This application claims priority tram United States Provisional Application No, 62/174,593 fifed on 12 June 2015, United States Provisional Application No. 62/174,603 tiled on 12 June 2015, United States Provisional Application No, 62/174,631 filed on 12 June 2015, and United States Provisional Application No. 62/180,861 filed on 17 June 2015 the teachings of each of which are incorporated herei n by reference in their entirety.

BACKGROUND

United States Patent No. 7, 1 §,159 B2 to Liu et ah 'Liu") discloses a composition of a polyester, a partially aromatic ptxlyamide, a cobalt salt and an ionic compatibilizer that is a eopoiyester containing a metal sulfonate salt, Liu teaches that the use of a transition metal catalyst to promote oxygen scavenging in polyamide cors.tai.ners is well known. Liu mtther teaches that blends of an ionic compatlbilixer (eopoiyester containing a metal sulfonate salt) and. a cobalt salt results in a container having improved gas barrier properties, improved haze and reduced yellowness. Liu also teaches that blends of polyesters and po!yamides suffer from issues of haze and yellowness.

United States Patent No. 8,871,846 B2 to Eava ("Lava") discloses a composition of a polyester, a polyamjde, a transition metal catalyst and an inert organic compound selected from the group consisting of paraffins, vegetable oils, poiyaSkylene glycols* esters of polyols, aSkoxylates, and mixtures of these substances with linseed oils being an example of such a vegetable oil. Fava discloses that the use of an inert organic compound, which, preferably is liquid at ambient temperature* in transition metal-based poSyester/polyamide compositions for the forming of articles, e.g. packaging, materials for personal care, medical pharmaceutical, household., industrial _* food and beverage plastic products, shows a considerable improvement of the oxygen scavenging performance and a considerable reduction or a complete elimination of the oxygen scavenging induction period compared with known transition metal-based polyesier/poiyainide blends not comprising an inert liquid organic compound.

SUMMARY

Disclosed herein is a preform having a preform wall which may comprise a composition comprising at least one polyester component, a transition metal catalyst, and a vegetable oil comprising at least one moleenle having a double allyi.ic structure, wherein the at least one polyester component may comprise at least one acid unit and at least one dio! unit, the concentration of the double a!lylie structures of the vegetable oil in the composition may be greater than 5.0 meq/kg of all of the polyester components, and the preform may have an to value of less than 260 in an equation :

where L ^* is a Hunter L ^' measurement in the range of between 0 and 100 excluding 0 and t is the tMekoess of the preform wall in mm.

It is further disclosed that the at least one polyester component ma be a copotyester containing a metal sulfonate salt group, it is further disclosed that the metal sulfonate salt group may be a metal sidfoisophthaiate derived from a metal salt ^' of 5-sdfbisophihaUe acid, its dimethyl ester or its glycol ester. It is further disclosed that the metal salt of S-sulibisophthalic acid. Its dimethyl ester or its glycol ester may further comprise a metal Ion selected from the group consisting of Na U\ FT ^" , ¾f ^: , Mn ^*' \ Co^ ^' and Ca ^: . It is further disclosed that the metal sulfonate salt group is preferably present in. a range selected from the grou consisting of 0.01 to ί 0.0.mole percent, 0.01 to 2.0 mole percent, 0.05 to 1.1 mole percent, 0.10 to 0.74 mole percent and OJO to 0 _* 6 mole percent based upon the total mo!es of acid units in all of the polyester components.

ft is further disclosed that the transition metal catalyst may be a compound containing at least one cobalt atom in a positive valence state. It is further disclosed that the transition metal catalyst is preferably a salt containing at least one cobalt atom in a positive oxidation state. It is further disclosed that the transition metal catalyst is preferably added to the composition at a level in a range selected from the group of between 10 and 600 ppm, between 20 and 400 pprn and between 40 and 200 ppm of metal relative to the total amount of the polyester components and vegetable oil present in the composition.

It is further disclosed that the vegetable oil may be selected from the group consisting of flax seed oil, linseed oil, evening primrose oil, borage oil, sunflower oil, soybean oil, grapeseed oil, corn oil, cotton seed oil., rice bran oil, oanola oil and peanut oil. It is further disclosed that the composition may have a concentration of the double ally tic structures of the vegetable oil in the composition greater than 7.0 meq kg of ail of the polyester components _* It Is further disclosed that t he composition may have a concentration of the double allylie structures of the vegetable oil in the composition greater than. 9.0 meq/kg of all of the polyester components. It is further disclosed thai the composition may have a concentration of the double a!!yiic structures of the vegetable oil in the composi tion greater than 14.0 me /kg of all of the polyester components.

It .is further disclosed that the composition may further comprise a poSyamide. It is further disclosed that the preferred potyamide is poiy-metaxyiylene adiparnide, it is further disclosed thai the polyamide may be present in the composition at a level in a range selected from the group consisting of between 0.1 and 0.9 % by weight of the total composition, 0.1 to 0.8 % by weight of the total composition, 0 _* 1 to 0 _* 7 ¾ by weight of the total composition and 0,1 to 0,6 % by weight of the total composition. Also disclosed herein is a preform having an ω value of less than 93. Also disclosed herein is a preform having an o value of less than 24. Also disclosed herein is -a preform having an o value of less than 20. Also disclosed herein- is a preform having an ω value of less than 15. Also disclosed, herein is a blaxially oriented container manufactured from a preform.

Also disclosed herein is a preform having a preform wall which may comprise a composition comprising at least one polyester component, a transition metal catalyst, and a vegetable oil C'YQ") comprisin at least one molecule having a doable allylic structure, wherein the at least one polyester component may comprise at least one acid unit and at least one d.iol unit, the concentration of the double a!lylic structures of the vegetable oil in the com position may be greater than 5,0 nieq/kg of all of the polyester components, and the preform may have an γ value of less than 50 in an equation: y— .... ^w .....w......V...O.......

f*V/outvo

where e½-vo s calculated according to the equation;

Ww/VD = (|7½ ) ^{x 1000}

where L is a Hunter L ^' measurement in the range of between 0 and .100 excluding 0 _» i is the thickness of the preform wall, i mm, and the composition comprises a vegetable oil, and where « o(«.vo ^i& calculated according to the equation:

<*>w/o«*VO ~ (jT^) ^{X 1000} where L is a Hunter L measurement in the range of between 0 and 100 excluding 0, t is the thickness of the preform wall, in mm, the composition is the same as the composition used to calculate the value o 6½ _% the preform, comprises the same dimensions and weight as the preform used to calculate the value of e vo, and the composition does not comprise a vegetable oil

It is further disclosed that the at least one polyester component is preferabl a eopolyester containing a metal sulfonate salt group. It is further disclosed that the metal sulfonate salt group is preferably a metal sulf isophthalate derived from a metal salt of 5-suI oisophthalie acid, its dimethyl ester or its glycol ester, it is further disclosed that the metal salt of S-suifoisophthalie acid, its dimethyl ester or its glycol ester may further comprise a metal, ion selected from the group consisting of Na Li ^'" , K Ztf ⁵ ", in~ Co^ and Ca^ _* It is further disclosed that the metal sulfonate salt group is preferably in a range selected, from the group consisting of 0.01 to 10.0 mole percent, 0,01 to 2.0 mole percent, 0.05 to .1.1 mole percent, 0.10 to 0.7-4 mole percent and 0.10 to 0,6 mole percent based, upon the total moles of acid units in all of the polyester components.

St is further disclosed that the transition metal catalyst may be a compound containing at least one cobalt atom in a positive oxidation state. K is further disclosed that the transition metal catalyst may be a salt containing at least ^' one cobalt atom in a positive oxidation state. It is further disclosed that the transition metal catalyst may be added to the com sition at a level in a range selected from the group of between 10 and 600 ppm, between 2.0 and 400 pprn and between 40 and 200 ppm of metal relative to the total amount of the polyester components and vegetable oil present in the composition.

It is farther disclosed that the vegetable oil is preferably selected from the group consisting of flax seed oil, linseed oil, evening primrose oil, borage oik sunflower oil, soybean oil, grapeseed oil, com oil, cotton seed oil, rice bran oil, canola oil and peanut oil. it is further disclosed, that the composition may have a concentratio of the double allylk structures of the vegetable oil in the composition greater than 7.0 meq/fcg of all of the polyester components. It i further disclosed that the composition may have a concentration, of the double aliySie structures of the vegetable oil. in the composition greater than. 9,0 meq/fcg of all of the polyester components, it is further disclosed that the composition may have a concentration of the double atiyiic structures of the vegetable oil In the composition greater than 14.0 me /kg of all of the polyester components.

It is farther disclosed that the composition may further comprise a polyamide. it is farther disclosed that the preferred polyamide is poly-metaxylylene adlpamide. It is further disclosed that the polyamide may be present in the composition at a level in a range selected from the gro up consisting of between 0.1 and. 0.9 % b weight of the total composition, 0.1 to 0,8 % by weight of the total composition* 0.1 to 0.7 % by weight of the total composition and 0.1 to 0.6 % by weight of the total composition.

Also disclosed herein is a preform having an γ value of less than 20. Also disclosed herein is a preform having an, y value of less than 1.0. Also disclosed herein is a preform having an value of less than 5, Also disclosed herein is a biaxiatly oriented container manufactured from a preform.

Also disclosed herein is an article having a wall comprising a composition which may comprise at least one polyester component, a transition metal catalyst, and vegetable oil comprising at least one molecule having a double allyiic structure, wherein the at least one polyester component may comprise at least one acid unit and at least one dio.1 unit, the concentration of the double alivlic structures of the vegetable oil in the composition ma be greater than 5.0 meq/kg of all of the polyester components, and the wall may have a wall thickness less than 3.5 mm.

It is .further disclosed that the at least one polyester component may be a copolyester containing a metal sulfonate salt group. It is further disclosed that the metal sulfonate salt group may bo a metal suifbisophthalate derived from a metal salt of S-sulfoisophthalic acid, its dimethyl ester or its glycol ester, it is further disclosed that, the metal salt of S-siilfoisophthalic acid, its dimethyl ester or its glycol ester may comprise a metal ion selected from the group consisting of Na ^r , Li ^" , ^T , Zn ^*' , n^ Co~ and Ca" ^'" , It is further disclosed thai the metal sulfonate salt group is preferably In. a range selected from the group consisting of 0.01 to 10.0 mole percent, 0,01 to 2.0 mole percent, 0.05 to LI mole percent, 0.10 to 0.74 mole percent and 0,10 to 0.6 mole percent based upon, the total moles of acid units in all of the polyester components.

It is further disclosed that the transition metal catalyst ma be a compound containing at least one cobalt atom in a positive oxidation state _* it is further disclosed that the transition metal catalyst is preferably a salt containing at least one cobalt atom in a positive oxidation state, it is further disclosed that the transition metal catalyst is preferably added to the composition at a level in a range selected from the group of between 10 and 600 ppm, between 20 and 400 ppm and between 40 atid 200 ppm of metal relati ve to the total amount of the polyester components and vegetable oil present in the composition.

It is further disclosed that the vegetable oil is preferably selected from the group consisting of flax seed oil, linseed oil, evening primrose oil, borage oil sunflower oil* soybean oil, grapeseed oil, corn oil, cotton seed oil, rice bran oil, canoia oil and peanut oil. It is further disclosed that, the composition may have a concentration of the double allylic structures of the vegetable oil in the composition greater than 7,0 meq/kg of all of the polyester components. It is further disclosed that the composition: may have a concentration of the double ally He structures of the vegetable oil in the composition greater than 9.0 meq kg of all of the polyester components. It is further disclosed that the compositio may have a concentration of the double allylic- structures of the vegetable oil in the composition greater than 14,0 meq/kg of all of the polyester components ,

It is further disclosed that the composition further may comprise a polyamide. It Is further disclosed that the preferred polyamide is poiy-metaxylylene adtpamlde. It is further disclosed that the polyamide may be present in the composition at a level in a range selected from the group consisting of between 0,1 and 0,9 % by weight, of the total composition, 0,1 to 0.8 % by weight of the total composition, 0,1 to 0,7 ¾ by weight of the total composition and 0,1 to 0.6 % by weight of the total composition. ίί is further disclosed that the article may have a wall thickness less than 3.0 mm. It is further disclosed thai the -article may also have a wall thickness less than 2,45 mm.. It is further disclosed thai the article .is a film. It is further disclosed that the article is a sheet. It Is fcrtlier disclosed that the article is. a preform. Also disclosed herein is a biaxiali oriented container manu acture from a preform,

BRIEF DESCRIPTION OF FIGURES

Figure 1. Is a graph of oxygen ingress data of the experimental runs 1 through 6 reported herein.

DETAILED DESCRIPTION

The -addition of a transition metal catalyst, specifically a cobalt compound and more specifically a cobalt salt, to blends of polyesters and poiyamides to create an active oxygen, scavenging system with the polyam!de reacting with the oxygen is well ^' known in the art. The addition of vegetable oils to polyester/polyamide eompositions for preforms and containers for initiating oxygen scavenging is also known in the art, see for example United States Patent No, S,S71,S46 B2 to Fava C'Fava").

Many vegetable oils are known to contain at least one molecule having a double ally!ic structure. One type of double all lic structure is a mono Diaiiylic havi ng the general structure:

Mono Diaiiylic structures are found in, for instance, linoleie acid, which is a common component of several vegetable oils. Another type of double allylic structure Is a bis Diaiiylic having the general structure:

Bis Diaiiylic structures are found in, for instance, hnoienic acid, which is a common component of several vegetable oils. What the inventors have found Is that the vegetable oil can be an. oxygen scavenger in. Its own right when the concentration, of vegetable oil in the composition is above a critical threshold, The critical threshold is considered to be the level at which the vegetable oil is n longer completely sohibilized in the polymer. Wi thout wishing to be bound by any theory, it Is believed that, if all of the vegetable oil Is solubilfoed in. the host polymer, there are no reactive sites available for scavenging oxygen. However, if the vegetable oil I added at a concentration such that not all of the vegetable oil is solubih¾ed. in the polymer, the vegetable oil will form reactive domains in the composition which are evidenced by increased haze. This increased haze can be controlled by controlling the co and or γ values for the composition as described herein, While the solubility of the vegetable oil in the- polymer will vary slightly depending on the type of vegetable oil used, in general the inventors have found that oxygen scavenging occurs when the vegetable oil is present In the composition at a level selected from the group consisting of greater than 0.6 % by weight relative to the total weight of the polyester components, the transition metal catalyst and the vegetable oil, greater than 0.5 % by weight relative to the total weight of the polyester components, the transition metal catalyst and the vegetable oil, greater than 0.4 % by weight relative to the total weight of the polyester components, the transition metal catalyst and the vegetable oil and greater than 03 % by weight relative to the total weight of the polyester components, the transition metal catalyst and the vegetable oil Thus, the composition results ^' in a preform, container* sheet or film having active oxy gen scavenging characteristics when substantially void of a polyamide.

Further, the inventors have found that the amount of time that the composition will scavenge oxygen is dependent upon the miHiequivalents per ^' kilogram (meq kg) of double allylie structures from the vegetable oil in the final composition. The miHiequivalents per kilogram (meq/kg) of double al!yiie structures is determined by -first calculating the mniole/kg of molecules containing mono Diallvlic structures and the mmole/kg of molecules containing bis DiailySie structures in the respective vegetable oil. For example, where the vegetable oil contains 15% by weight Iinoleic acid having a molecular weight of 280.45, the mmole/kg of mono

Diallylie .structures in the vegetable oil is 534.85, ((^ ^ ^ ¾; 10,000 ~ 534-85), Where the vegetable oil also contains 54% by weight lindlenic acid having a molecular weight of 278.43* the mmole/kg of bis Diallylic structures in the vegetable oil is 1,939.45, ( ,,,, \ x 10,000 ~

1,939,45). Once the mmole kg of mono Diallylic structures and bis Diallylic streetares in the vegetable oil is known, this value can be used to calculate the meq/kg of double allylie structures n the vegetable oil by adding the mniole/kg of .mono Diallylic structures to the .mmole/kg of bis Diallylic structures multiplied by two _* The mmole/kg of bis Diallylic structures is multiplied by two to take into account the fact that the bis Diallylic structures contain, two reactive sites,. For example, a vegetable oil containing 1.5% by weight Iinoleic acid and 54% by weight fi.nol.enic acid contains 4,413.75 meq/kg of double allylie structures, (534.85 - (1,939,45 x 2) = 4,413.75). Once the meq/kg of double allylie structures in the vegetable, oil Is known, this value can be used to calculate the miiiiequivalents per kilogram of polyester components In the final corn-position by dividing this number by the weight of the polyester components in the composition. To ensure- acceptable oxygen scavenging performance and longevity it is preferred that the vegetable oil have a concentration of double al ly tic structures greater than 1 00 .eq/fcg, greater than I 500 meq/kg, greater than 2000 meq kg, or greater than..2300 m.eq/kg, where the concentration is a measure of the mifliequivalents rf the double allyiie structure relative to the weight of the vegetable oil. Accordingly, this discovery is- to a composition for containers comprising at least one polyester component which Is a copolyester containing a metal sulfonate salt group, a transition metal catalyst, and a vegetable oil comprising at least one molecule having a double .allyiie structure, wherein the copolyester containing a metal sulfonate salt group comprises at least one acid unit and at least one dial unit, the concentration of the double allyiie structures of the vegetable oil in the composition is greater than 5,0 meq/kg of ail of the polyester components, greater than 7,0 meq/kg of all of the polyester components, greater than 9.0 meq kg of all of the polyester components, or greater than 14.0 meq/kg of all of the polyester components.

The composition may also contain poiyamide. Where a polyarokle is included it is preferred, thai the poiyamide is poly-me axylylene adipamide, Poiy-metaxyiylene adipamide is a partially aromatic- poiyamide sold commercially as MXD6 available from Mitsubishi Gas Chemieal Co. Where the poiyamide is present it is preferred that the poiyamide is present at level in a range selected from the group consisting of between 0.1 and 0.9 % by weight, of the total composition, 0.1 to 0.8 % by weight of the total composition, 0.1 to 0.7 % by weight of the total composition and 0.1 to 0,6 % by weight of the total composition. In one embodiment, the composition may be substantially void of a poiyanikle or entirely void of a poiyamide.

Also disclosed in this specification is a preform made from the polyester composition of at least one polyester component which is a copolyester containing a metal sulfonate salt group, a transition metal catalyst, and a vegetable oil comprising at least one molecule having a double allyiie structure.. As explained in detail, herein, the metal sulfonate salt group has bee .found t dramatically increase the amount of oxygen scavenging of the vegetable oik

One problem associated with using the vegetable oil is that the amount of vegetable oil required for oxygen sca venging increases the haziness or m ilklness of the article as measured by Hunter ΐΛ Techniques disclosed in this specification disclose how to make an article with much less Hunter 1 reduction from the control, and in some instances no reduction in Hunter L ^* >

Specifically, it i disclosed that the Hunter L ^" reduction can be reduced by increasing the amount of cooling applied to the article, it has been found that when the cooling is increased, it is possible to produce a preform having a value, i¾ of less than 260, less than 93, less than 24, less than 20, or less than 15 in an equation where l is a Hunter L measurement In me range of between 0 and. 100 excluding 0 and t is the thickness of the preform wall in am,

More specifically, it is disclosed how to make a preform having limited reduction in Hunter L ^* compared, to a control preform without vegetable oil as measured on two preforms having the same dimensions and composition, sa e for the fact that one of the preforms has the vegetable oil. The two preforms can be compared according to the formula;

where owo -is calculated according to the equation:

where L ^* is a Hunter L ^* measurement in the range of between 0 and 100 excluding 0„ i is the thickness of the preform wall in mm, and the composition comprises a vegetable oil, and. where ¾wo«tvo -is calculated according to the equation:

«w/ ₀ titVO = ( ^ ) ^{x 1000}

where L is Hunter L ^' measurement in the range of between 0 and 100 excluding 0 _» t is the thickness of the preform wail in mm, the composition is the same as the composition used to calculate the value of t» _w /vo _> the preform comprises the same dimensions and. weight as the preform used, to calculate the value of ft ^' ½/vo _> a d the composition does not comprise a vegetable oil.

When the preform comprising vegetable oil is made according to the teachings of this specification, it will, have a γ value of less than 50, with less than 20 being more preferred, with less than .1.0 being even more preferred and less than 5 being the most preterred.

More specifica!lyv it is disclosed thai there is minima! variation in haze or ml!kiness from the control without vegetable oil when the wall of the article has a wall thickness of less than.3 _> S .mm, preferably less than 3.mm or less and more preferably less than 2.45 mm. where the article is a film, a sheet, a preform* or a biaxially oriented container manufactured from said preform.

The polyester component is a polyester formed by the reaction product of at least on dicarboxyiic acid or Its ester derivative and at least one diol. One useful polyester is a polyester with more than 85% of its acid units being derived from terephfhalie acid.

One example of a polyester component i a copoiyesier containing a metal sulfonate salt group which can be prepared by polymerization procedures well-known in the art. The copolyester containing a metal sulfonate salt group may be prepared by melt phase polymerization involving the reaction of at least one diol unit with at least one dicarboxylio acid or its corresponding ester (the at least one acid unit) and a metal salt of S-si f isophthaiie acid or its corresponding ester.

In general, the copoiyesier containing a metal sulfonate salt group may be prepared, for example, b melt phase polymerization involvin the reaction of at least one diol with at least one dicarboxylie acid or its corresponding ester and a metai salt of S-sulfoisophthalie acid or its corresponding ester. Various copolymers resulting from use of multiple dio!s and dicarboxylie acids may also be used. Polymers containing repeating units of only one chemical composition are hom.opoly.mers. Polymers with two ot more chemically different repeat units i the same macromoiecule ate termed copolymers. The diversit of the repeat units depends on the number of different types of monomers present in the initial polymerization reaction, in the case of polyesters, copolymers include reacting one or more dlois with a diaeid or multiple cliaeids,. and are sometimes referred to as terpolymers. For example, a polyethylene terephthalate copolymer comprised of ierepiithalie acid, isophthallc acid and the lithium salt of S-su!fbisophthalic acid is a copoiyesier.

Suitable dicarboxylic acids include those comprising from about 4 to about 40 carbon atoms. Specific dicarboxylie acids include, but are not limited to, ierephtlialie acid, isophthalic acid, naphthalene 2, 6-dicarboxylic acid, cyclohexanediearboxyiie acid* eyciohexanedtacetic acid, dipheiiyl-4,4 ^, -dicaf boxy lie acid, I _s 3 -plienylenedioxydi acetic acid, 1 ,2~pheny lenedioxydiaeetic acid, 1,4-phenylenedioxydiacetic acid, succinic acid, gloiaric acid, adipk acid, azelaic acid, sebaeic acid, iuran~2 _! 5-dicarboxyIie acid and the like. Specific esters include, but are not limited to, phthalic esters and napMhalic dieslers. A useful polyester is a polyester with more than 85% o lis acid units being deri ved from terephthalic acid.

^" These acids or esters may be reacted with an aliphatic diol preferably having from about 2 to about 24 carbon atoms, a eyeloaliphatie diol havin from about 7 to about 24 carbon atoms, an aromatic diol. having fro about 6 to about 24 carbon atoms, or a glycol ether having from 4 to 24 carbon atoms. Suitable diols and glycol ethers include,, but are not limited to, ethylene glycol, 1,4-butanediol, tximethylene glycol, 1 ,6-hexanedioi, 1,4-cyeiohexanedimethanol, diethylene glycol, resorcirsol, i ^propanediol, neopbenthyl glycol, isosotbide, 2,2,4,4- tetramethyl- 1 ,3-cyclobutanedioi (TMCD) and hydroquinone,

Polyfunetional comononiers can also be used, typicall in amounts of from about 0,0 f to about 3 mole percent, Suitable comononiers include, but are not limited to, trimellitic anhydride, trtmethylolpropane, pyromeliitic dianhydride (P DA), and pentaerytliritol. Polyester-forming polyacids or polyols can also be used. Blends of polyesters and eopoiyesters may also be useful in the present invention.

It is also well known that di-ethyle e glycol is formed irs-situ in the manufacture of polyesters having ethylene glycol as their starting diol and that, about 2 to 3 percent of the total

to moles of the final dial units in the polyester will be dietbylene glycol, Therefore, the composition may have 97 mole percent of its dioi units as ethylene glycol and 3 mole percent of its dioi units as di-ethylene glycol.

The ester ification or polycondensaiion reaction of the carboxylic acids or their esters with the dioi.(s) typically takes place .i the presence of a catalyst. Suitable catalysts include, but afe not limited to, antimony oxide, antimony triacetate, antimony ethylene glycolate, organornagnesium, tin oxide, titanium aSkoxides, dibutyl tin diSaurate, and germanium oxide. These catalysts may be used in combination with zinc, m ng nese, or magnesium acetates or benzoates. Catalysts comprising antimony are preferred.

The metal sulfonate salt group is preferably a metal sulfoisophihalate derived from a metal salt of S-sulfoisophthaSic acid its dimethyl ester or its glycol ester. The metal salt of 5- sulfoisop!hthalic acid comprises a metal ion selected from the group consisting of Na , Ι.Γ, K ^* _t Zn ^2" , Mn ^" Co ^" \ Ca ⁱ⁺ and the like. The copolyester containin the .metal sulfonate salt group is made by eopoiymerixing the metal sulfonate into the polymer chain,

The importance of the metal sulfonate salt can be seen in Figure I. As shown in Figure .1, compositions disclosed in Table 1 herein made without the metal sulfonate salt exhibited minimal oxygen scavenging and often times variable and unpredictable oxygen scavenging, Surprisingly, the presence of the metal sulfonate salt, even at very low levels, increased the oxyge scavenging performance of the vegetable oil and eliminated most, if not all of the variations and. unpredictability.

One suitable copolyester containing a metal sulfonate salt group is a copolymer of polyethylene terephtbalate (PET) modified with a metal sulfoisoplithalaie derived from the di- ester or di-carboxy c acid of a metal sulfoisophihalate in the approximately 1:1 stoichiometric reaction of acids, or their di-esters, with ethylene glycol. Specific copolymers and terpoiymers also include crystallizable and non-crystal Sizable polyesters comprising a metal sulfotsophthalate in combination with isophthalic acid or its diester, 2,6 naphthaSate dicarboxySic acid or its diester, and/or oyclohexane dimethanol.

The amount of metal sulfonate salt group in the polyester component, in particular, metal sitlfoisophihaSate (derived from a metal salt of 5-sulioisoplithalic acid), is preferably in the range of about 0,01 to 10,0 mole percent based on the total acid units in ail of the polyester components of the composition, with an optimal, amount being in the range of about 0,0.1 to about..2.0 mole percent based on the total acid units in all of the polyester components of the composition* with the range of about 0.05 to about 1,1 mole percent based on the total acid units .in ail of the polyester components of the composition being more optimal, and about 0,10 to about 0,74 mole percent based on the total acid units in all of the polyester components of the composit ion being even better yet, with the range of about 0,10 to about 0,6 mole percent based on the total acid units in ail of the polyester components of the composition being the most optimal range. The amount of metal sulfonate salt group in the composition is calculated on the basis of the moles of the total acid groups in all of the polyester components present in the composition.

One preferred metal su!foisophihaiate is derived from S-Hthiumsulfotsophthalic acid. The molecular structure of S-Iitliitm si foisophihahc acid is:

5-lithi «>su!fo!SQp.hihah ^' c acid (LiSlPA) or sulfonic acid lithium, salt modified isophthaiie acid.

As Is evident from the above diagram, the 5-liihiumsoifoisophtha!ie acid is a lithium sulfonate and comprises lithium suiioisophthalate. The lithium suiioisophthalate refers to the compound as it Is appears incorporated Into the polymer chain. This is also known as the repeating unit of 5-Hthiumsulfoisophthaiic acid _* Lithium sulfoisophchalate therefore is the 5- HthtumsolfQisophtbalic acid less one water molecule, with one hydroxy! group removed from one of the carboxyl end groups and a hydrogen removed from the other carboxyl end group. This molecule is then attached to one or more monomers (Rj and ?) lit the polymer backbone.

^■ »~

The metal sulfonate salt group, in this case lithium su!fotsophihaiate, is the molecule between the two R groups. Again, R could be the same monomer, in the case of PET, the R's are likely the same being the ethylene glycol moiety as reacted into the polymer chain.

Typical levels of the metal sulfonate salt group In a polyester polymer range from 0.01 mole percent to 15 mole percent with respect to the total number of moles of the respective acid unit. For example, a typical homopo!ymer polyester has 100 mole percent terephthalic acid units and 100 mote percent glycol units (ethylene glycol and di-ethylene glycol) _* A polyester containing 5 mole percent of a metal salt of suifoisophthalic acid co-monomer would be derived from 95 moles of terephthalie acid., 5 moles of metal sulfonate (such as 5 itfiium$ulfotsophthalie acid) and 100 moles of ethylene glycol. Similarly, it may be a vanta e us to add another co- monomer such as isophthalk acid. For example, a 2 mole percent isophthalate polymer would contain 93 moles terephthalie acid, 2 moles of isophthalic acid, 5 moles of metal sulfonate (such as 5-litfrium$ulibisopht½iie acid) and 100 moles ethylene glycol to make 100 moles of the polymer repeat unit

Example* of copolyesters containing a metal sulfonate salt group employed in the present invention are those prepared b virtually any polyeondensation polymerization procedure, The traditional techniques can be divided into the ester, acid, and modified processes. In the ester process* the dimethyl ester of the diearboxytic acid or acids is reacted with the dio! or diols in the presence of heat and the methanol removed yielding the bis-hydroxyethyt ester of the acids. The bis-hydroxyethyl ester is then polymerized in its liquid form by subjecting the material t vacuum and heat to remove the glycols and increase the molecular weight A typical process for the object polymer would start with these ratios: 98 moles of dimethyl terephtlialate, 2 moles of dimethyl lithium salt of sn foisophthalate and 220 moles of dio!., typically ethy lene glycol., Of the 220 moles of diot, 120 are excess which are removed during processing _* it should be noted that it is possible to obtain the sulfonated co-monomer in either its bis~(hydraxyetliyi) or dimethyl ester form.

For clarification, the phrase copolymerked with at least X percent of a specific acid means that the compound is considered as part of the aeid. group of the polymer, such as terephthai c or isophthalic acid. It provides the reference to determine how many moles of the compound to use. The phrase does not mean that the compound must be added to the process as an acid. For example, S-lithiumsulioisophthalic acid could be copolymerized into polyeth lene terephthalate as the acid, with two earboxylie end groups, the dimethyl ester of the catboxyiie acid, or the bishydroxy ester of the dimethyl ester or even, very low molecular weight oligomers of a glycol acid polymer where the acid units are at least in part, the sulfbisophthaiate salt

The phrase '*copoiymeri.¾ed salt of the acid" should not limit the claim to only using the acid form, but should he read to mean the compound is one of the acid groups in the polymer.

The phrase "copolymerized with'* means that the compound has been chemically reacted with the polymer, such as in the polymer chain or as a pendant group _* For example, a polyester copoiymerked with lithium sulfoisophthalate, or modified by copolvmerizing at least 0.01 mole percent S-iithiumsulfbisophihalic acid into the polyester, means that the lithium siilfoisophthaSate is bonded to the polymer, including bound into the polymer chain, with at least one chemical bond. The phrases are indifferent to how the material is incorporated into the polymer. A polyester copoly.mer.ized with lithium, solfoisophthalate, or modified by copolymerizing at least 0.01 mole percent lithium snifoisophthalate into the polyester refers to a polyester containing the lithium suifoisaphthaiaie whether that lithium sulfoisoph ha e was incorporated, using but not limited to 5-hthitmisui.foisophthalie acid, lithium solfobenzoie acid, th dimethyl ester of 5- lithmmsulfolsophthatlc acid, the methyl ester of lithium suifobenzolc acid, the di-alcoho! of lithium sidfossophtha!ate, the lithium suliohydroxy benzene;, the lithium salt of hydroxy benzene sulfonic acid, or oligomers or polymers containing the li thium, sulfoisophthalate.

The phrases " nd der vatives" and "and I s derivatives* ^* refer to the various ftracttonalked forms of the metal sulfonate salt which can be copolymerized Into the polymer. For example, lithium, suifblsophthalaie "and its derivatives" refers collectively and is not limited to 5- lithitsmsulfolsophthaSlc acid, the dimethyl este of S-iithluirrsuSfoisophihalic acid, the bis- hydroxyethyl ester of 5-lithiutnsu!fo ^' isophfha!ic acid _f the di-aleohol of lithium stdfoisophfhaSate, low molecular weight oligomers, and high I.V. polymers containing, lithium sidfossophtha!ate in the polymer chain.

The same nomenclature applies to the glycol or dioL

In the ac d process, the starting materials are the diearboxyiic acids, with water being the primary by-product. The charge ratio In. a typical, acid process is 98 moles ierephihaiic acid, 2 moles of a metal salt of sulfoisophthalic acid (e.g. 5-iKhiumsulfoisophthalic acid - USIPA), and 120 moles of diols, typical ethylene glycol. After reaction of the diols with the acids, the material is subjected to the same polymerization process conditions as the ester process.

The modified processes are variations of either process: combining the intermediary product at certain steps. One example is to pre-po!ymerize the raw materials without the metal salt of sulfoisophthalic acid to a .low molecular weight In the case of the examples described below _. , the molecular weight of the low molecular weight polyester was typically in the range 0,096 to OJ03 di/g having a carboxyS end group number ranging from 586 to 1740 equivalents per 1,000,000 grams of polymer. The molecular weight could be easily varied without undue experimentation as it has been, for man years by those of ordinary skill in the art when optimizing the addition point for their additives.

Another example of a variation is to use the acid process with just terephthalio acid, to produce its low molecular weight intermediate and the ester process used to produce the bis- hydroxy eth l ester of the homopolymer sulfonated polyester. These two Intermediates arc then combined and polymerized to a copolymer. Another variation is to add the finished modified polymer to the melt reactor and let the melt process depolymerise the modified polymer and then form a copolymer.

The copoSyester of this invention may also contain small amounts of phosphorous compounds, such as phosphates. Also, small amounts of othe polymers such as po!yoiefins can be tolerated in the continuous matrix. After completion of the melt phase polymerization, the polymer is either made into a form .such as a film or part or stranded -and cut into .smaller chips, such as pellets. The polymer is usually then crystallized and subjected to a solid phase (solid state) polymerization (SSP) step to achieve the intrinsic viscosity necessary for the manufacture of certain articles such as bottles. The crystallization and lymerizati n can be performed in a tumbler dryer reactor in a batch- type system. The solid phase polymerization ca continue in the same tumble dryer where the polymer is subjected to high vacuum to extract the polymerization by-products.

Alternatively, the crystal lizati n and polymerization can. be accomplished in a continuous solid state polymerization process whereby the polymer flows from one vessel to another after its predetermined treatment in each vessel. The crystallization conditions are relative to the polymer's crystallization and. sticking tendencies. However,, preferable temperatures are from about iOO °C to about 235 C. In the case of cfystaSlisabie polyesters, the solid phase polymerization conditions are generaliy 10 X below the melt point of the polymer, in the ease of ndn-crystatlisable polyesters, the solid phase polymerization temperature is generally about 10 °C below temperature where the polymer begins sticking to itself. While traditional solid phase polymerization temperature for crystalHsable polymers range from about 200 °C to about 232 °C, man operations are from abou 215 *C to about 232 °C. Those skilled in the art will realize that the optimum solid phase polymerization temperature is polymer specific and depends upon the type and amount of copolymers in the product. However, determination of the optimum solid phase polymerization conditions is frequently done in industry and can be easily done w ithout undue experimentation.

The solid phase polymerization may be carried out for a time sufficient to raise the intrinsic viscosity to the desired level* which will depend upon the application. For a typical bottle application, the preferred intrinsic viscosity (I.V.) is from about 0.65 to about .1.0 deciliter/gram, as determined by the method described in the methods section. The time required to reach this L V, from about 8 to about 21 hours.

Vegetable oils of the present invention may be selected from the group consisting of flax seed oil, linseed oil, evening primrose oil, borage oil, sunflower oil, soybean oil, grapeseed oil, corn oil* cotton seed oil, rice bran oil, cano!a oil and peanut oil _* Preferably the vegetable oil comprises at least one molecule having a double ai!yhe structure. One type of double allyiic structure is a mono DiaSlylic having the genera! structure Mono Diallylic structures are found in, for ^' instance, linoleic acid, which is a common component of many vegetable oils. Another type of double al!ylic structure is a bis Diallylic having the general structure

Bis Diallyli structures are found in, for instance, linolenic acid, which is also a common component of several vegetable oils.

Examples of molecules having a double allylic structure found in many vegetable oils include Hnoleic acid artel gamma linolenic acid. Linoleic acid has the general structure of:

OH

Gamma linolenic

One especially preferred vegetable oil is fla seed oil. Flax seed oil is raw, cold pressed oil. derived from, the seed from the plant Linum usitatissimum. Flax, seed oil is a poly-unsaturated ester having a mixture of fatty acids, primarily In the form of triacySglycerides, with each triacylgiyceride comprised of three acids selected from the group consisting of triply saturated at ha-iinolenic acid, saturated acid palmitic acid, saturated acid stearic acid, monosaturated oleic acid, and doubly saturated linoleic acid. The poly-unsaturated ester of flax seed oil has the general structure of:

and isomers thereof.

Flax seed oil is well known for having trie alpha4i.no lenic acid as i s largest constituent Flax seed oil is available as the cold pressed oil (known simply as flax seed oil) or as a chemically treated and heated oil derived from the flax seed (known as Unseed oil). The cold pressed flax seed oil is preferred over the chemically treated and heated linseed oil as it is generally .regarded as safe for human consumption.

Vegetable oil is used as an oxygen scavenger in the compositions disclosed herein. Preferably, the vegetable oil is added at a level uch that the concentration of double allylic structures of the vegetable oil in the composition Is greater than 5.0 meq/kg of the total polyester components, greater than 7,0 meq kg of the total polyester components, greater than 9.0 meq kg of the total polyester components,, or greater than 14,0 meqkg of the polyester components. The vegetable oil can be added during the polymerization process of the copolyester containing a metal sulfonate salt group but is preferably added after the polymerization process, such as at the extruder or durin injection molding.

In one embodiment, oxygen scavenging may be assisted by the use of a transition metal catalyst. One preferred transition metal catalyst Is compound containing at least one cobalt atom in a positive oxidation state. A more preferred transition metal catalyst is a salt containing at least one cobalt atom in a positive oxidation state- One preferred transition metal catalyst is a cobalt salt in which the cobalt forms at least a portion of the compound's cation. Preferred cobalt salts Include cobalt chloride, cobalt ^" acetate, cobalt propionate, cobait steatate, cobalt octoate, cobalt neodecanoate, cobalt oleate, cobalt Hnoleate, cobalt salts of faitv acids, cobalt salts of short chained faftv acids, cobait salts of medium chained fatty acids, cobait salts of Song chained fatty acids, cobalt carbonate and combinations thereof.

The preferred cobalt salt is an organic cobait salt with the inorganic cobait salts which can be solubifee in the polyester being less preferred.

The cobalt atom of the cobalt compound ma also exist in the anion of the compound, such as lithium cobaltate (LiCoQj) and potassium tris(oxalato)cobaltate( I). The cobaltate may also be formed in situ by the reaction of the cobalt atom in the presence of the polyesters carboxyiic acids in the presence of an alkali metal base.

The cobait compound may also be a cobalt ^" complex such as cobalt glyeolate,

"The transition metal catalyst is preferably in a range of between 10 and 600 ppm of metal relative to the total amount of the polyester components and vegetable oil present In the composition with a level, in the range of between 20 and 400 ppm relative to the total amount ^" of the polyester components and vegetable oil present in the composition being more preferred and a level in the range of between. 40 and 200 ppm relative to the total amount of the polyester components and vegetable oil present in the composition being most preferred.

The transition metal catalyst may be added during the polymerization process of the polyester component and/or the copolyester containing a metal sulfonate salt or it ma be added a the polymerizatio process, such as at the extruder or during injection molding.

In some embodiments, the polyester may be polymerized in the presence of a phosphorous compound, such as poiyphosphoric acid, phosphoric aetd _» or trieihyi phosphate, for example. When the polyester Is polymerized in the presence of a phosphorous compound., it is preferred to keep the molar ratio of the amount of moles of phosphorous to the moles of cobalt ions in a. range selected from the group consisting of 0 to 1.7, 0 to 1.2, 0 to 1.1, 0 to 1.0, 0 to 0,8, and 0 to 0,6.

The components of the composition (the polyester component, the transition metal catalyst and vegetable oil) are often melt blended in an injection molding extruder to make a film, sheet or preform. When the composition is injection molded to make a preform., the preform can then, be biaxiai.ly stretched, such by reheat, blow molding, to form a biaxiai.ly oriented container.

It was further found that vegetable oil at the disclosed levels often produces a hazier or milkier article, compromising the article's aesthetic characteristics. While such articles can have better aesthetic characteristics by masking or covering up the mfikiness using a full-body label wrap or by the use of an additional colorant that will mask haziness as disclosed in United States Patent No, 7,833,59-5 B2, the teachings of which are hereb incorporated by reference in their entirety, it is preferable to arrive at an article having improved visual characteristics without the need for a full-body label wrap or the use of an additional colorant.

It was discovered that the rnilkiness can he reduced b adding additional, cooling after injection molding. Additional cooling can he achieved by reducing the injection molding- temperature, decreasing the temperature of the injection molding cooling liquid, increasing the time that the composition is held in the mold, decreasing the wall thickness of the article or any combination thereof When additional cooling is achieved by decreasing the wall thickness of the article, it is preferred that the wall thickness be less than 3.5 mm, with a wall thickness less than 3.0 mm being more preferred and a wall thickness less than 2 _* 45 mm bein even more preferred.

The milkiness/haze of the article can be determining by calculating the val ue of to in an equation: ω = (~J™) x 1000

W X V

where If is a H unter L* measurement in the range of between 0 and 100 excluding 0 and t is the thickness o f the preform wall in mm. Preferably, the val ue of is less than 260 with an to value less than 93 being more preferred, -an w value less than 24 being even more preferred, an to value less than 20 being still .more preferred and m ø> value less than 5 being most preferred.

The increase in mHkiness can also be assessed by determining the value of γ in an equation

&½/VO

Y

^w out o

where o> _¾¥ o is calculated, according to the equation

«w/vo - (u^) wo

where L is a Hunter L measurement in the range of between 0 and 100 excluding 0, t is the thickness of the preform wail in mm, and the composition comprises a vegetable oil, and where ®w¾uivo * ^s calculated according to the equati

where L ^* is a Hunter L ^* measurement in the range of between 0 and 100 excluding 0, t is the thickness of the preform wall in mm, the composition is the same as the composition used, to calculate the value of a yo? ^' the preform comprises the same dimensions and weight as ^' the preform used to calculate the value of evvo, and the composition does not comprise a vegetable oil Preferably the value of γ is less than 50 with a γ value less than 20 being more preferred, a y value less than 10 being even more preferred and a γ value less than 5 being most preferred.

The compositions disclosed herein may include additional additives including colorants, pigments, fillers, acid -scavengers, processing aids, coupling, agents, lubricants, stearates, blowing agents, poiyhydrie alcohols, nucleating agents, antioxidants, antistatic agents, ϋ V absorbers, slip agetns, and-fbgging agents, anti ^condensation agents, suspension stabilizers, anti-blocking agents, waxes and mixtures thereof. These additives are added at levels not inconsistent with the end use to make a commercially acceptable container. Generally, these additives are added at a level less than 5 % by weight of the composition..

EXAMPLES

The ability of a vegetable oil to scavenge oxygen was tested according to the following procedures, The PET resins (PETS, PET.2, SiPAL, SIPA2) were dried (177 °C, .5 hours, desiccated air) using, a ConAif D175 Desiccant Carousel, then cooled and held at 135 in the dryer until injection molding. The experimental compositions for injection molding were prepared by mixing the various PET/S1PA resins and vegetable oils together in a metal can. Compositions comprising at least one polyester component, a transition, metal catalyst -and a vegetable oil were blended in an Arburg 420C injection molding extruder and molded into preforms. The compositions were injection molded into either 28 gram preforms having a 4 mm wall thickness or .18 gram preforms having a 2,44 M wall thickness as indicated in the tables below. These preforms were then blown into 500 ml. bottles. Unless otherwise indicated, the materials used in the experimental compositions include;

PET1. ^:::: 8OO6OC0 PET resin containing 102 ppm cobalt from, cobalt neodeeanoate available from M ^' &G Polymers USA, LLC, Apple Grove, W V, USA ΡΕΓ2 = 80Q6C PET resin available from M&G Polymers USA, LLC, Apple

Grove, WV, USA

SIPA1 ~ Poliprotect S resin comprising 033 mole % LiSIPA and containing 138

ppm cobalt from cobalt neodeeanoate available from M&G Polymers

USA, LLC, Apple Grove, WV, USA

.SIPA2 ~ VFR 10644 resin comprising 0.5 mole % LiSIPA available from M&G

Polymers US A, LLC, Apple Grove, WV, USA

Co ^™ Cobalt Neodeeanoate, 20.5% Co, Product No. 1354 available from

Shepherd Chemical, Norwood, OH, USA

FSOT - Conventional Grade Flax Gil available from TA Foods, Yorkton,

Saskatchewan, Canada

FS02 ^:; = High-Omega Flax Oil from Flax seed strain uL.ki VT SO availa le from

TA Foods, Yorkton, Saskatchewan, Canada

EPR ^™ Bulk Evening Primrose Oil - Organic 9%GLA available from Jedwards

International, Braintree, MA, US A

GSO - Bulk Grape Seed Oil - ^' Virgin Organic available from Jedwards

international* Braintree, MA, USA

BO ^::: Bulk Soybean. Oil - Organic available from Jedwards International,

Braintree, MA, US

SFO - Bulk Sunflower Oil - Organic available from Jedwards International*

Braiotree, MA, USA

Unless otherwise indicated, the 28g preforms were Injection molded using the following injection molding conditions:

IM1 ^™ Injection molded using an Arburg 420C injection molding machine having a 30 mm diameter screw having a 23.1 length/diameter ratio rotating at 102 rpm, 525 °F (274 °C) injection molding temperature, 2000 psi back pressure, 21 second cycle per preform, 8 seconds of cooling in the mold, subject to 32 °F (0 °C) chiller water. IM2™ Injection molded using an Arburg 420C injection molding machine having a. 30 mm. diameter screw having a 23J length/diameter ratio screw rotating at 1.02 rpm. 540 ^e F (282 ^a C) injection molding temperature, 2000 psi back pressure, 18 second cycle per preform, 5 seconds of cooling in the mold, subject to 4.1. ^C' F (5 ^¾ C) chiller water.

Compositions comprising the components listed i Table 1. below were tested. In each run, the specific PET and SIPA components were blended to achieve the reported final SiPA mole %, Runs 1 through 3 utilized PETl resin. Runs 4 through 6 utilized PET.2 resin in combination with SlPAl resin. The SIPA mole % reported Irs Table I Is the measure of the moles of metai sulfonate salt group based upon the total moles of acid units in all of the polyester components in the composition,. The amount of cobalt reported in Table 1 is the measure of ppm cobal t from cobalt neodecanoate relative to the total amoun t of the pol yester components and the vegetable oil present in the composition. The weight % of FSOl reported in Table 1 is the measure of the weight of flax seed oil relative to the total weight of the polyester components,, the transition metai catalyst (cobalt salt) and the flax seed oil. The double atlylic concentration reported in Table 1 is the milliequivaients of the double al lytic structures in FSOl relative to the total weight of the polyester components (PE and. SIPA) in kilograms.

TABLE 1

After blowing the bottles, each bottle was tested for oxygen ingress using a Mbox 4-

Traee Fiber Optic Trace Oxygen Meter (Model Qxy-4-Traee«04»Q06) made by PreSens GmbH (www,presens.de, Regeusburg, Germany). The meter reads a sensor dot which has been placed Inside the sealed bottle. The principle of the sensor operation is based on the quenching of luminescence caused by the collision between molecular oxygen and luminescent dye molecules in the excited state. The sensor dots and meter were calibrated according to the standards and. procedures given by the manufacturer. The amount of dissolved oxygen In the liquid sealed inside each bottle is calculated by the Flbox software.

In a continuously purged nitrogen box, freshly blow molded bottles are conditioned for 1.8 to 24 hours and then filled with 500 mL of ^' deoxygenated water and carbonated by the addition of citric acid (5.54 g) and sodium bicarbonate (95.81 g) to give the desired degree of earbonatio.il (3.1 volumes of C b). The bottles had aft overflow olume of 534 ml.. After filling, a transparent gas-tight plastic insert, which has a Fsbox sensor affixed to the interior top of the insert, is fitted into the mo unt of each bottle. The top exter tor of the plastic insert has a threaded. hole for the attachment of the fiber optic coupler used to read the Fibox sensor. The filled bottle with gas-tight Insert is sealed with a metal retainer cap. The metal cap has an opening to permit reading of the Fibox sensor by the meter.

To take a reading, the bottles are shaken for 10 minutes (Eberbach Reciprocating Shaker,

Model 6000) to ensure equilibration between, the oxygen dissolved: in the liquid and the oxygen in the bottle headspaee. The fiber optic cable is attached to the top of the gas-tight plastic bottle insert. The meter reads the sensor dot and calculates the dissolved 0;< concentration while the bottle is gently shaken while lying on its side.

An initial baseline oxygen reading is made on each newly filled bottle. The bottles are then aged under tow light conditions in a room controlled at 71,6 tfc 1 °F (22 ± 0.5 °C) and 43 ± 2% RH. The dissolved ¾¾ concentration readings (ppm <¾ mg L) -are taken a regular time intervals until the test is terminated. The change in dissolved ppm <¾ mg L from the baseline

(Δθ·?) for each run is reported below in Table 2 with a graph of the change in dissolved ppm (¾ mg/L reported in Figure 1.

TABLE 2

42 1.030 0.073 -0.003 0.000

43 1.243

45 1.659

49 0.948 0.097 0.000 0.001

50 1.419

55 0.002 0.006

56 0.958 0.125

57 1.728

60 2.090

63 1.084 0.156 0.007 0.006

64 1.827

70 1.190 0.192 0.014 0.009

71 2.058

77 1.35! 0.239 0.009 o.oi i

83 1.502

84 0.286 0.022 0.018

91 1.634 0334 0.028 0.024

97 1.802

98 0.419 0.036 0.034

105 1.987 0.452 0.046 0.045 i n 2.148

112 0.517 0.059 0.060

119 0.569 0.077 0.080

125 0.636

1 J J 0.716 0.119 0.139

139 0.824

140 0.148 0.195

147 0.851 0.173 0.238

153 0.956

168 0.298 0.431

174 1.174

175 0.359 0.500

181 1.274

182 0.411 0.574

189 0.486 0.651

1 5 1.428

196 0.569 0.73?

202 1.520

203 0.656 0.837

209 1.564

210 0.752 0.920

216 1.612

7 |7 0.899 1.103

^ 1.677

224 0.950 U54 230 1.695

231 1.043 ί .234

237 1.739

238 1.051 1 ,245

244 1.800

245 1.202 ί .422

251 1.843

252 1.310 i .500

258 1.901

* Cells without a reported value represent days an. which, a dissolved oxygen reading was not taken for the ma in question.

The results reported .in Table .2 above and visually displayed, in Figure 1. sho that the composition of at least one polyester which, is a copolyester containing a metal sulfonate salt group, cobalt neodecanoate and vegetable oil scavenges oxygen (results in a less C ingress as indicated by the lower ΔΟ-? at comparable reading tirn.es) irrespecti ve of cooling conditions and without the need for an additional polyam.ide component.

Additional oxygen scavenging testing was performed using different vegetable oils. The composition of these tests -are summarized below in Table 3. In each, run, the specific PET and SIPA components were blended to achieve the reported final SIPA mole %. Each run utilized PET2 resin in combination with S1PA1 resin. The SIPA mole % reported in Table 3 is the measure of the moles of metal sulfonate salt, group based upon the total moles of acid units in all of the polyester components in the composition. The amount of cobalt reported in Table 3 is tbe measure of ppm cobalt from cobalt neodecanoate relative to the total amount of the polyester components and the vegetable oil present in the composition. The weight % of the vegetable oil reported, in Table 3 is the measure of the weight o.f vegetable oil relative to the total weight, of the polyester components, the transition metal catalyst (cobalt salt) and the vegetable oil. The double ally!ie concentration reported in Table 3 is the milliequivalents of the double aliylic structures in the vegetable oil relative to the total weight of the polyester components (PET and SIPA) in

TABLE 3

These compositions were tested for oxygen scavenging performance using the Fibox 4-

Trace Fiber Optic Trace Oxygen Meter (Model Oxy-4-Trace~04~006) and the testing method described above. The results of these tests are reported below in Table 4.

TABLE 4

As can be seen in Table 4, each vegetable oil tested will not scavenge oxygen at a lower concentration in the composition (Runs 7, 10, 1.3 and 16). However, when, added at a higher concentration. (Runs 8, 9, 1 !,. 12, 14, .1.5, 17 and I S) the vegetable oil will scavenge oxygen.

Additional testing was performed to determine the aesthetic appearance of the compositions according to the following procedures. Compositions comprising at least one polyester component, a transition, metal catalyst and a vegetable oil were blended in an injection molding extruder and molded into preforms. Each preform was tested for color and haze using a HunterLab ColorQuest XE Spectrophotometer. Each preform was measured 4 times at 90° intervals in an immobilization j ig> and the average measurement was recorded. As the preform is hollow tube, the color find .haze values are the values measured through the entire pre.tb.wn. (I.e. two sidewalk).

The. L ^* color measurement of each preform was then used to calculate a value of to using the equation: ώ ^™ f ,

VI ^* X V ) 1000 where L ^* is a Hunter L ^* measuremen in the range of between 0 and 100 excluding 0 and t Is the thi.ckrs.ess of the preform, wall in mm.

The Hunter Haxe, Hunter L ^" , Hunter a ^* , Hunter h\ and & values of each preform are reported below in Table 5 along with the composition and structure of each preform. For runs 28 to 35, which are 18g preforms, one of the following injection, molding conditions were used.

IMS - Injection molded using an Arburg 420C injection molding machine having a 30 mm. diameter screw having a 23.1 length/diameter ratio screw rotating at 102 rpm. 525 °F (274 °C) injection, molding temperature, 2000 psi back pressure,. 17 second cycle per preform, S seconds of cooling in the mold subject to 32 ^C' F (0 °C) chiller water.

JM4 ^™ Injection molded using an, Arburg 4.20C injection molding machine having a 30 mm diameter screw havin a 23.1 length diameter ratio screw rotating at 102 rpm, 540 °F (282 °C) injection molding temperature, 2000 psi back pressure. 14 second cycle per preform.. 5 seconds of cooling in. the moid subject to 40 °F (4.4 °C) chiller water.

The results reported in Table 5 show that, when additional coolin was applied to the preform by increasing the injection molding cooling conditions (i.e. longer cycle time, longer cooling in. the mold, colder chiller water, lower injection molding temperature), reducin the preform thickness or a combination thereof the aesthetic appearance of the preform was improved s evidenced by a lower <a value.

in each run, the specific PET and Si PA components were blended to achieve the reported final SIP A mole %. Runs 19, 20 and 20 ^s utilized PET! resin In combination with PET2 resin and SIPAl resin. Runs 21, 22, 22', 25, 26, 26% 29, 30, 30', 3 , 32, 32', 33, 34, 34\ 35, 36 and 36' utilized PET2 resin. In. combination with SIPAl resin. Runs 23, 24, .24*, 27, .28 and 28' utilized SIPAl resin in combination with S1PA2 resin. The SSPA mole % reported In Table 5 is the measure of the moles of metal -sulfonate salt group based upon, the tot al, moles of acid units in all. of the polyester components in. the composition. Preforms with vegetable oil ( ^M w VO") were then compared against preforms of identical compositions and structures without vegetable oil (w/ouiVO") to calculate a value of γ using the equation:

where e vo ^' is calculated according to the equation; ω,ν/νο = ( 7 ^™ ~) 1000 where L ^' is a Hunter L ^* measurement in the range of between 0 and 100 excluding 0, t is the thickness of the preform wall in mm, and the composition comprises a vegetable oil, and where r w usvo Is calculated according to the equation

where L ^' is a Hunter L measurement in the range of between 0 and 100 excluding 0, t is the thickness of the preform wall in mm, the composition is the same as the composition used to calculate the value of co _w vo _> the preform comprises the same dimensions and weight as the preform used, to calculate the value of e _w vo _> and the composition does not comprise a vegetable oil.

The results of these comparisons are reported below in Table 6. As shown in Table 6, when additional, cooling was applied to the preform by increasing the injection molding cooling conditions (i.e. longer cycle time, longer cooling in the mold, colder chiller water, lower injection molding temperature), reducing the preform thickness or a combination thereof, acceptable aesthetic appearance is achieved as evidenced by a Sow γ value,

TABLE 6

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