for packaging premernyh materials remains impossible in those cases, when to provide the required shelf life of the product necessary protective properties against atmospheric gases (mainly oxygen). Compared to traditional packaging materials such as glass, steel, polymers have insufficient protective properties, which limits their use for packaging products that are sensitive to atmospheric gases, especially when the effects of atmospheric gases lasts quite a long time. Packaging industry is still in need of packing materials, which have the original flexibility of polymeric materials and at the same time, have protective properties of glass and steel.

In the packaging industry technology developed to improve the protective properties of plastic containers by creating containers that have a superior protective properties, approaching, but not comparable with the properties of glass, steel and aluminium. The polyethylene terephthalate (PET) and similar polyesters for packaging found in a very wide range wide distribution, especially for the manufacture of bottles, due to the transparency and hardness, specific for PET bottles. PAT found a large spread in shallalah, where the need for protective properties of small. A striking example is the use of PET for the manufacture of bottles for soft drinks. However, the protective properties of the PET has limited its use for packaging products sensitive to oxygen.

In the packaging industry it is generally accepted that the polyamides have excellent passive protective properties against oxygen, which is comparable with properties similar packaging products of polyesters. Suitable passive protective polymer is a polymer exhibiting the ability to slow the permeability of oxygen through it when compared with the permeability of oxygen through other resins.

Further, it was reported that the polyamide known MXD-6, has some active ability to absorb oxygen. MXD-6 is a poly(m-xylylenediamine), which is a polyamide derived from equal molar amounts of the two monomers: (1) meta-xylocaine and (2) adipic acid. Active protection from oxygen polymer is a substance that can interrupt the flow and absorb oxygen by a chemical reaction with oxygen), if he can penetrate the packaging. This path also allows astranet create protective properties against oxygen known as creating "active shielding material and its concept differs from the concept of passive shielding materials, which hermetically isolates the product from oxygen by passive method.

When MXD-6 (about 4 wt.%) mixed with PET (about 96% by weight), the resulting mixture has a permeability to oxygen of approximately 70% of the permeability of such articles of unmodified PET. Presumably, this 30% improvement compared to the unmodified PET can be attributed to the improvement of the passive protective properties of the above mixture. When the oxidation catalyst is added to the mixture (e.g., about 50-200 ppm of cobalt based on the weight of the mixture), the mixture acquires a superior active properties to absorb oxygen. The permeability of the mixture of oxygen under these conditions is reduced to until the active absorbing capacity is not depleted. Protective properties characteristic of the mixture, are suitable for packaging products with low requirements and only when a large flow of the mixture. However, MXD-6 is a relatively expensive polyamide, and use it for packing in large quantities reduces the efficiency of such packaging. The more common polyamides having a smaller value, such as the well-known poly(hexamethylenediamine) is characterized by an improved passive properties of the o-passive protective properties, which can be obtained at reasonable cost and which has sufficient capacity to absorb oxygen and protective properties to make possible the retention period of 6 months to two years for products that are sensitive to oxygen. The present invention satisfies this need.

The essence of the invention and an overview of the state of the art.

In the application of the U.S. 08/717370, filed September 23, 1996, indicated that some hydrocarbons such as polyolefins (especially polydiene) contained in small quantities in the form of blocks of oligomeric polyolefin block sobolifera, give the ability to actively absorb oxygen packaging polyesters, which did not show any ability to actively absorb the oxygen in the absence of oligomeric blocks of polyolefin. Described in the application sobolifera, absorbing oxygen, consisted mainly of segments of the packaging polyester and oligomeric segments polyolefin only in such quantity that provides the ability to absorb the oxygen that is required for packaging. Sobolifera described in the application 08/717370, usually contain about 0.5-12 wt.% segments oligomeric polyolefin, and the rest - segments complicated Polga polyolefin, the rest is a complex segments of polyester. Such block-Capoliveri containing a small amount of oligomeric segments of polyolefin, possessed properties (such as melting point, viscosity, and transparency), very similar to the properties of the unmodified polyester of the polyester segments. In particular, the layers in layered packaging and bottles, containing one or more layers of unmodified complex polyester and one or more layers of block sobolifera absorbing oxygen, as described above, meshed with each other, and packaging articles seemed more monolithic than layered.

For the purposes of this invention, the applicants have expanded the concept of introducing segments oligomeric polyolefins with a high ability to absorb oxygen at polyamide-forming unit-copolyamids, containing mainly the polyamide segments and the segments oligomeric polyolefin in an amount to provide the ability to absorb oxygen, and Capoliveri described in the application 08/717370, copolyamids according to the invention have properties that are very similar to the properties of the polyamide from which the received segments. A typical application of such polyamides - layered structure, Haus copolyamid (in which segments copolyamid obtained from polyamide, which is made from the inner and/or outer layers and segments, absorbing oxygen, represent segments of the oligomeric polyolefin). This structure provides copolyamid layer properties, very similar to the properties of the layers of unmodified polyamide, which is very important for layered structures according to this invention. The basic concept of the present invention, however, is the introduction to the copolyamids very effective in absorbing oxygen oligomeric segments of the polyolefin while maintaining the properties of the unmodified polyamide in copolyamid. High capacity actively to absorb oxygen from the described copolyamids due to the ability to actively absorb oxygen oligomeric segments of the polyolefin. As stated above, usually believe themselves polyamides have excellent passive properties to protect from oxygen compared with complex polyesters. Thus, another important concept of this invention consists in the combination of excellent passive protective properties and ability to actively absorb oxygen in contrast to the unmodified complex unmodified polyester or polyamide.

The polymer having an active say oxygen (due to chemical reaction with oxygen), as penetrates through the package. Active absorption of oxygen also allows you to remove unwanted oxygen (often called oxygen in the free space above the product from the cavity of the packaging, where the specified oxygen can get during packing or filling. This method of imparting protective properties against oxygen, when a substance absorbs oxygen or react with oxygen, known as creating "active protective layer, it is based on a different concept than the creation of a passive protective properties based on physical isolation of the product from oxygen in the manifestation of passive properties. Only the active oxygen scavengers can remove the unwanted oxygen (inevitably fall into the packaging process) from the cavity of the package. Active absorption of oxygen implies, therefore, the absorption of the material introduced into the wall of the packaging. The material absorbs over time, and the ability to actively absorb oxygen gradually disappears or at least is reduced. However, it is possible exhaustion of the ability to absorb oxygen can be adjusted so that it only occurred once over the desired shelf life upakovan (CMB) described the SMV system Ohvag, absorbing oxygen. The referenced patent provides for the use of polyamide (mixed with polyester) as an active oxygen scavenger. In this patent it is proposed to use polyamide mixed with the polyester used for the manufacture of bottles, such as PET, is provided by the presence of a catalyst such as a transition metal. These mixtures are used to perform at least one layer in a single-layer or multilayer packaging or in the wall of the bottle. According to the patent SMV in the mixture responsible for the active uptake of oxygen is polyamide. According to a preferred variant of 96 wt.% PET mixed with 4 wt.% polyamide, often denoted MXD-6. MXD-6 is a polyamide obtained from equivalent amounts of the two monomers: (1) methoxylamine and (2) adipic acid. The blend PET/ MXD-6 is typically used in the presence of approximately 200 ppm of cobalt, which catalyzes the active absorption of oxygen. In EP-A-0507207 described composition for the absorption of oxygen, including Ethylenediamine hydrocarbon polymer and a transition metal, which catalyst.

The present invention provides for the use of copolyamids capable of absorbing oxygen is este, providing absorption of oxygen. The copolyamids according to the invention are usually used in the presence of a catalyst such as a transition metal, and used in the form of at least one layer in a single-layer or multi-layer wall of the bottle or packaging. A significant difference between this invention and patent SMV is: (1) the invention provides copolyamide, containing mainly the polyamide segments, and in the patent SMV described blend of polyester/polyamide, mainly containing polyester (patent SMV does not describe the use of polyolefin), (2) the oligomeric segments of the polyolefin in the copolyamids according to the invention are fragments that react with oxygen and absorb oxygen, (3) the ability to absorb oxygen copolyamids according to the invention is significantly greater than that of a mixture of PET/ MXD-6 and (4) the copolyamids according to the invention are typically used in packages based on polyamides and bottles, while the blend PET/MXD-6 is designed for packaging and bottles-based polyesters (PET).

Brief description of drawings

In Fig.1 shows a cross section of a preferred construction of the walls of the bottle and the film structure.

In Fig. 2 shows a graph showing the IPN.

A detailed description of the preferred options.

As mentioned above, the polyamides generally have excellent passive protective properties compared with complex polyesters used in packaging products. This is true for less expensive and well-known polyamides, such as poly(hexamethylenediamine), as well as more rare and relatively expensive polyamides, such as MXD-6. The polyamides used for the manufacture of plastic bottles or other packaging products may be the same polyamides, which received the polyamide segments in absorbing oxygen copolyamids according to the invention. In the field of polyamides are well known to produce polyamides joint polymerization (usually taken in equal molar amounts and in the presence of a suitable catalyst) of two chemical substances described by formulas I and II, with the receipt of polyamide with a repeating unit of the formula III.

R1in the dicarboxylic acid of the formula I can be any substituted or unsubstituted divalent organic radical, aromatic, aliphatic, alicyclic, or their mixture. R2in the diamine of the formula II refers to any substituted or unsubstituted organic dohwa the cases R1and R2(both, separately and/or independently from each other) may contain olefinic unsaturation. Such unsaturated compounds, if used, are included in the scope of this invention. In addition, specialists obviously, you can use other types of compounds represented by formulas I and II, which will lead to the same polyamides described by formula III. For example, mono - and dihalogenide or mono - and diesters of acids of formula I will receive (after polymerization) of the same polyamide of the formula III. Similarly, the substitution of some or all four hydrogen atoms in the diamine of formula II also will (after polymerization) to obtain the same polyamide of the formula III.

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Preferred polyamides suitable for use according to this invention include linear polyamides, for example those in which the dicarboxylic acid of the formula I selected from the list comprising aliphatic dicarboxylic acid such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, various naphthalenesulphonate acid and mixtures thereof. Preferred diamines of formula II include polyallylamine, for example hexamethylenediamine were,components, well known in the art and can be obtained by polymerization of dicarboxylic acids or suitable derivatives) of the formula I and of the diamine (or suitable derivatives) of the formula II. In many cases, the polyamides suitable for use according to this invention, are commercially available and are manufactured by a number of manufacturers, such as a series of polyamides Amodelmade of AMCO Chemical Company, and a series of polyamides Zytel, manufactured by Du Pont. According to some aspects of the invention can also be used secondary polyamides as part or all of the downloadable mixture.

Other suitable polyamides according to this invention include branched polyamides. These branched polymers can be obtained using mainly difunctional carboxylic acids together with some carboxylic acids having a functionality of more than two, by the polymerization of these acids with polyamines. In addition, the branched polymers can be obtained by using mainly diamines together with certain polyamines containing more than two amine groups, by the polymerization of these polyamines with multifunctional acids. Examples nishikida).

When the monomers of formula I and formula II react with the formation of a repeating structure of formula III, this type of polymerization is known as polycondensation or condensation polymerization. In the book "GLOSSARY OF CHEMICAL TERMS" C. A. Hampel and G. G. Hawley, Von Nostrand, 1976 on page 67 the definition of the term "condensation polymerization". According to this source the condensation polymer is a linear or three-dimensional macromolecule produced by the interaction of two organic molecules usually with the formation of water or alcohol as by-products. The reaction is repeated or is a multistage as education macromolecules. These duplicate stage known as polycondensation. Examples of condensation polymers described polyesters and polyamides. In 1929 Carothers (W. H. Carothers, J. Am. Chem.Soc. 51, 2548 (1929)) proposed to divide the polymers into two broad classes. One class was condensation polymers whose molecular formula structural (duplicate) of the link or links are missing atoms contained in the monomer or monomers from which they are formed or to which they can be decomposed by chemical means. Another class Carothers are addit actorname link monomer, from which the resulting polymer.

The polymers and copolymers having a value according to this invention, Carothers was attributed to condensation polymers by the polymerization conditions and the formula of the repeating units in the polymers in comparison with the monomers to receive them. According to one aspect of the present invention proposed new condensation copolymers containing in the main segments of polyamide and hydrocarbon segments, absorbing oxygen, in an amount to provide the desired ability to absorb oxygen. As will be described in detail below, these hydrocarbon segments of the condensation copolymer are actually segments of the oligomers of the additive type. Of course, applicants need to pay attention to the characteristics and selection of the appropriate hydrocarbon segments that can be entered in copolyamide and to provide the necessary ability to absorb oxygen, without causing a harmful effect on the valuable characteristics and properties of packaging materials and segments obtained on their basis, in the copolymer.

Applicants have found that hydrocarbons such as polyolefins (especially polydiene), provided good absorbing properties, as is confirmed, what segments of polyolefins in copolyamids will give the ability to actively absorb the oxygen polyamides exactly the same as it was observed for spoliation containing blocks of oligomeric polyolefin. Usually the ability to absorb oxygen from polyamides was most when used polyolefin oligomers with low molecular weight, typically in the range of 100-10000. Particularly preferred polyolefin oligomers having a molecular weight in the range of 1000-3000. Preferred oligomeric polyolefins suitable for the introduction of hydrocarbon segments in absorbing oxygen copolyamids are polypropylene, poly(4-methyl)-1-penten and polybutadiene. Although the oligomer of polyoxypropyleneglycol is not a hydrocarbon, it is also potentially useful substance that absorbs oxygen. Of the above polymers are especially preferred is polybutadiene oligomer, as it has a high ability to absorb oxygen and commercially available in the form necessary to obtain copolyamids according to the invention, absorbing oxygen, the preferred method according to the invention.

As mentioned above, the oligomeric segments of the polyolefin must be contained in Topoli is to absorb oxygen. One reason for the introduction of oligomeric segments polyolefin only in such quantity that ensures the achievement of this goal is the desire to preserve the properties of the polyamide, as close as possible to the properties of homopolyamide. In practice, it has been found that the content of oligomeric segments polyolefin is 0.5-12% by weight of copolyamid. Preferably, this content was approximately 2-8% by weight copolyamid. Particularly preferably, the content of oligomeric segments polyolefin equal to 2-6% by weight copolyamid.

The copolyamids according to the invention have the ability to absorb oxygen in glassy solid at ambient temperatures from 0oWith up to 60oC. This interval is below the glass transition temperature (Tgthese compounds. This feature significantly distinguishes them among the known oxygen absorbers, which absorb oxygen at room temperature (or even lower), but still above Tg. It is well known that the gas permeability increases significantly above Tgwhen the material is not rigid and, consequently, the ability to absorb such absorbers disappears. Another big advantage they absorb oxygen in the absence of water or moisture (and also in the presence of moisture or water). This allows the use of absorbing oxygen copolymers according to the invention for the packaging of dry materials, such as electronic industry, dry snacks, medical subjects. This ability to absorb oxygen in a dry environment distinguished by absorbing oxygen copolymers according to the invention from many famous sinks that require the presence of water or at least moisture. Usually getting absorbing oxygen copolyamids described above, includes a step consisting in the introduction of the functional group in at least one or more (preferably more) end center of the absorbing oligomeric polyolefin, which must be entered in the form of segments in the copolyamids.

Added terminal functional group must be able to react polycondensation to form due to condensation polymers, them being introduced. It is obvious that it may be more than two limit for functionalization, when stitching or oligomeric branching polyolefin. In these cases, when you enter two or more functional groups, usually E. what are amino groups, introduced to many end centers of the oligomeric molecules of the polyolefin. Specialists it is obvious that this invention is practicable even when the ends of the oligomeric molecules of the polyolefin are different, but chemically compatible end functional groups. As noted previously, the only requirement is that the limit functional group must be able to react polycondensation. Not an exhaustive list of end functional groups include hydroxyl, carboxyl, anhydrous, alcohol, alkoxy, phenoxy, amine and epoxy groups. Preferred terminal functional groups are hydroxyl, carboxyl and amine groups. Obviously, this stage of the retrieval process can be avoided by using oligomeric polyolefins, which already contain the appropriate functional end groups and commercially available by themselves. In this regard, applicants are particularly preferred are hydroxyl end groups, as oligomeric polyolefins with terminal hydroxyl groups, suitable for introduction in absorbing oxygen copolyamids according to the invention, commercially available and have CE>/P>< / BR>
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In formulas IV, V and VI (RSA) refers to a bivalent fragment oligomeric polyolefin. Although the formulas IV, V and VI reflect bifunctional compounds (RSA) can be associated with only one functional group or functional groups can be more than two, when joining or branching (RSA) lead to more than two centers functionalization. In the formula IV (RSA) contains two carboxyl groups. Formula V represents (NGO) with terminal hydroxyl groups, and the formula VI (NGO) with terminal amino groups. While in formulas IV, V and VI are reflected compounds in the hydrogen form, specialists clear that one to all hydrogen atoms in the compounds of formulas IV, V and VI can be substituted organic radical, such as alkyl, cycloalkyl, phenyl, thus these compounds can still be used to obtain absorbing oxygen copolyamids according to the invention. When using substituted compounds of formulas IV, V and VI in the formation of copolymers will be easy to produce other by-products. As indicated above, this invention can be performed in the presence of only one functional group (NGO) or with more than two functional groups (NGO). Formula IV,the Method of obtaining these compounds with terminal functional groups of no importance for the present invention. Commercially available forms of the compounds of formula V which are particularly preferred include products R20LM and R45HT, which , polybutadiene, the company Elf Atochem.

The similarity of the chemical structure of the compounds described by formulas I and IV, are easily noticeable. As the polycondensation proceeds in the interaction of end groups may be copolycondensation, containing mainly the polyamide segments, and some segments of the oligomeric polyolefin. For a better understanding of their composition may be useful to consider them as the product of substitution desired number of slices of the formula IV in an equivalent amount (in moles) of the fragments of the formula I with the formation of copolycondensation containing polyamide segments and segments oligomeric polyolefin. As previously indicated, the copolymers are present polycondensate characterized by unusual characteristic consists in the fact that some segments are parts of a polymer additive type (in fact, the oligomer). It's just as easy noticeable similarity of the compounds of formula II and formula VI. Copolycondensation can be obtained by substitution of the desired number of slices of the formula VI in mo is ment copolycondensation, for these two types of substitution segments similar to the nature of the reactions of formation of this or unmodified polyamide. It can be expected that similar are also formed by-products. The compounds of formula V containing two terminal hydroxyl groups. Desired number of these compounds may be replaced by an equivalent number of fragments of the formula II with the formation of copolymer a bit of a different type. This method formed copolycondensation polymer, which is near the oligomeric segments of the polyolefin are ester groups of the polyester. As will be shown below, they constitute only a very small percentage, for example, from poliamidnykh relations, and formed copolycondensation containing a number of polyether groups, which are suitable for the purposes of this invention, as copolycondensation according to the invention, containing 100% polyamide groups between segments.

Important is the fact that oligomeric polyolefin with the ability to absorb oxygen is embedded in copolycondensation in the form of segments, thereby providing the resulting product the ability to absorb oxygen while retaining all of the valuable characteristics of the original is REGO polyolefin in polycondensate in small quantities, disclosed by the applicants, provides a very accurate and effective dispersion of fragments, absorbing oxygen, copolycondensation. Achieving uniform dispersion of fragments, absorbing oxygen, copolycondensation while maintaining the properties of the polyamide-predecessor is a key characteristic of this invention that distinguishes copolycondensation, absorbing oxygen, according to the invention from the known. Attempt to get absorbing oxygen materials by obtaining physical mixture defunctionalizing oligomeric polyolefin and polyamide usually results in the emulsion is not suitable for packaging purposes. However, when oligomeric polyolefins with terminal functional groups is mixed or combined with the polyamide at temperatures above 200oWith to melt the polyamide formed copolycondensation according to the invention by at least partial interesterification. Therefore, combinations and mixtures of polyolefin oligomers with terminal functional groups of the polyamide, even if they are so called, may be covered by this invention, as the combination and mixing at temperatures of melting polyamides results in Somaliland is About) with two terminal hydroxyl groups, having a molecular weight in the range of about 100-10000. Particularly preferred source of oligomeric a polyolefin is a polybutadiene (PBD) with two terminal hydroxyl groups with a molecular weight in the range of about 1000-3000. The copolymers obtained with the use of PBD with a preferred value of molecular weight, usually have a single Tg(measured by the method of differential scanning calorimetry) of about 100-130oWith and have the ability to absorb oxygen at temperatures less than Tg. Although the copolymers with a single Tgare preferred, specialists clear that the copolymers with multiple Tgcan also be used, provided that the lowest glass transition temperature higher than the temperature of use packaging. The advantage of having Tgabove the temperature of use packaging is design flexibility of the container associated with its rigidity. It is obvious that the rigidity of the container can be adjusted also by the thickness of the walls, which allows to obtain a flexible film, in these copolymers.

One purpose of this invention is to create a copolyamids, containing mainly the polyamide segments is the temperature of the environment temperature below their glass transition. This means that the copolymers absorb oxygen in the solid state. This characteristic distinguishes the copolymers according to the invention from many well-known oxygen absorbers, which are used as absorbers above the glass transition temperatures, i.e. in the solid state. Experts will become apparent many benefits of sinks that are in the solid state, including the ability to be processed into a film or container that can be made from the copolymer completely and still keep its shape when the ambient temperature. For the purposes of this invention at ambient temperature mean normal storage temperatures in the range of 0oWith up to 30oC. in order to withstand the temperature of hot filling products, temperature range should be equal to from about 0oWith up to 60oC. the Copolymers according to the invention exist in the solid state even in the extended temperature range from approximately 0oWith up to 60oC. the Copolymers according to the invention can be obtained using any method polycondensation, including continuous and/or periodic methods, typically used in the preparation of polyamides. The only disturbances and 50 mol.% compounds of the formula II, introduces fragments of at least one of the compounds of formulas IV, V or VI, and the corresponding molar amount of compounds of formulas I or II is derived from the polymerization process. Otherwise copolycondensation can be obtained from polyamide, which is optionally subjected to polymerization with the oligomeric polyolefin with terminal functional groups by heating the components to obtain the extruder homogeneous melt. Heating in the extruder can be performed under vacuum or without vacuum. Specialists this method is known as reactive extrusion. During such processes the reactive extrusion process begins polycondensation and formed product which is partially or fully copolymer containing segments of the original polyamide and oligomeric segments of the polyolefin, and not a simple melt mixture of individual source components. Reactive extrusion is the preferred method of obtaining copolycondensation according to the invention.

During the processes of direct polycondensation of substitution desired quantity oligomeric polyolefin with terminal functional groups on a roughly equivalent amount of one of the monomers to obtain a non-modified oligomeric polyolefin with terminal functional groups may substitute an equivalent molar amount of one of the monomers to obtain a polyamide. In the case of direct polycondensation number oligomeric polyolefin with terminal functional groups, which absorbs oxygen may vary within wide limits up until the resulting copolymer exhibits desirable properties, such as the ability to absorb oxygen and transparency that is required for the use intended. Usually, when copolycondensation receive prior to introduction into the packaging of the product must be stored in an inert environment. In most cases, the ability of copolycondensation to absorb oxygen occurs immediately after the end of induction period of exposure to oxygen. The ability to absorb oxygen can be significantly reduced if the copolymers to leave in the environment of oxygen (or air) over a long period of time. In addition, prolonged exposure to high temperature in the presence of oxygen can further reduce the ability of the copolymers to absorb oxygen when they are processed into packaging products and there is the possibility of thermal decomposition and destruction. Premature loss of ability to absorb oxygen to the processing of the copolymers in the packaging of the product can be regulated is ensity according to the invention can be obtained by any suitable method, the preferred method of obtaining copolycondensation according to the invention is a reactive extrusion, as described briefly above and in more detail below and in the examples of embodiment of the invention. Participating only in the process of reactive extrusion process or in the process in conjunction with the stage of processing, the original polyamide in the extruder is in an inert atmosphere, preferably under nitrogen atmosphere. Oligomeric polyolefin with terminal functional groups fed into the extruder separately and introduced into the mixing zone in the extruder. The rate of introduction of the polyamide in the extruder is controlled so as to provide sufficient time to melt the polyamide and its reaction with the oligomeric polyolefin with terminal functional groups to obtain a method of transesterification of the copolymer. The preferred residence time is from about 5 minutes at a preferred temperature of about 260-300oC. Oligomeric polyolefin with terminal functional groups introduced through a separate hole in the extruder and the speed of oligomeric polyolefin adjusted so as to provide the number of segments oligomeric polyolefin necessary to achieve W polyolefin is from about 0.5 weight. % to about 12 wt.% the total weight of copolycondensation. In the extruder can also be used catalyst (interesterification/ parametervalue), which contributes to the transformation, for example, the transition metal carboxylate in an amount of about 10-300 ppm based on the mixture in the extruder. The preferred interesterification catalysts are cobalt carboxylates, particularly preferred octoate cobalt, as it promotes rapid reaction and commercially available at a reasonable price and in a concentration that is ready for use. As noted above, the interesterification reaction allowed to proceed in the extruder for about 3-5 minutes at a temperature of about 260-300oC. Under these conditions oligomeric polyolefin with terminal functional groups forms by interesterification copolyamid copolymer. To better understand under transesterification should understand the reaction, in which the oligomeric fragments polyolefin with terminal functional groups are replaced by fragments of monomers forming polyamide, originally contained in the original polyamide. Regardless of the mechanism forms a copolymer with oligomeric fragments polyolefin with one or more kontsa granules, it is desirable to control the amount of moisture absorbed by the copolymer, in order to minimize the need for drying prior to processing to packaging products. Monitoring of moisture absorption is possible to carry out two-stage method. First, the copolymer extrudate can be cooled using the process of hardening in non-aqueous environment before cutting into pellets as described in U.S. patent 5536793. This method allows to obtain granules with low moisture content. Then the granules are packaged in impermeable to moisture containers (e.g., banks) for storage.

Granules can be used from containers directly in the methods of processing from the melt, typically used in the packaging industry, for example, by extrusion, cast film, extrusion of sheets, forming, obtaining coating from the melt. If you want to drying, it is desirable to dry the pellets in a vacuum furnace or a furnace with desiccant in nitrogen atmosphere. In order to minimize the loss of the copolymer's ability to absorb oxygen, it is possible to obtain the copolymer during the stage of packaging products from the melt. This depends on the flexibility of the method of manufacture and is generally preferable for ways Extrusionstechnik oxygen, if they are part of a bottle or film.

Supplements that may also be contained in copolycondensation according to the invention include heat stabilizers, antioxidants, dyes, nucleating crystals, foaming agents (when you need to get the foam), fillers, accelerators, biodegradation, splitters, extenders chain. As is obvious to experts, the introduction of such additives can obtain copolymers covered by this invention. The copolymers according to the invention is also suitable for the manufacture of opaque products, such as trays of hard opaque crystalline copolycondensation that contain small amounts of nucleating crystals, such as polyolefins. In addition, the copolymers according to the invention can be used for the manufacture of porous structures, when the foamed copolymers with obtaining products with lower density, which further reduces the cost of the container. For some purposes it is useful to apply a mixture of copolycondensation according to the invention. Typically, the copolymers according to the invention is mixed with other polycondensate, especially polyamides. However, for some purposes, suitable even incompatible mixture.

Although what about under certain circumstances, the copolymers can be obtained by the method of addition polymerization or a combination of polycondensation method/addition polymerization. Previously it was stated that R1in the formula I and/or R2in the formula II can contain at least one olefinic unsaturation. The availability of centres of olefinic unsaturation in the chain of the polyamide creates the condition under which the oligomeric segments of the polyolefin can be introduced into the polyamide by the method of addition polymerization. The availability of the sites with the olefinic unsaturation in the polyamide chain also creates the condition under which the unsaturated fragments capable to enter into the polycondensation can be introduced into the polymer chain by reaction of accession. Maleic anhydride and acrylic acid are both refinancing and represent examples of such fragments, which can be introduced into the polymer chain in places unsaturation by joining and creating polycondensation at the other end of the molecule. These entered centers polycondensation will then react polycondensation with the compounds described by formulas IV, V and VI, which leads to the introduction of the polyamide segments of the oligomeric polyolefin. Even when1and R2in formulas I and II are both saturated, there is another possible way of introducing the oligomeric segments of the polyolefin. Nasysheniya, for example, in the locations of the centers polycondensation located at the ends of the polyamide macromolecules. Such processing of polymers is well known and often referred to as "madeinitaly". Being introduced in the process of condensation in the polyamide (or along the chain or at the ends of the polyamide molecules), parts of maleic anhydride create reinstatement centers, which impose oligomeric olefins by the reaction of accession. The copolyamids containing oligomeric segments of the polyolefin obtained in one of these mixed methods, are covered by the invention.

The polyamides used in the packaging industry, is well known. They are usually obtained by polycondensation of one or more acidic reactants with one or more diamines in the conditions of the polycondensation in the presence of a suitable catalyst for polycondensation. Such processes polycondensation with obtaining polyamides are well studied, well known in and of themselves do not constitute the subject matter of this invention. Although most of polyamides win in the properties according to this invention, some of the more often used in the packaging industry and are preferred for the purposes of this Sonova acid, phthalic acid, isophthalic acid, terephthalic acid, natalijagolosova acid, substituted derivatives of these acids and mixtures thereof. Diamines components preferred polyamides include polyethylenimine, including hexamethylenediamine were, xylylenediamine, menagerie aromatic diamines, such as benzydamine, polynuclear aromatic diamines, such as naphthaleneamine, substituted derivatives of these diamines, and mixtures thereof.

Experts obviously that can be used by various derivatives of the above-mentioned digisat and diamines, which lead to the formation of the same polyamides in the conditions of the polycondensation. Typically, the segments are polyamides in copolyamids according to the invention will be segments of the polyamides obtained by condensation of the above digisat and diamines.

Upon receipt of copolycondensation according to the invention by a method of transesterification/ parametervalue in the reactive extruder, as described above, copolycondensation first granularit and then processed into packaging products, bottles and films. The preferred structure type wall packaging, bottles or film is a three-layer structure shown in Fi the data of polyamide and can be made from recycled polyamide, as it is not in contact with the cavity packing or Packed material. The inner surface of the bottle or the walls of the package 22, which defines the cavity of the package, is formed over a thin layer 28 of unmodified packaging polyamide. The middle layer 30 is made of copolyamids according to the invention. Although the structure shown in Fig.1, may require a special extrusion equipment, it is preferred for the following reasons: (1) it is a structure with a relatively thick layer of polyamide, which is exposed to oxygen and is a good passive protective layer from atmospheric oxygen, (2) an inner layer in contact with the Packed material is also made from polyamide, which is used for a very long time for packing materials consumed, (3) placement of copolyamids according to the invention between two layers of unmodified polyamide with good passive protective properties allows you to isolate the copolymer, absorbing oxygen, from direct contact with air or oxygen and thereby retain their ability to absorb the oxygen that is consumed only in the case of oxygen, passing through layers of unmodified polyamide, and (4) with whom trozei without the use of a tie coat of adhesive. Preferred layered structure described above, the easiest to get coextruding one layer of a copolymer having two layers of unmodified polyamide. The copolymer chemically similar remotefilename the polyamide that the three layer uniformly connected with each other and form when cooled monolithic structure. You don't need layers of adhesive. However, in the products obtained according to the invention, when the secondary use does not matter, to improve the adhesion, protective properties, reduce costs, you can enter additional layers are not of the polyamides. You can get the preferred three-layer structure of other methods, in addition to extrusion, for example by coating melts or connection of individual words when heated. Any method except coextrusion, can have the following disadvantages: (1) reduction of absorptive capacity in unwanted and/or harmful effects of air or oxygen in the copolymer, absorbing oxygen, and (2) additional stages of processing. For the manufacture of bottles, the combination of three layers using adhesives will prevent recycling, if the adhesive has not been obtained on the basis of polyamide or if it was nesovmestimoe, as in the manufacture of bottles. In fact, in the case of films may be even desirable to use layers of copolymers according to the invention in combination with layers of other materials, for example polyvinyl alcohol or polyolefin. At that time, as coextrude these copolymers is the most preferred method, you can also use other methods. For example, there may be obtained a mixture of these copolymers in the form of a concentrate with other polyamides for the manufacture of films or bottles or it can be used to perform interior surface coating or layer in a multilayer structure, for example, for packaging of electronics parts.

According to one broad aspect of the invention, it provides a laminated material comprising at least one layer of the packaging material and at least one layer of copolyamid according to the invention, which is an active oxygen scavenger, and the specified copolyamide contains mainly the polyamide segments and the segments oligomeric polyolefin in an amount to provide the ability to absorb oxygen. The expression "mainly" used above means that copolyamide contains at least 50 wt.% segment, preferably about 2.0 to 8.0%, and most preferably about 2.0 to 6.0% by weight copolyamid. The layer of the packaging material is usually made from a thermoplastic. However, copolyamids according to the invention can be used as the active oxygen absorbers to absorb oxygen from the free space above the product in the form of an internal coating of cans or glass containers/bottles. In the case of these products the layer of the packaging material can be a metal or glass. The preferred layer of the packaging material is a layer of polyamide, particularly preferred are polyamides on the basis of which the received segments of polyamide copolyamids. Other preferred polymers of which is the layer of the packaging material are polyesters, especially polyesters used for the manufacture of bottles. The use of copolyamids according to the invention in a layered structure containing a layer of a complex of the polyester, is particularly advantageous when it is necessary to passive protective properties against gas, superior properties, for example, PAT. In particular, beer bottles must have the ability not only to protect against the penetration of oxygen and absorb colorsi carbon in beer. The layer of polyamide, absorbing oxygen, provides excellent passive protective properties, allowing to reduce the volatilization of carbon dioxide from the beer through the absorber layer based on the complex polyester.

For some applications there are methods of increasing the ability to absorb oxygen these copolymers. For example, at the stage of receipt of the product to the copolymer can be added to the oxidation catalyst. The catalyst can be entered separately to increase the absorption of oxygen and can be entered in addition to the residual oxidation catalyst, if he left after the stage of obtaining a copolymer. The presence of such a catalyst are added and used in the amount of 10-2000 ppm based on the weight of copolymer, increases the rate of absorption of oxygen, often substantially. The preferred catalysts are polyvalent transition metals, such as iron and manganese. Especially preferred is cobalt.

The copolymers according to the invention can be used in combination with other systems, absorbing oxygen. For example, according to one aspect of the increasing ability to absorb oxygen products manufactured by Italia together with copolymers. Finished products, such as bottles containing photoactive compounds, as well as copolymers, exposed to UV light sufficient to activate the photoactive material to absorb oxygen before use (i.e. filling bottles or transportation of the finished product.

According to still another aspect of the invention additional oxygen scavengers are used in the cavity of the packaging along with the copolymers according to the invention, which constitute the packing material. Typically, these additional oxygen scavengers have the form of a bag (sachet), especially in the case of inedible the oxygen-sensitive materials, such as electronics parts. In the case of edible sensitive to oxygen substances additional materials that absorb oxygen, can take the form of a Mat, similar to that often used by butchers for cutting meat or poultry. Additional oxygen scavenger may also be applied as a layer on the stopper of the bottle. In many cases, according to this invention, the additional oxygen scavenger is a completely different system compared to copolyamids according to the invention.

According to another aspect of the mini-container/jar or separately, or together with known polymers used for coating glass/metal containers. In any case, there are passive and active protective materials, as glass/metal container itself is a passive protective material. In any case, the copolymers according to the invention thus receive the order to include thermosetting resin or mixture of resins that can be applied by sputtering on the inner wall of the container. Capable of spraying the resin can easily be obtained by mixing a small amount of the copolymer according to the invention with a thermosetting resin, typically used for coating on the banks. It may be necessary to obtain a copolymer with a higher content of oligomeric segments of the polyolefin in excess of 12 wt.%, in order to require only a minimum amount of copolymer for blending with resin applied by spray. The advantage of facing the cover glass/metal container containing an active oxygen scavenger, is that it gives the chance to absorb the oxygen in the free space above the product. The application of internal coatings banks to remove oxygen in svobodnogo products which the user needs to separate from the product and remove.

As has been shown in several cases, the recycling of bottles, made with the use of copolymers according to the invention, is an important aspect of the present invention. In addition, the bottle must be able to recycling together with other bottles made from polyamides without special processing, such as separation layers or depolymerization. The nature of the material of the bottle according to the invention, allows to meet the requirements for recycling. In Fig. 1 shows a cross-section of the preferred structure of the wall of the bottle. In Fig.1 layers 26 and 28 preferably made of unmodified polyamide used for packaging. The outer surface 24 is formed with a thicker layer of polyamide (which may already be secondary), and the inner surface 22 (packaging or cavity of the bottle) is formed over a thin layer 28 is typically the primary polyamide. The middle layer 30 is made of copolymers, absorbing oxygen, according to the invention. For a normal bottle with a volume of about 0.5 l of the layer of copolymer of absorbing oxygen is about 5% by weight butilkov oligomeric polyolefin, at around 12%, the polyamide of the layer, contains 88% polyamide segments, and typically the polyamide contains 96% polyamide segments when using the usual amount of oligomeric segments of the polyolefin. This means that the finished bottle consists of at least of 99.4 wt.% polyamide, usually made of 99.3 wt.% polyamide. This high concentration of polyamide in the finished bottle allows it to be recycled.

The main field of application of the copolymers, absorbing oxygen, according to the invention is the manufacture of packaging products mentioned above several times. Basically these products are used for packaging of perishable foods and perishable items. A non-limiting list of perishable products, especially those in need of such packing described in the description, include dairy products such as milk, yogurt, ice cream, cheeses, prepared foods, such as cooked meat and soups, meat products such as sausages, cold cuts, chicken and beef, a La carte foods, such as ready meals and ready-made snacks, ethnic foods, such as pasta and spaghetti sauce, condiments such as barbecue sauce, the e vegetables and cereal dishes for Breakfast, baked goods such as bread, crackers, biscuits, muffins, cakes, snacks such as candy, chips, snacks, cheese, various oils, such as peanut butter, a mixture of peanut butter and jelly, jams and marmalade and spices in a fresh or dried state. In General, the described copolymers and packaging products can be used to improve the protective properties of packaging materials for all products, regardless of whether they are food, drinks, or something else that deteriorates in the presence of oxygen. Packaging articles containing the active copolyamids according to the invention are used to increase shelf life of products sensitive to oxygen. The copolyamids according to the invention is also suitable for use in packaging a variety of non-food items, as they are able to absorb oxygen in the presence or in the absence of water or moisture.

Examples of series 1.

Preparation and properties of polyamides.

The copolymers listed in tables 1 and 2, unless otherwise noted, were obtained in the following way. The synthesis was carried out in a twin-screw extruder of the Werner and Pfleiderer ZSK-30 together with the rotating augers with respect to the length of the auger is e polyamides AMODEL2010 or ZYTEL330 in the form of granules, which were first dried before at 125oWith in the oven with desiccant. AMODEL2010 is polyphthalamide containing about 40 mol.% parts of terephthalic acid and about 60 mol.% parts of isophthalic acid and 100 mol.% links diamine (HMDA). ZYTEL330 represents polyphthalamide containing about 30 mol.% parts of terephthalic acid and about 70 mol.% parts of isophthalic acid and 100 mol.% links HMDA.

Dried pellets of polyamide loaded into the extruder via the feeder in a nitrogen atmosphere. Oligomer polybutadiene (PBD) with terminal hydroxyl groups were kept in the vessel for viscous liquids under pressure of nitrogen, and from there moved using a volumetric pump in the molten polyamide through the hole for injection of the reagents into the extruder. Used oligomer represented PBD-diol with a molecular weight of about 1230 (R20LM manufactured by Elf Atochem). The feed rate of the polyamide was 6.7 kg/h (14,8 f/h), and feed rate PBD was equal to 28 g/hour (0,062 f/h) were copolyamide containing about 96 weight. % polyamide segments and about 4 wt.% the PBD segments. The residence time in the extruder was approximately 3-4 minutes, devasena in the reaction, was removed using a vacuum pump. The polymer extrudate was cooled on a metal tape company Sandvik and stirred. The granules were Packed in foil packs, impervious to moisture and gas. In order for the copolymer did not contain oxygen, the entire extrusion line was maintained in a nitrogen atmosphere, including the preliminary washing of the packages for storage. It should be noted that the copolyamids in these experiments were obtained without catalyst for interesterification. Can be added to the mixture in the extruder interesterification catalyst, which represents a transition metal in an amount of about 50-300 ppm based on the weight of the mixture in the extruder.

The polymers obtained by the process of reactive extrusion, as described above, were subjected to the tests determining the absorption of oxygen, thermal properties, characteristic viscosity, molecular weight distribution, mechanical properties and dynamic mechanical properties. Some of the data obtained are shown in table 1. Some granules were treated with osmium tetroxide, which marks only the oligomeric segments of polyolefin (PO) copolymers. Were also obtained electron micrographs of thin sections of the granules of the product, labeled tetraoxygenated on education copolyamides in the extruder, since (1) is the characteristic viscosity IV extruded polymer is higher than that of the original materials, (2) glass transition temperature (Tg) copolymer fell slightly, and (3) this is evidenced by the size of the diameter of the segment ROO.

Shown in table 1 polymer 117-2B was obtained using a 50-50 weight. % mixture 117-1A and 117-2. Tgwas determined by the method of differential scanning calorimetry. IV was determined by the method ASTM D2857 in a solvent mixture of phenol-TSE at 25oWith and has the dimension DL/g Mnand Mwwere determined by using gel permeation chromatography (ASTM D3593 and ASTM D4001) using columns Shodex A-80MS, hexafloride-propanol buffer, representing triacetate, sodium, as solvent. Impact strength Izod was determined by the method of ASTM D256 and has the dimension of kg-m/cm (ft-lb/inch) incision.

The absorption of oxygen by copolyamids - series 1.

Oxygen uptake by the polymers of series 1 was determined by placing 25 g of granules in the vessels of the ball with a volume of 500 ml, equipped with a septum for sampling. Samples kept at 60oWith furnace and monitored oxygen content in the vessels using the analyzer Mocon HS750, peri who can be found in table 2 and shown graphically in Fig.2. The number of samples in Fig.2 and table 3 are preceded by the digit "19440", which means the internal control number and have no meaning when the interpretation of the results. The data obtained show clearly that the copolyamids according to the invention have the ability to absorb oxygen. The main purpose of this invention to provide polyamide, already possessing excellent passive protective properties against oxygen compared with polyesters, ability to actively absorb oxygen reached.

Numeric values in rows 2-7 and columns 2-6 in table 2 indicate the amount of oxygen in the percent remaining in the samples of air contained in the vessels of the ball with a volume of 500 ml with samples of the polymer weight of 25 g of Polymer ID#120-1 - polymer, absorbing oxygen, as described in the application U.S. 08/717370, it is included in table 2 together with a control sample of unmodified AMODELand ZYTELfor comparison purposes. It should be emphasized that the experiments whose results are shown in table 2, carried out in the absence of cobalt or other transition metal (metals) as promoter/catalyst reaction with oxygen, and oxygen uptake copolymer.

In practice apoliprotein metal. The transition metal is usually introduced into the copolymer during the manufacture of packaging products. The preferred catalyst is cobalt, particularly preferred carboxylate of cobalt and preferably octoate cobalt.

Examples of series 2.

Preparation and properties of polyamides.

A second series of experiments obtain copolymers was performed using as a polyamide and, therefore, the source of polyamide segments copolyamide MXD-6. MXD-6 is a poly(m-xylylenediamine) and described in the application above. The process of obtaining in this series 2 was carried out, as in the case of series 1, in the extruder, but instead AMODELand ZYTELused MXD-6. The copolymer MXD-6 in the experiments of series 2 was extrudible through the slotted cylinder 15.2 cm, produced Extrusion Dies, Inc. (ID), and has filed for two cooling device, and then allocated in the form of a film winding device with a constant tension. The finished film was placed in foil packs, the resealable sealing. The packages were purged with nitrogen and closed. The feed rate of the polymer, the speed of the augers, the temperature in the extruder, the magnitude of the vacuum and the residence time was adjusted so that mobilisation series 1 and series 2. Film of the unmodified MXD-6 indicated by the index ID#157-1, and the copolymer MXD-6 with 4 wt.% PBD indicated by the index ID# 158-1. In table 3 all pressure values in columns 10-13 characterize gauge pressure.

The absorption of oxygen by copolyamids - series 2.

The polymers obtained in the experiments of series 2, was evaluated on the absorption of oxygen by placing the film samples weighing 10 g (instead of 25 g of the granules in series 1) in vessels of the ball with a volume of 500 ml, equipped with a septum for sampling. Samples kept at 60oWith furnace and monitored oxygen content in the vessels using the analyzer Mocon HS750, selecting periodically aliquot portion of gas volume of 2 cm3. The obtained data are presented graphically in Fig.2 together with the data of the experiments of series 1. In Fig.2 shows that 10 g copolyamid in the form of a film is almost as effective as 25 g copolyamid in the form of granules in the case of oxygen. There are several factors that complicate direct comparison. Samples of the films provide greater availability of oxygen absorber in comparison with samples of the granules. In addition, the polyamides have the best passive protective properties than polyesters, therefore, the oxygen is more difficult to achieve fragments, absorbing the olo 10-2000 ppm (calculated on the weight of the copolymer) of catalyst transition metal. The transition metal is usually introduced into the copolymer in the manufacturing process of the packaging of the product. As indicated above, the preferred catalyst is cobalt, particularly preferred cobalt as cobalt carboxylate and particularly preferred octoate cobalt.

As you can see from the examples, the copolyamids according to the invention have a significant capacity to actively absorb oxygen, which enhances their already excellent passive protective properties against oxygen compared with the complex polyester. Copolymers mainly used in the form of a layer in a multilayer package, especially when there is an additional passive protective layer that protects the copolymers according to the invention, actively absorbing oxygen from the oxygen (from the air), and when the adjacent layer is chemically similar to copolyamids. But experts it is obvious that the possible applications of the copolymers, which are included in the scope of this invention.

1. A laminate that protects from oxygen containing layer of the packaging material and the layer of copolyamid actively absorbing oxygen containing mainly polyamide segments and the segments oligomannosides state below its glass transition temperature and is capable of absorbing oxygen in the solid state at temperatures in the range of 0 - 60oC.

2. Layered material under item 1, characterized in that the packaging material is a thermoplastic polymer.

3. Layered material under item 1, characterized in that the packaging material is a complex polyester.

4. Layered material under item 1, characterized in that the packaging material is a polyamide.

5. Layered material under item 4, characterized in that the polyamide segments in copolyamide obtained from the polyamide used as a packaging material.

6. Layered material under item 1, characterized in that the content of oligomeric segments polyolefin is 0.5 - 12% by weight of the copolymer.

7. Layered material under item 1, characterized in that the oligomeric polyolefin selected from the group consisting of polypropylene, poly(4-methyl)-1-pentene, polybutadiene and mixtures thereof.

8. Layered material under item 1, characterized in that the molecular weight of the oligomeric polyolefin equal 1000-3000.

9. Packaging the product, the wall of which contains layered material under item 1, located inside the wall.

10. The way to protect the product from oxygen, consisting in their packaging in a packaging article, the wall is in store oxygen, including copolyamide, containing mainly the polyamide segments and the segments oligomeric polyolefin in an amount to provide the ability to absorb oxygen, and a catalyst comprising a transition metal in an amount of 10-2000 hours/million based on the weight of copolyamid and copolyamide able to absorb the oxygen in the solid state at ambient temperature.

12. Material, absorbing oxygen under item 11, wherein the transition metal is cobalt.

13. Material, absorbing oxygen under item 12, wherein the source of cobalt is octoate cobalt.

14. Material, absorbing oxygen on p. 11, characterized in that it further includes a photoactive substance, which, after sufficient activation by irradiation accelerates the absorption of oxygen by copolyamids.

 

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