MXPA99002736A - Transparent oxygen-scavenging article including biaxially-oriented polyester - Google Patents

Abstract

A transparent oxygen-scavenging article for packaging oxygen-sensitive products, such as beer, juice, ketchup, etc. The oxygen-scavenging article includes a biaxially-oriented aromatic polyester polymers such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), and an oxygen-scavenging aromatic ester polymer compatible with the polyester polymer. The oxygen-scavenging polymer includes aromatic groups and alpha-hydrogen carbonyl groups of formula (I). Examples are polyesters from succinic, glutaric, adipic or suberic acid with hydroquinone, bisphenol A, styrene oxide or distyrene glycol or an aliphatic dicarboxylic acid containing copolyethylene naphthalate. Both polymers could form a copolymer, a blend or preferably different layers of the article. The oxygen-scavenging polymer may be incorporated into a barrier package at a competitive price, and provide the desired properties of transparency, thermal resistance, and pressurized strength.

Description

TRANSPARENT ARTICLE OF OXYGEN ELIMINATION THAT INCLUDES BIAXALLY ORIENTED POLYESTER Field of the Invention The present invention relates to oxygen scavenging materials and containers for retaining oxygen sensitive products, and more particularly to a transparent article incorporating an aromatic ester, oxygen scavenging polymer and a biaxially oriented polyester, the article which It is useful to protect oxygen sensitive products from deterioration.

Background of the Invention Plastic packaging has certain inherent benefits over glass and metal packaging, such as light weight, variability in package design, non-brittleness, and reduced manufacturing cost. However, plastic packaging can have greater permeability to certain gases (oxygen and carbon dioxide) and liquids (water) than glass or metal. These gases / liquids penetrate through the plastic and reduce life in REF .: 29821 shelf of the product contained therein. Several specialized plastic and layered structures have been developed to provide commercially acceptable plastic barrier containers with acceptable shelf life for certain oxygen sensitive products, such as juice and ketchup. There are two general types of oxygen barrier materials, passive and active. A "passive" barrier prevents the penetration of oxygen into the container. For example, with the multi-layer technology it is possible to incorporate thin layers of costly barrier polymers, for example, the polyvinyl chloride copolymer (PVDC) or the ethylene-vinyl alcohol copolymer (EVOH)), or thin layers of metallic films, in combination with commercially available plastic resin structural layers, for example, polyethylene terephthalate (PET). In an "active" barrier system, an oxygen "scavenger" is incorporated into an individual or multi-layered plastic structure to consume oxygen and initially present and / or generated from inside the container, as well as to prevent oxygen exceeded reach inside the container. In this way, oxygen scavengers both remove oxygen from inside the container and prevent its entry into the container. Another important parameter and design for the oxygen barrier packaging is thermal resistance. Frequently, the product must be "sterilized" in a process that exposes the container to high temperatures and / or pressures. For example, in a commercial "hot fill" process, the product (for example, juice) is at a temperature of 80-85 ° C when it is introduced into the container, the container is then sealed (lid) and let the juice / container cool. The container must withstand both the hot fill temperature and the vacuum generated in the sealed container as the product cools, without distortion. Commercially successful hot fill containers have been developed by Continental PET Technolgies, Inc. of Boedford, New Hampshire, which provides a 1.5 to 4 fold improvement in the oxygen barrier property over a single layer PET container, commercial, normal. These multi-layer juice containers include two thin, intermediate barrier layers of EVOH placed between the inner and outer virgin PET layers, and a core or core PET layer either virgin or recycled. However, there are products that are even more "oxygen sensitive" than juice. For example, most beers require at least 10 times greater oxygen barrier protection than what is provided with a PET, single-layer, commercial, normal container. In addition, most beer is packaged in a "wet pasteurization" process in which beer is introduced into the container at a temperature of about -1 to 7 ° C, the container is sealed, and the sealed container is then immerse in a 60-75 ° C bath for at least 10 minutes (see Figure 12). This pasteurization process can be considered even more degrading than hot filling since the container is exposed to an elevated temperature for a much longer period of time. As well, the beer is carbonated and in this way the sealed container must retain a pressurized liquid during this prolonged, high temperature emission. Both the increased temperature and the pressure produce an expansion pulse in the side walls of the container, forces that can delaminate the layers in a multi-layer container. Yet another problem that must be overcome for the packaging of beer in plastic containers is the penetration of carbon dioxide (C02). To maintain shelf life, the container must provide a C02 barrier that minimizes the amount of C02 left by the beer during the designated shelf time. Beer bottling companies currently have millions of dollars in research in wet pasteurization equipment and therefore it is doubtful that they will adopt a new packaging unless they can withstand this process. A PET container, single-layer, commercial, normal can not survive the wet pasteurization process, nor provide the necessary barrier properties. The known multilayer PET / EVOH containers also can not provide the necessary barrier properties for beer, at a competitive price. Attempts have been made to provide an individual or multilayer container including polyethylene naphthalate (PEN), a polyethylene terephthalate-like polyester (PET), but having a substantially increased oxygen barrier property and increased thermal resistance. However, the cost of PEN is significantly higher than PET, which is not an effective cost alternative that has not yet found widespread acceptance. Additionally, the materials used must be approved by the government authorities, for example, the North American Administration of Elements and Drugs for the packaging of food products. All of these factors, coupled with the greater expansion (of raw materials and processing cost) of the known oxygen scavenging polymers, have impeded the commercial acceptance of a plastic barrier packaging for beer. Thus, despite a long-recognized and large-scale need for the potential market, there is a growing need for improvements in plastic barrier packaging that can withstand the severe thermal, pressure and gas permeability requirements for a container plastic for beer.

Brief Description of the Invention The present invention is directed to a transparent oxygen scavenging article, which includes a biaxially oriented aromatic polyester polymer and an aromatic ester removing polymer. The elimination polymer has alpha-hydrogen-carbonyl groups: O I -O-C-ÍCHAr where n = 2 or more, which provides a function of oxygen removal. The relative weight percentages of the fa-hydrogen carbonyl groups and the aromatic groups are selected to provide a desirable rate of oxygen removal and a TG that allows biaxial orientation of the polyester polymer without substantial loss of transparency. Aromatic groups provide individual or multiple aromatic rings in the structure or side chain of the elimination polymer, preferably including a structure: and in the side chain The article may be a film or package, or a portion thereof; examples include an elongated film in the transverse directions and a blow molded container that has been subjected to axial and radial expansion. The article can be an individual layer or multiple layers. The removing polymer can be provided in a separate layer of the polyester, or it can be mixed with or copolymerized with the polyester. The object of the present invention is to provide an orientation polymer that is compatible with aromatic polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), such that the polyester can be biaxially oriented without loss of transparency. The transparency can be defined as the percent of light mist transmitted through the article wall or film thickness, Hr (as defined below), measured according to ASTM method D 1003 using a difference meter of color, normal. The article preferably has a percent haze of less than 10 percent, and more preferably less than 5 percent. The process compatibility of the polyester removal polymer is indicated by the glass transition temperatures (Tg) of the two polymers, so that either a separate mixture, copolymer or layer of the polymers can be processed in the same temperature range without the loss of transparency, that is, prior to a temperature below Tg and elongate in transverse directions to biaxially orient the polyester. Preferably, the average biaxial elongation ratio is from 9: 1 to 15: 1. The Tg of the scavenging polymer can be adjusted by varying the percentage of the aromatic groups in the polymer, with increasing amounts of aromaticity increasing TG. In general, the TG of a polymer used in a commercial plastic container must be at least 5 percent above ambient use temperature, for example, if a bottle of carbonated beverage will be used in an environment where the temperature can reach 35 ° C, the polymer must have a TG of at least 40 ° C or the polymer can melt (not be a solid article). The TG also determines the temperature above which an aromatic polyester must be heated to allow biaxial elongation, which orients and partially crystallizes the polymer to provide structural strength. For example, PET has a TG of about 70 ° C, and PEN has a TG of about 120 ° C; for ease of processing, the polymers typically stretch in a range of orientation temperature of at least 20 ° C above TG (eg, at least 90 ° C for PET, at least 140 ° C for PEN, and vary with the polymer content). It is desirable for the elimination polymer to have a TG below the orientation temperature of the polyester to be biaxially oriented (eg, PET or PEN), but not too low that the scavenging polymer crystallizes (becomes). not transparent or opaque) during the orientation process. The TG of the elimination polymer must be at least 10 ° C below the orientation temperature used to biaxially orient the polyester. A preferred range of TG for a scavenging polymer having an amorphous nature (i.e., does not crystallize more than 3% under any condition), is 0-15 ° C below the TG of the polyester, more preferably 3-7 ° C below, and most preferably about 5 ° C below . A preferred range of TG for a scalable polymer removal polymer is 0-15 ° C above the TG of the polyester, preferably 3-7 ° C above, and more preferably above 5 ° C. In this way, in order to maintain a solid article under conditions of commercial use, generally accepted, the elimination polymer must have a TG of at least 40 ° C, preferably at least 48 ° C, and more preferably in the range of 70-135 ° C. For ease of processing with PET polymers, the elimination polymer preferably has a TG of 70-85 ° C, and for ease of processing with PEN polymers a TG of 120-125 ° C. For amorphous scavengers, a TG less than 90-100 ° C for use with PEN polymers is acceptable. In general, the relative molar or weight percentages of the various groups in the elimination polymer are selected to optimize the desired elimination and compatibility characteristics. In this way, increasing the groups to the fa-hydrogen-carbonyl will increase the rate of oxygen removal. The ester (CO) groups provide compatibility with the polyester. Increasing the aromatic groups increases the TG. The increase in the length of the aliphatic chain (adjacent to the carboxy group) can increase the oxygen scavenging capacity (elimination performance over shelf life of the container) as described below. While not wishing to be limited to any theoretical explanation, it is believed that the oxygen scavenging properties of these polymers result from the presence of carbonyl groups that provide non-uniformity, such as kinking, in the molecular support structure at or near the location of the carbonyl group. It is believed that this non-uniformity decreases the chemical stability of the hydrogen atoms attached to the alpha atoms to the carbonyl carbon. As a result, these hydrogen atoms have a significantly reduced binding strength which is then much more readily disassociated by diatomic gaseous oxygen, and thus has a relatively high propensity to react with oxygen, resulting in the oxygen scavenging property. This is in contrast to the known oxygen reagent materials that use carbon-carbon double bonds (unsaturation) in the polymer structure to provide oxygen reactivity. As a result, the oxygen scavenging polymers of the present invention need not include any of the two carbon-carbon endings of the structure to achieve elimination. The aliphatic chain (eg, (CH2) n adjacent to the carbonyl carbon is believed to provide continuation sites (cascade) for oxygen consumption, as illustrated in the steps of Figures 13A-13K.

In Figure 13A, it was started with an ester group having an aliphatic chain of 2 carbon atoms attached to the carbonyl, and an oxygen molecule (0 = 0) was approached (to be consumed). In Figure 13B, the oxygen molecule has released an alpha-hydrogen to form a radical on the alpha-carbon and radicalize the oxygen molecule as: "0-OH." In Figure 13C, the alpha-carbon radical is satisfied , at least temporarily, by the union of the radical "0-0-H. An additional oxygen molecule is added to the reaction and is eventually consumed. In Figure 13D, the free oxygen molecule releases a second alpha-hydrogen, producing a new radical in the first alpha-carbon and again forming a free radical "OOH." In Figure 13E, three reactions occur simultaneously: 1. The H in the free radical -OOH combines with the 0-0-H at the end of the bound OOH to the alpha-carbon, to produce water (recycled in Figure 2. When the water is produced, the previous free radical OOH becomes simple oxygen 0 = 0. 3. The radical in the alpha-carbon changes to the oxygen atom bound to form a double bond (shown by arrow.) In Figure 13F, stable end reactants are shown. carbonyl is in the position of the previous alpha-hydrogen, a water molecule is formed, and now an oxygen molecule is free, in Figure 13G, either the free oxygen molecule or 0 = 0, or any other oxygen molecule available, releases an alpha-hydrogen from the recently f Ormado carbon-carbon (second), producing a radical in the second alpha-carbon and a radicalized oxygen molecule, free "0-0-H. In Figure 13H, the radicalized oxygen molecule '0-0-H binds itself to the second alpha-carbon by temporarily satisfying the radicals. Another molecule of oxygen that is going to be consumed is added. The water molecule that results from the previous steps that is not included for any longer in any reactivity.

In Figure 131, the newly arrived 0-0-H oxygen molecule releases the remaining alpha-hydrogen to produce a "0-0-H radicalized, free and forms a radical in the second alpha-carbon." In Figure 13J , again there is a reaction of several steps, similar to that shown in Figure 13E, where the 0-0-H of 0-0-H joined to the second alpha-carbon, releases hydrogen from the free radical "0-0-H to produce water. This again produces an oxygen molecule, or 0 = 0. The remaining radical of the second alpha-carbon is moved to the remaining bound oxygen atom to form a double bond to oxygen. Figure 13K, the final form of the molecular structure is shown with all alpha-hydrogens released to produce water, and all alpha-carbons become carbonyl. Also shown is the de-radicalized oxygen molecule, recently coming from the radical "0-0-H." This illustrates the continuous elimination (cascade) function of the aliphatic chain, where the longer the chain the higher the number It is understood that this extends to the elimination potential over time, that is, extends shelf life of the container.

The compatibility of the scavenging polymer and the polyester is generally indicated by a substantial correspondence of the solubility parameters. For example, the Van Krevelen solubility parameters (as hereinafter defined herein) for the scavenging polymer and the polyester are preferably within 3 units and more preferably within 1 unit. The solubility map improves the mixing and addition of the polymers. The compatibility of the scavenging polymer and the polyester can be further indicated by the crystallization rate, with the crystallization rate of the scavenging polymer less than or equal to that of the polyester. This provides process compatibility to improve the biaxial orientation of PET, in either a mixture, copolymer or a separate layer, without loss of transparency. The aromatic ester removing polymer may be a homopolymer, a random copolymer, an alternating copolymer, a block copolymer. The elimination polymer should include alpha-hydrogen groups of a carbonyl to provide the functionality of oxygen scavenging, and aromatic and ester groups for compatibility with the polyester. The polymer may include other functional groups, so long as compatibility with the polyester is maintained. For example, an elimination homopolymer, preferred has the repeat unit, individual exposed subsequently referred to as REVPET: The repeating unit REVPET has the same amount of aromaticity (an individual ring of structure) and n number of ester groups (two) as PET and the same 2-carbon (ethyl) group in the structure. An exact match of the solubility parameter is provided. An alternative homopolymer has the individual repeat unit defined later, it is referred to as a modified REVPET: o o lí p I The modified REVPET has a very close correspondence to the solubility parameter. There is an extra carbon atom in the aliphatic carbon chain that reduces TG. Depending on the application, it may be desirable to form a copolymer (for example, by adding additional groups that modify the TG or the rate of crystallization). Various other elimination polymers are described in the detailed description. A preferred, clear, oxygen scavenging article is a multilayer container, such as a blow molded container, having one or more layers of a biaxially oriented PET polymer and one or more layers of a removal polymer such as REVPET. The thickness of the REVPET layer (s) can vary from relatively thin (eg, about 2% by weight of the container) to relatively thick (eg, about 40% by weight of the container). In one embodiment, a condensation, scavenging, aromatic ester polymer can be prepared from an aliphatic dicarboxylic acid having the formula: ## STR4 ## HO-C- ^ CH ^ -C-OH wherein n = 2 or more, and preferably 2-10, or an acid derivative (e.g., dimethyl ester, acid chlorides, acid anhydrides, diacyl chlorides), to provide the alpha-hydrogen-carbonyl groups. The aliphatic dicarboxylic acid (or derivatives) is reacted with one or more aromatic glycols or diacetates, which has the general formula: 0 0 1 1 I C-C ~ 0- < CH2) n ~ R'-fCI r-C) - c- H-O- (CHa) m-R CHJn-O-H where n and m are the same or different integers from 0 to 6, and R1 and R1 'are the same or different side chain, or structure, aromatic groups, previously described (see pages 4-5, of the English text) . These glycols and diacetates provide the aromatic rings and adjacent oxygens. The structure oxygen in the ester group of the aromatic ester polymer). Preferably, the molar ratio of aromatic groups of ester groups: alpha-hydrogen-carbonyl groups is 1: 2: 2 for polycondensation homopolymers. The copolymers often have different relationship to optimize the TG of the elimination polymer. It is expected that cobalt will improve the rate of removal of oxygen from the elimination polymers of the aromatic ester of this invention. Preferably, 50-500 microns of cobalt per gram of elimination polymer is added. Preferably, cobalt is added in the form of cobalt neodecanoate or cobalt acetate. Alternative intensifiers include magnesium and manganese acetates. These and other features of the present invention will be described more apparently in the following detailed description and drawings.

Brief Description of the Figures Figures 1A-1K show methods for making various polymers including a two step method of the prior art for preparing PET (Figure 1A), and in Figures 1B-1K methods for making various oxygen scavenging polymers useful in the present invention; Figure 2 is a vertical cross section of a multilayer preform useful in the manufacture of a beverage container according to an embodiment of the present invention; Figure 3 is a side elevation view of a multilayer pressurized container made from the preform of Figure 2; Figure 4 is a horizontal cross-section taken along line 4-4 of Figure 3, showing the side wall of several layers of the container; Figure 5 is a vertical cross section of a blow molding apparatus for making the container of Figure 3; Figure 6 is a vertical cross-section taken along line 6-6 of Figure 3, showing one foot of the base of the container; Figure 7A is a fragmentary, enlarged, cross-section of a crystallized neck top and cap, according to one embodiment; Figure 7B is a fragmentary, enlarged cross-section of an amorphous neck finish and lid, according to another embodiment; Figures 8A and 8B are elevation, side views of a roadway preform and the resulting vessel according to another embodiment of the present invention; Figure 9 is a sectional, schematic view through a preform for making a can according to an alternative embodiment; Figure 10 is a sectional, schematic view of an intermediate article made from the preform of Figure 9, which includes as a lower portion a can that is biaxially oriented through the finish, and an upper portion that is removed and discarded; Figure 11 is a sectional view, schematic through a preform according to another embodiment having a particular insert of neck and portions forming the base and the body, of several layers; Y Figure 12 is a graph illustrating changes in internal temperature in the pressure during a typical pasteurization cycle, for an 11-ounce glass container, of the prior art filled with a 2.5 volume carbonated juice product; Figures 13A-13K are a series of steps showing the oxygen consumption by the aliphatic chain of the alpha-hydrogen-carbonyl group.

Detailed description The present invention relates to aromatic ester elimination polymers, which have alpha-hydrogen-carbonyl oxygen scavenging groups, which can be mixed or copolymerized (includes transesterification) with an aromatic ester polymer, or used in a layer structure with the polyester polymer, to form a transparent article for the storage of oxygen sensitive products. In a main embodiment, described herein, the elimination polymer is used for the injection molding of substantially transparent preforms, the blow molding of these preforms to form substantially transparent containers for beer, juice, ketchup and other oxygen-sensitive products. . The particular materials, wall thicknesses, layer structure and container design will depend on the particular application of the product and the conditions of filling, sterilization and use, but the common goal is to provide an active barrier protection in an effective cost manner. for use with commercially available aromatic polyester resins (eg, PET and PEN), such that the final container provides substantial transparency, is light in weight and has a structural integrity required for a commercially acceptable polyester container. In the present invention, the aromatic ester oxygen scavenging polymer must have chemical and physical properties that allow substantially transparent preforms and packaging structures to be formed, either partially or completely therefrom. For example, apart from its oxygen removal potential during use, the elimination polymer must be substantially chemically inert under the conditions used to make preforms and packaging structures, and under the unfilled conditions of these preforms and packaging structures. For example, it may be desirable that the end groups of the polymer have reduced chemical reactivity. Preferably, the oxygen scavenging polymer should not substantially adversely affect the transparency, melting temperature, viscosity or other processing parameters of the polymer composition. In addition, in selected embodiments, the oxygen scavenging polyester must be chemically inert substantially in the direction of elements and / or beverages proposed to be stored within the packaging structure. By way of introduction, some well-known principles of PET manufacturing will be described first. A diacid may be condensed with a glycol, or a self-condensed hydroxy acid, in order to form a linear polyester such as PET. Figure IA (taken from K. Wissermal and HJ Arpe, Industrial Organic Chemistry, Section 14.4, Applications of Terephthalic Acid and Dimethyl Terephthalate, Verlag Chemical Press, pages 349-351 (1978)), describes a two-step process for manufacturing of PET. In a first step, dimethyl terephthalate (DMT) is trans-esterified with ethylene glycol with a loss of CH3OH; As an alternative first step (not shown), terephthalic acid (TPA) can be esterified with ethylene glycol producing an H20 test. The first step is carried out at a temperature in the order of 100-150 ° C and a pressure of 10-70 bar, in the presence of for example, copper, cobalt or zinc acetate catalysts. The resulting intermediate is bis (2-hydroxyethyl) -terephthalate. As a second step, the intermediate product is subjected to the catalytic polycondensation to produce PET; this is typically done at a temperature of about 10-20 ° C above the melting point of PET (246 ° C), under vacuum, and usually with a catalyst, such as Sb203. During the polycondensation step, the ethylene glycol is removed, the resulting PET melt is then cooled and granulated. In Figure IA and the subsequent figures, the atoms / groups that are removed in a square with an arrow are shown, for ease of identification of the reaction sites. PET is a thermoplastic polyester, used in tension oriented form for both a packaging film and for blow molded soft drink containers. It is commercially available as either a homopolymer or more typically as a copolymer with small amounts of other monomers to improve processability or performance (e.g., thermal resistance). For example, there are well-known PET copolymers which include variable amounts, usually up to about 10% of other monomers, which are compatible with PET and do not substantially detract from the desired PET structural properties or processing parameters. They can also be used in the context of the present invention. Thus, as used herein, "PET" is used to include homopolymer and PET copolymers.

Figure IB: REVPET Figure IB illustrates a method for making an oxygen scavenging polymer referred to herein as "REVPET". The repeating unit for REVPET (shown in Figure IB) has the same numbers of carbon, oxygen and hydrogen atoms, and thus the same molecular weight, as the repeating unit for PET (shown in Figure IA). As a result, the REVPET has a high level of compatibility with PET that allows it to be mixed and / or copolymerized with PET, used in a layer structure with PET, where the PET can be oriented biaxially and remain substantially transparent. As used herein, "transparent" is intended to include substantially transparent since it is commercially acceptable to have any reduction in the transmission of light caused by crystallization or the like, in general referring to a transparent container. A definition of transparency is discussed later with respect to ASTM method D1003. The structural difference between REVPET and PET (as illustrated in Figures 1A-1B), is that in the REVPET the oxygen structure in each ester group (COO) is adjacent to the aromatic ring, and thus the CH2 group adjacent to the C of the ester group) provides a functional group of alpha-hydrogen carbonyl for the removal of oxygen. The REVPET has two alpha-hydrogen-carbonyl groups per repeating unit, which provides a relatively high degree of oxygen removal. The two ester groups, the individual aromatic ring and the two methyl groups in the structure provide a match of the solubility parameters with PET, allowing the use of mixtures, copolymers and layered structures with good addition between the layers and transparency. The Table in Appendix C, just before the claims on page 49 (from the English text), lists various properties of REVPET (and other polymers shown in Figures 1B-1K) for comparison with PET.

The properties include: TG vitrea transition temperature Tm melting temperature SOL solubility parameter (Van Krevelen, discussed below) ADEN density of amorphous polymer CDEN density of crystallized polymer PERM permeability of nitrogen of amorphous polymer AROM percentage of molecular weight of aromatic rings to the total weight of the polymer of elimination (per repetition unit); exception for biphenol A where the percentage by weight of the aromatic rings includes CH3-C-CH3 between the 2 rings CARB percentage of the molecular weight of C and O of the carbonyl group to the total weight of the elimination polymer (per repeating unit, exception for nilons where the number multiplied by 1.5 to include impact carbonyl has an adjacent NH. ALPHA percentage of molecular weight of (CH2) n in aliphatic group adjacent to the carbonyl carbon to the total weight of the elimination polymer (per repeating unit); the exception for nylons where the number multiplied by 1.5 to include impact carbonyl has an adjacent NH.

The first column, TG, is an important parameter as discussed previously. The elimination polymer must have a TG at least 10 ° C below the orientation temperature of the polyester polymer with which it is combined (in the transparent article). The REVPET has a TG of 43 ° C, well below the typical PET orientation temperature (for example, 90 ° C and above). The second column, Tm, shows that the REVPET has a melting temperature of 214 ° C. The third column, the solubility parameter, shows that the REVPET has exactly the same solubility parameter (20.53) as the PET. The fourth and fifth columns, the densities of the amorphous and crystalline polymers, are identical for REVPET and PET. Also, it is identical to nitrogen solubility (PERM). The last three columns, AROM, CARB, and ALPHA, attempt to quantify the molecular weight percent of three functional groups in the elimination polymer that have a significant effect on performance. The AROM, the percentage by weight of the aromatic rings, has a greater effect in the TG, that is to say, the increase of the percentage of the aromaticity, in general, increases the TG. For example, the REVPET has rather a low TG in comparison to the last elimination polymers described. A higher TG will provide a higher usage temperature, and will reduce the potential for the removal polymer to crystallize (or opaque) during the orientation process. CARB, the percentage by weight of carbonyl (CO), has a greater effect on the rate of elimination, that is, the more alpha-hydrogen-carbonyl groups, the greater the rate of elimination. ALPHA, the percentage by weight of the aliphatic chain, has a large effect on the long-term potential for elimination, that is, an increase in the length of the chain increases the potential sites for elimination and thus increases life on shelf that the container can provide. The example calculations for these parameters are presented in Appendix C. The preferred ranges are: AROM: 30 to 70 CARB: 5 to 30 ALPHA: 5 to 30 The reaction indicated in Figure Ib can be implemented according to several well known processes as follows: PREPARATION OF POLY HYDROQUINONE SUCCINATE, REVPET, BY THE INTERFACE POLYCONDENSATION PROCESS (see WM Eareckson III, J. Polymer Science, 40, 399 (1959) ): To a mixer 0.05 moles of hydroquinone, and 0.1 mole of sodium hydroxide in 300 ml (milliliters) of water are added. It is also dissolved in a solution of 3.0 g (grams) of sodium lauryl sulfate in 30 ml of water. The speed is regulated so that at a low speed a second solution of 0.5 moles of succinyl chloride in 150 ml of hexane is added rapidly.

This mixture is stirred at high temperature for 10 minutes then poured into acetone. The polymer is filtered, washed with water, and dried to provide an 80% yield. Bisphenol A can be replaced by hydroquinone to make a higher TG polymer (see Figure 1J below). Other acid chlorides can be replaced by succinic acid chloride to increase the elimination potential or adjust the TG. A substitution of glutaric acid with succinic acid will give modified REVPET, described later. When an aliphatic acid is used, it may be advantageous if the pyridine is replaced by sodium hydroxide and water in the above reaction. ANOTHER METHOD OF PRREPARATION OF HYDROQUINONE SUCCINATE (REVPET) (see British Patent 636,429 by Eric R. allsgrove and franck Reeder, issued on April 26, 1950). Combine 10 parts of hydroquinone diacetate with 9.5 parts of succinic acid and O.lk parts of p-Me-C6H4S03H. They are heated at 180 ° C for 45 minutes, then 200-220 ° C for one hour, then 280 ° C for 3 hours all at atmospheric pressure, and finally at 280 ° C for (hours at 1 mm Hg while bubbling Nitrogen through the molten mixture As a further alternative, isomers of the aforementioned monomers can be used to make small adjustments in the TG and major adjustments in the levels of crystallinity For example, resorcinol can be substituted: at various molar concentrations for hydroquinone in the above methods to make REVPET; for example, substituting 20 molar of resorcinol will increase the TG by 2 ° C and will reduce the crystalline nature by 50%.

Figure 1C: Modified REVPET Figure 1C illustrates a method for making a second oxygen scavenging polymer referred to herein as a modified REVPET. The only difference between modified REVPET and REVPET is the addition of a CH2 in the aliphatic chain. As shown in the table in Appendix C on page 49 (from the English text), the modified REVPET has a solubility parameter (SOL) of 20.18, compared to 20.53 for PET. The extra carbon atom (in the aliphatic carbon chain) also reduces TG, compared to the TG of REVPET. It may be desirable to add additional functional groups that will increase TG. Examples of these TG modifications are described below for the methods / polymers of Figures 1D-1K. The process conditions for making modified REVPET are similar to those for making REVPET described above, where glutaric acid is replaced by succinic acid.

Figure 1: Polymer ID Figure ID shows a method for making another aromatic ester oxygen scavenging polymer useful in the present invention and referred to herein as polymer ID. The repeating unit (shown in Figure 1C) includes two fa-hydrogen-carbonyl groups, two ester groups, six aromatic rings (two in the structure and four in the side chains), and an aliphatic 3-carbon group. The six aromatic rings increase the TG (in comparison to PET), however the extra carbon atom in the aliphatic chain (3CH2) decreases the TG (in comparison to the 2-carbon chain in PET)., by changing the various functional groups in the polymer, and / or similarly by varying the relevant proportions of the functional groups in the polymer, TG can be generally increased or decreased. These functional groups, and their regularity, can similarly affect the rate of crystallization. In general, a skilled person will now be able to determine the appropriate proportions of various groups for a given application, based on the process conditions necessary to achieve a transparent oxygen scavenging polymer that includes biaxially oriented PET, and if mixed or copolymerizes an aromatic ester polymer, with PET, or alternatively is provided in a separate layer structure. Similarly, starting materials can be varied depending on what is commercially available and the costs of these components.

METHOD FOR PREPARING ID POLYMER FROM DIMETHYL ESTER OF DIPHENIC ACID, DIESTIRENE GLYCOL AND DIMETHYL ESTER OF GLUTARIC ACID In a 1-liter, 3-necked flask, sealed, with stirring, it is mixed with 0.25 moles of the two dimethyl esters and 1.1 moles of glycol, and 0.0464 g of cobalt acetate. The vessel is pressurized to 10 psi and the heat is slowly increased with stirring to a light boil of about 180 ° C. Slowly raise the temperature just to keep the boil slightly until it is maintained at 10 psi below 10 ° C. It is maintained at 250 ° C for 2 hours. After releasing the pressure and change to vacuum. Add 0.033 g of Sb03 mixed in a small amount of glutaric acid dimethyl ester. Increase the temperature to 280 ° C. Hold the pressure at l Torr for 4 hours.

Figure 1E: Polymer 1E Figure 1E shows another aromatic ester oxygen scavenging polymer for use in the present invention. The repeating unit (shown in Figure 1E) includes two alpha-hydrogen-carbonyl groups, two esters, an aliphatic chain of 4 carbon atoms, and an aromatic structure (which includes two rings) in the structure. of 4 carbons will reduce the TG (compared to the 2-carbon chain in PET), the aromatic ring is (in comparison to the individual ring in PET) will increase the TG.The polymer 1E has an estimated TG of 71 ° C (see Appendix C on page 49, of the English text) which is just above that of PET (70 ° c) and in the preferred range Polymer 1E is commercially available from Dow Chemical, Midland, Michigan, USA. the components can be adjusted for a specific application.In general, to increase the level of oxygen removal, the level of the alpha-hydrogen-carbonyl groups will be increased by substituting more adipic acid and reducing the amount of diglycidyl ether of bisphenol A. A modified version of polymer 1E made with succinic acid has a TG of 70 ° C.

Figure 1F: Polymer 1F Figure 1F shows an alternative, alternative, aromatic ester oxygen scavenging polymer referred to herein as polymer 1F. The repeating unit includes two alpha-hydrogen-carbonyl groups, two ester groups, a 4-carbon aliphatic chain in the structure, and an aromatic side chain. Again, the relative proportions of the ingredients can be modified for a specific application. An alternative polymer made with succinic acid, instead of adipic, will have a higher TG (see Table in Appendix C on page 49 of the English text). Additional increases in TG are possible when using diethyrene oxide (instead of styrene oxide) with adipic acid, or diethyrene glycol (instead of styrene oxide) with adipic acid, or diethylene glycol (instead of styrene oxide) with succinic acid.

Figure 1G; REVPEN Figure 1G illustrates the process for making an additional elimination polymer, referred to herein as REVPEN. This is similar to REVPET (Figure IB), but is based on naphthalene instead of benzene. REVPEN is prepared by condensing 1,2 or 2,6-naphthalene diacrylate and succinic acid ester dimetic. The reaction conditions are similar to those for making REVPET, but at a higher temperature (for example, 300 ° C) in a final stage. A modified version of REVPEN is shown below, which has an additional CH group on each side of the aromatic ring: O -C-O-CHj- - (??) - CH2 Figure 1H: POLYMER 1H Figure 1H shows a random polymer of groups A, B and C, where A is provided by naphthalene dicarboxylate (NDC), B is provided by adipic acid, and C is provided by ethylene glycol (where the lost atoms and molecules are show in a box with an arrow). The resulting 1H polymer is basically a random copolymer of PEN and aliphatic acid. For every two components of naphthalene, there is an aliphatic component (molar parts). This is a highly crystalline, solid polymer, which is stable at higher temperatures. This allows the polymer to dry easily and remain solid to increase molecular weight. Polycondensation polyesters, which have highly crystalline structures and high melting temperatures, can remain solid to increase molecular weight. Transparent, multi-layer blow molded bottles have been made from preforms, including virgin PET layers and 1H polymer layers. There is good adhesion between the layers, which prevents delamination. More generally, the aliphatic acid component (here adipic acid) can have a group (CH2) n where n = 2 to 10.

METHOD FOR PREPARING A COPOLYMER OF DIMETHYL 2,6-NAFTALENDICARBOXYLATE / ADDITIVE ACID WITH ETHYLENE GLYCOL-POLYMER 1H In a 2-neck, 3-liter reaction flask, with stirring, mix 2.4 moles (580 g) NDC, 1.2 moles (175 g) of adipic acid, 8 moles (496 g) of ethylene glycol and 0.4725 g of Sb03. Test with nitrogen through the 8 psi system, heat the sample to 175 ° C and maintain for 10 minutes. Then increase the temperature to 210 ° C and hold for 5 minutes. Again increase the temperature to 240 ° C and hold for 1 hour after the sample becomes clear. Increase the temperature to 260 ° C and keep for 1 hour. Increase the temperature to 275 ° C and keep for 3 hours. Change from vacuum pressure and keep at 275 ° C under stable vacuum for 4 more hours. The final vacuum must be below 1 torr.

Figure II: Polymer II In Figure II, a hydroxy acid acid monomer substituted with an acetate at one end and an allyl methyl ester at the other end; this monomer reacts with itself to produce another oxygen scavenging polymer having the repeating unit shown. In polymer II it has an aromatic ring, an ester group, a fa-hydrogen-carbonyl group, and an aliphatic two-carbon chain.

METHOD FOR POLYMERIZING 4- (ACETILOXY) BENCENOPROPANOIC ACID TO ELABORATE THE POLYMER II) Place 1 mole (136 g) of acid, 0.13 g of Sb03 and 0.19 cobalt acetate in a 1-liter, 2-neck flask, sealed with agitation. Heat at 150 ° C with light agitation under a nitrogen purge of 0.25 1 / minute at 10 psi. Increase the heat until light vision occurs, then reduce the purge to maintain at 10 psi. Continue increasing the temperature to maintain boiling and 10 psi at a temperature of 180 ° C. Keep the temperature and pressure for 40 minutes. Put vacuum and raise the temperature to 210-220 ° C for 90 minutes.

Figure 1J. Polymer 1J Figure 1J shows the condensation of bisphenol A diacetate and adipic acid to make polymer 1J, which has two alpha-hydrogen-carbonyl groups, two esters, an aromatic structure (with two rings) and a 4-carbon aliphatic chain group . As shown in the table in Appendix C on page 49, (of the English text), polymer 1J has a relatively high TG of 91 ° C. A modified polymer subsequently listed as polymer 1J in the table, identified as: "Bis Acetate A / Suberic Acid", has a TG less than 79 ° C, which is in the preferred range for use with PET orientation temperatures. The following process can be used to prepare a polymer from bisphenol a diacetate and suberic acid: PREPARATION OF A BISPHENOL A AND SUBERIC ACID POLYMER (see, for example, Preparative Methods of Polymer Chemistry, 2nd Edition, Sorensen, Campbell, page 149) In a first step, bisphenol A diacetate is prepared by dissolving 11 g (grams) ) of bisphenol A in a solution of 9 g (.22 mol) of sodium hydroxide in 45 ml of water in a 250 ml Erlenmeyer flask. The mixture is cooled in an ice bath and a small amount of ice is added to the flask. Then, 22.4 g (0.22 mol) of acetic anhydride are added and the flask is stirred vigorously in an ice bath for 10 minutes. The white solid is filtered, washed with water, and recrystallized from ethanol. A mixture of bisphenol A diacetate, 312 g (1 mole), 174 g (1 mole) of suberic acid, 0.60 g of toluene sulfonic acid (monohydrate) is placed in a 2-neck, 2-liter flask with stirrer. The flask is purged with nitrogen while stirring for 20 minutes. The temperature is then increased to 180 ° C while stirring and purged with nitrogen at ambient pressure. The acetic acid is distilled as the temperature is slowly increased from 180 ° C to 250 ° C while the pressure is slowly reduced to about 1 torr. The melt is maintained at 250 ° C and 1 torr for 1 hour.

When an aliphatic acid is used, it may be advantageous if the pyridine is replaced by sodium hydroxide and water in the above reaction.

Figure 1K: Polymer 1K Figure 1K shows a ring opening polymerization of a cyclic ester. Caprolactone (cyclic) is combined with a cyclic carbonate ester to produce the 1K polymer. The resulting polymer has two alpha-hydrogen-carbonyl groups, an aromatic structure of two rings in the structure (bisphenol A) and an aliphatic chain of 5 carbons. As shown in the Table of the Appendix on page 49 (from the English text), the 1K polymer has a TG of 85 ° C, where the preferred range for use with the PET polymers. The 1K polymer has a good match of the solubility parameter with PET (20 versus 20.53). Methods for polymerizing cyclic carbonate and lactone esters are described in George Odian, Principles of Polymerization, 3rd edition, John Wylie & Sons, Inc., New York (1991), pp. 569-573.

The oxygen scavenging polymers, described above (shown in Figures 1B-1K) can be used alone, or mixed or copolymerized with an aromatic polyester copolymer, preferably a PET or PEN polymer, to provide an oxygen scavenging material. This material can then be incorporated into a packaged structure to provide a desired level of oxygen scavenging property, as described below.

Recent Pasteurizable Beer Figures 2-6 illustrate a method for making a 1 liter, pasteurizable, clear beer crosslinking using a multilayer structure and the oxygen scavenging polymer of this invention. Shown in Figure 2 is a multilayer preform 30, injection molded. The preform is substantially cylindrical, as defined by the vertical center line 32, and includes an upper or finished neck portion 34 integral with a lower body forming portion 36. The neck portion has an upper seal surface 31 defining the open upper end of the preform, and an outer surface, generally cylindrical with threads 33 and a lower flange 35. Below the flange is the body forming portion 36 which includes a cylindrical, upper portion 41, a flattened, projecting portion 37 that increases radially inward in the wall thickness from the top to the bottom, a panel forming section 38, cylindrical having a substantially uniform wall thickness, and a thickened, base forming section 39 which is thicker than the panel forming section 38. The closed end of the bottom of the preform 40 is substantially hemispherical and may be thinner than the portion 39 of base formation. The preform 30 has a five layer structure (3M, 5L) of three materials, and is substantially amorphous and transparent. The multiple layers of the preform comprise, in serial order, outer layer 42 of virgin PET, outer intermediate layer 43 of .EVOH, and core core layer 44 of oxygen-inhibiting material, intermediate layer, inner EVOH, and layer 46 interior of virgin PET. The virgin PET may be any commercially available PET, bottle grade homopolymer or copolymer having an intrinsic viscosity of about 0.909 dl / g. EVOH is commercially available with an ethylene content of 32% mol from Evalca, Omaha, Nebraska, USA, or Kuraray Co. Ltd, Osaka, Japan. The core layer is REVPET as previously described (Figure IB), which has an intrinsic viscosity of about 0.70 dl / g, a TG of 43 ° C, and a melting point of 214 ° C. The REVPET polymer includes 150 micrograms of cobalt per gram of REVPET polymer, added as cobalt neodeconate. The preform 30 is adapted to make the pressurized, pasteurizable 1.0 liter crosslinking for beer, shown in Figure 3. The preform 30 has a height of approximately 150 mm, and an outer diameter in the panel forming section 38 of approximately 23.8 mm. The total wall thickness of the panel forming section 38 is approximately 4.1 mm. The thickness of the various layers of the side wall are: outer and inner layers each approximately 1.1 mm thick; inner and outer intermediate layers each approximately 0.1 mm thick; and core layer approximately 1.7 mm thick. For carbonated, pasteurizable beverage containers of approximately 0.3 to 1.5 liters in volume, having a panel wall thickness of from about 0.25 to about 0.38 mm, and filling about 2.0 to about 4.0 volumes in aqueous C02 solution, section 38 of panel formation, of the preform which is preferably subjected to a planar elongation ratio, average of approximately 13.0 to 14.5. The planar flattening ratio is the ratio of the average thickness of the forming portion 38 of the preform to the average thickness of the container panel 86 (as shown in Figure 3); there are averages, along the length of the respective preform and the portions of the container. The radial elongation of the average panel is preferred about 4.0 to 4.5, and the axial elongation of the average panel is about 3.0 to 3.2. This produces a panel in vessel 86 with the desired biaxial orientation and desired visual transparency. The specific panel thickness and the elongation ratio selected depend on the measurements of the bottle, the internal pressure, and the processing characteristics (as determined, for example, by the intrinsic viscosity of the particular materials used). The preform shown in Figure 2 can be injection molded by a sequential, metered process described in U.S. Patent Nos. 4,550,043, 4,609,516, 4,710,118; 4,781,954; 4,990,301; 5,049,345; 5,098,274; and 5,582,788, owned by Continental PET Technologies, Inc., of Bedford, New Hampshire. In this process, predetermined quantities of the various materials are introduced into the gate of the preform mold as follows: a first injection of virgin PET that forms the preform layers, interior and exterior, partially solidified, as it moves upwards from the mold cold exterior and core walls; a second injection of EVOH that will form the inner and outer intermediate layers; a third injection of the oxygen scavenging material that pushes the EVOH towards the side wall (to form the thin barrier layers) which forms a core core layer of the oxygen scavenging material. A final injection of virgin PET can be used to clean the nozzle and finish at the bottom of the preform with virgin PET. After the mold is filled, the pressure is increased to pack the mold against the shrinkage of the preform. After packaging, the mold pressure is partially reduced and maintained while the preform is cooled. In a normal process, each of the polymer melts is injected into the mold at a rate of approximately 10-12 grams per second, a packaged pressure of approximately 7500 psi (509 x 106 N-rn "2) is applied during about 4 seconds, and then about 4,500 psi (30 x 106 N'm "2) is decreased for the next 15 seconds, after which the pressure is released and the preform is ejected from the mold. Increasing the pressure above these molds can force higher levels of interlayer bonding, which can include cabin entanglement, hydrogen bonding, low level interlayer crystallization and interlayer penetration; this may be useful in particular applications to increase the resistance to separation of the layers in both the preform and the container. In addition, the increased pressure maintains the preform against the cold mold walls to solidify the preform without fog, ie, loss of transparency, at the minimum possible cycle time. Still further, faster injection speeds can produce higher melting temperatures within the injection cavity, resulting in increased mobility of the polymer that improves migration and entanglement during the improved pressure portion of the injection cycle., and thus increases the resistance to delamination. As an additional option, increasing the average temperature of the preform and / or decreasing the temperature gradient across the preform wall can further reduce the separation of layers by minimizing the shear stress at the boundaries of the layer during the expansion of the preform. Figure 5 illustrates a blow molding apparatus 70 with elongation to make the container 80 from the preform 30. More specifically, the body forming section 36 of the preform, substantially amorphous and transparent, is reheated to a temperature above the glass transition temperatures of the inner / outer PET and the block oxygen removal layers, and the heated preform is then placed in blow molds 71. An elongation rod 72 axially stretches (stretches) the preform within the blow mold to ensure full axial elongation and center of the preform. The region 39 of the base formation, thickened in the preform, resists axial deformation compared to the portions 38 and 37 of formation of the shoulder panel. This produces greater axial elongation in the resulting panel and the protruding portions of the container. A blowing gas (shown by arrow 73) is introduced to radially cool the preform to correspond to the configuration of an inner molding surface 34 of the blow mold. The formed container remains substantially transparent, but has undergone a biaxial stress-induced orientation to provide the increased strength necessary to resist carbonation and the increased temperature and pressure of the pasteurization. Figure 3 shows the 1.0-liter pasteurizable multi-layer drink bottle 80 made from the preform of Figure 2. The forming portion 36 of the preform body has been expanded to form a body 81 of container, biaxially oriented, transparent. The scraped, upper finish 34 has not expanded, but is of sufficient thickness or construction of material to provide the required strength. The bottle has one end 82 open top and receives a screw cap (see Figure 7A-7B). The expanded container body 81 includes: (a) a flattened, upper, projecting section 83 with an outwardly projecting profile, and generally increasing in diameter from below the neck-terminated flange 35 to a panel section 86 cylindrical; it is preferred to provide a rounded shoulder 83 (hemispherical) because this shape minimizes the biaxial orientation and minimizes the applied stress levels. Greater orientation and less effort will decrease the increase in container volume due to sliding at elevated temperatures (during pasteurization), and thus minimize any fall in fill level; also, it is preferable to provide a small transition radius 84 between the neck finish 34 and the shoulder 83 to minimize the non-oriented area at the top of the shoulder (an unoriented area may be prone to slip); (b) panel section 86 substantially cylindrical preferably has a radially high and thin configuration, ie, a diameter height ratio in the order of 2.0 to 3.0, in order to minimize the effort on the side wall (and minimize slippage); relatively shallow transition regions 87 and 88 are provided at the upper and lower ends of the panel 86, respectively. Larger transition areas will be the most likely to expand (lengthen) during pasteurization and cause an increase in volume (drop in level fill); for the same reason; preferably ribs (which can slide) are not provided in the panel section 86; (c) a base with feet 90 has a substantially hemispherical bottom wall 92, and for example, five ducks 91 extending downwardly from the bottom wall to form five foot pads 93 on which the container rests; the legs 91 are placed symmetrically around the circumference of the container, furthermore, it is preferred to provide a high depth base, ie, close to a hemispherical base, in order to minimize the resistance and resistance against the insulation, it is also preferred to provide a Angled foot pad that can move outward under the glide and still stay within the diameter of the container. The panel forming section 38 of the preform can be lengthened to an average planar elongation ratio in the order of 3.0 to 14.5; the virgin PET layers of the resulting panel section 86 have a stress-induced crystallinity, on average in the order of 20% to 30%, preferably in the order of 25% to 29%. The ledge 83 is subjected to an average planar elongation ratio of about 10.0 to about 12.0, the virgin PET layers of the resulting ledge 83 having an average crystallinity of about 20% to 25%. The hemispherical bottom wall 92 at the base suffers an average planar elongation of about 5.O to 7.0, and the virgin PET layers have about 5% to 15% average crystallinity, the legs and feet undergo an average planar elongation of about 13.0 to 14.0, and virgin PET layers have approximately 20% to 26% average crystallinity. The oxygen removal layer of the core obtains a good average crystallinity of about 2% less than the virgin PET layers in each respective area of the container, for example, 18, 28% of the panel, 18-23% of the shoulder, -12% in the wall of the hemispheric bottom, and 18-24% of the legs and feet. Figure 4 shows a cross section of the panel wall 86, which includes the inner layer 95 of the virgin PET, the core layer 26 of the oxygen scavenging material, the outer layer 96 of virgin PET, and the intermediate, interior, and exterior layers 98, 99 of EVOH. In this embodiment, the relative percent by the total weight of the various layers in the panel section is about 30% for the inner layer 95, about 40% for the core layer 96, and about 30% for the outer layer 97 (layers 98, 99 of EVOH together are less than 2% by weight). The intermediate, inner layer of EVOH will become permeable to oxygen when the water vapor of the product penetrates through the inner 95 layer of PET; this will allow the oxygen to the container to penetrate the layers 95 and 98 and reach the core layer 96 where it is consumed. In contrast, the outer, intermediate layer 99 remains relatively close and resists that external oxygen enters the container. In an alternative embodiment, it may be desirable to replace for REVPET in the core layer a layer of PET and REVPET, where 5-20 weight percent of the core layer is REVPET; this would provide a higher TG.

The preferred features of the container base with feet are shown more clearly in Figure 6. As a basis of comparison, a known, non-pasteurized, disposable, 5-foot PET carbonated drink beverage container has a profile relatively low base (? of approximately 45 ° C). In contrast, the present base preferably has a relatively high base profile in the order of 60 ° or better. Figure 6 shows solid lines a base that has a complete hemisphere A where? = 90 °, and in dashed lines a truncated hemisphere B where? = 60 °, which is the angle that the radius R, which defines the wall 92 of the hemispherical bottom, extends from the vertical center line (CL) of the container body. The relative heights of the base are illustrated as HA for the complete hemi, and HB for the truncated hemi. It is preferable to provide a base height between HB and HA, and preferably where? be greater than 65 °. In addition, it is preferred to provide an angled foot pad. The foot pad extends between points G and K on leg 91 (for? = 90 °), or 91 * (for? = 60 °). The foot pad is preferably separated at a distance of LF from the vertical center line CL to a point G which is vertically aligned with a center point of the radius RG. The radius RG forms the outer edge of the foot pad. The foot pad forms an acute angle a with a horizontal surface 102 on which the base rests. Preferably, LF is in the order of 0.32R to 0.38R, it is already in the order of 5 ° to 10 °, to allow each foot and foot pad to move under the slip, and even within the diameter of the container . Figure 7A is an enlarged cross-section of a certain enclosure of neck opaque according to one embodiment. More specifically, the non-oriented neck finish 110 has been thermally crystallized (opaque) for example, by exposure to high temperature; this increases the strength and improves its resistance to the increased pressure temperature of the pasteurization. The heat-treated area may extend just below the flange 111. A cover 116 has an annular ring 117 of a resilient material (eg, plastisol or other thermoplastic elastomer) that seals the upper sealing surface 112 of the finished or finished If there is any deformation of the finish or neck finish during pasteurization, line 117 is deformed to ensure a tight seal and prevent leakage. In an alternative modality shown in Figure 7B, a neck finish 120 is provided, substantially amorphous and non-oriented, ie, it has not crystallized. In this case, the amorphous neck finish is provided with a laminated sheet liner 124, which is within an inner surface of a cap 126, and which can be sealed, for example, with heat, or sealed in a manner adhesive to the top sealing surface 122 of the neck finish. Again, if there is any deformation of the neck finish, the liner 124 ensures an airtight seal to prevent leakage.

Other Modalities Figure 8 shows another embodiment comprising a half-liter non-pasteurizable beer container. In this example, the bottler extensively filters the beer, so that the bottle does not need to be subjected to heat treatment. A preform is shown in Figure 8A 200 for making the bottle, which includes the finished or threaded termination 201, the flared shoulder portion 202, the cylindrical body portion 203, and the closed bottom 204. The preform 200 and the blow molded container 210, resulting (Figure 8B) has a five-layer structure (not shown), which includes the inner or outer layers • Virgin PET (62 percent by weight per total weight), a post-consumer PET core layer (35 weight percent), and 2 thin intermediate layers of REVPET homopolymer, such as the oxygen scavenging polymer (3 weight percent).

The REVPET has an intrinsic viscosity of 0.70 dl / g, a TG of 43 ° C and a melting point of 214 ° C. The virgin PET is Shell 8006, which has a nominal 0.80 IV, and which includes a 4 mole percentage of isotonic acid copolymer (available from Shell Oil Company, Houston, Texas, U.S.A.). In contrast to the previous embodiment, this beer bottle has a champagne base 212, which includes a fixed ring 214 that surrounds a central flexing dome 216. This container provides a shelf life for beer of approximately 16 weeks.

Another embodiment comprises a relatively wide-mouth container, such as a canister that includes the polyester oxygen scavenging material. The can can be formed from a preform according to the process described in U.S. Patent No. 4,496,064 to Beck et al, which issued on January 29, 1985, and is thus incorporated by reference into its entirety Figure 9 shows a preform 142 (of the Beck patent) including a support flange 144, a thin, outer body portion 145 that widens into a generally cylindrical, thick body portion 146, and a portion 148 background, generally hemispheric. The Beck process allows a high degree of biaxial orientation to be obtained in all portions of the resulting container, so that the container has economical thin walls and the desired strength characteristics. In this case, the preform expands to form an intermediate article 150, which includes a lower portion of 150 ° in the shape of the desired container, and an upper portion 154. The lower portion includes a cylindrical body 132, a concave bottom 134, the tapered shoulder 136, the mouth 138, an annular flange 130. The upper portion uses the flange 130 at point 164 (as when cutting or cutting with laser), and can be discarded, or ground and the material reduced. In general, it is not necessary to technically crystallize or otherwise reinforce the upper end of the container, because the biaxial orientation provides the necessary strength. A method for trimming the expanded preform to remove the upper unoriented portion is described in United States Patent No. 4,539,463 to Piccioli et al., Issued September 3, 1985, and is hereby incorporated by reference. In its whole. Yet another method for providing a multi-layer expanded preform container with a crystallized neck finish is disclosed in U.S. Patent Application Serial No. 08 / 534,126, entitled "Preform And Container With Crystalized Neck Finish And Method Of Making The Same ", which was presented on September 26, 1995 by Collette et al. (document 7191), is hereby incorporated by reference in its entirety. As described herein, a grader (e.g., rotary or oscillatory) has two surfaces, each with a set of preform molding cores, and simultaneously places the two core assemblies in two different sets of molding cavities. preform In the first set of cavities (first molding station), a neck portion, amorphous or crystallized, of high TG, is formed in a set of cores, while in the other set of cavities (second molding station), it is formed. form in a plurality of amorphous body formation portion in the other set of nuclei. The cores are sequentially placed in each of the first and second molding stations. By molding simultaneously in the two sets of cavities, an efficient process is provided. By molding the neck and body forming portions separately in different cavities, different temperatures and / or pressures can be used to obtain different demolding conditions and thus different properties in the two preform portions. For example, as shown in Figure 11, in one embodiment, a polyester preform (to make a hot refillable container) has a portion 180 of crystallized neck of CPET.; CEPT is a terephthalic polyester with nucleating agents that render the polymer rapidly recrystallizable during injection molding. The CPET is sold by Eastman Chemical Company, Kingsport, Tennessee, USA. The body forming portion 181 is a three-layer structure of two materials (2M, 3L), which includes the inner and outer layers of virgin polyethylene terephthalate (PET), and a core layer of the oxygen scavenging polymer of the invention. . The base forming portion 182 is similar to the body forming portion, but may include a core layer 183 of virgin PET in at least the bottom portion and possibly extending through the exterior of the preform. Alternatively, the core layer 183 in the base may be of a high TG polymer to improve the thermal externality of the resulting container base; This is particularly useful with champagne-type container bases. The higher TG polymer can be injected via a third extruder. Numerous alternative higher TG polymers can be used in place of CPET, such as: acrylate polymers; homopolymers, copolymers or mixtures of polyethylene naphthalate (PEN); polycarbonates; polyarylates; etc. As for the body forming portion, numerous alternative polymers and layer structure are possible, which incorporate PEN, ethylene / vinyl alcohol (EVOH) or nylon barrier layers MXD-6, etc. The container is useful in a variety of applications, including refillable containers, teurizable and hot refillable containers. As a further alternative, instead of or in addition to providing the oxygen scavenging material as part of the wall of a container, the material could be provided as an insert that can be provided to a container. For example, the insert may consist of an oxygen scavenging material coated with a polymer that is impermeable to oxygen when dried, and permeable when wet; moisture in the product that penetrates the coating, allowing oxygen to penetrate the oxygen elimination core layer.

Alternative Materials and Measurement of Properties The PET polymer as used herein includes homopolymers, copolymer and blends of PET with other known compatible polymers, which include other polyesters such as polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polyethylene naphthalate (PEN), and a PET copolymer, substituted with cyclohexane-dimethanol, known as PETG (available from Eastman Chemical Company, Kingsprot, Tennessee USA). Preferably at least 90 mol% will be terephthalic acid and at least 909 mol% a glycol or aliphatic glycols, especially ethylene glycol. Post-consumer PET (PC-PET) is made from PET plastic container and other recyclables that are returned by consumers for a recycling operation, and has now been approved by the FDA for use in certain containers. food. The PC-PET is known to have a certain level of I.V. (intrinsic viscosity), moisture content, and contaminants. For example, the typical PC-PET (which has a maximum half-inch flake size) has an I.V. average of approximately 0.66 dl / g, a moisture content of less than 0.25%, and the following levels of contaminants. PVC: < 100 ppm aluminum: < 50 ppm olefin polymers: (HDPE, LDPE, PP); < 500 ppm paper and labels: < 250 ppm colored PET: < 200 ppm other contaminants: < 500 ppm. PC-PET can be used alone or in one or more layers to reduce cost or for other benefits. Another useful aromatic polyester is polyethylene naphthalate (PEN), PEN provides a 3-5X improvement in oxygen and carbon dioxide barrier properties and improved thermal resistance, to some extent, compared to PET. Polyethylene naphthalene (PEN) is a polyester produced when 2,6-naphthalene decarboxylate (NDC) is reacted with ethylene glycol. The PEN polymer comprises a repeating unit of ethylene 2,6-naphatalate. PEN resin is available having an inherent viscosity of 0.67 dl / g and a molecular weight of about 20,000 from Amoco chemical Company, Chicago, Illinois. The PEN has a glass transition temperature TG of about 120 ° C and a melting temperature TM of about 267 ° C. PET and PEN can be mixed or polymerized in various amounts. In the ranges of about 0-20% PEN and 80-100% PEN, the material is crystalline, while from about 20-80% PEN of the material is substantially amorphous. Other biaxially orientable aromatic polyesters, useful include.

Polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polycyclohexanedimethanol terephthalate, polypropylene naphthalate, polybutylene naphthalate, polycyclohexanedimethanol naphthalate.

The multilayer preform / container may also include one or more layers of an oxygen / carbon dioxide / moisture barrier material such as ethylene / vinyl alcohol (EVOH), PEN, polyvinyl alcohol (PVOH), polyvinylidene chloride (PVDC), nylon 6, recrystallizable nylon (MXD-6), LCP (liquid crystal polymer), amorphous nylon, polyacrylonitrile (PAN) and styrene-acrylonitrile (SAN). The properties of some of these barrier materials are included in the Table of Appendix C on page 49, of the English text, for comparison purposes.

It may be desirable to use as a catalyst for the removal of oxygen, compounds such as cobalt, manganese, or magnesium with organic ligands. Examples include cobalt neonateonate, cobalt acetate, magnesium acetate and manganese acetate. It is believed that cobalt can reduce the binding energy at the alpha-hydrogen-carbonyl site, to provide increased reactivity with oxygen. Organic ligands are believed to promote the ingress of oxygen into the polymer, facilitate the movement of oxidation gases (see Figures 13A-K). The intrinsic viscosity (I.V.) affects the processability of the system. Polyethylene terephthalate having an intrinsic viscosity of about 0.8 is widely used in the carbonated soft drink (CSD) industry. Polyester resins for various applications can vary from about 0.55 to about 1.04, and more particularly from approximately 0.65 to 0.85 dl / g. The intrinsic viscosity measurements of the polyester resins are made according to the procedure of ASTM D-2857, by employing 0.0050 ± 0.0002 g / ml of the polymer in a solvent comprising o-chlorophenol (melting point 0 ° C), and respectively, at 30 ° C. The intrinsic viscosity (I.V.) is given by the following formula: I.V. = (In (VSo? "./ Vaol.)) / C where : Vsoln. is the viscosity of the solution in any unit; VSol. it is the viscosity of the solvent in the same units; and C is the concentration in grams of the polymer per 100 ml of solution.

The polymers as used herein (oxygen scavenging polymer, aromatic ester and biaxially oriented polyester polymer) are higher polymers, having a molecular weight of at least about 50,000, for which the melt viscosity is a parameter of important process. If the melt viscosity is too high, it is not possible to pass the polymer through the injection manifold fast enough to produce commercial preforms. Another important parameter is the melting strength; if the melting strength is too low, it is not possible to maintain the integrity of the layer in a multilayer structure having one or more relatively thin layers. In general, as the molecular weight of the polymer increases, both the melt viscosity and the melt strength increase. Those skilled in the art can determine an appropriate combination of melt viscosity or melt strength for the elimination polymer and the polyester polymer. The melt viscosity is generally represented as a melt index, measured in accordance with ASTM 1238B. For example, Shell 8006 virgin PET has a melt index of 29 g / 10 minutes. It has been found that an adjacent elimination layer should preferably have a melt index of 50-100 g / 10 minutes.

The body of the blown container must be substantially transparent. A measure of transparency is the percent of fog for the light transmitted through the wall (HT) that is given by the following formula: where Yd is the diffused light transmitted by the thickness of the specimen, and Ys is the specular light transmitted by the thickness of the specimen. The diffused and specular light transmission values are measured according to the method of ASTM D 1003, using any normal color difference measure, such as model D25D3P manufactured by Hunterlab, Inc., Reston, Vrginia, U.S. A. The body of the container must have a percent of haze (through the panel wall) of less than about 10%, and more preferably less than 5%.

The portion that forms the body of the preform must also be substantially amorphous and transparent, having a percent of fog through the wall of no more than about 10%, and most preferably no more than about 5%. The container will have varying levels of crystallinity at various positions along the bottle height from the neck to base termination. The percent crystallinity can be determined in accordance with ASTM 1505 as follows: % crystallinity = [(ds-da) [(dc-da)] X100 where ds = density shows in g / cm3, da = density of an amorphous polymer of zero percent crystallinity, and de = density of the calculated crystal of the unit cell parameters. The panel portion of the container is stretched or elongated larger and preferably has a percent average crystallinity of at least about 15%, and more preferably at least about 20%. In general, a range of crystallinity of 25 to 29% is useful in the panel region.

Additional increases in crystallinity can be achieved by adjusting the heat to provide a combination of stress induced crystallization and heat induced crystallization. The heat-induced crystallinity is achieved at low temperatures to preserve transparency, for example, by keeping the container in contact with a mold blown at low temperature. In some applications, a high level of crystallinity of the surface of the side wall alone is sufficient.

The oxygen scavenging material of this invention can be made by a major batch process, wherein the oxygen scavenging polymer is first prepared, and then mixed or copolymerized with the PET polymer. A master batch process for combining an oxygen scavenging polymer with PET is described in commonly owned and co-pending US Patent Application Serial No. 08 / 355,703, filed December 14, 1994 entitled OXYGEN-SCAVENGING COMPOSITIONS FOR ULTILAYER PREFORM AND CONTAINER (document No. 7180), which was published as WO 96/18685 on June 20, 1996, and is hereby incorporated by reference in its entirety.

The average molecular weight of the exemplary polymer can be selected, for various purposes. One purpose is to improve the mixability with the PET polymer, and for this purpose, the average molecular weight of the oxygen scavenging polymer is preferably in a range of 70,000-100,000, more preferably 78,000-94,000. The compatibility of the oxygen scavenging polymer with the PET polymer can be determined by preparing and combining (mixing or copolymerizing) samples thereof. Alternatively, it can be determined based on several known compatibility indicators. For example, it has been found that REVPET has a solubility parameter, determined in accordance with a known method of Van Krevelen, which is substantially identical to that of unmodified PET. There is a commercially available computer program known as Polymer-CAD, Version 1.6, published by Novel Advanced Systems For Engineering And Research, P.O. Box 130304, Ann, Arbor, Michigan 48113-0304, USA, which allows calculating several fundamental properties of a polymer from its structure based on different construction methods of additive groups. For example, using the following structure for REVPET: - formula: C10H8O4 - molecular weight: 192.170800 - structure The cohesive energy and the solubility parameters are determined using methods of contribution of molar traction constant, and direct. A molar volume of 144.24 cm3 / mol is used, at 298 ° K. See Van Krevelen, D.W. and Hoftyzer, P.J., Appl. Polymer Sci., 13, pages 871 (1969); and Van Krevelen, D.S., Propierties Of Polymers, 3rd Edition, Elsevier Science Publishers (1990). The method uses the contribution of groups to the molar volume of the amorphous polymer, followed by that for the crystalline polymer in cm 3 / mol (gram basis). This is an aggregation of data from four methods. two for calculating the Cohesive Energy (Ecoh) of Bunn, CW., J. Polymer Sci., 16 p. 323 (1995), and Hostyzer, p.J., and Van Krevelen D.V., International Symposium On Macromolecules (IUPAC), Paper No. Illa, 15 (1970); and two to calculate the Attraction Constant (F) from Small, P.A., J. Appl. Chem., 3, page 71 (1953), and Van Krevelen, D.S., Fuel, 44, page 236 (1965). The Bunn method applies at the boiling point only, while the others apply at 298 ° K. The solubility parameter (Van Krevelen 1) for REVPET is calculated to be 20.5283 Jl / 3 / cm3 / 2, using a tensile constant F (Van Krevelen) = 2961 (J-cm3) 1/3 / mol (where J = Joules and cm = centimeters), and a cohesive energy Ecoh (Van Krevelen) of 60784.3 J / mol, where the safety parameter = (Ecoh / molar volume) 1/2, and Ecoh = Fl / 2 / molar volume. The solubility parameter for unmodified PET is the same: 20.5283.

Including the end of the detailed description (before the claims), under the subheading Appendix A, is a sample of the output generated by the Polymer-CAD program for PET having the designated structure. The output includes: volumetric properties, calorimetric properties, transition temperature; cohesive energy and solubility; refractive index and molar refraction; electrical properties; magnetic properties, mechanical properties; acoustic properties, permacor and permeability; and thermal decomposition temperatures. Similarly, Appendix C shows the output of the sample for REVPET.

The closer the matching of the solubility parameters for the oxygen scavenging polymer and the PET polymer is, the more polymers are expected to be compatible. It is preferred that the polymers have a solubility parameter within three units, and more preferably within a unit, as determined by the above computation program (Van Krevelen 1). Included before the claims as appendix C is a list of solubility parameters (SOL) and other properties of various polymers. As discussed previously, PET and REVPET have the same solubility parameter value (20.53). The modified REVPET has a value of 20.18. in contrast, Nylon MXD-6 has a much higher value of 26.8, which is well outside the preferred range of 3 units and shows that this polymer is much more compatible with PET.

That fall within the preferred range of 3 units are: REVPET (Figure IB); Modified REVPET (Figure 1C); Dies tirengl i col / diic acid / glutaric acid (Figure ID); Bis A Epoxy / Adipic Acid (Figure 1E); Styrene oxide / Adipic acid (Figure 1F); Bis A Acetate / Adipic Acid (Figure 1J); Bis A Acetate / Subarian Acid (see text referring to Figure 1J); Styrene Oxide / Succinic Acid (see text referring to Figure 1J); Dies tireno oxide / Adipic acid (see text referring to Figure 1J); Diethylene glycol / Succinic acid (see text referring to Figure 1J); Y Bis Cyclic A-Ester-Calprolactone (Figure 1K) Measurement of Oxygen Alignment It is a purpose of the present invention to provide an oxygen scavenging material that can be effectively used commercially for food, beverages and other products. It is particularly useful in the product based such as beer, because the beer quickly loses its flavor to the migration of oxygen. This is true for products such as citrus products, tomato-based products, and aseptically packaged meat. It is also useful for making carbonated soft drink containers. Depending on the application, a specific elimination rate may be desirable or may be required as discussed hereinafter.

By "oxygen removal rate" herein is meant to refer to the amount of oxygen in a packaging structure that is removed in units of nanograms (ng) of oxygen per square centimeter (cm2) of the surface area of the container, per day (that is, units of ng / cm2 / day). In this way, as the surface area of the container increases, the elimination capacity of the container must be increased to maintain the same speed.

Also, because beer is much more sensitive to oxygen than juice, for containers of similar dimensions, the oxygen removal rate in a container designed to contain beer must be greater than the oxygen removal rate of a container designed to contain fruit juices The package must have an oxygen scavenging rate of at least 5 ng / cm2 / day, more preferably at least 30 ng / cm2 / day.

An "elimination performance ratio" as used herein refers to the oxygen permeability ratio of a control container formed from aromatic polyester only, to the permeability of a package that includes both the polyester and a polymer. of the aromatic ester oxygen removal of this invention, where the two containers have the same dimensions. For example, a single-use beer container (e.g., 8-12 ounces) should have an elimination performance ratio of at least about 4, and preferably about 10 or greater. A container of fruit juice for individual use (eg, 8-12 ounces) should have an elimination performance ratio of at least about 1.5, more preferably at least about 4, and more preferably at least about 8. .

A container is designed to have a shelf life of several weeks or months. For example, a typical requirement for beer is 1 part per million (ppm) of oxygen over a shelf life of 112 days. A 1 liter bottle in this way can have 1000 micrograms of cumulative 02 during its shelf life (1 ppm = 1 microgram per cubic centimeter (cc) volume).

By way of example, a control container is made of a virgin bottle-grade PET monolayer having a thickness of 13 mils, a diameter of 2.6 inches, and a height of 4.75 inches. The estimated surface area of the container was approximately 60 square inches. The container is filled with deoxygenated water. The rate at which oxygen passes from outside to the interior of this control vessel was measured using an oxygen analyzer (model LC700F, Serial No. 695935, available from Mocon Inc., Minneapolis, Minnesota USA), in accordance with ASTM S1307-90. The oxygen input rate for this control bottle was 30,000 ng / container / day. Dividing the oxygen entry velocity by the surface area produces a ratio of oxygen input per square area of 77 ng / cm2 / day. In general, a container is designed so that the rate of oxygen removal corresponds to the rate of oxygen ingress. In this example, a container of the same dimensions made from a monolayer of REVPET has a rate of oxygen input per square area of 1 or less ng / cm2 / day. In this container, 1 ng / cm2 / day equals 70 ppb of oxygen • Total accumulated for 112 days. This is a 77-fold improvement over the control vessel. If PEN is used instead of PET, then the control bottle will have an oxygen ingress rate of 6,000 ng / container / day or 18.6 ng / cm2 / day. If desired, various catalysts can be used to increase the rate of oxygen removal of the oxygen scavenging material. For example, Eastman 9921 is a PET polymer that has residual cobalt; Cobalt acts with a catalyst during the preparation of the PET. The residual cobalt has been found to act as a catalyst for the removal of oxygen when the PET polymer is mixed or copolymerized with various oxygen scavenging compositions. Eastman '9921 is available from Eastman Chemical, Kingsport, Tennesee, USA. Similarly, the presence of water has been found to improve the rate of oxygen removal. In an exaggerated use of the container for a liquid product containing water, this improvement will occur inherently. For example, it has been observed that wet samples are still removed at a rate as much 4 times as the dried samples.

Pasteurization process The carbonated, pasteurizable beverage containers of the prior art are typically made of glass or metal because they can withstand the prolonged high temperatures and high internal pressures of the pasteurization cycle. Figure 2 graphically illustrates, as a function of time, the increase in internal temperature and pressure during a wet process pasteurization cycle, known for a 16-ounce glass container, and filled with a juice product carbonation 2.5 volumes "2.5 volumes" means that the volume of carbon dioxide at 0 ° C under one atmosphere is 2.5 times the volume of the liquid. The typical pasteurization cycle, as shown in Figure 12, includes five steps. (1) inversion in bath 1, which has a bath temperature of about 43 ° C, for about 12.5 minutes in order to increase the container and the contents up to about the bath temperature 1. (2) immersion of bath 2, which has a bath temperature of about 77 ° C, for the time from 12.5 to 21 minutes in order to increase the contents and the vessel to about the temperature of bath 2; (3) immersion in the bath 3, which has a bath temperature of about 73 ° C, during the time of 21 to 31.5 minutes in order to maintain the container and the contents at about the temperature of the bath 3; (4) immersion in the bath 4, which has a bath temperature of about 40 ° C, during the time of 31.5 to 43 minutes in order to decrease the container and the contents to approximately the temperature of the bath 4; and (5) immersion in rapid cooling bath 5 for the time of 43 to 5 minutes in order to cool the container of the contents to about 10 ° C.

The temperature curve 12 shows that the container contained therein remains above 70 ° C for about 10 minutes (in bath 3), during which time the internal pressure significantly increases approximately 110 psi (1 x 106). Nm-2). This maintenance period of 10 minutes at a temperature of about 70 to 75 ° C provides effective sterilization for most carbonated beverage products, including those containing 100% fruit juice. A glass container can withstand these temperatures and pressures without deformation.

A plastic container including the oxygen scavenging polymer of this invention can be made to withstand the temperatures / pressures of pasteurization by one or more of: using a higher TG (more thermally resistant) polyester; adjustments to the design of the container; use of heat-induced crystallinity; use of the crystallized neck finish, etc. While various embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that various changes and modifications may be made without departing from the scope of the invention as defined in the appended claims.

Appendix A Route: Name: PET Formula: C1OH804 Molecular weight: 192.170800 Structure: Volumetric Properties: Using the volume contributions of Van der Waals Used Molecular Weight: 192,171 Vw = 94.16 cm3 / mol Va = 1.6Vw = 150.656 cm3 / mol Density (a) = 1.27556 cm3 / mol Vc = 1.435Vw = 135.12 cm3 / mol Density (c) = 1.42223 gm / cm3 Using the Molar Volume contributions of Van Krevelen Molecular Weight used: 192,171 Va = 144.24 = cm3 / mol Density (a) = 1.3323 gm / cm3 Vc = 131.36 = cm3 / mol Density (c) = 1.46293 gm / cm3 Using Fedors Group Contributions Molecular Weight Used: 192,171 Va = 120.6 = cm3 / mol Density (a) = 1.59346 gm / cm3 Calorimetric Properties Using the Satoh-Shaw Method Molecular weight used: 192.171 Cps = 1.15262 J / (gm K) Cpl = 1.58141 J / (gm K) Transition Temperatures Using Van Krevelen Vitrea Transition Temperature contributions: Molecular Weight used: 192,171 Tg = 350.73 K Using Van Krevelen's Crystalline Fusion Point Contributions: Molecular Weight used: 192,171 Tm = 566,683 K Solubility and Cohesive Energy: Using Methods of Constant Molar and Direct Attraction: Molecular Weight used: 192.171 Molar Volume Used: 144.24 cm3 / mol of Van Krevelen 1 Ecoh (Bunn to Tb) = 46340 J / mol Sol. Param. (Bunn to Tb) = 17.924 J? L / 2 / cm? 3/2 Ecoh (Hoftyzer &Van 60340 J / mol Krevelen) = Sol. Param. (Hoftyzer &Van 17.924 J? L / 2 / cm? 3/2 Krevelen) = F (Small) = 3158 (J. Cm3)? (1/2) / mol Ecoh (Small) = 69141.5 J / mol Sol. Param. (Small) = 21.8941 J? L / 2 / cm? 3/2 F (Van Krevelen) = 2961 (J. Cm3)? (1/2) / mol Ecoh (Van Krevelen) = 60784.3 J / mol Sol. Param. (Van Krevelen) = 20.5283 J? L / 2 / cm? 3/2 Using contributions from the Fedors Group Molecular Weight used: 192,171 Molar Volume Used: 144.24 cm3 / mol from Van Krevelen 1 Ecoh (Fedors) = 77820 J / mol Sol. Param. (Fedors) = 23.2275 J? L / 2 / cm? 3/2 Refractive Index and Molar Refraction: Using several methods for the contributions of Goedhart: Molecular Weight used: 192.171 Molar Volume Used: 144.24 cm3 / mol of Van Krevelen 1 R (Lorentz &Lorentz) = 47,748 cm3 / mol Refractive Index (Lorentz &Lorentz): 1.57624 R (Gladstone &Dale) = 83.082 cm3 / mol Refractive Index (Gladstone &Dale) = 1.576 R (Vogel) = 299.48 gram / mol Refractive Index (Vogel) = 1.55841 Electrical Properties: Using several methods to. Van's contributions Krevelen Molecular Weight used: 192.171 Molar Volume Used: 144.24 cm3 / mol of Van Krevelen 1 P (Lorentz &Lorentz) = 64.3 cm3 / mol Dielectric Constant (Lorentz &Lorentz) = 3.41306 P (Vogel) = 359.88 gram / mol Dielectric Constant (Vogel) = 3.50704 Magnetic Properties: Using the Van Krevelen Diamagnetic Susceptibility Contributions Molecular Weight used: 192,171 Molar Diamagnetic Susceptibility: 0.0001015 cm3 / mol Diamagnetic Susceptibility: 5.28176e-007 cm3 / mol Mechanical properties Using Sound Velocity Functions for the contributions of Rao & Hartmann Molecular Weight used: 192,171 Molar Volume Used: 144.24 cm3 / mol of Van Krevelen 1 UR = 8310 (cm3 / mol) cm / s)? L / 3 TM = 6450 (cm3 / mol) cm / s)? L / 3 Density = 1.3323 gm / cm3 Elastic Modules: Lot (K) = 4.87185e + 010 Dync / cm2 Effort (G) = 1.06524e + 010 Dync / cm2 Cutting Tension (E) = 2.97861e + 010 Dync / cm2 Contamination Ratio = 0.398101 Acoustic properties Using Sound Velocity Functions for the contributions of Rao & Hartmann Molecular Weight used: 192,171 Molar Volume Used: 144.24 cm3 / mol of Van Krevelen 1 UR = 8310 (cm3 / mol) cm / s)? L / 3 TM = 6450 (cm3 / mol) cm / s)? L / 3 Density = 1.3323 gm / cm3 Sound speed: Longitudinal (uL) = 2173.2 m / s Shear force (uSh) 894.174 m / s Extension (uext) = 1495.22 m / s Permacor and Permeability: Using Permacor Method Salame Molecular Weight used: 192.171 Permacor (pi) = 58.8 Nitrogen Permeability = 7.64892e-016 cm2 (s.Pa) a 298 K Thermal Decomposition Temperatures: Using Temperature Contributions from Decomposition (1/2) of Van Krevelen Molecular Weight used: 192,171 Td (l / 2) = 718,111 K The (*) before a property name indicates values of a missing group Appendix B Path: C: \ Program Files \ PCAD \ Plmrl. ecb Name: REV PET Formula: C1OH804 Molecular weight: 192.170800 Structure: Volumetric Properties: Using the volume contributions of Van der Waals Used Molecular Weight: 192,171 Vw = 94.16 cm3 / mol Va = 1.6Vw = 150.656 cm3 / mol Density (a) = 1.27556 cm3 / mol Vc = 1.435Vw = 135.12 cm3 / mol Density (c) = 1.42223 gm / cm3 Using Van Molar Volume Contributions Krevelen Molecular Weight used: 192,171 Va = 144.24 = cm3 / mol Density (a) = 1.3323 gm / cm3 Vc = 131.36 = cm3 / mol Density (c) = 1.46293 gm / cm3 Using Fedors Group Contributions Molecular Weight Used: 192,171 Va = 120.6 = cm3 / mol Density (a) = 1.59346 gm / cm3 Calorimeter Properties: Using the Satoh-Shaw Method Molecular Weight used: 192.171 Cps = 1.15262 J / (gm K) Cpl = 1.58141 J / (gm K) Transition Temperatures: Using Transition Temperature contributions Van Krevelen Vitrea: Molecular Weight used: 192,171 Tg = 110.76 K Using Van Krevelen's Crystalline Fusion Point Contributions: Molecular Weight used: 192,171 Tm = 420,797 K Solubility and Cohesive Energy: Using Methods of Constant Molar and Direct Attraction: Molecular Weight used: 192,171 Molar Volume Used: 144.24 cm3 / mol of Van Krevelen 1 Ecoh (Bunn to Tb) = 46340 J / mol Sol. Param. (Bunn to Tb) = 17.924 J? L / 2 / cm? 3/2 Ecoh (Hoftyzer &Van 60340 J / mol Krevelen) = Sol. Param. (Hoftyzer &Van 20.4531 J? L / 2 / cmA3 / 2 Krevelen) = F (Small) = (3158 J.cm3)? (1/2) / mol Ecoh (Small) = 69141.5 J / mol Sol. Param. (Small! 21.8941 J? L / 2 / cm? 3/2 F (Van Krevelen) = 2961 (LT.cm3) - (1/2) / mol Ecoh (Van Krevelen) = 60784.3 J / mol Sol. Param. (Van Krevelen) 20.5283 LT? L / 2 / cm? 3/2 Using contributions from the Fedors Group Molecular Weight used: 192,171 Molar Volume Used: 144.24 cm3 / mol of Van Krevelen 1 Ecoh (Fedors) = 77820 J / mol Sol. Param. (Fedors) = 23.2275 J? L / 2 / cm? 3/2 Refractive Index and Molar Refraction Using several methods for the contributions of Goedhart: Molecular Weight used: 192,171 Molar Volume Used: 144.24 cm3 / mol of Van Krevelen 1 R (Lorentz &Lorentz) = 47.244 cm3 / mol Refractive Index (Lorentz &Lorentz): 1.56883 R (Gladstone &Dale) = 83.242 cm3 / mol Refractive Index (Gladstone &Dale) = 1.57017 R (Vogel) = 299.88 gram / mol Refractive Index (Vogel) = 1.55528 Electrical Properties Using various methods for Van's contributions Krevelen Molecular Weight used: 192.171 Molar Volume Used: 144.24 cm3 / mol of Van Krevelen 1 P (Lorentz &Lorentz) = 64.3 cm3 / mol Dielectric Constant (Lorentz &Lorentz) = 3.41306 P (Vogel) = 359.88 gram / mol Dielectric Constant (Vogel) = 3.50704 Magnetic Properties: Using the Van Krevelen Diamagnetic Susceptibility Contributions Molecular Weight used: 192,171 Molar Diamagnetic Susceptibility: 0.0001015 cm3 / mol Diamagnetic Susceptibility: 5.28176e-007 cm3 / mol Mechanical properties Using Sound Velocity Functions for the contributions of Rao & Hartmann Molecular Weight used: 192,171 Molar Volume Used: 144.24 cm3 / mol of Van Krevelen 1 UR = 8310 (cm3 / mol) cm / s)? L / 3 TM = 6450 (cm3 / mol) cm / s)? L / 3 Density = 1.3323 gm / cm.3 Elastic Modules: Lot (K) = 4.87185e + 010 Dync / cm2 It is force (G) = 1.06524e + 010 Dync / cm2 Cutting Tension (E) = 2.97861e + 010 Dync / cm2 Ratio of 0.398101 Contamination Acoustic Properties: Using Sound Velocity Functions for the contributions of Rao & Hartmann Molecular Weight used: 192,171 Molar Volume Used: 144.24 cm3 / mol of Van Krevelen 1 UR = 8310 (cm3 / mol) cm / s)? L / 3 TM = 6450 (cm3 / mol) cm / s)? L / 3 Density = 1.3323 gm / cm3 Sound speed: Longitudinal (uL) = 2173.2 m / s Shear force (uSh! 894.174 m / s Extension (uext) = 1495.22 m / s Permacor and Permeability: Using Permacor Salame Method: Molecular Weight used: 192,171 Permacor (pi) = 58.8 Nitrogen Permeability = 7.64892e-016 cm2 (s.Pa) at 298 K Thermal Decomposition Temperatures: Using Decomposition Temperature Contributions (1/2) of Van Krevelen Molecular Weight used: 192,171 Td (l / 2) = 645,597 F The (*) preceding a property name indicates values of a missing group APPENDIX C TG ° C TM ° C SOL ADEN CDEN PERM AROM CARB ALPHA FIG NAME ÍA PET 72 260 20.53 1.33 1,463 7.7-16 39.6 IB REVPET 43 214 20.53 1,332 1,463 7.7-16 39.6 29 15 1C REV PET 35 195 20.18 1,284 1,412 2-15 37 27 20 MODIFIED ID DIESTIRENGLI 103 256 20.46 1.22 1.36 4.6-15 67 7 6 COL / ACID DI FÉNICO / ACIDO GLUTARICO 1E BIS TO EPOXY 71 238 21.9 1.13 1.26 4-16 40 12 12 / ADIDIC ACID 1F OXIDE 27 155 19.25 1.17 1.29 7.8-15 31 23 23 STYRENE / ADIDIC ACID OXIDE OF 41 184 19.64 1.23 1.36 2.9-15 35 25 13 STYRENE / SUCCINIC ACID OXIDE OF 60 199 19.5 1.16 1.28 5.4-15 48 17 17 DIESTIRENO / ACIDI ADIPICO DIESTIREN- 73 224 19.97 1.20 1.33 1.8-15 52 19 9 GLYCOL / ACID SUCCINIC II ACID 4- 51 194 20.2 1.22 1.35 2.9-15 51 19 19 (ACETILOXI) B ENCEN- PROPANOICO 1J BIS A 91 276 19.7 1.16 1.28 7-15 57 17 17 ACETATE / ACID ADIPICO BIS A 79 259 19.4 1.13 1.25 1-14 53 15 23 ACETATE / ACID SUBERICO 1K BIS A ESTER 85 292 20 1.13 1.25 10-15 57 8 21 CYCLIC CAPROLACTONE MXD6 73 266 26.8 1.18 1.31 3.17 31 34 28 PV011 82 156 30.36 1.14 1.27 7-20 0 EVOH 43 70 26.4 1.055 1.177 9-18 0 POLYCETONE 5 36 27.67 1.21 1.34 1.6-13 0 67 33 ALIFATIGA Example 1: An example of weight percent calculations of AROM, CARB and ALPHA for molar weight of REVPEN = 242 14C * 12 = 168 10H * 1 = 10 40 * 16 = 64 242 AROM 10C + 6H = 126/242 = 52% CARB CO + CO = 56/242 = 23% ALPHA (CH2) 2 = 28/242 = 12% Example 2: An Example of weight percent calculations of AROM, CARB and ALPHA by polymer 1-J, molar weight = 338: 21C * 12 = 252 22H * 1 = 22 40 * 16 = 64 338 AROM C6H4 + C6H4 + = 194/338 = 57% C (CH3) 2 CARB CO + CO = 56/242 = 17% ALPHA (CH2) 4 = 56/242 = 17% Example 3: An Example of weight percent calculations of AROM, CARB and ALPHA by MXD6, molar weight = 246: 13C * 12 = 156 18H * 1 = 18 2N * 36 = 72 246 AROM C6H4 = 76/246 = 31% CARB CO + CO + CO * .5 + CO * .5 = 84/246 = 34% Note: Factor of 1.5 entered since each one is close to an NH (see page 13) ALPHA (CH2) 4 + CH * .5 + CH .5 = 70/246) 28% Note: Factor of 1.5 entered since each one is close to an NH (see page 13)

Claims (52)

1. A transparent, multi-layered, oxygen scavenging article, characterized in that it comprises: a layer of a biaxially oriented aromatic polyester polymer, and a layer comprising a catalyst and a scavenging polymer, of aromatic ester, including functional groups of elimination of oxygen, of alpha-hydrogen-carbonyl, of the formula: O S _0_C- (CH2) n- wherein n = 2 or more, and aromatic group providing individual or multiple aromatic rings is a structure or side chain of the elimination polymer; wherein the relative weight percentages of the alpha-hydrogen-carbonyl groups, and the aromatic groups are selected to provide both a desired rate of oxygen removal and a glass transition temperature TG of the elimination polymer that permits biaxial expansion of both the layers of both polymer layers while achieving the biaxial orientation of the aromatic polyester layer in the transparent article.

2. The article according to claim 1, characterized in that the elimination polymer is selected from the group consisting of homopolymer, random copolymer, alternating copolymer and block copolymer.

3. The article according to claim 1, characterized in that the aromatic polyester is selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polycyclohexanedimethanol terephthalate, polypropylene naphthalate, polybutylene naphthalate, polycyclohexanedimethanol naphthalate, and copolymers and mixtures thereof.

4. The article according to claim 3, characterized in that the aromatic polyester is selected from the group consisting of PET homopolymer and copolymers.

5. The article according to claim 3, characterized in that the aromatic polyester is selected from the group consisting of PEN homopolymer and copolymers.

6. The article according to claim 1, characterized in that the aromatic groups include a ring structure selected from the group consisting of: and a side chain ring structure selected from the group consisting of:

7. The article according to claim 1, characterized in that the aromatic groups have an aromatic ring, two aromatic rings, or a double aromatic ring.

8. The article according to claim 1, characterized in that the aromatic groups are of the formula: CH, CH,

9. The article according to claim 1, characterized in that the elimination polymer has a repeating unit of the formula: CHS C-0- < ? -C - ^ - O-C- (CH,) n- CH, where n = 2 or more.

10. The article according to claim 9, characterized in that n = 4.

11. The article according to claim 1, characterized in that the elimination polymer has a repeating unit type REVPET of the formula: OR -c-o- or -0-c- (CH2) n- where n = 2 or more.

12. The article according to claim 1, characterized in that the elimination polymer has a repeating unit type REVPEN of the formula: O 0 where n = 2 or more

13. The article according to claim 1, characterized in that the elimination polymer has a weight percentage of AROM aromatic groups in a range of 30 to 70.

14. The article according to claim 1, characterized in that the elimination polymer has a weight percentage of CARB carbonyl groups in a range of 5 to 30.

15. The article according to claim 1, characterized in that the elimination polymer has a weight percentage of ALPHA alpha groups in a range of 5 to 30.

16. The article according to claim 1, characterized in that the elimination polymer has a repeating unit with an aromatic group, two ester groups, and two alpha-hydrogen-carbonyl groups.

17. The article according to claim 1, characterized in that n = 2, 3 or 4.

18. The article according to any of claims 1, 10, 11, 12 and 16, characterized in that n = 12.

19. The article according to claim 1, characterized in that the elimination polymer has a repeating unit of the formula:

20. The article according to claim 1, characterized in that the elimination polymer has a repeating unit of the formula:

21. The article according to claim 1, characterized in that the elimination polymer has a repeating unit of the formula:

22. The article according to claim 1, characterized in that the elimination polymer has a repeating unit of the formula:

23. The article 'according to claim 1, characterized in that the elimination polymer is a random condensation polymer of ethylene glycol with the following two components: H -0-C- (Crl) ^ - c-o- fl where n = 2 to 10

24. The article according to claim 1, characterized in that the elimination polymer has a Van Krevelen solubility parameter which is within 3 units of the Van Krevelen solubility parameter of the aromatic polyester.

25. The article according to claim 24, characterized in that the Van Krevelen solubility parameter of the elimination polymer is within one unit of that of the aromatic polyester.

26. The article according to any of claims 24 and 25, characterized in that the Van Krevelen solubility parameter (SOL) is defined by: SUN (Ecoh / molar volume) 1/2 where Ecoh is the cohesive energy defined by Ecoh = F1 2 / molar volume, and F is a constant of attraction of Van Krevelen.

27. The article according to claim 1, characterized in that the article has a defined transparency with a percent of haze (Ht) for the light transmitted through a thickness of the article, given by the formula: Ht = [Yd + (Yd + Ys)] X 100 where Yd is the diffused light transmitted by the thickness, Ys is the specular light transmitted by the thickness, and the transmitted values of the diffused and specular light are measured according to the method D 1003 of ASTM, where H is less than 10 %.

28. The article according to claim 27, characterized in that Ht is less than 5%.

29. The article according to claim 1, characterized in that the biaxially oriented article has an average crystallinity of at least 15% as determined by ASTM 1505 of: of crystallinity = [(ds - da) / (de - da)] x 100 where ds = article density g / cm3, da = amorphous polymer density of zero percent crystallinity, and de = calculated crystal density of the unit cell parameters.

30. The article according to claim 29, characterized in that the article has an average crystallinity of at least 20%.

31. The article according to claim 1, characterized in that the elimination polymer has a TG of at least 10 ° C below the orientation temperature at which the aromatic polyester undergoes the biaxial expansion.

32. The article according to claim 31, characterized in that the aromatic polyester is PET and the elimination polymer has a TG of 70-85 ° C.

33. The article according to claim 31, characterized in that the aromatic polyester is PEN and the elimination polymer has a TG of 120-135 ° C.

34. The article according to claim 1, characterized in that the elimination polymer has a crystallization rate no greater than a crystallization rate of the aromatic polyester.

35. The article according to claim 1, characterized in that the article is selected from the group consisting of a film, a package, preform, a blow molded container, and a portion thereof.

36. . The article according to claim 35, characterized in that the article is a wall portion of a pressurized, pasteurizable container.

37. The article according to claim 1, characterized in that the article is a container having an oxygen removal rate of at least 5 ng / cm2 / day.

38. The article according to claim 1, characterized in that the article is a package that has an elimination performance ratio of at least 1.5.

39. The article according to claim 1, characterized in that the article is a package having an elimination performance ratio of at least 4.

40. The article according to claim 1, characterized in that the article is a package having an elimination performance ratio of at least 8.

41. The article according to claim 1, characterized in that the article is a package that has an elimination performance ratio of at least 20.

42. The article according to claim 1, characterized in that the article is a package having an elimination performance ratio of at least 40.

43. The article according to claim 1, characterized in that the article is a wall portion of a blow molded container having: an oxygen removal rate of at least 5 ng / cm2 / day; an average biaxial elongation ratio from 9: 1 to 15: 1; Y at least one layer of the removing polymer and a catalyst and at least one layer of the aromatic polyester polymer selected from the group consisting of PET, PEN, and copolymers and mixtures thereof.

44. The article according to claim 1, characterized in that the elimination polymer has a molecular weight of at least 50,000 and a TG in a range of 70 to 135 ° C.

45. An oxygen scavenging packaging material, transparent to retain an oxygen sensitive product, the material is characterized in that it includes a scavenging polymer comprising: a scavenging polymer, an aromatic ester and a catalyst, and an aromatic polyester polymer, biaxially oriented, the elimination polymer including aromatic groups and alpha-hydrogen-carbonyl groups, functional, oxygen scavenging, the material including one or more of a mixture, copolymer or layer structure of the polyester polymer and the polymer of elimination having an elimination performance ratio of at least 10, wherein the ratio is defined as the oxygen permeability of an elaborated control material of the polyester polymer alone, to the oxygen permeability of the elaborated oxygen packaging material both of polyester polymer and of elimination polymer.

46. An oxygen scavenging container, transparent to retain an oxygen sensitive product, the package which is characterized in that it includes a scavenging polymer comprising an aromatic ester polymer and a catalyst, and a biaxially oriented aromatic polyester polymer, the polymer of elimination which includes aromatic groups and functional groups for elimination of oxygen, of alpha-hydrogen-carbonyl, the material that includes one or more of a mixture, copolymer or layer structure of the polyester polymer and the elimination polymer and the container that It has an oxygen removal rate of at least 5 ng / cm2 / day.

47. An oxygen scavenging container, transparent to retain an oxygen sensitive product, the package which is characterized in that it includes a scavenging polymer comprising an aromatic ester polymer and a catalyst, and a biaxially oriented aromatic polyester polymer, the polymer of elimination which includes aromatic groups and functional groups for elimination of oxygen, of alpha-hydrogen-carbonyl, the material that includes one or more of a mixture, copolymer or layer structure of the polyester polymer and the elimination polymer and the container that it has a life in instant of one part per million of oxygen during a period of 112 days.

48. A container having a multilayer, transparent wall formed by biaxial expansion, the multilayer wall is characterized in that it includes: a core layer of an oxygen scavenging material comprising a catalyst and a scavenging polymer, of aromatic polyester which includes oxygen elimination functional groups, of alpha-hydrogen-carbonyl, in the formula: O i _0-C- (CH2) n- where n = 2 or more, and aromatic groups providing individual or multiple aromatic rings in a structure or side chain of the elimination polymer; inner and outer intermediate layers, of an oxygen barrier material; and inner and outer layers, of an aromatic polyester polymer, biaxially oriented; wherein the oxygen scavenging layer is adapted to undergo biaxial expansion with the layers of the polyester polymer and remain transparent while providing an oxygen scavenging rate of at least 5 ng / cm2 / day.

49. The packaging material or container according to any of claims 46-49, characterized in that the aromatic polyester is selected from the group consisting of PET, PEN and copolymers and mixtures thereof.

50. A method for making a transparent, multi-layer, oxygen scavenging article, characterized in that it comprises: providing a layer of a polyester, aromatic polymer; providing a removal layer comprising a catalyst and a polymer removal, aromatic ester, comprising functional groups oxygen scavenging alpha-hydrogen-carbonyl of the formula: O I _0_C_ (CH2) n- wherein n = 2 or more, and aromatic groups that provide individual or multiple aromatic rings in a structure or side chain of the elimination polymer; the percentages by weight of the aromatic and alpha-hydrogen-carbonyl groups are selected to adjust a vitreous transition temperature of the elimination polymer; and biaxially expanding the elimination polymer layer and the polyester polymer layer in order to biaxially orient the polyester polymer layer and form the transparent article.

51. The article according to claim 31, characterized in that the aromatic polyester is PEN and the elimination polymer is amorphous and has a TG of 90-100 ° C.

52. The article according to claim 1, characterized in that the layer comprising the catalyst the elimination polymer is a mixture.