RU2370365C2 - Sectioned polymer tablets - Google Patents

Abstract

FIELD: pharmacology.

SUBSTANCE: polymer tablet includes oxygen-sensitive component, oxygen-indifferent component and reaction promoter. Oxygen-sensitive component is placed in first sectioned area, oxygen-indifferent component is placed in second sectioned area. Oxygen-sensitive component becomes oxygen-active in the presence of promoter. Promoter is represented by any substance initiating or accelerating reaction of oxygen-sensitive component with oxygen, and oxygen-indifferent component contacting promoter causes oxygen consumption increase not more than by 10% compared to oxygen consumption without promoter. Promoter amount in direct contact with oxygen-sensitive component is insufficient to initiate of catalyse reaction with oxygen significantly. Also invention claims other versions of polymer tablet and method of thermal tablet processing.

EFFECT: possible thermal processing of components in multicomponent tablets and/or storage in open air or in the presence of oxygen without significant quality deterioration.

178 cl, 4 dwg

Description

This patent application claims the priority of provisional patent application US registration number 60/572225 of May 18, 2004; US Provisional Application, Registration Number 60/605658 of August 30, 2004; US Provisional Application, Registration Number 60/613097 of September 25, 2004; provisional application for a US patent, registration number 60/646329 of January 24, 2005, and provisional application for a US patent, registration number 60/677829 of May 5, 2005. The ideas of these provisional patent applications are hereby incorporated by reference.

FIELD OF THE INVENTION

The invention relates to polymer tablets that contain at least two sectioned zones.

State of the art

Many industrial products consist of several components in order to practically improve their properties. Multicomponent articles made of thermoplastic and thermoset materials are usually produced using an extruder that mixes the final melt, which uniformly combines various components to produce an article such as sheet, film, fiber, container, or an injection molded part, often called a workpiece. The product, in particular the workpiece, is often further processed to obtain another product such as a bottle, pallet, can or bag.

As packaging requirements become more complex, many components are required to improve the functional properties of the packaging. One of the most important properties is impermeability to steam or special compounds such as oxygen. Oxygen-proof materials are expensive, and therefore it is advisable to minimize their cost in the final packaging.

Reduced oxygen transmission rates can be achieved using passive or active barrier methods. Passive barrier methods reduce the transmission rate of steam or liquid into the package. In contrast, in active barrier methods, material (s) are included in the walls of the package that react with the vapor or liquid in question and thus prevent them from passing through the tank wall.

Modern packages include a material with the properties of a passive barrier in a separate layer in the tank wall. This is accomplished using one extruder to melt the main component and shape the product, while the second extruder melts the barrier material and introduces the barrier material into a separate layer of the product forming the tank wall. US 4,501,781, for example, describes improving passive impermeability by introducing a polyamide layer and a polyester layer to form a multilayer reservoir. US 4,501,781 also teaches that polyamide can be homogeneously mixed with polyester in the wall of the tank, as opposed to placing the polyamide in a separate layer.

As discussed in US Pat. No. 5,340,884, the polyamide can be mixed with the polyester in the later stages of the production of the polyester. For example, the polyamide can be mixed with the molten polyester as it is withdrawn from the polycondensation reactor to form a homogeneous mixture in one tablet. As noted in US Pat. No. 5,340,884, mixing with the molten polyester when it is removed from the polycondensation reactor is undesirable if the polyester / polyamide mixture undergoes further heat treatment such as solid phase polymerization, since an undesirable color and / or turbidity. Therefore, the purpose of this invention is to enable crystallization and / or polymerization in the solid phase of a tablet containing a polyester and polyamide, without adversely affecting the properties of any of the materials.

The active barrier method, as described in US Pat. No. 5,021,515, involves reacting the component with oxygen in the wall of the tank. This reaction has become known as oxygen uptake. US patents 5021515, 5049624 and 5639815 describe packaging materials and methods using polymer compositions capable of absorbing oxygen; such compositions contain an oxidizable organic polymer component, preferably polyamide (more preferably m-xylylene adipamide, commonly referred to as MXD6) and a metal oxidation promoter (such as a cobalt compound).

US Pat. No. 5,529,833 describes a composition comprising an ethylene unsaturated hydrocarbon as an oxygen scavenger, catalyzed by a promoter such as a transition metal catalyst with chloride, acetate, stearate, palmitate, 2-ethylhexanoate, neodecanoate or naphthenate counterion. Preferred metal salts are selected from cobalt (II) 2-ethylhexanoate and cobalt (II) neodecanoate.

US patents 6406766, 6558762, 6346308, 6365247 and 6083585 report the functionalization of an oxidizable component such as a polybutadiene oligomer and its introduction by reaction into the main chain of such a base polymer as polyethylene terephthalate (PET). Such a composition can be introduced into the wall of the tank as a separate layer of the wall of the tank or make up the entire wall.

Another active barrier method is elemental or reduced metal scavengers. These metals, usually in the presence of a promoter such as sodium chloride, do not react with oxygen until they are exposed to moisture, which triggers the reaction. The advantage of a metal absorber is that a tablet containing a metal-based absorber will not react with oxygen until it is placed in contact with moisture, a component external to the tablet. Using an agent external to the composition of the tablet to initiate the reaction makes it a system that starts from the outside. This contrasts sharply with previously considered organic systems that are active when the ingredients are combined to make a reservoir or tablet. It should be noted that there are several oxygen-active compounds that have both internal oxygen chemical activity and promotable and / or triggered activity.

In the traditional method of manufacturing multicomponent objects with a passive barrier material, the individual components are introduced into the throat of a single extruder to mix the final melt to obtain a uniform mixture. Often the components are incompatible, which means that they form at least two phases and form dispersions of minor components in the main component. In the case where the components are soluble and therefore compatible with each other, minor components are absorbed by the main component with the formation of one phase. Sometimes the components interact or react with each other, as, for example, in the case of thermosetting products.

US Pat. No. 5,627,218 describes interactive / interreactive reactions as reactions in which, after melt mixing, interactions between the contained materials begin. In addition, interactive / interreactive reactions are characterized by US Pat. properties and takes place to a large extent after the material is given the final shape. Curing after molding can be carried out slowly, or at any time you can act and curing in an oven. "

The traditional method of feeding components into the throat at the final stage of melt extrusion is very expensive. Each component must be fed with precision to each extruder. This creates many conveying and feeding systems for each extruder. Therefore, it is desirable to provide a single feed stream to the extruder, wherein a single feed stream contains properly measured amounts of different components in each tablet.

One solution to the dosage problem is pre-mixing the components in a larger, more economical extruder and feeding the pre-mixed material to a large number of final melt-mixing extruders in which the product is manufactured. Although pre-mixing gives some money savings, it adds additional processing steps.

In another method, the minor components of the product are pre-mixed and concentrated in the masterbatch or concentrate of the loaded tablets, and the minor components of the product are at much higher levels than in the finished product. Indeed, the minor component of the finished product may actually be present in the masterbatch at a level higher than the main component in the finished product. The concentrate is then physically mixed with tablets consisting essentially of the main component. Physical mixing is carried out in such proportions as to create the desired ratio of components in the finished product. Then the physical mixture can be added to the final extruder to mix the melt as a single charge. Alternatively, the concentrate and the main component can be added to the final extruder to mix the melt in two batches. This reduces the number of feed streams and the dosage error when the amount of minor component (s) in the final product is very small.

However, the masterbatch approach suffers from the fact that there is more than one feed to the final extruder for melt mixing. Also, premixing fails when the tablet obtained with premixing requires additional processing to the final stage of mixing the melt. Often in a subsequent processing such as thermal exposure, compounds are formed and released from one component that degrade the properties of the other component. These compounds can be classified as heat treatment by-products.

A heat treatment by-product is a compound contained in a component and released during heat treatment, obtained during heat treatment, or both. The isolation of a heat treatment by-product means that the compound (by-product) is released or carried away from the component during the heat treatment.

Standing out from the first component, the by-product contacts and reacts with the second component or by-product of the second component, creating a negative effect such as an undesirable color change, smell or gas. By-products of heat treatment are not limited to reaction products, they can be unreacted monomers, low molecular weight oligomers, decomposing stabilizers, catalysts or other additives released during heat treatment.

Representatives of such systems are polyester-polyamide blends. Both polyesters and polyamides are extremely hygroscopic. The moisture present in the liquid phase hydrolyzes the polymer chain, reduces the molecular weight and decreases the strength of the polymer. Therefore, both of them must be dried before the final mixing in the melt immediately before molding the product. When stored under such standard conditions as those normally encountered in a warehouse (e.g. relative humidity 50%,> 25 ° C, air), polyester and polyamide can absorb moisture to levels that far exceed the limits allowed by trade (> 1000 ppm). Industrial practice is to dry the compound to a moisture content of less than 50 ppm. After preliminary compounding, the polyester-polyamide tablets crystallize and then transfer to the final extruder for melt mixing. The polyester-polyamide tablets must be dried immediately before being added to the extruder for melt mixing. In this drying operation, at least 50% of the moisture contained in the compound prior to the thermal drying step is usually removed.

Drying the polyester in the presence of polyamide creates a highly colored material. Discoloration of the final product occurs both when the tablets with a homogeneously mixed polyester and polyamide are dried and then extruded into the final product, and when individual polyester tablets are dried in the presence of polyamide tablets and then extruded into the final product.

Drying in a nitrogen atmosphere does not mitigate this problem, since by-products formed from the components during nitrogen drying are the same by-products that are formed by drying with hot air. It is believed that polyester forms by-products such as acetaldehyde during heat treatment, which is removed during the drying process. Brandi and Schraldi (Polymer Preprints 2004 45 (1), 992) indicate that the yellow color introduced by drying is created by the reaction of acetaldehyde formed by the reaction of the polyester with the amino end groups of the polyamide.

The color change of the polyester-polyamide system is enhanced in industrial applications, where the dryer contains a regeneration layer that removes water from the air and returns anhydrous air containing acetaldehyde and other materials. Although moisture from the recirculated air has been removed, acetaldehyde and other materials remain and return with anhydrous air, further complicating the problem. The use of the masterbatch does not affect or hardly affects the problem. It is believed that finely dispersed particles of polyamide have a large surface area for interaction with by-products formed during the drying process. It is also unclear whether the color is the result of more than one such reaction as a reaction with acetaldehyde, followed by a reaction with oxygen.

Solid phase polymerization effectively increases the molecular weight (measured by intrinsic viscosity) of both polyesters and polyamides. In the process of solid phase polymerization, temperatures are lower on the tablets than the temperature at which the tablets become liquid. This temperature effect occurs in the presence of a driving force such as an inert gas or vacuum. The by-products of the polymerization reaction are removed from the tablet, thereby shifting the equilibrium towards increasing the molecular weight of the polymer. Since both polyester and polyamide are pelletized during production, US Pat. No. 5,340,884 advocates combining them at the point where one or the other tablet is cut in its initial manufacture. The combination of polyester and polyamide, where one or the other is cut into tablets, eliminates the subsequent stage of extrusion and cutting. However, combining the polyester and polyamide in the first cutting step requires that the resulting multicomponent polyester-polyamide tablet undergo and undergo heat treatment steps known as crystallization, solid state polymerization and drying steps. These heat treatment stages can proceed at three temperatures from 40 ° C to a temperature slightly lower than the temperature at which the tablet becomes liquid, for example, 1 ° C or, more typically from commercial considerations, 5 ° C lower than the temperature at which the tablet becomes liquid.

Although US Pat. No. 5,340,884 promotes the combination of polyester and polyamide in the first cutting step, it is noted and the examples below demonstrate that homogeneously dispersed combinations of polyamide and polyester in masterbatches, concentrates and premixes cannot be subjected to solid phase polymerization without spoiling the molecular weight of the polyamide and without making a strong color change. US Pat. No. 5,340,884 minimizes this by using a pre-compounded polyamide concentrate for blending with polyester. Although pre-compounding the concentrate may reduce some of the effects of subsequent heat treatment, it is not very effective. The polyamide-polyester concentrate suffers from the same problems as the co-drying of separate tablets of polyester and polyamide.

During crystallization, the material in the tablets is transformed from essentially amorphous to crystalline. Polymer tablets are usually amorphous, but will crystallize when exposed to heat and time. Crystallinity is often expressed as a percentage of crystallinity, it is often interpolated, dividing the difference between the density of the material and the density of the amorphous material by the difference between 100% crystalline density and amorphous density (0% crystallinity). For polyethylene terephthalate, or a copolymer of polyethylene terephthalate, the amorphous density is 1.355 g / cm ³ , the crystalline density is 1.455 g / cm ³ , and therefore, the expression for a given sample has the form:

(Ds - 1,335) / (1,455 - 1,355),

where Ds is the density of the sample in g / cm ³ .

The degree of crystallinity can also be determined using differential scanning calorimetry (DSC), which relates the amount of heat required to melt the material with the amount of heat required to melt the sample with 100% crystallinity.

Pre-mixing the oxygen-active components in the tablet suffers from the same limitations as the polyester-polyamide mixture. Pre-mixing of oxygen-active tablets is particularly expensive since pre-mixed tablets are oxygen-active and must be stored and transported in the absence of oxygen. Therefore, oxygen-active tablets are packaged in the absence of oxygen in a nitrogen atmosphere in sealed film bags.

In addition, pre-mixed oxygen-active tablets are not suitable for such subsequent heat treatment as drying. The pre-combined polyester and oxygen-active material must be dried before final melt mixing. Thus, the tablets must be able to withstand the drying process. Drying with hot air significantly reduces the ability of the oxygen-active material to absorb oxygen.

US 6406766 teaches that post-polymerization processes, such as drying, removal of volatile components, crystallization, and solid state polymerization, reduce the ability to absorb oxygen, and states that the loss of oxygen absorption activity can be minimized by such operations in the absence of oxygen and limiting exposure to the copolymer of oxygen after such operations.

Despite its limitations, in a modern industrial approach, the oxygen-sensitive material is pre-mixed with the promoter / catalyst in the masterbatch containing the main component of the finished product to form the oxygen-active material, the oxygen-active material is transported in film bags, and then the masterbatch is dried in the presence of nitrogen or in vacuum immediately before adding to the final extrusion process for melt mixing.

In one alternative, separate tablets are used: one tablet containing an oxygen-sensitive component, and another tablet containing a main component and a promoter. There are several problems with this alternative. Firstly, the exact dosage of the components is difficult due to the delamination caused by the different specific gravity and electrostatic properties of the tablets. Secondly, pre-compounding the oxygen-sensitive component with other components and adding a promoter / catalyst at the final stage of melt mixing can eliminate storage costs, but again introduces the complexity of the dosage and separate supply systems.

US Pat. No. 5,627,218 and its supplement, US Pat. No. 5,747,548, describe sectionalized (divided into zones) tablets in which the interactive or interreactive components are contained in different sections or zones of the tablet until the final melt mixing step. Interactive / interreactive components are chemicals that are thermally activated to take part in a chemical reaction after using tablets in a molding operation. An type of reaction is considered interactive or interreactive if its components have reactions that must be carried out before completion so that the products can be brought into conformity with the standard and the growth of macromolecules during molding is limited to prevent the product from becoming too rigid for molding . In contrast, the sectionalized tablet composition of US Pat. Interactive / interreactive compound reaction rates are almost always low. After mixing in the melt, interactions between the contained materials begin. The reaction times of the reagents contained in the tablet are usually large compared with the time required for the molding or extrusion process. The resulting increase in molecular size and complication of bonds improve physical properties and occur almost always after the material is given the final shape. Curing after molding should be slow or it should be possible at any time to affect curing in the oven.

Reactive extrusion processing is typical for thermosets. Although theoretically some polyester-polyamide mixtures may react slightly, which is known as transamination, this reaction will be too fast and definitely will not form a molecular weight or increase viscosity, nor will it continue after the melt extrusion step. Polyethylene terephthalate is not known to react with poly-m-xylylene adipamide (MXD6).

In patents US 5627218 and US 5747548 reported that sectioned tablets contain one or more chemicals that are thermally activated to participate in a chemical reaction after using tablets in molding operations. Catalysts that enhance the reaction may also be included. In addition to at least two chemicals, these patents also discuss chemically inactive additives such as reinforcing fibers, paints, lubricants and the like.

By keeping the interactive / interreactive components separate prior to melt mixing, one tablet is used, and complex feeding systems associated with the final stage of melt mixing can be avoided. Neither US Patent 5,627,218 nor US Pat.

US 6669986 describes the use of a sectioned tablet to facilitate drying of non-crystallizable polyesters, surrounding them with crystallizable polyesters to avoid clogging or clogging. To accomplish this, US 6669986 teaches that the components must be similar in chemical nature and discusses the problem of how to protect the physical form of non-crystallizable polyester from sticking together. US 6669986 does not disclose or discuss the use of a sectioned tablet to protect products from a chemical reaction, in particular a reaction with heat treatment by-products or a reaction with an external compound such as atmospheric oxygen.

US 6669986 also describes the protection of tablet ingredients from water when water triggers a metal-based oxygen scavenger reaction. As previously discussed, this is protection against the trigger mechanism, and protection against interaction with the compound or when the promoter is inside the tablet is not described. However, US 6669986 does not disclose the protection of components from reaction with oxygen or by-products of other components.

Patents US 5747548 and US 6669986, both describe how to make such divided into sections or zones of the tablet. Examples of formulations not contemplated in the prior art are tablet formulations where at least one component reacts with by-products of another component, where such by-products are products of further processing such as heat treatment, or when at least one of the components reacts with environmental compounds such as oxygen in the air.

SUMMARY OF THE INVENTION

The present invention relates to a method and necessary conditions for the simultaneous heat treatment of at least two compounds, when one of the compounds reacts with a by-product of heat treatment or a compound in the environment. The method includes creating tablets with different regions, the components being located in these regions so as to control the destruction of the compounds in the tablet at subsequent processing steps, including when storing the tablets in an oxygen-containing medium such as air. In particular, the structure of the tablet allows heat treatment of materials and minimizes or prevents chemical reactions with by-products formed during heat treatment, minimizes or prevents the reaction of components in the tablet with environmental compounds such as oxygen in the air, and controls the increase in molecular weight of one from compounds relative to another.

More specifically, the present invention discloses a polymer tablet comprising an oxygen-sensitive component, an oxygen-inert component and a reaction promoter, the oxygen-sensitive component being in the first sectioned zone and the oxygen-inactive component in the second sectioned zone.

The invention further relates to a polymer tablet containing an oxygen active component and an oxygen inert component, the oxygen active component being in the first sectioned zone and the oxygen inert component in the second sectioning zone.

The invention further relates to a polymer tablet containing a first component and a second component, wherein the first component during heat treatment releases a by-product that is active to the second component and / or by-product released by the second component, the first component being in the first sectioned zone, and the second component is in the second partitioned zone.

The invention further relates to a polymer tablet, which consists of a first sectioned zone and a second sectioned zone, wherein the first sectioned zone consists of a thermoplastic polyester and the second sectioned zone consists of polyamide, wherein the first sectioned zone is at least 0, 1 percent of the total volume of the polymer tablet, and the second sectioned area is at least 0.1 percent of the total volume of the polymer tablet.

The invention further relates to a polymer tablet containing a first component and a second component, the first component being selected from the group consisting of an oxygen-sensitive compound, an oxygen-active compound, an oxygen inert compound, a reaction promoter, a heat-treating compound a by-product that is active to the second component and / or a by-product secreted by the second component, and the second component is different from the first component and selected from the group consisting of an oxygen-reactive compound, an oxygen-active compound, an oxygen-inert compound, a reaction promoter, a compound that, when heat treated, releases a by-product that is active to the first component and / or a by-product released by the first component, the first component being in the first sectioned area , and the second component is in the second partitioned zone.

The invention further relates to a method for heat treating a polymer tablet containing a first component and a second component, the first component being selected from the group consisting of an oxygen sensitive compound, an oxygen active compound, an oxygen inert compound, a reaction promoter, a compound, emitting during heat treatment a by-product that is active to the second component and / or by-product emitted by the second component, and the second component is different from the first component and select wounds from the group consisting of an oxygen-sensitive compound, an oxygen-active compound, an oxygen inert compound, a reaction promoter, a compound that, by heat treatment, releases a by-product that is active to the first component and / or by-product secreted by the first component, and wherein the first component is in the first sectioned area, and the second component is in the second sectioned area, including heating the polymer tablet to a temperature lying in the range from 40 ° C to pace a temperature that is at least 1 ° C lower than the temperature at which the tablet becomes liquid.

Brief Description of the Drawings

1 shows a polymer tablet with two sections or zones in a core-shell configuration.

Figure 2 shows a polymer tablet with two sections or zones in a core-shell configuration, where the core is encapsulated, surrounded or enclosed in an outer shell layer.

Figure 3 shows a polymer tablet with three sections or zones in a multilayer configuration or sandwich configuration.

Figure 4 shows a polymer tablet of three partitioned zones configured in two concentric layers surrounding the core.

DETAILED DESCRIPTION OF THE INVENTION

One advantage of the invention relates to heat treatment of a composition, in which at least one compound during heat treatment creates and releases by-product (s) that affects the properties of the final composition. By placing the components in different sections, interaction with the byproducts formed is minimized.

In addition, an advantage of the present invention is that it allows oxygen-active systems to be subjected to subsequent heat treatment operations such as drying, removal of volatile components, crystallization, solid phase polymerization, and storage of oxygen such as air.

Drying, crystallization, and solid state polymerization are thermal processes that benefit from this invention. The heat treatment provided for in this invention is carried out below a temperature at which the contents of the tablet become sufficiently liquid to cause mixing of the zones.

Heating the tablet until all the thermoplastic components in the tablet become liquid is known as extrusion processing. Although extrusion processing refers to heat treatment, it does not belong to the type of heat treatment carried out in accordance with the present invention, and therefore is excluded. Therefore, the expression “rapid heating of a tablet, so that a sufficient amount of the contents of the tablet becomes substantially liquid, so that the zones are mixed,” as used herein, is not the heat treatment provided for the invention.

A particular embodiment of the invention is an inner compartment surrounded by an outer compartment. It should be understood that in such an embodiment, the effect of temperature can melt or liquidize the material in the encapsulated core without melting the shell surrounding the core. This tablet with a liquefied internal compartment and a hard shell is not considered a liquid tablet.

Thus, the problems of the reaction of the by-product associated with heat treatment, as defined in this application, and the reaction with oxygen during storage can be significantly reduced, if not eliminated, by appropriately placing the components in zones or sections of a tablet with a partitioned or zone structure. In one embodiment, a sectioned tablet minimizes exposure to various components of heat treatment by-products. In another embodiment, the oxygen sensitive components remain inactive to external materials such as oxygen until the melt is finally mixed. In a third embodiment, the oxygen inert component surrounds the oxygen active component and prevents oxygen from accessing the oxygen active component.

In a fourth embodiment, the by-product of the sensitive component is surrounded by a compound that is chemically similar to the material forming the by-product, but the surrounding material does not form by-products. Then this tablet is placed together with tablets from the material giving the by-product, and processed thermally. A modification of the fourth embodiment is when a chemically similar material is placed between the material active on the by-product and the material forming the by-product.

The fifth embodiment is an additional sectioned tablet with a high concentration of one component surrounded by a protective layer of another component. For example, a tablet with a 95% polyamide central zone surrounded by a 5% polyester shell zone may be used. This tablet can be subjected to all the thermal processes of the polyester tablets, or it can be added to the dryer feeding the extruder.

In a sixth embodiment, at least one acetaldehyde scavenger is placed in a tablet, kept substantially separate from the formed acetaldehyde, and removed by heat treatment. After heat treatment, the absorber is distributed in the polymer during the final extrusion with melt mixing and absorbs the residual acetaldehyde remaining after solid phase polymerization and acetaldehyde formed in the melt extrusion stage. A homogenously distributed tablet may require more reagent or catalyst. This is due to the fact that the content of acetaldehyde in the polyester immediately after the polymerization stage in the melt is very high.

Patents US 5258233, 5340884 and 5650469, the ideas of which are incorporated herein by reference, report the use of polyamide to interact with and absorb acetaldehyde from a polyester polymer. Thus, it will be apparent to one skilled in the art that although polyester and polyamide are used in the detailed description of the invention, the polyamide can be substituted with any compound that reacts with or catalyzes the reaction of acetaldehyde. For example, US Pat. No. 6,272,212, whose ideas are incorporated herein by reference, discloses the use of organic scavengers containing heteroatoms that react with acetaldehyde to form 5- or 6-membered rings not bridged, with anthranylamide being the preferred scavenger. US 6,569,479 teaches the use of catalysts to initiate the reaction of acetaldehyde with oxygen. Other examples of compounds used to reduce acetaldehyde are active oxidation catalysts that catalyze the reaction of acetaldehyde with oxygen, and hydride transfer catalysts that catalyze the hydride transfer reaction between acetaldehyde and an organic donor molecule such as 1,8-diaminonaphthalene, 3, 4-diaminobenzoic acid, anthranilamide, biuret, malonamide, allantoin, salicylamide, salicylanilide, o-phenylenediamine, 3,4-diaminobenzoic acid, 1,8-diaminonaphthalene, o-mercaptobenzamide, N-ac ethyl glycinamide, malonamide, 3-mercapto-1,2-propanediol, 4-amino-3-hydroxybenzoic acid, 4,5-dihydroxy-disodium salt of 2,7-naphthalenedisulfonic acid, biuret, 2,3-diaminopyridine, 1,2- diaminoanthraquinone, dianilinoethane, allantoin, 2-aminobenzenesulfonamide and 2-amino-2-methyl-1,3-propanediol, or an active oxidation catalyst selected from the group consisting of cobalt salt, manganese salt and a compound containing an amine, phosphine or alcohol complex with a metal of variable valency. The hydride transfer catalyst may be selected from the group consisting of aqueous zirconium oxide, aqueous niobium oxide and aqueous tantalum oxide.

It should be especially noted that this effect is applicable to compounds that react with acetaldehyde, and to compounds that catalyze a decrease in the level of acetaldehyde. Thus, the expression “acetaldehyde scavenger” refers to a compound that directly reacts with acetaldehyde or a compound that catalyzes the reaction of acetaldehyde with another compound. Some of these compounds are described in patent application US 2005/0014929 entitled "Method for Reducing the Aldehyde Content of Polyesters", the teachings of which are incorporated herein by reference. One of these compounds is zirconium oxide. Examples of commercially available acetaldehyde scavengers are anthanilic amide (Colormatrix Corporation, Cleveland, Ohio, USA) and bis (2,4-dicumylphenyl) pentaerythritol diphosphite (Clariant Corporation, Cesa-nox NTA0050113).

In a seventh embodiment, the material active on the by-product is surrounded by material that does not form a by-product. Such a structure may be a polyamide surrounded by polyneopentyl terephthalate. This tablet will be mixed with polyethylene terephthalate tablets and then the mixture will be thermally processed at the same time. Alternatively, a structure having 3 partitioned zones comprising a core 41, which consists of polyamide, may be used, the core being surrounded by an intermediate layer 42, which consists of polyopentyl terephthalate, which in turn is surrounded by an outer layer 43, consisting of polyethylene terephthalate.

The following demonstrates how a tablet with a partitioned structure solves the problems of simultaneous heat treatment of two or more components when at least one component reacts with a by-product of the other component. Heat treatment consists in exposing the tablets to temperatures above 70 ° C, with or without air or an inert gas, for example, in vacuum, but at a temperature lower than that at which the tablet melts. It should be noted that this temperature may be greater than the melting point of one of the polymers when this polymer is surrounded by a shell of a polymer with a higher melting point. Examples of such heat treatment are drying, crystallization, removal of volatile components and solid phase polymerization, also known as solid state polymerization, as described below.

Patents US 5627218 and 5747548, the ideas of which are introduced here by reference, report on many methods of obtaining sectioned tablets. In one embodiment, the tablet has at least two zones, or regions, preferably a core and a shell. Unless otherwise indicated, the preferred structure of the tablet is a core-shell with hermetically sealed edges, as reported in patent US 6669986, the ideas of which are introduced here by reference.

The core-shell structure is prepared using two extruders. If a third material in a different zone is desired, an additional extruder is required. The first extruder supplies liquid raw materials forming a core material that is linearly extruded in the center of the strand. At the same time, the shell material is extruded in a second extruder into a shell layer that concentrically covers the core. US 6669986 discloses an apparatus with heads having multiple openings for the manufacture of tablets of a core-shell structure. Figure 1 shows a tablet divided into a core and a shell containing a core 1, which is mainly coated with a shell 2. In a preferred embodiment, the polyester will be extruded into the outer shell 2, and the polyamide (MXD6) will be extruded into the core 1. The specialist will understand that the strand may consist of more than two annular concentric layers, as, for example, in figure 4. This can be done using a different extruder and a different die.

The first step is the extrusion of a multilayer strand. One component is extruded in the center of the tablet, and the other component is extruded around the central component. The extruded multilayer strand is cut with a granulator before or after it cools down, if required, and molded into multilayer tablets.

Then the strand is cooled in the usual way. For example, a strand can be immersed in a cold water tank. The water-cooled multilayer strand is preferably fed to the granulator after removing moisture from the surface, often carried out by a mixer dryer.

The granulator cuts a multilayer strand into pieces of a certain length by controlling a circular knife or the like. When cutting the multilayer strand as it is, multilayer tablets in the form of double columns are obtained containing core material and sheath material.

As a rule, multilayer tablets with an outer diameter of about 2 to 8 mm are produced. The present invention is also not limited to tablets made from strands. For example, as disclosed in US Pat. No. 5,627,218, thermoplastic polymers can be molded into laminated sheets, which are then also cut into cubes. The structure contains at least two layers, but the preferred structure for the molded structure according to this invention is depicted in figure 3. In a multilayer structure or sandwich structure, there are at least three layers, the middle layer 33 being located between the first outer layer 31 and the second outer layer 32.

Partitioned zones can be divided into a first partitioned zone, a second partitioned zone, and so on, sequentially numbered as the number of zones increases. For example, the core-shell structure has at least two partitioned zones. The core-shell structure may have more zones, depending on the number of concentric rings.

The size of the partitioned zones distinguishes it from the zone corresponding to a homogeneous dispersion. With a homogeneous dispersion, zones are created, but they are finely dispersed, with each zone constituting a very small percentage of the total volume of the tablet. The partitioned area will be a much larger percentage of the total volume.

This is easily shown using the core-shell structure shown in FIG. 1. The percentage of the volume of the partitioned zone (core) of the entire tablet is the ratio of the diameter of the core to the diameter of the cylindrical part of the tablet. You can also use the ratio of the radii. This ratio can be estimated by looking at the extrusion head and using the ratio of the diameters of the holes forming the strand. The actual ratio can be measured by SEM (scanning electron microscopy), examination under a microscope or separation of components and calculating the necessary volumes associated with the density-adjusted mass of the extracted components.

To be considered a partitioned zone, the volume of the zone must be at least 0.001 percent of the total volume of the tablet. In practice, more preferably 0.01 percent of the volume, with most preferably at least 0.1 percent of the volume.

One explanation for the superiority of the multicomponent tablet is that, due to its proper location, the reactive component is not exposed to the released by-product. In most thermal processes, by-products extend from the center of the tablet and diffuse through the polymer to the outer wall, from where the by-products are removed from the surface of the tablet. Therefore, it is considered beneficial, but not essential for the invention, to place a component releasing a reactive by-product between the outer wall of the tablet and a component that reacts with the by-product. An example of such a structure is a polyester shell and a polyamide core. The inverse structure of the arrangement of the reactive component between the wall and the component emitting the by-product will pass the by-product through the reactive component, possibly decomposing and discoloring the reactive component.

Another possible explanation for the best behavior of a partitioned heterogeneous structure over a homogeneous dispersion is the difference in surface area. A homogeneous dispersion breaks the reactive material into small particles, forming a huge surface area for reaction with the by-product. Keeping the reactive material distributed heterogeneously minimizes the surface area available for the reaction and can allow the reactive component to surround the byproduct component.

A preferred implementation is a core-shell structure in which the core contains m-xylylene adipamide polyamide (MXD6) with a number average molecular weight of 4,000 to 50,000, and the shell contains a polyester, in particular polyethylene terephthalate, or a polyethylene terephthalate copolymer with an intrinsic viscosity (IV) of 0, 4 to 1.2 dl / g. After the tablet is made, both materials can then be further processed under standard conditions of crystallization, solid phase polymerization or air drying, without causing a significant color change in the finished product compared to the control sample, which was MXD6 homogeneously distributed in the polyester and subjected to the same heat treatment.

In particular, it is contemplated that the tablet contains at least one component with an IV of 0.2 to 1.2 dl / g. For example, a film-forming polyester with an IV of at least 0.45 dl / g, intermediates with an IV of 0.49 to 0.59 dl / g, more preferably 0.52 to 0.56 dl / g can be used. The tablet may also use a polyester resin for bottles with an initial IV of 0.59 to 0.69 dl / g, more preferably 0.61 to 0.64 dl / g, with a typical bottle IV of 0.72 up to 0.84 dl / g, more preferably 0.74 to 0.82 dl / g. For packaging pallets, a typical IV is from 0.85 to 1.02 dl / g, more preferably from 0.89 to 0.95 dl / g. It should be noted that although the measured CV of the polymer is the only value, this value is averaged for a mixture of molecules of different chain lengths. A typical increase in IV during heat treatment is at least 0.1 dl / g, but can go up to 0.2 or even 0.4 dl / g.

It does not matter for the invention whether the materials are crystalline or amorphous. For example, one embodiment is a tablet with a 0.49 XB PET coating, surrounding a core containing nylon MXD6 with a number average molecular weight before crystallization of 25,000 (MXD6 grade 6007, Mitsubishi Gas Chemical). The same tablet after crystallization is also one of the embodiments, as well as the same tablet that was solid-phase polymerized, after which the intrinsic viscosity of PET was 0.84, and the number average molecular weight of nylon MXD6 also increased. The drying of the tablet, which has been solid-phase polymerized, is also one of the considered heat treatment embodiments.

It is obvious to a person skilled in the art that the molecular weight often increases during heat treatment and that the position of the component in the tablet will affect the increase in CV. Once the final molecular weight of each component has been decided, one skilled in the art will select a lower initial molecular weight of each respective component so that the final molecular weight of each component after heat treatment becomes the desired molecular weight of each component required in the final product. This initial CV can be easily determined by traditional iterative optimization methods.

The specialist will also understand that it is possible to make a tablet with characteristic viscosities that differ significantly in different zones. For example, it is well known that multifunctional comonomers such as pyromellitic dianhydride (PMDA) and pentaerythritol increase the rate of solid-phase polymerization of the polyester, as well as lower the temperature for solid-phase polymerization. This allows you to reduce the effects of high temperatures for a long time. The divided into zones tablet with PET / PMDA in the shell will allow the processing of materials that cannot withstand the conditions of traditional solid state polymerization. In this embodiment, the tablet is formed from PET and a suitable amount of PMDA in the outer shell, and a material that cannot withstand traditional time and temperature is located in the core. Many acetaldehyde scavengers and barrier polymers such as polyethyl vinyl alcohol (EVOH) fall into this category. The tablet experiences solid phase polymerization conditions at a lower temperature or for a shorter time, and in some cases at a lower temperature for less time than under traditional conditions.

Another preferred embodiment, as shown in FIG. 2, is to close the edges of the tablet so that the inner core 21 is completely surrounded and covered by the shell 22. This structure surrounds the reactive material and overlaps the edges so that they do not react with side heat-treated products that are present in the environment, or with oxygen, which may be present in the atmosphere during storage.

US 6669986 teaches that multilayer spherical, elliptical or disk-shaped tablets, the entire perimeter of which, including the end surface of the core material, are coated with shell material, can be made by rounding off the trimmed end. One way to obtain a tablet with an outer shell layer that encloses the contents of the inner layer (s) is to cut a tablet from a strand next to the extrusion head underwater. The preferred tablet structure is the MXD6 core surrounded by a polyester copolymer.

It should be understood that the absolute separation of the partitioned zones is not essential. Even if the materials may be in separate zones, there may be some polyamide (MXD6) in the polyester zone and some polyester in the polyamide (MXD6) zone.

Indeed, the polyamide zone or polyester zone may have a compatibilizer homogeneously distributed in this zone to help compatibilize the polyamide with the polyester in the final melt blending step.

Examples of such compatibilizers are given in patent application US 2004/0013833 A1, which describes a low turbidity reservoir that includes at least a first layer containing a compatibilized polymer mixture, said compatibilized polymer mixture containing a polyamide, PET or PET-containing copolymer, and at least one compatibilizer selected from isophthalic acid modified PET (IPA) and PET ionomers. This application also describes other compatibilizers. This application describes IPA-modified PET as preferably containing 1 to 6 mole percent IPA (isophthalic acid). A preferred PET ionomer is sulfonated PET. Other compatibilizers include PET modified with p-toluenesulfonic acid, PET modified with pyromellitic dianhydride, and PET modified with maleic anhydride, ionomers such as polyolefin modified with acrylic acid, and low molecular weight epoxy resin-E44 based on bisphenol azite, bifunctional stapler.

A preferred compatibilizer is an ionic compatibilizer, preferably a copolyester containing a metal sulfonate salt group. The metal ion of the sulfonate salt may be Na +, Li +, K +, Zn ++, Mn ++ and Ca ++. The sulfonate salt group is attached to an aromatic nucleus such as a benzene, naphthalene, diphenyl, oxydiphenyl, sulfonyl diphenyl or methylenediphenyl core.

Preferably, the aromatic acid core is sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid and their esters. The preferred range for the ion compatibilizer is from 0.1 to 2.0 mol% by weight of the corresponding acid or glycol moiety.

The compatibilizer may be present in the sectioned tablet as the third component and may be in any compartment. Alternatively, an ionic compatibilizer may be introduced into the molecular chain of the polyester resin.

The authors of this application also found that cyclohexanedimethanol modified PET (CHDM), commercially available under the name PETG from Eastman Chemical (USA), is also a compatibilizer (see Example 3). It should also be understood that compatibilizers, in particular polyester based compatibilizers, need not be placed in the polyamide compartment.

For clarity, it is assumed, in particular, that the smaller zone contains the material of the main zone. For example, the series of Examples 4 demonstrates the surprising result that for a tablet with a polyester shell and a polyamide core, the color of the final product can be maintained and transparency improved when the core contains both polyamide and polyester in high ratios of at least 1: 1.

It was also found that a core of pure polyamide creates voids at high strand production speeds. High capacities with reduced voids were obtained when PET was placed in the core along with MXD6. Thus, at least for the shell: polyethylene terephthalate or polyethylene terephthalate copolymer and core: MXD6 structure, the core should contain polyethylene terephthalate and / or polyethylene terephthalate copolymer in order to improve compatibility and eliminate voids at high capacities. The preferred amount of polyester in the core is the minimum amount necessary to keep the polyester as a continuous phase and the polyamide as a dispersed phase. This preferred amount will vary with the CV of the polyester and polyamide. There is every reason to believe that these phenomena will also apply to other structures, including the polyester / organic scavenger structure discussed below.

Another way to reduce voids is to traditionally control the temperature of the water and the cooling time of the strand after extrusion and before tabletting. The formation of voids for the shell: PET, core: MXD6 structure can be reduced by increasing the cooling time and increasing the temperature of the cooling water to slow down the cooling so as to minimize the uneven cooling of the shell and core.

Suitable thermoplastic polymers for use in the present invention include any thermoplastic homopolymers or copolymers. Examples thereof include aliphatic, partially aromatic and aromatic polyamides, polyethylene terephthalate, copolymers of polyethylene terephthalate, polybutylene terephthalate and its copolymers, polytrimethylene terephthalate and its copolymers, polyethylene naphthalate and its copolymers, branched polyesters, polystyrenes, polycarbonyl acrylate, polycarbonylate acid, polyvinyl methyl ether, ethylene vinyl acetate copolymer, ethylene methyl acrylate copolymer, p polyethylene, polypropylene, copolymers of ethylene with propylene, poly (1-hexene), poly (4-methyl-1-pentene), poly (1-butene), poly (3-methyl-1-butene), poly (3-phenyl -1-propene) and poly (vinylcyclohexane). Some examples of oxygen-inert thermoplastic polymers include polyethylene terephthalate, copolymers of polyethylene terephthalate, polybutylene terephthalate and its copolymers, polytrimethylene terephthalate and its copolymers and polyethylene naphthalate, branched polyesters, polycarbonate, polyvinyl vinyl diryllinyl vinyl polyvinyl vinyl polyvinyl vinyl vinyl ether, ethylene vinyl acetate copolymer, ethylene methyl acrylate copolymer.

The thermoplastic polymer used in the present invention preferably comprises a polyester polymer or copolymer such as polyethylene terephthalate or a crystallizable polyethylene terephthalate copolymer. A copolymer of polyethylene terephthalate, or a polyethylene terephthalate copolymer, is also called copolyethylene terephthalate. The polyethylene terephthalate copolymer, or polyethylene terephthalate copolymer, is a polyester in which at least 85% of the repeating acid units of the total number of acid units are terephthalic acid units or of the terephthalic acid diester unit, at least 85% of the repeating glycol units of the total number of glycol units units of ethylene glycol, and the remaining acid and / or glycol units are repeating units of at least one other type. The third recurring unit may be, for example, isophthalic acid, 2,6-naphthalenedicarboxylic acid, cyclohexanedimethanol or 1,4-butanediol.

For clarity, the term “unmodified PET” refers to polyethylene terephthalate or copolyethylene terephthalate. The term “crystallizable” refers to the ability of a polymer to crystallize to some extent, as measured by differential scanning calorimetry (DSC). Typical crystallinity levels range from 5 up to 65 percent, depending on the type of heat treatment and the nucleation method used. Typically, a polymer will be considered amorphous if its crystallinity is less than 5%.

There are two types of crystalline structures, one refers to stress-induced crystallinity, which orders molecules under the action of a force on a material at an elevated temperature, but below the melting point. This type of crystallinity is also known as orientation, and occurs when fibers are pulled or when bottles are blown and drawn. Due to the ordering and orientation of the crystals, stress-induced crystallinity materials are usually transparent. Stress-free crystallinity occurs when an amorphous material is heated in the absence of stress. The material turns white. This crystallinity is rare in nature and very unstable. Embodiments of the present invention can be implemented on amorphous tablets (tablets with a crystallinity of less than 5%), tablets with crystallinity caused by stresses, tablets with crystallinity not caused by stresses, and tablets with both types of crystallinity. Tablets with both types of crystallinity are obtained by orienting the strand during extrusion and exposing the sliced tablets or strand to heat sufficient to turn some of the tablet material remaining amorphous into crystalline morphology not induced by stress.

It should be understood that a thermoplastic polymer suitable for use in the present invention can be made in the form of a film, sheet or injection molded product.

The polymers used in the present invention can be obtained by conventional polymerization methods well known in the art. Polyester polymers and copolymers can be prepared by melt polymerization involving the reaction of a diol with a dicarboxylic acid or its corresponding diester. Various copolymers resulting from the use of several diols and dicarboxylic acids may also be used. Polymers containing repeating units of only one chemical composition are homopolymers. Polymers with two or more chemically different repeating units in the same macromolecule are called copolymers. For clarity, the polymer of terephthalate, isophthalate and naphthalate with ethylene glycol, diethylene glycol and cyclohexane dimethanol contains six different monomers and is considered a copolymer. The variety of repeating units depends on the number of different types of monomers present in the initial polymerization reaction. In the case of polyesters, the copolymers include the interaction of one or more diols with one or more dicarboxylic acids and, sometimes, are also called ternary copolymers. In addition, randomization of monomers is not necessary. The term "copolymer" or "ternary copolymer" refers to a polymer with different monomers, whether they are distributed blockwise or statistically.

Suitable dicarboxylic acids include acids containing from about 6 to about 40 carbon atoms. Specific dicarboxylic acids include, but are not limited to, terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexane dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, 1,3-phenylenedioxyacetic acid phenylenedioxyacetic acid, 1,4-phenylenedioxyacetic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and the like. Particular esters include, but are not limited to, phthalic esters and naphthoic diesters.

Also included are monomers that form polyester ionomers such as metal sulfonates. These include lithium, sulfur and phosphorus salts with sulfonated isophthalate.

These acids or esters can react with an aliphatic diol having from about 2 to about 10 carbon atoms, a cycloaliphatic diol having from about 7 to about 14 carbon atoms, an aromatic diol having from about 6 to about 15 carbon atoms, or glycol ether having from 4 to 10 carbon atoms. Suitable diols include, but are not limited to, 1,4-butenediol, trimethylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, resorcinol and hydroquinone.

Polyfunctional comonomers may also be used, typically in amounts of from about 0.1 to about 3 mole percent. Suitable comonomers include, but are not limited to, trimellitic anhydride, trimethyl propane, pyromellitic dianhydride (PMDA), and pentaerythritol. Polyester-forming polyacids or polyols may also be used.

One preferred polyester is polyethylene terephthalate (PET homopolymer) formed by the reaction of terephthalic acid or its ester with ethylene glycol in a stoichiometric ratio of about 1: 1. Another preferred polyester is polyethylene naphthalate (PEN homopolymer) formed by the reaction of naphthalenedicarboxylic acid or its ester with ethylene glycol in a stoichiometric ratio of from about 1: 1 to 1: 1.6. Another preferred polyester is polybutylene terephthalate (PBT). PET copolymers, PEN copolymers and PBT copolymers are also preferred. Particular copolymers and ternary copolymers of interest are PET with a combination of isophthalic acid or its diester, 2,6-naphthoic acid or its diester and / or cyclohexane dimethanol.

The esterification or polycondensation reaction of a carboxylic acid or ester with glycol usually occurs in the presence of a catalyst. Suitable catalysts include, but are not limited to, antimony oxide, antimony triacetate, antimony ethylene glycolate, organomagnesium compound, tin oxide, titanium alkoxides, dibutyltin dilaurate and germanium oxide. These catalysts can be used in combination with zinc, manganese or magnesium acetates or benzoates. Antimony-containing catalysts are preferred. Since this tablet is intended for food packaging, other suitable polyesters are listed in US 21 CFR 177.1000-177.2910 (Revised Edition, April 1997).

Another preferred polyester is polytrimethylene terephthalate (PTT). It can be obtained, for example, by reacting 1,3-propanediol with at least one aromatic dicarboxylic acid or its alkyl ester. Preferred dicarboxylic acids and alkyl esters include terephthalic acid (TPA) or dimethyl terephthalate (DMT). Accordingly, the PTT preferably contains at least about 80 molar percent of either TPA or DMT. Other diols that can be copolymerized into such a polyester include, for example, ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol. Aromatic and aliphatic acids that can be used simultaneously to produce a copolymer include, for example, isophthalic acid and sebacic acid.

Preferred catalysts for producing PTT include titanium and zirconium compounds. Suitable titanium catalyst compounds include, but are not limited to, titanium alkylates and derivatives thereof, titanium complex salts, titanium complexes with hydroxycarboxylic acids, coprecipitated titanium dioxide — silicon dioxide, and titanium dioxide containing hydrated alkali. Specific examples include tetra- (2-ethylhexyl) -titanate, tetrastearyl titanate, diisopropoxy-bis (acetylacetonato) -titanium, di-n-butoxy-bis (triethanolaminato) -titanium, tributyl monoacetyl titanoic acid, triisopropyl mono-nitroacetan titanoic acid potassium hexafluorotitanate and complexes of titanium with tartaric acid, citric acid or lactic acid. Preferred titanium catalyst compounds are titanium tetrabutylate and titanium tetraisopropylate. Suitable zirconium compounds may also be used.

The polymer preferred in the present invention may also contain small amounts of phosphorus compounds such as phosphates and a catalyst such as a cobalt compound, which typically gives a blue tint. Other additives that may be included are infrared absorbers such as carbon black, graphite, and various iron compounds.

The molten phase polymerization described above may be followed by a crystallization step and then a solid phase polymerization (SSP) step to increase the molecular weight (measured by intrinsic viscosity) needed to make the bottles. Crystallization and polymerization can be carried out in a drum dryer in a batch type system. Alternatively, crystallization and polymerization can be carried out in a continuous solid state process in which the polymer flows from one apparatus to another after a predetermined heat treatment in each apparatus.

The crystallization conditions for PET preferably involve a temperature of from about 100 ° C to about 150 ° C. Typical heat treatment operations for crystallizing PET increase the crystallinity of the PET in the tablet by at least 5 percent. In embodiments of the invention, the degree of crystallinity of any component such as PET or polyamide can be increased by 5 percent, or the total increase in the degree of crystallinity of these two components can be 5 percent. It should be noted that the increase in crystallinity in percent is neither a weighted average of the components, nor a percentage or value relative to the previous degree of crystallinity. The increase in crystallinity in percent, or increase in crystallinity, is an absolute increase in the degree of crystallinity. When the crystallinity of PET and polyamide is combined, the increase in crystallinity is the absolute increase in crystallinity of PET plus the absolute increase in crystallinity of polyamide. For example, the expression “increase in crystallinity by at least 5 percent” means that at least 5 percent of the component has transitioned from an amorphous to a crystalline state. This does not mean that a tablet with a crystallinity of 20%, which has experienced a 5% increase in crystallinity, has 21% crystallinity. This means that the tablet has 25% crystallinity. In many cases, an increase in the degree of crystallinity will be an increase of at least ten percent, and in some cases even by 15-20 percent.

Solid phase polymerization conditions preferably involve a temperature of from about 200 ° C to about 235 ° C, more preferably from about 215 ° C to about 235 ° C. Solid phase polymerization can be carried out for a time sufficient to increase the molecular weight to the desired level, which will depend on the application and the initial characteristic viscosity. For a typical bottle application, the preferred molecular weight corresponds to an intrinsic viscosity of from about 0.68 to about 0.88 deciliters / gram, as determined by the method described in the "Methods" section. The time required to achieve this molecular weight can vary from about 8 to about 45 hours. A typical increase in IV is at least 0.1 dl / g, with an increase of 0.2 to 0.4 dl / g more typically.

In one embodiment, the thermoplastic polymer matrix of the present invention may comprise recycled polyester or materials made from recycled polyester such as polyester monomers, catalysts, and oligomers. It was found and shown in Examples 4B and 4C that PET with at least 75% homogeneously distributed MXD6 can successfully polymerize in the solid phase if it is placed in the core of the core-shell structure when the total MXD6 content in the polymer tablet is up to 5 % This important finding means that recycled polyester from used containers consisting of PET containing dispersed polyamides such as MXD6 can be crystallized, solid phase polymerized and dried without enhancing the color commonly associated with recycled polyester containing such dispersed polyamides like nylon MXD6. The recycle process only requires placing the recycle PET containing MXD6 nylon in the core, and the recycle PET or unused PET that does not contain MXD6 in the casing. In a typical recycle process, the PET in the core will contain at most 10%, more likely much less than 5% by weight of MXD6.

Another component of this embodiment is a compound that either produces a by-product during heat treatment that reacts with another component, or reacts with a by-product formed by another component during heat treatment. Note that both components may react with a by-product of the other.

If the preferred material for the first component is a polyester, then the preferred material of the second component is polyamide. Polyamides suitable for the present invention can be characterized as containing repeating units of aminocaproic acid or AD, wherein A is a dicarboxylic acid residue such as adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, resorcyndicarboxylic acid or naphthalenedicarboxylic acid or a mixture thereof, and D is a diamine residue such as m-xylylenediamine, p-xylylenediamine, hexamethylenediamine, ethylenediamine or 1,4-cyclohexanedimethylamine, or a mixture thereof. These polyamides can be ranked by number average molecular weight, measured by end-titration, from 2,000 to 60,000. These polyamides can also be characterized as a homocondensation product of aminocaproic acid and / or a reaction product of a dicarboxylic acid residue such as adipic acid, isophthalic acid, terephthalic acid , 1,4-cyclohexane dicarboxylic acid, resorcyndicarboxylic acid or naphthalenedicarboxylic acid, or a mixture thereof, with a diamine residue such as m-xylylenediamine, p-xylylenediamine, hexame thylenediamine, ethylenediamine or 1,4-cyclohexanedimethylamine, or a mixture thereof.

In many of the combinations, those skilled in the art will recognize the well-known commercially available polyamides. The reaction product of the sebacic acid residues with hexamethylenediamine is nylon-610, and the reaction product of the adipic acid residues and hexamethylenediamine is nylon-66. Nylon-612 is another nylon that can be used in the invention. Nylon-6 is a special type of polyamide which is obtained by opening caprolactam and then polymerizing the resulting aminocapric acid having the formula H ₂ N- (CH ₂ ) ₅ —COOH. A preferred polyamide is the reaction product of adipic acid residues and m-xylylenediamine, known as poly-m-xylylene adipamide. This product is known as MXD6 or MXD6 nylon and can be ordered from Mitsubishi Gas Chemical, Japan.

In addition, the polyamide can be modified with monomers that form such polyamide ionomers as metal sulfonates. These include lithium, sulfur and phosphorus salts with sulfonated isophthalate. They can be introduced, for example, as dicarboxylic acid, a pre-reacted diester or diamine. US 3,328,484, the teachings of which are incorporated herein by reference, describes such modified copolyamides.

The advantage of this invention over pre-mixing is shown in examples 2A, 1B and 2B. In Example 2A, a tablet with a polyester shell and a polyamide (MXD6) core was made, which was held at 140 ° C and <1.33 mbar for 5 hours to crystallize the material. After crystallization, the tablet was kept in vacuum at a pressure of <1.33 mbar (<1 mm Hg) and a temperature of 230 ° C for approximately 13 hours to increase the molecular weight. Then the tablets were dried for 6 hours in air at 160 ° C and were molded under pressure in the workpiece.

A uniformly distributed compounded control sample of PET / MXD6 (Example 2B) was held at a pressure of <1.33 mbar (<1 mm Hg) and a temperature of 140 ° C for 5 hours to crystallize the material, and then dried in air at 160 ° C for 6 hours and was molded under pressure in the workpiece.

A control sample with physical mixing (Example 1B) was made by drying individual PET and MXD6 tablets in the presence of dry air at 160 ° C for 6 hours and injection molding into blanks.

The color parameters of the workpiece made from a uniformly distributed control sample was b * = 23.1, the color of the control sample with physical mixing was b * = -5.8. For comparison: the color of an embodiment of the invention was b * = -4.7.

These experiments not only demonstrate the profitability of a tablet with a partitioned structure, they also open the way for the simultaneous heat treatment of two materials. Such heat treatment includes, but is not limited to, crystallization, drying, solid phase polymerization, or any combination thereof. Although these experiments were carried out in rotary vacuum mixers, they were easily carried out on an industrial scale with fluidized bed vibrating crystallizers in the presence of air or an inert gas such as nitrogen, and in continuous solid state polymerizers in the presence of an inert gas such as nitrogen.

A second advantage of the present invention is a tablet which contains at least one oxygen inert polymer such as a polyester, at least one oxygen sensitive component and at least one reaction promoter which, when contacted with the oxygen sensitive component or initiates or catalyzes a reaction with oxygen of the oxygen sensitive component and thus makes the oxygen sensitive component an oxygen active component.

For the purposes of this description, a component that reacts with oxygen is known as an oxygen-active component or oxygen scavenger. The reaction of the component with oxygen is often promoted by an additional component, which is also present in the wall of the package. A component that becomes oxygen active in the presence of a promoter is called an oxygen sensitive component. A promoter typically initiates and often catalyzes the reaction of an oxygen-sensitive component with oxygen. After the oxygen-sensitive component experiences the action of the promoter and becomes active to oxygen, the oxygen-sensitive component is converted to the oxygen-active component. The oxygen sensitive / active component may be an organic, inorganic or metal in a reduced valence state.

In contrast, the term “oxygen-inert component” refers to a component that, upon contact with the promoter, does not become oxygen active to the extent that the oxygen-sensitive component becomes an oxygen active component. This can be easily determined by combining an oxygen-sensitive component with a promoter and measuring oxygen consumption. Then, the proposed oxygen inert component is combined only with the promoter and oxygen activity is measured. It has been found that most organic compounds exhibit some very small degree of oxygen activity. Therefore, in order to be an oxygen inert component in the context of this description, a component with a promoter, as compared to a component without a promoter, must detect an increase in the amount of oxygen absorbed by less than 10%, and preferably no increase. A slightly larger increase can be caused by trace amounts of catalyst, impurities, or even a promoter, which alone can react with oxygen to a small extent.

In this embodiment, the polymer, the oxygen-sensitive component and the promoter are heterogeneously arranged in the zones or compartments of the tablet, so that the promoter in direct contact with the oxygen-sensitive component is not sufficient to substantially initiate or catalyze a reaction with oxygen, but the promoter is more than enough to do this when the ingredients are homogenized when mixed at the final stage of melt extrusion.

A critical factor is that the promoter and the oxygen-sensitive component are arranged in tablets substantially heterogeneously, opposite to homogeneous dispersion or solubilization in each other. In one embodiment, the oxygen-sensitive component is in the compartment of either the core or shell, and the promoter is distributed within the oxygen-inert component in an amount sufficient to initiate and / or catalyze the reaction of the oxygen-sensitive component with oxygen when the tablet is processed on the final stages of mixing in the melt. With this configuration, the oxygen-sensitive component remains substantially inactive to oxygen until it is coupled to the promoter upon final melt mixing. Now, the tablet of the invention can be stored in an oxygen-containing medium such as air and heat treated in the presence of oxygen, since the oxygen-sensitive compound does not show or exhibits low oxygen activity until it is finally mixed in the melt.

The oxygen-active compound may be one of many compounds. The oxygen active compound in this particular embodiment is an oxygen sensitive component that requires a reaction promoter to initiate or catalyze a reaction with oxygen. Active Food Packaging, M. L. Rooney ed., 1995, p. 74-110, the teachings of which are incorporated herein by reference, describe various types of oxidizable organic oxygen-sensitive compounds. Oxygen-sensitive compounds are typically ethylenically unsaturated organic compounds and contain at least one allylic hydrogen, which is cleaved in the presence of oxygen and a promoter that is an initiator or catalyst. In this context, the catalyst may be the initiator, but the initiator is not always the catalyst. Typically, the reaction with oxygen without the presence of an initiator or catalyst is very slow, or does not occur at all. The initiator is that it triggers a quick reaction of the compound with oxygen. The catalyst can both start the reaction and increase the reaction rate, but it does not participate in the reaction.

It should also be noted that polyamides, like polyolefins, become active against oxygen in the presence of a transition metal catalyst and are therefore also oxygen sensitive components. Thus, polyamides are also one of the preferred oxygen sensitive components for the second aspect of the invention. Particularly suitable oxygen sensitive components are the polyamides described in the previous embodiment. Of these polyamides, a fragment of m-xylylene adipamide is preferred. Polybutadiene, polybutadiene oligomers and terpenes are other examples of oxygen-sensitive materials that are promoted (initiated and / or catalyzed) by a transition metal catalyst.

Other examples of oxidizable organic compounds are listed in US Pat. No. 6,067,666, the teachings of which are incorporated herein by reference. Particular examples include polybutadiene, non-hydrogenated polybutadiene oligomers, polypropylene oxide oligomers and aromatic compounds with methyl side groups. Many forms of polybutadiene are suitable, including those with a high content of cis, high vinyl and syndiotactic microstructures.

In addition, for physical mixing with the main component, the oxygen sensitive component must be chemically functionalized in one or more places and react with a material compatible with the main component. Such funcionalization can place at least one carboxyl, hydroxyl or amino group in the component. Preferably, there are two functional groups located at each end of the molecule. Materials compatible with the polyester type are reaction products of predominantly polycondensate segments selected from the group consisting of polyesters listed in US 21 CFR 177.1590 and polyamides with a small amount of oxygen-sensitive segments of the molecule selected from the group consisting of functionalized polybutadiene unhydrogenated polybutadiene oligomers, polypropylene oxide oligomers and aromatic compounds with a methyl side group. USA Decree 21 CFR 177.1590 describes polycondensates as polyester elastomers obtained by transesterification when one or more of the following phthalates: dimethyl terephthalate, dimethyl orthophthalate and dimethyl isophthalate, are reacted with alpha-hydro-omega-hydroxypoly (oxytetramethylene) 4-butanediol, so that the final elastomer has a number average molecular weight of from 20,000 to 30,000. These condensates can also be described as polycondensates consisting of one or more phthalates selected from the group consisting of terephthalate, ortho phthalate and isophthalate, wherein said polycondensate also contains one or more glycols selected from the group consisting of alpha-hydro-omega-hydroxypoly (oxytetramethylene) and 1,4-butanediol, and the polycondensate has a number average molecular weight of from 20,000 to 30,000 Alpha-hydro-omega-hydroxypoly (oxytetramethylene) is the polymer form of 1,4-butanediol. Monoethylene glycol (ethylene glycol) and its polymer, also known as polyethylene glycol, are also suitable.

Typically, the best compatibility is obtained when the oxygen scavenger material itself reacts with the main component. US 6,406,766 describes how this can be implemented. Since US 6,406,766 teaches the introduction of functionalized polybutadiene into the polyester segment, the authors of this invention consider functionalized polybutadiene as a monomer for the polyester segment. For the purposes of this description, the term “functionalized polybutadiene” is equivalent to the term “polybutadiene monomer” found in US Pat. No. 6,067,666. Preferably, the functionalized oxygen scavenger reacts with the same type of material as the main component. In other words, the best compatibility with polyethylene terephthalate is obtained when a functionalized oxygen scavenger has reacted with polyethylene terephthalate or copolyethylene terephthalate.

A promoter is an initiator or catalyst and is any compound that initiates or accelerates the reaction of an oxygen-sensitive component with oxygen. The promoter is usually a transition metal, most preferably a cobalt salt such as cobalt neodecanoate, and is not consumed in reaction with oxygen to an oxygen-sensitive material. In addition, the oxygen sensitive component is sufficiently inactive to oxygen if the promoter is not present in sufficient quantity. The promoter may also require exposure external to the tablet, such as radiation energy (light, UV radiation, microwave radiation), or contact with another substance such as water to initiate a reaction with oxygen or release the initiator.

The amount of promoter is usually determined experimentally based on the amount of oxygen required, the type of oxygen-sensitive component and the type of promoter. In general, the amount of promoter varies from 30 to 1000 ppm of metal ions to a component that is sensitive to oxygen. More preferably, this value is from 50 to 500 ppm, with the most desirable range being from 100 to 300 ppm of metal ions by weight of the oxygen sensitive component.

The ratio between the oxygen sensitive component and the oxygen inert component depends on the efficiency of the oxygen sensitive component interacting with oxygen when it becomes oxygen active. Effective oxygen uptake occurs when the content of the oxygen sensitive component and / or the oxygen active component is from 1 to 12 weight percent. More preferably, the oxygen sensitive / active component should be present at a level of 2 to 8 percent by weight of the polymer tablet. For most industrial applications, a level of 4 to 6 weight percent will be suitable.

In a preferred embodiment, an unpromoted oxygen sensitive component, preferably a polyamide such as MXD6, unhydrogenated butadiene oligomers or unhydrogenated polybutadiene oligomers included in the main polyester chain, are placed in the tablet core, and the cobalt promoter and polyester are placed in a shell or outer configuration layer. In this configuration, the cobalt promoter remains in the polyester phase (oxygen inert) to the final melt mixing stage, when the oxygen-sensitive component is distributed over the polyester and comes into close contact with the cobalt salt, thereby initiating and catalyzing the reaction of oxygen with the sensitive oxygen component. At this point, the oxygen-sensitive component becomes an oxygen-active component.

It will be apparent to those skilled in the art that the amount of promoter can be minimized by determining the maximum level of promoter that can be added to the oxygen sensitive component so as not to significantly promote the reaction with oxygen, and by determining the total amount of promoter necessary to promote the reaction under conditions of complete dispersion and placing at least the remaining amount of the promoter in a polyester shell.

A third embodiment provides for the placement of an already-initiated / catalyzed or otherwise activated oxygen-active component in the core, and the placement of a highly impervious component between the oxygen-active component and the outer border of the tablet, for example, in a shell. A preferred implementation will be a shell that surrounds the oxygen-active material and reduces the amount of oxygen reaching the oxygen-active component, thereby preserving the degree of activity of the component to oxygen during storage. Again, the preferred core materials are MXD6 with cobalt salt, polybutadiene with cobalt salt and non-hydrogenated polybutadiene introduced by the reaction in the polyester, in combination with cobalt salt. These components are surrounded by a shell of polyethylene terephthalate or its crystallizable copolymer. The polyester is then crystallized, virtually eliminating the penetration of oxygen into the oxygen-active component in the core.

It should also be noted that a functionalized (non-hydrogenated) oxygen-active component can be present in two forms. First, it may be present as a functionalized material that has not yet entered the main polymer chain. The reaction of entering the main chain of a component in another zone will occur upon final mixing in the melt. A similar reaction is described in US Pat. No. 5,747,548. However, US Pat. No. 5,747,548 is limited to structures in which the components are dissimilar and become chemically interreactive with each other upon final melt mixing. US Pat. No. 5,747,548 does not say anything about systems that react with external compounds such as oxygen, or about systems that only react in an extruder.

For clarity, the present invention is applicable to tablets, which may also have interactive / interreactive components, in addition to reaction with by-products and / or oxygen. The oxygen sensitive or oxygen active component may or may not be one of these interactive / interreactive components. A critical factor for this embodiment is the presence of a reaction promoter with a compound external to the tablet, such as oxygen, and that the promoter is kept separate from the oxygen sensitive compound, or that the oxygen active component is shielded from oxygen, so in any embodiment the degree of activity of the tablet to oxygen at room temperature (23 ° C +/- 5 ° C) is reduced by 20% compared with the control tablet.

The lack of oxygen activity of the zoned tablet of the invention was demonstrated in the series of Examples 5. The oxygen activity of the zone structure (5C) containing the PET, oxygen sensitive component (MXD6) and the oxygen reaction promoter (cobalt neodecanoate) is similar to the control activity (5A ) containing only PET and an oxygen sensitive component. The amount of oxygen reacted after the first day is actually the same as for the partitioned structure, which does not show an increase in absorption over a seven-day period. Apparently, the low result in the control sample on the seventh day is a consequence of the fact that the sample was placed in the ampoule only some time after manufacture. During this time, a small amount of internal oxygen activity has already worked.

In comparison, comparative example (5B) reacted with or absorbed almost double the amount of oxygen over a seven-day period. Preservation of the ability to absorb oxygen is demonstrated in Example 5D, which was a 5C zoned structure re-pelletized to mix all the ingredients. Thus, the components are separated until they are ready to combine at the last possible moment, and the oxygen-sensitive material is converted into an oxygen-active material.

Another embodiment of the invention provides for the placement of an acetaldehyde scavenger or acetaldehyde reaction catalyst in one of the zones. One class of compounds that react with acetaldehyde and have been discussed previously are polyamides. Zirconia particles are known to also reduce the amount of acetaldehyde. Since zirconium oxide is particles, high levels of this compound can lead to turbidity of the final product. The advantage of concentrating zirconia in one zone is that it remains relatively unused until solid state polymerization occurs, when the level of acetaldehyde drops sharply from the level usual for the melt polymerization stage. When zirconium oxide is introduced into the core of the core-shell structure prior to solid phase polymerization, less zirconium oxide will be required since large amounts of acetaldehyde are removed during solid phase polymerization.

Test methods

The amount of oxygen reacted with the tablets of the invention was measured and compared with a control tablet of a similar size with the same amount of ingredients. In the case of control, the ingredients are uniformly distributed over the tablet. Or alternatively, the promoter is distributed in an oxygen sensitive component, which is then dispersed in an oxygen inert material.

Oxygen activity can be determined by placing control tablets in a sealed vessel and the same number of sectioned tablets of similar size and weight in a sealed vessel of the same size. The vessels are kept at the same temperature and the decrease in oxygen in each vessel is measured at a specific point in time, preferably after seven days. For example, you can place the same number of tablets of the same size in gas chromatographic ampoules and seal them tightly. Ampoule A will contain a homogeneous dispersion. Ampoule B will comprise an embodiment. Ampoules are kept in the same medium (temperature preferably 23 +/- 5 ° C) for seven days. The actual temperature level is not as significant as holding both ampoules at the same temperature profile for seven days. After seven days, each ampoule is analyzed for its oxygen content. The decrease in oxygen content, compared with atmospheric oxygen, is the amount of oxygen absorbed or reacted. Changes in tablet weight are expressed by dividing the amount of oxygen consumed by the amount of material in the ampoule and express the value in cubic centimeters of absorbed (reacted) oxygen per gram of polymer. If the tablets are the same size and an equivalent number of tablets has been used, this normalizing adjustment is not necessary. The same test can be carried out by placing tablets in a film bag and analyzing the gas in the film bag to reduce oxygen. With a successful design, at least 20 percent less oxygen is consumed in the seven-day period than the control sample.

Intrinsic viscosity

The intrinsic viscosity of low crystallinity poly (ethylene terephthalate) intermediate molecular weight and related polymers that are soluble in a 60/40 phenol / tetrachloroethane mixture was determined by dissolving 0.1 grams of polymer or crushed tablet in 25 ml of a 60/40 phenol / tetrachloroethane mixed solution and determining the viscosity of the solution at 30 +/- 0.05 ° C relative to the solvent at the same temperature using a Ubbelode type 1B viscometer. Intrinsic viscosity is calculated using the Billmeier equation based on relative viscosity.

The intrinsic viscosity of high molecular weight or high crystalline poly (ethylene terephthalate) and related polymers that are not soluble in the phenol / tetrachloroethane mixture was determined by dissolving 0.1 grams of polymer or a crushed tablet in 25 ml of a trifluoroacetic acid / dichloromethane 50/50 mixture and measuring the viscosity of the solution at 30 +/- 0.05 ° C relative to the solvent at the same temperature using a Ubbelode viscometer type OC. The intrinsic viscosity is calculated according to the Billmeier equation and converted using linear regression to obtain results that are consistent with the results obtained using phenol / tetrachloroethane 60/40 solvent. Linear regression gives IV (phenol / tetrachloroethane 60/40) = 0.8229 × IV (trifluoroacetic acid / dichloromethane 60/40) + 0.0124.

Determination of crystallinity

Determining the degree of crystallinity can be carried out by several conventional methods. However, for tablets containing several compounds, in any method, the measured density or the required amount of heat (DSC method) are adjusted to the weighted average amount of the compound in the tablet.

Separation of components and determination of the amount of components in a tablet

The amount of each component in a tablet can be determined by many different methods. For example, you can find out how much compound was added during the manufacture of the tablet, you can physically separate the components, or you can separate the components by selectively dissolving one of the components, removing the solvent and weighing. In the case of a polyamide / PET composition, formic acid can be used to isolate the polyamide from the core into the solution, leaving the PET coating. The amount of PET can be weighed directly, and the amount of polyamide is determined by the difference. If the polyamide core contains other compounds that are insoluble in formic acid, the solution can be filtered and the polyamide can be precipitated from formic acid by adding water. Then the sample is dried and the amount of polyamide is determined by direct weighing. In any case, small amounts of additives or other non-polyamide, non-PET materials will not affect the absolute value of crystallinity to any significant degree.

After isolation of the individual component from the tablet, its crystallinity or intrinsic viscosity can be determined.

Experimental results

In all the experimental work, the polyester and polyamides were pre-dried and the tablet size was 2 grams / 100 tablets. A preferred tablet size was less than 1.5 grams / 100 tablets, more preferably less than 1.8 grams / 100 tablets.

A series of examples 1: Crystallization and drying in air.

1A - Sectioned Tablet

A sectioned tablet was made from 95 weight percent of a copolymer of polyethylene terephthalate with XB 0.84 (CLEARTUF ^® MAX from M&G Polymers, USA) in the shell and 5 weight percent of nylon MXD6 (grade 6007, XB 1.181, manufactured by Mitsubishi Gas Chemical, Japan) in the core. The tablet was thermally treated at 140 ° C and a pressure of <1.33 mbar in a rotating vessel for 5 hours to crystallize the material (crystallinity not induced by stresses), dried in air for 6 hours at 160 ° C and cast under pressure into 52 grams blanks. Hunter color parameters for the workpiece were: L * = 52.1, a * = -0.95 and b * = -4.91.

Comparative Examples 1B, 1C, 1D

1B - Polyester and polyamide dried in the same vessel

A polyethylene terephthalate copolymer was prepared by taking the amorphous starting polyester resin from Example 1A with an XB 0.52 and treating it thermally at 140 ° C. and a pressure of <1.33 mbar in a rotating vessel for 5 hours to crystallize the material. After crystallization, the tablets were held at <1.33 mbar and 230 ° C for approximately 13 hours in the same rotating vessel to form an IV IV of 0.84 dl / g. At the same time, tablets with 95 weight percent polyethylene terephthalate copolymer and 5 weight percent polyamide from Example 1A were placed in the same dryer with atmospheric air for 6 hours at 160 ° C. and then injection molded into blanks. The color parameters of the workpiece were: L * = 53.3, a * = -0.36 and b * = -5.82.

1C - Drying in individual vessels

The polyethylene terephthalate copolymer tablets of Example 1A and the polyamide tablets of Example 1A were dried in separate vessels. The polyester was dried in atmospheric air at 154.4 ° C overnight. The polyamide was dried overnight in a vacuum oven at 107.2 ° C. The dried tablets were finally melt mixed in a proportion of 94.5 weight percent polyester and 5.5 weight percent MXD6 in the same injection molding machine and under the same conditions as in Example 1A, and cast into preforms. The average color parameters of the three blanks were: L * = 50.12, a * = 0.10 and b * = -7.47.

1D - Crystallized and dried homogeneous dispersion

The dried tablets of copolyethylene terephthalate (PET) of Example 1A and nylon MXD6 of Example 1A were homogeneously melt-blended (compounded) in a proportion of 94.5 weight percent to 5.5 weight percent, extruded and cut into tablets. Melt-mixed tablets of PET and MXD6 crystallized by holding the tablets at a pressure of <1.33 mbar and a temperature of 140 ° C in a rotating vessel for 6 hours, dried in air for 6 hours at 160 ° C, and then injection molded into the same shaped blanks as in example 1A. Hunter color data was determined on the same blank. Hunter color indicators were: L * = 47.75 / 46.7, a * = -2.19 / -2.17, and b * = 11.35 / 12.9.

Table I
Color parameters of the workpiece after crystallization
and subsequent drying of the resin in air Thermal process: crystallization, then air drying L * a * b * Sectioned tablet 52.1 -0.95 -4.91 Polyester and polyamide dried in the same vessel 53.3 -0.36 -5.82 Drying in individual vessels 50.12 0.10 -7.47 Crystallized and dried homogeneous dispersion 47.75 -2.19 +11.35

A series of examples 2 - Crystallization, solid phase polymerization and drying in air.

2A - Sectioned Tablet

The tablet, divided into a core-shell, was made from the copolyethylene terephthalate of Example 1B in a shell (95.1% by weight) and the polyamide of Example 1A in a core (4.9% by weight). The multicomponent tablets were held at a pressure of <1.33 mbar at 140 ° C in a rotating vessel for 5 hours to crystallize the material. After crystallization, the tablets were held at a pressure of <1.33 mbar and a temperature of 230 ° C for approximately 13 hours to form a molecular weight. The intrinsic viscosity of the tablets was 0.58 before solid phase polymerization and 0.85 dl / g after solid phase polymerization. The tablets were dried in air at 160 ° C for 6 hours and extruded into the same preforms as in Example 1A. Hunter color parameters for the blanks were: L * = 48.2, a * = -1.87, and b * = -4.71.

Comparative example

2B - Melt mixing, homogeneous dispersion, crystallization, solid phase polymerization and air drying

Tablets of polyamide homogeneously dispersed in PET were made by melt mixing 95 weight percent of the polyethylene terephthalate copolymer of Example 1B with 5 weight percent of the polyamide of Example 1A. Homogeneous mixed PET and polyamide tablets were thermally treated at 140 ° C and a pressure of <1.33 mbar for 5 hours in a rotating vessel to crystallize the material. After crystallization, the tablets were held at <1.33 mbar and 230 ° C in the same vessel for approximately 13 hours to increase the intrinsic viscosity to 0.84 dl / g. The tablets were then dried in air for 6 hours at 160 ° C and injection molded into the same preforms as in Example 1A. Hunter color parameters for the workpiece were: L * = 42.93, a * = -0.61 and b * = +23.14.

Table II
The color parameters of the workpiece after crystallization,
solid phase polymerization and subsequent drying of the tablets
on air Configuration: crystallized, solid state polymerized, then air dried L * a * b * Sectioned tablet 48,2 -1.87 -4.71 Homogeneous dispersion 42.93 -0.61 +23.14

Series 3 - Compatibilizers

These experiments were carried out by placing a polyester (grade PETG 6763 from Eastman Chemical, USA) modified with cyclohexane dimethanol (CHDM) in a core with a polyamide, with and without pyromellitic dianhydride (PMDA), solid-phase polymerizing the tablet, drying the tablets in air, before casting the tablets under pressure into 27 gram billets and blowing 500 ml bottles. The results indicate that the use of CHDM-modified polyester yields less turbidity than isophthalic acid-modified PET, and that the use of PMDA, as indicated below, further reduces turbidity.

Series 3A, 1 and 2 - PET modified with isophthalic acid, with and without pyromellitic anhydride (PMDA)

1. In these two series of experiments, a sectioned tablet was made using the polyester of Example 1B as a shell. The core was 15 percent by weight of the tablet and contained 33.33 weight percent of the polyamide of Example 1A and 66.67 weight percent of a 0.66 percent polyester modified with 10 mol percent of isophthalic acid. Then, the tablet was polymerized in a solid phase under vacuum to an HV of 0.76, after which it was dried in air, injection molded into 27 gram billets and blown into 500 ml bottles. Hunter bottle haze measured through the side wall was 18 percent.

2. The second series was carried out similarly to the 3A series 1. The difference was that the core contained 0.35 weight percent PMDA. These tablets were solid-phase polymerized to XB 0.81 (I.D6-3B1-08), then dried in air, pressure-molded into 27 gram billets and blown into 500 ml bottles. Hunter bottle haze measured through the side wall was 9.7 percent.

Series 3B, 1 and 2 - Cyclohexanedimethanol Modified PET (CHDM), with and without PMDA

1. In these two series of experiments, a sectioned tablet was made using the polyester of Example 1B as a shell. The core was 15 percent by weight of the tablet and contained 33.33 weight percent of the polyamide of Example 1A and 66.67 weight percent of a 0.67 cyclohexane dimethanol modified polyester (grade PETG 6763 from Eastman Chemical, USA). Then the tablet was solid-phase polymerized in vacuo to ХВ 0.66, then it was dried in air, cast under pressure into 27-gram blanks and blown into 500 ml bottles. Hunter bottle haze measured through the side wall was 13.3 percent.

2. The second series was carried out similarly to 3B 1. The difference was that the core contained 0.35 weight percent of PMDA and polyamide, and another polyester was adjusted accordingly. These tablets were solid-phase polymerized to HV 0.79, then dried in air, pressure-molded into 27 gram billets and blown into 500 ml bottles. Hunter bottle haze measured through the side wall was 10.7 percent.

Example 4. Polyester sheath and core of polyamide and polyester

In example 4A, control sectional tablets were made by encapsulating the polyethylene terephthalate copolymer of Example 1B, which was 95 percent by weight of the tablet, and into the MXD6 core (grade 6007, Mitsubishi Gas Chemical, Japan), which was 5 percent by weight of the tablet.

In Example 4B, copolyethylene terephthalate, constituting 90 percent by weight of the tablet, was placed in a shell and the core contained MXD6 (grade 6007, Mitsubishi Gas Chemical, Japan), 5 percent by weight of the tablet mixed with a polyethylene terephthalate copolymer (5 percent by weight of the tablet) . The ratio of PET in the core to MXD6 in the core was 1: 1.

In Example 4C, copolyethylene terephthalate, 85% by weight of the tablet, was placed in the shell, and the core contained MXD6 (5% by weight of the tablet) (grade 6007, Mitsubishi Gas Chemical, Japan) mixed with a polyethylene terephthalate copolymer of 10% by weight of the tablet. The ratio of PET in the core to MXD6 in the core was 3: 1.

Examples 4A, 4B and 4C were heat treated for 12 hours in rotary vacuum mixers at 230 ° C and a pressure of <1 mm Hg. The resins were then dried in air at 300 ° F for about 17 hours, cast into 27 gram billets and blown into 0.5 L bottles. The data in table III show only slight color deterioration.

Table III
Workpiece color measurement Structure Harvesting, L * Harvesting, a * Procurement b * 0.5 L bottle, b * 4A 95% sheath: PET, 5% core: ratio MXD6: PET = 1: 0 38.5 -0.9 -0.53 6.13 4B 90% sheath: PET, 10% core: MXD6 ratio: PET = 1: 1 39.1 -1.16 -1.16 13.5 4C 85% sheath: PET, 15% core: ratio 5% MXD6: PET = 1: 2 43.9 -0.86 4.84 13.63

Example 5. Oxygen-Active Components Separated by Section

This series of experiments demonstrates the effectiveness of the oxygen promoter content separately from the oxygen sensitive component.

In Example 5A (control), sectioned tablets were made by encapsulating the copolyethylene terephthalate (oxygen inert component) of Example 1B, which was 95 percent by weight of the tablet, and MXD6 (grade 6007, Mitsubishi Gas Chemical, Japan), which was 5 percent by tablet mass.

In Example 5B (comparative example), the tablet of the comparative example was made by uniformly distributing a polyethylene terephthalate copolymer (about 95 percent by weight of the tablet), MXD6 (grade 6007, Mitsubishi Gas Chemical, Japan), which was about 5% by weight of the tablet, and cobalt neodecanoate (Shepherd Chemical, 20.5%), 125 ppm. Specific gravities were: 5396 grams - a copolymer of ethylene terephthalate (an oxygen inert component), 284 grams - MXD6 (an oxygen sensitive component) and 0.71 grams - ground cobalt neodecanoate tablets (promoter).

In Example 5C (working example), sectioned tablets were made by encapsulating the copolyethylene terephthalate of Example 1B (approximately 95 percent by weight of the tablet) and ground cobalt neodecanoate tablets (125 parts per million parts by weight of the tablet), and MXD6 (grade 6007, Mitsubishi) in the core Gas Chemical, Japan), approximately 5 percent by weight of the tablet.

In Example 5D (confirmatory example), the sectioned tablets of Example 5C were pelletized repeatedly to mix the core and shell together.

All tablets were made the same size and then analyzed for oxygen uptake at room temperature, placing approximately 4 grams of tablets in a gas chromatographic ampoule, sealing the ampoule and analyzing the amount of oxygen absorbed. Each ampoule was analyzed only once. Seven-day absorption results are shown in Table IV.

The experiment is very variable at low levels of oxygen uptake. Many polymers, in particular immediately after tabletting, show a low oxygen activity when measured, which does not increase with time. For example, in Example 5A, the system is non-reactive (no cobalt) and the one-day sample shows a total of 0.0104 cm ³ , while the seven-day sample shows 0.0009 cm ^{3 of} reacted oxygen. The lack of activity to oxygen in the example according to the invention (5C) is indicated by the low activity after one day, which is close to the activity of the control example, and the absence of an increase in oxygen absorption from the first day to the seventh. A confirmatory example shows a similar low activity on the first day, but a marked increase in oxygen uptake after seven days, which indicates that the materials became active when combined into a homogeneous dispersion.

Table IV
Oxygen absorption structure Structure reacted O ₂ cm ³ per gram of tablets after 1 day reacted O ₂ cm ³ per gram of tablets after 7 days 5A - control Shell: 95% PET
Core: 5% MXD6 0.0104 0,0009 5B - comparative example homogeneous dispersion:
95% PET, 5% MXD6, 125 ppm Co neodecanoate 0.0210 5C - working example Shell: 95% PET, 125 ppm Co neodecanoate
Core: 5% MXD6 0.0113 0.0130 5D - confirmatory example (re-pelletized 5C) re-pelletized 5C homogeneous dispersion 95% PET, 5% MXD6, 125 ppm Co neodecanoate 0.0114 0,0346

Claims (178)

1. A polymer tablet containing an oxygen sensitive component, an oxygen inert component and a reaction promoter, wherein the oxygen sensitive component is in the first sectioned zone and the oxygen inert component is in the second sectioned zone, wherein said oxygen sensitive component becomes active towards oxygen in the presence of a promoter, said promoter being any compound that initiates or accelerates the reaction of an oxygen sensitive component with oxygen the house, and the specified oxygen inert component when placed in contact with the promoter detects an increase in oxygen consumption by no more than 10% compared with the case when it is without a promoter, and the number of promoter in direct contact with the oxygen sensitive component is not enough to substantially initiate or catalyze a reaction with oxygen. 2. The polymer tablet according to claim 1, where the oxygen inert component contains a thermoplastic polyester. 3. The polymer tablet according to claim 2, where the second sectioned area is a shell, and the first sectioned area is the core. 4. The polymer tablet according to claim 3, where the core is enclosed in a shell. 5. The polymer tablet according to claim 2, where the oxygen-sensitive component contains an oxidizable organic compound. 6. The polymer tablet according to claim 5, where the reaction promoter is a transition metal. 7. The polymer tablet according to claim 6, where the transition metal is in the form of a salt of a transition metal and / or oxide of a transition metal. 8. The polymer tablet according to claim 6, where the transition metal is selected from the group consisting of cobalt, iron, manganese and nickel. 9. The polymer tablet according to claim 6, where the transition metal is cobalt. 10. The polymer tablet of claim 5, wherein the oxygen sensitive component comprises at least one compound selected from the group consisting of polybutadiene, functionalized polybutadiene, non-hydrogenated polybutadiene oligomers, propylene oxide oligomers and aromatic compounds with a methyl side group. 11. The polymer tablet of claim 10, where the second sectioned area is a shell, and the first sectioned area is the core. 12. The polymer tablet according to claim 11, where the core is enclosed in a shell. 13. The polymer tablet of claim 11, wherein the reaction promoter is a transition metal. 14. The polymer tablet of claim 13, wherein the transition metal is in the form of a transition metal salt and / or transition metal oxide. 15. The polymer tablet of claim 13, wherein the transition metal is selected from the group consisting of cobalt, iron, manganese, and nickel. 16. The polymer tablet of claim 13, wherein the transition metal is cobalt. 17. The polymer tablet according to claim 5, where the oxygen-sensitive component contains at least one compound selected from the group consisting of polybutadiene and functionalized polybutadiene. 18. The polymer tablet of claim 17, wherein the second sectioned zone is a shell and the first sectioned zone is a core. 19. The polymer tablet of claim 18, wherein the core is encapsulated. 20. The polymer tablet of claim 17, wherein the reaction promoter is a transition metal. 21. The polymer tablet of claim 20, wherein the transition metal is in the form of a transition metal salt and / or transition metal oxide. 22. The polymer tablet according to claim 20, where the transition metal is selected from the group consisting of cobalt, iron, manganese and nickel. 23. The polymer tablet of claim 20, wherein the transition metal is cobalt. 24. The polymer tablet of claim 5, wherein the oxidizable organic component comprises polyamide, which is a homocondensation product of aminocaproic acid and / or a reaction product of a dicarboxylic acid residue such as adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, resorcyndicarboxylic acid or naphthalenedicarboxylic acid, or a mixture thereof, with a residue of a diamine such as m-xylylenediamine, p-xylylenediamine, hexamethylene diamine, ethylenediamine or 1,4-cyclohexanedimethylamine, or a mixture . 25. The polymer tablet according to paragraph 24, where the reaction promoter is a transition metal. 26. The polymer tablet of claim 25, wherein the transition metal is in the form of a transition metal salt and / or transition metal oxide. 27. The polymer tablet of claim 25, wherein the transition metal is selected from the group consisting of cobalt, iron, manganese, and nickel. 28. The polymer tablet of claim 25, wherein the transition metal is cobalt. 29. The polymer tablet of claim 25, wherein the oxidizable organic component is MXD-6 nylon. 30. The polymer tablet according to clause 29, where the second sectioned area is a shell, and the first sectioned area is the core. 31. The polymer tablet of claim 30, wherein the core is encapsulated. 32. The polymer tablet according to clause 29, where the reaction promoter is a transition metal. 33. The polymer tablet of claim 32, wherein the transition metal is in the form of a transition metal salt and / or transition metal oxide. 34. The polymer tablet of claim 32, wherein the transition metal is selected from the group consisting of cobalt, iron, manganese, and nickel. 35. The polymer tablet of claim 32, wherein the transition metal is cobalt. 36. The polymer tablet of claim 2, wherein the thermoplastic polyester is polyethylene terephthalate or copolyethylene terephthalate. 37. The polymer tablet according to clause 36, where the second sectioned area is the shell, and the first sectioned area is the core. 38. The polymer tablet according to clause 37, where the core is enclosed in a shell. 39. The polymer tablet according to clause 36, where the reaction promoter is a transition metal. 40. The polymer tablet according to § 39, where the transition metal is in the form of a salt of a transition metal and / or oxide of a transition metal. 41. The polymer tablet of claim 39, wherein the transition metal is selected from the group consisting of cobalt, iron, manganese, and nickel. 42. The polymer tablet according to § 39, where the transition metal is cobalt. 43. The polymer tablet according to clause 36, where the oxygen-sensitive component contains an oxidizable organic compound. 44. The polymer tablet according to item 43, where the reaction promoter is a transition metal. 45. The polymer tablet according to item 44, where the transition metal is in the form of a salt of a transition metal and / or oxide of a transition metal. 46. The polymer tablet according to item 44, where the transition metal is selected from the group consisting of cobalt, iron, manganese and nickel. 47. The polymer tablet according to item 44, where the transition metal is cobalt. 48. The polymer tablet according to clause 36, where the oxygen-sensitive component contains at least one compound selected from the group consisting of polybutadiene, functionalized polybutadiene, non-hydrogenated polybutadiene oligomers, propylene oxide oligomers and aromatic compounds with a methyl side group. 49. The polymer tablet of claim 48, wherein the second sectioned zone is a shell and the first sectioned zone is a core. 50. The polymer tablet according to § 49, where the core is enclosed in a shell. 51. The polymer tablet of claim 48, wherein the reaction promoter is a transition metal. 52. The polymer tablet of claim 51, wherein the transition metal is in the form of a transition metal salt and / or transition metal oxide. 53. The polymer tablet of claim 51, wherein the transition metal is selected from the group consisting of cobalt, iron, manganese, and nickel. 54. The polymer tablet of claim 51, wherein the transition metal is cobalt. 55. The polymer tablet according to clause 36, where the oxygen-sensitive component contains at least one compound selected from the group consisting of polybutadiene and functionalized polybutadiene. 56. The polymer tablet of claim 55, wherein the second sectioned zone is a shell and the first sectioned zone is a core. 57. The polymer tablet of claim 56, wherein the core is encapsulated. 58. The polymer tablet of claim 55, wherein the reaction promoter is a transition metal. 59. The polymer tablet of claim 58, wherein the transition metal is in the form of a transition metal salt and / or transition metal oxide. 60. The polymer tablet of claim 58, wherein the transition metal is selected from the group consisting of cobalt, iron, manganese, and nickel. 61. The polymer tablet of claim 58, wherein the transition metal is cobalt. 62. The polymer tablet according to clause 36, where the oxygen-sensitive component contains polyamide, which is a homocondensation product of aminocaproic acid and / or the reaction product of a dicarboxylic acid residue such as adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, resorcyndicarboxylic acid or naphthalenedicarboxylic acid, or a mixture thereof, with a diamine residue such as m-xylylenediamine, p-xylylenediamine, hexamethylenediamine, ethylenediamine or 1,4-cyclohexanedimethylamine, or see yeah. 63. The polymer tablet of claim 62, wherein the reaction promoter is a transition metal. 64. The polymer tablet of claim 63, wherein the transition metal is in the form of a transition metal salt and / or transition metal oxide. 65. The polymer tablet of claim 63, wherein the transition metal is selected from the group consisting of cobalt, iron, manganese, and nickel. 66. The polymer tablet of claim 63, wherein the transition metal is cobalt. 67. The polymer tablet of claim 36, wherein the oxygen sensitive component is MXD-6 nylon. 68. The polymer tablet of claim 67, wherein the second sectioned zone is a shell and the first sectioned zone is a core. 69. The polymer tablet of claim 68, wherein the core is encapsulated. 70. The polymer tablet of claim 67, wherein the reaction promoter is a transition metal. 71. The polymer tablet of claim 70, wherein the transition metal is in the form of a transition metal salt and / or transition metal oxide. 72. The polymer tablet of claim 70, wherein the transition metal is selected from the group consisting of cobalt, iron, manganese, and nickel. 73. The polymer tablet of claim 70, wherein the transition metal is cobalt. 74. The polymer tablet of claim 36, wherein the oxygen-sensitive component is a reaction product of predominantly polycondensate segments consisting of one or more phthalates selected from the group consisting of terephthalate, orthophthalate and isophthalate, wherein said polycondensate further comprises one or more glycols selected from the group consisting of alpha-hydro-omega-hydroxy-polyoxytetramethylene, 1,4-butanediol, polyethylene glycol and ethylene glycol, and polyamides with a small number of segments sensitive to oxygen to a component selected from the group consisting of functionalized polybutadiene, non-hydrogenated polybutadiene oligomers, propylene oxide oligomers and aromatic compounds with a methyl side group. 75. The polymer tablet of claim 67, wherein the second sectioned zone is a shell and the first sectioned zone is a core. 76. The polymer tablet of claim 68, wherein the core is encapsulated. 77. The polymer tablet of claim 67, wherein the reaction promoter is a transition metal. 78. The polymer tablet of claim 70, wherein the transition metal is in the form of a transition metal salt and / or transition metal oxide. 79. The polymer tablet of claim 70, wherein the transition metal is cobalt. 80. A polymer tablet containing the first component and the second component, where the first component during heat treatment releases a by-product that is able to react with the second component and / or with the by-product released by the second component, where the first component is in the first sectioned area and the second component located in the second sectioned zone, where the specified heat treatment occurs at a temperature above 70 ° C and less than the temperature at which the tablet melts. 81. The polymer tablet of claim 80, wherein the tablet consists of a core and a shell, where the shell consists of a first component and the core consists of a second component. 82. The polymer tablet of claim 81, wherein the second component is enclosed in a first component. 83. The polymer tablet of claim 80, which consists of a first sectioned zone and a second sectioned zone, where the first sectioned zone consists of thermoplastic polyester, the second sectioned zone consists of polyamide, where the first sectioned zone is at least 0.1% of the total the volume of the polymer tablet, and the second sectioned area is at least 0.1% of the total volume of the polymer tablet. 84. The polymer tablet of claim 83, wherein the second sectioned zone has a core shape and the first sectioned zone has a shell shape. 85. The polymer tablet of claim 84, wherein the second sectioned area is enclosed in a first sectioned area. 86. The polymer tablet of claim 83, further comprising a third sectioned zone, which consists of a thermoplastic polyester, wherein the second sectioned zone is between the first and third sectioned zones. 87. The polymer tablet of claim 83, wherein the thermoplastic polyester is a polyneopentyl glycol terephthalate. 88. The polymer tablet of claim 87, wherein the tablet further includes a third sectioned zone that comprises a second thermoplastic polyester. 89. The polymer tablet of claim 86, wherein the polyamide is a homocondensation product of aminocaproic acid and / or a reaction product of a dicarboxylic acid residue such as adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, resorcyndicarboxylic acid or naphthalenedicarboxylic acid, or a mixture thereof, with a residue of a diamine such as m-xylylenediamine, p-xylylenediamine, hexamethylenediamine, ethylenediamine or 1,4-cyclohexanedimethylamine, or a mixture thereof. 90. The polymer tablet of claim 89, wherein the polyamide is MXD-6 nylon. 91. The polymer tablet of claim 83, wherein the thermoplastic polyester is polyethylene terephthalate or copolyethylene terephthalate. 92. The polymer tablet of claim 84, wherein the polyamide is MXD-6 nylon and the thermoplastic polyester is polyethylene terephthalate or copolyethylene terephthalate. 93. The polymer tablet of claim 85, wherein the polyamide is MXD-6 nylon and the thermoplastic polyester is polyethylene terephthalate or copolyethylene terephthalate. 94. The polymer tablet of claim 92, wherein the intrinsic viscosity of the polyethylene terephthalate or copolyethylene terephthalate is at least 0.49 dl / g. 95. The polymer tablet of claim 93, wherein the intrinsic viscosity of the polyethylene terephthalate or copolyethylene terephthalate is at least 0.49 dl / g. 96. The polymer tablet of claim 92, wherein the intrinsic viscosity of the polyethylene terephthalate or copolyethylene terephthalate is at least 0.59 dl / g. 97. The polymer tablet of claim 93, wherein the intrinsic viscosity of the polyethylene terephthalate or copolyethylene terephthalate is at least 0.59 dl / g. 98. The polymer tablet of claim 92, wherein the core further comprises a thermoplastic polyester. 99. The polymer tablet of claim 98, wherein the thermoplastic polyester is present in the core as a continuous phase. 100. The polymer tablet according to item 93, where the core contains, in addition, a thermoplastic polyester. 101. The polymer tablet of claim 100, wherein the thermoplastic polyester is present in the core as a continuous phase. 102. The polymer tablet of claim 98, wherein the thermoplastic polyester present in the core includes a recycled thermoplastic polyester. 103. The polymer tablet of claim 100, wherein the thermoplastic polyester present in the core includes a recycled thermoplastic polyester. 104. The polymer tablet of claim 94, wherein the tablet further comprises a compatibilizer selected from the group consisting of cyclohexanedimethanol modified polyesters and ionic compatibilizers. 105. The polymer tablet of claim 95, wherein the tablet further comprises a compatibilizer selected from the group consisting of cyclohexanedimethanol modified polyesters and ionic compatibilizers. 106. The polymer tablet of claim 96, wherein the tablet further comprises a compatibilizer selected from the group consisting of cyclohexanedimethanol modified polyesters and ionic compatibilizers. 107. The polymer tablet of claim 104, wherein the second sectioned zone has a core shape and the first sectioned zone has a shell shape. 108. The polymer tablet of claim 97, wherein the tablet further comprises a compatibilizer selected from the group consisting of cyclohexanedimethanol modified polyesters and ionic compatibilizers. 109. The polymer tablet of claim 80, wherein the first component is polyethylene terephthalate or copolyethylene terephthalate and the second component reacts with or catalyzes a reaction with acetaldehyde at room temperature. 110. The tablet of claim 109, wherein the second component is selected from the group consisting of heteroatom-containing organic compounds that can react with acetaldehyde to form 5- or 6-membered rings not connected by bridges, active oxidation catalysts that catalyze the reaction of acetaldehyde with oxygen, and hydride transfer catalysts that catalyze the hydride transfer reaction between the organic donor molecule and acetaldehyde. 111. The tablet of claim 110, wherein the heteroatom-containing organic compound is selected from the group consisting of 1,8-diaminonaphthalene, 3,4-diaminobenzoic acid, anthranilamide, biuret, malonamide, allantoin, salicylamide, salicylanilide, o-phenylenediamine, 3,4-diaminobenzoic acid, 1,8-diaminonaphthalene, o-mercaptobenzamide, N-acetylglycinamide, malonamide, 3-mercapto-1,2-propanediol, 4-amino-3-hydroxybenzoic acid, disodium salt of 4,5-dihydroxy- 2,7-naphthalenedisulfonic acid, biuret, 2,3-diaminopyridine, 1,2-diaminoantraquinone, dianilinoet a, allantoin, 2-aminobenzenesulfonamide, and 2-amino-2-methyl-1,3-propanediol. 112. The tablet of claim 110, wherein the active oxidation catalyst is selected from the group consisting of cobalt salt, manganese salt, and a compound containing an amine, phosphine, or complex of an alcohol with a metal of variable valency. 113. The tablet of claim 110, wherein the hydride transfer catalyst is selected from the group consisting of aqueous zirconium oxide, aqueous niobium oxide, and aqueous tantalum oxide. 114. The tablet according to claim 91, wherein the thermoplastic polyester does not have stress induced crystallinity. 115. The tablet according to p, where the thermoplastic polyester has at least 10% crystallinity, not induced by stress. 116. The tablet according to paragraph 92, where the thermoplastic polyester does not have crystallinity induced by stress. 117. The tablet according to paragraph 92, where the thermoplastic polyester has at least 10% crystallinity, not induced by stress. 118. The tablet according to paragraph 93, where the thermoplastic polyester does not have crystallinity induced by stress. 119. The tablet according to p, where the thermoplastic polyester has at least 10% crystallinity, not induced by stress. 120. The polymer tablet of claim 92, wherein the intrinsic viscosity of the polyethylene terephthalate or copolyethylene terephthalate is at least 0.72 dl / g. 121. The polymer tablet of claim 93, wherein the intrinsic viscosity of the polyethylene terephthalate or copolyethylene terephthalate is at least 0.72 dl / g. 122. The polymer tablet of claim 120, wherein the tablet further comprises a compatibilizer selected from the group consisting of cyclohexanedimethanol modified polyesters and ionic compatibilizers. 123. The polymer tablet of Claim 121, wherein the tablet further comprises a compatibilizer selected from the group consisting of cyclohexanedimethanol modified polyesters and ionic compatibilizers. 124. A polymer tablet containing an oxygen active component and an oxygen inert component, wherein the oxygen active component is in the first sectioned zone and the oxygen inert component is in the second sectioned zone, where the oxygen active component contains the oxygen sensitive component and a promoter, and an oxygen-sensitive component becomes active to oxygen in the presence of a promoter, which is any compound that initiates or accelerates the interaction of senses Yelnia oxygen component with oxygen, wherein said first kernel is partitioned area and said second area is partitioned between the core and the outer boundary of the tablet. 125. The polymer tablet of claim 124, wherein the oxygen inert component consists of a thermoplastic polyester. 126. The polymer tablet of claim 125, wherein the second sectioned zone is a shell and the first sectioned zone is a core. 127. The polymer tablet according p, where the core is enclosed in a shell. 128. The polymer tablet of claim 125, wherein the oxygen-active component consists of an oxidizable organic compound. 129. The polymer tablet of claim 125, wherein the oxygen-sensitive component comprises at least one compound selected from the group consisting of polybutadiene, functionalized polybutadiene, non-hydrogenated polybutadiene oligomers, propylene oxide oligomers and aromatic compounds with a methyl side group. 130. The polymer tablet of claim 129, wherein the second sectioned zone is a shell and the first sectioned zone is a core. 131. The polymer tablet of claim 130, wherein the core is encapsulated. 132. The polymer tablet according p, where the oxygen-sensitive component contains at least one compound selected from the group consisting of polybutadiene and functionalized polybutadiene. 133. The polymer tablet of Claim 132, wherein the second sectioned zone is a shell and the first sectioned zone is a core. 134. The polymer tablet according to p, where the core is enclosed in a shell. 135. The polymer tablet of claim 125, wherein the oxygen-active component is a polyamide that is a homocondensation product of aminocaproic acid and / or a reaction product of a dicarboxylic acid residue such as adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, resorcyndicarboxylic acid or naphthalenedicarboxylic acid, or a mixture thereof, with a diamine residue such as m-xylylenediamine, p-xylylenediamine, hexamethylene diamine, ethylenediamine or 1,4-cyclohexanedimethylamine, or a mixture thereof. 136. The polymer tablet of Claim 135, wherein the oxygen active component is MXD6 nylon. 137. The polymer tablet according p, where the second sectioned area is a shell, and the first sectioned area is the core. 138. The polymer tablet according p, where the core is enclosed in a shell. 139. The polymer tablet of claim 125, wherein the thermoplastic polyester is polyethylene terephthalate or copolyethylene terephthalate. 140. The polymer tablet of claim 139, wherein the second sectioned zone is a shell and the first sectioned zone is a core. 141. The polymer tablet of claim 140, wherein the core is encapsulated. 142. The polymer tablet of claim 139, wherein the oxygen active component comprises an oxidizable organic compound. 143. The polymer tablet of Claim 142, wherein the oxygen-active component comprises at least one compound selected from the group consisting of polybutadiene, functionalized polybutadiene, non-hydrogenated polybutadiene oligomers, propylene oxide oligomers and aromatic compounds with a methyl side group. 144. The polymer tablet of claim 143, wherein the second sectioned area is a shell and the first sectioned area is a core. 145. The polymer tablet of claim 144, wherein the core is encapsulated. 146. The polymer tablet of claim 139, wherein the oxygen-active component is a polyamide which is a homocondensation product of aminocaproic acid and / or a reaction product of a dicarboxylic acid residue such as adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, resorcyndicarboxylic acid or naphthalenedicarboxylic acid, or a mixture thereof, with a diamine residue such as m-xylylenediamine, p-xylylenediamine, hexamethylene diamine, ethylenediamine or 1,4-cyclohexanedimethylamine, or a mixture thereof. 147. The polymer tablet of claim 146, wherein the oxygen active component is MXD-6 nylon. 148. The polymer tablet of claim 147, wherein the second sectioned area is a shell and the first sectioned area is a core. 149. The polymer tablet according to p, where the core is enclosed in a shell. 150. The polymer tablet of claim 140, wherein the oxygen-active component is a reaction product of predominantly polycondensate segments consisting of one or more phthalates selected from the group consisting of terephthalate, orthophthalate and isophthalate, wherein said polycondensate also contains one or more glycols selected from the group consisting of alpha-hydro-omega-hydroxypolyoxytetramethylene, 1,4-butanediol, polyethylene glycol and ethylene glycol, and polyamides with a small number of segments of oxygen sensitive components an agent selected from the group consisting of functionalized polybutadiene, non-hydrogenated polybutadiene oligomers, propylene oxide oligomers and aromatic compounds with a methyl side group. 151. The polymer tablet of Claim 141, wherein the oxygen-sensitive component is a reaction product of predominantly polycondensate segments consisting of one or more phthalates selected from the group consisting of terephthalate, orthophthalate and isophthalate, wherein said polycondensate also contains one or more glycols selected from the group consisting of alpha-hydro-omega-hydroxy-polyoxytetramethylene, 1,4-butanediol, polyethylene glycol and ethylene glycol, and polyamides with a small number of oxygen sensitive segments Components selected from the group consisting of functionalized polybutadiene, unhydrogenated polybutadiene oligomers, oligomers of propylene and aromatics with a lateral methyl group. 152. The method of heat treatment of a polymer tablet according to any one of the preceding paragraphs, comprising heating the polymer tablet to a temperature in the range from 40 ° C to a temperature that is at least 1 ° C lower than the temperature at which the tablet becomes liquid. 153. The method according to p, where the heat treatment includes exposing the tablet to a temperature lying in the range from 70 ° C to a temperature that is at least 5 ° C lower than the temperature at which the tablet becomes liquid. 154. The method according to p, where the polymer tablet is thermally processed in the specified temperature range for a time sufficient to increase the crystallinity of the first component or second component by at least 5%. 155. The method according to p, where the first component is the first thermoplastic resin and the second component is the second thermoplastic resin, and the tablet is thermally processed in the indicated temperature range for a sufficient time, so that the total increase in the degree of crystallinity of the first component and the second component is at least 5%. 156. The method according to p, where the polymer tablet before heat treatment contains moisture, and the polymer tablet is heat treated in the indicated temperature range for a sufficient time to remove at least half of the moisture present before the heat treatment. 157. The method of claim 155, wherein at least one of the thermoplastic resins has at least 0.2 dl / g of IV before heat treatment, and where the polymer tablet is thermally treated in the indicated temperature range for a sufficient time to increase the IV of thermoplastic a resin having at least 0.2 dl / g of at least 0.1 dl / g before heat treatment 158. The method of heat treatment according p, where the first component is a polyester selected from the group consisting of polyethylene terephthalate and crystallizable copolyethylene terephthalate. 159. The method according to p. 158, where the heat treatment includes exposing the tablet to a temperature of from 70 ° C to a temperature that is 5 ° C lower than the melting temperature of the polyester crystals. 160. The method according to p, where the polymer tablet is thermally processed in the specified temperature range for a sufficient time to increase the crystallinity of the first component or second component by at least 5%. 161. The method according to p, where the second component is the second thermoplastic resin, and the tablet is thermally processed in the indicated temperature range for a sufficient time, so that the total increase in the degree of crystallinity of the first component and the second component is at least 5%. 162. The method according to p, where the polymer tablet before the heat treatment contains moisture, and the polymer tablet is heat treated in the specified temperature range for a sufficient time to remove at least half of the moisture present before the heat treatment. 163. The method according to p, where at least one of the first or second components has at least 0.2 dl / g prior to heat treatment of IV, and where the polymer tablet is thermally processed in the indicated temperature range for a sufficient time to increase IV of a component having at least 0.2 dl / g of at least 0.1 dl / g prior to heat treatment of an IV. 164. The method according to p, where the second component is a polyamide. 165. The method according to p, where the heat treatment includes exposing the tablet to a temperature of from 70 ° C to a temperature that is 5 ° C lower than the melting point of the polyester crystals. 166. The method according to p, where the polymer tablet is thermally processed in this temperature range for a sufficient time to increase the crystallinity of the first component or second component by at least 3%. 167. The method according to p, where the polymer tablet before heat treatment contains moisture, and the polymer tablet is heat treated in the indicated temperature range for a sufficient time to remove at least half of the moisture present before the heat treatment. 168. The method according to p, where at least one of the first or second components has at least 0.2 dl / g prior to heat treatment of the IV, and where the polymer tablet is thermally processed in the indicated temperature range for a sufficient time to increase IV of a component having at least 0.2 dl / g of at least 0.1 dl / g prior to heat treatment of an IV. 169. The method according to p, where the polyamide contains a residue of a repeating unit of aminocaproic acid, and / or a repeating unit of AD, where A is a residue of a dicarboxylic acid, such as adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, resorcyndicarboxylic acid or naphthalenedicarboxylic acid, or a mixture thereof, a D is a residue of a diamine such as m-xylylenediamine, p-xylylenediamine, hexamethylenediamine, ethylenediamine or 1,4-cyclohexanedimethylamine, or a mixture thereof. 170. The method according to p, where the heat treatment includes exposing the tablet to a temperature of 70 ° C to a temperature that is 5 ° C lower than the melting temperature of the polyester crystals. 171. The method according to p, where the polymer tablet is thermally processed in the specified temperature range for a sufficient time to increase the crystallinity of the first component or second component by at least 5%. 172. The method according to p, where the polymer tablet before the heat treatment contains moisture, and the polymer tablet is heat treated in the indicated temperature range for a sufficient time to remove at least half of the moisture present before the heat treatment. 173. The method according to p, where at least one of the first or second components has at least 0.2 dl / g prior to heat treatment of IV, and where the polymer tablet is thermally processed in the indicated temperature range for a sufficient time to increase IV of a component having at least 0.2 dl / g of at least 0.1 dl / g prior to heat treatment of an IV. 174. The method according to p, where the polyamide is nylon MXD-6. 175. The method according to p. 174, where the heat treatment includes exposing the tablet to a temperature of from 70 ° C to a temperature that is 5 ° C lower than the melting point of the polyester crystals. 176. The method according to 174, where the polymer tablet is thermally processed in this temperature range for a sufficient time to increase the crystallinity of the first component or second component by at least 5%. 177. The method according to p, where the polymer tablet before heat treatment contains moisture, and the polymer tablet is heat treated in this temperature range for a sufficient time to remove at least half of the moisture present before the heat treatment. 178. The method according to clause 174, where at least one of the first or second components has at least 0.2 dl / g prior to heat treatment of IV, and where the polymer tablet is thermally processed in this temperature range for a sufficient time to increase IV of a component having at least 0.2 dl / g of at least 0.1 dl / g prior to heat treatment of an IV.

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