Recycled polyethlene terephthalate compositions

Abstract

This disclosure relates to alternative additives to rPET compositions that have the advantage of being biobased, more sustainable, and less impactful on the environment than petroleum solutions. The additives of Formula 1 disclosed herein allow for multiply recycled PET to perform as well virgin PET. Formula 1: wherein R1 and R2 are independently a C12-C22 branched or linear alkyl group.

Description

PT-2269-WO-PCTRECYCLED POLYETHLENE TEREPHTHALATE COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63 / 748.186, filed on January 22, 2025, the entire disclosure of which is hereby incorporated by reference in its entirety.TECHNICAL FIELD

[0002] This application relates to specific compositions containing recycled polyethylene terephthalate and methods of utilizing recycled polyethylene terephthalate.BACKGROUND

[0003] Polyethylene terephthalate (PET) is an important polyester polymer material, widely used in the manufacture of films, molded and biaxially oriented polyester products. The most common application for PET homopolymer and copolymers is in the manufacture of bottles, although many other uses are known. PET is ubiquitously present in the eyes of the modem consumer. It is virtually everywhere in products, packaging, and most importantly bottles. This highly successful material has come with unfortunate environmental costs as PET is one of the most significant sources of environmental pollution and stress on landfills.

[0004] While dramatic efforts have been made to reduce dependance on PET, one of the best opportunities to lower the production of virgin PET lies with recycling to yield recycled PET also known as ’rPET" Recycling PET helps reduce the amount of plastic waste that ends up in landfills and oceans. By reusing existing plastic, the need for new plastic production is minimized, conserving fossil fuels and reducing greenhouse gas emissions. The PET resin association, however, estimates that only about one third of PET bottles used in the US are recycled annually.

[0005] While rPET retains many of the desirable properties of virgin PET, such as strength, durability, and clarity during initial recycling; recycling can degrade the quality of PET, making rPET less durable and weaker than virgin PET. This effect is more dramatic when PET is recycled multiple times. In addition, rPET will typically exhibits an increase in melt viscosity which requires manufactures to increase processing temperatures, pressures, and times. Finally, rPET may have inconsistent color, which can affect the appearance of the final product to allow rPET to perform more like virgin PET. These factors can limit the acceptance and utilization ofPT-2269-WO-PCTrPET. If users cannot rely on a consist quality and performance of rPET, they will revert to utilizing virgin PET with all the attendant ecological impacts.

[0006] Improving the performance of rPET may involve using various additives to enhance its properties and make it more suitable for different applications. Some common types of additives include the following.a. Intrinsic Viscosity (IV) Enhancers: These additives help to restore the intrinsic viscosity of rPET, which can be reduced during the recycling process. Enhancing IV improves the material's strength and processability.b. Colorants and Toners: Recycled PET often has a yellowish tint, which can be undesirable. Colorants and toners, such as those from Avient, Corp., can mask this yellowing and improve the aesthetic appeal of rPET products.c. Reheat Additives: These additives improve the efficiency of the bottle blowing process by enhancing the thermal stability of PET. This helps in reducing energy consumption and improving the quality of the final product.d. Chain Extenders: Chain extenders are used to rebuild the molecular weight of rPET, which can be degraded during recycling. This improves the mechanical properties and allows for higher usage of rPET in various applications.e. Slip Agents: These additives reduce surface friction, making the processing of rPET more efficient. They help in increasing throughput during injection molding processes.f. Acetaldehyde Scavengers: Acetaldehyde can be produced during the recycling of PET, leading to off-tastes and odors in packaged products. Scavengers help to reduce and control acetaldehyde levels, preserving the quality of the product.

[0007] These additives play a crucial role in enhancing the performance and sustainability of rPET, making it a more viable option for various applications but they all come with cost and performance disadvantages. There continues to be a desire to identify new effective non-petroleum based additives for rPET that can mirror, or even exceed, the performance of virgin PET.SUMMARY

[0008] The present disclosure provides alternative additives for rPET compositions that have the advantage of being biobased, more sustainable, and less impactful on the environment than petroleum solutions. The additives disclosed herein allow for rPET to perform as well as, or better than, virgin PET. The additives also allow for increased ease of preparing blown or stretchedPT-2269-WO-PCTarticles from rPET. By lowering the force or temperature for manufacturers in the process stage of rPET article formation, energy and costs can be significantly lowered. One needs to consider that given the fact that it is estimated that over 500 billion PET bottles are manufactured globally each year, even a very small improvement in efficiency in the blowing process would yield dramatic global cost and energy savings.

[0009] Being able to make PET compositions (virgin and recycled) that have lower stress at different strain rates (improved stretchability) has a number of benefits, especially in PET bottle making. Having PET that stretches better / more and at lower stress can help reduce cost by reducing material usage (resulting in lighter weight bottles), reducing scraps because of better mold release, and reducing cycle time by eliminating the need for extra processing steps for mold release. Having a PET composition that stretches better and easier can also improve sustainability by reducing energy' consumption by reduction of processing temps and pressure needed during the blowing process, increasing the amount of recycled PET that can be used, and reducing the amount of PET material needed per bottle. PET compositions of the present disclosure have these advantages as will be seen from the Examples.BRIEF DESCRIPTION OF THE FIGURES

[0010] Figure 1 shows the dimensions of a typical PET bottle preform.

[0011] Figures 2 and 4 show injection molded PET preforms which are stuck together due to insufficient cooling time.

[0012] Figures 3 and 5 show relative stacking of treated and untreated preforms.

[0013] Figures 6 and 7 show relative volume of blown preforms.

[0014] Figure 8 is the graphical depiction of the blown preforms.DETAILED DESCRIPTION

[0015] Reference will now be made in detail to certain aspects of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s).

[0016] Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-rangesPT-2269-WO-PCTencompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of '‘about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y.” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.

[0017] As used herein, the singular forms “a,” “an,’" and “the"’ and similar referents in the context of describing the elements (especially in the context of the following claims) include plural referents unless the context clearly dictates otherwise. For example, reference to “a substituent” encompasses a single substituent as well as two or more substituents, and the like. It is understood that any term in the singular may include its plural counterpart and vice versa, unless otherwise indicated herein or clearly contradicted by context.

[0018] The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” has the same meaning as “A, B, or A and B.”

[0019] In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section. Any publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.

[0020] As used herein, the terms “for example,” “for instance,” “such as,” or “including'’ are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the applications illustrated in the present disclosure and are not meant to be limiting in any fashion.

[0021] As used herein, an acid is a chemical species that donates a proton (hydrogen ion, H+) or, more broadly, accepts an electron pair, while a base is a chemical species that accepts a proton or donates an electron pair. Several complementary definitions are relevant and may be invoked depending on reaction medium and mechanism.PT-2269-WO-PCT

[0022] According to the Bronsted-Lowry definition, an acid is a proton donor and a base is a proton acceptor. Acid-base conjugate pairs are related by the transfer of a proton. For example, methanesulfonic acid donates a proton to form its conjugate base, methanesulfonate, while a basic species such as sodium hydroxide accepts a proton to form water. In esterification and transesterification contexts, Bronsted acids can protonate carbonyl oxygen to increase the electrophilicity of the carbonyl carbon, thereby accelerating nucleophilic attack by an alcohol. Conversely, Bronsted bases can deprotonate an alcohol to increase its nucleophilicity or catalyze transesterification via alkoxide formation.

[0023] According to the Lewis definition, a Lewis acid is an electron-pair acceptor and a Lewis base is an electron-pair donor. This definition encompasses non-protic acid-base behavior and is especially relevant to coordination and carbocation-stabilized mechanisms. Representative Lewis acids useful in esterification / transesterification include metal salts and complexes (e.g., tin, titanium, or aluminum alkoxides) that accept electron density from a carbonyl oxygen, polarizing the C=O bond and facilitating nucleophilic addition. Representative Lewis bases include alcohols, amines, phosphines, and alkoxides, which donate electron pairs to electrophilic centers or coordinate to metals to modulate catalytic activity.

[0024] Exemplary acid catalysts include strong Bronsted acids such as methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, and acidic ion-exchange resins, and Lewis acids such as tin(II) or tin(IV) salts, titanium alkoxides, aluminum chloride, and zirconium compounds. Exemplary base catalysts include alkali and alkaline-earth hydroxides and alkoxides (e.g., sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide), organic superbases (e.g.. DBU, TBD). and basic ion-exchange resins. Selection and dosage of an acid or base catalyst can be tailored to balance reaction rate, color formation, side-reactions (e.g., etherification, dehydration), downstream neutralization, and ease of removal. In certain aspects, an acid value target guides reaction endpoint, and catalysts may be neutralized after esterification (e.g., with a slight excess of a mineral base) followed by filtration through bleaching clay or silica to remove salts and catalyst residues.

[0025] In the methods described herein, the acts can be carried out in any order without departing from the principles of the disclosure, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.PT-2269-WO-PCT

[0026] The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. In some aspects, substantially means greater than 90% or between 90% ang 100%.

[0027] As used herein, the following terms have the following meanings unless expressly stated to the contrary .

[0028] The terms “esterification or esterified” means the creation of an ester bond including: 1) the dehydration reaction of an alcohol with an acid; 2) transesterification, the reaction of an alcohol with an ester to form a new ester; or 3) interesterification.

[0029] The term “Acid Value” (AV) as used herein is defined as the weight of KOH in mg needed to neutralize the organic acids present in 1g of test sample and it is a measure of the free fatty acids present in the composition. AV can be determined by the AOCS Official Method Cd 3d-63.

[0030] The terms C12-C22 alkyl; C14-C18 alkyl; and Ci6-Cis; means alkyl groups containing 12-22, 14-18, and 16-18 carbons. Any similar numerical ranges should be considered likewise. In some aspects alkyl groups may be branched. In other aspects, alkyl groups may be unbranched or straight. In other aspects, the alkyl groups may be a mixture of branched or unbranched. One or more of the alkyl groups may be saturated, unsaturated, or a mixture there of.

[0031] Polyethylene terephthalate (PET) is a type of thermoplastic polymer resin from the polyester family. Its chemical structure consists of repeating units of the monomers ethylene glycol and terephthalic acid. The term “PET” as used herein in describing some embodiments of the present invention should be understood to have a broad meaning. It includes all polymeric and copolymeric forms of polyethylene terephthalate. Thus, the term PET should be considered, in this context, to be a generic term to include all polymers derived from aromatic diacids including all terephthalate polymers and their derivatives, both known and those yet to be discovered. In some aspects, the PET is polyethylene terephthalate.

[0032] Recycled polyethylene terephthalate (rPET) as used herein means PET that has been used to produce an article and subsequently been collected and processed into pellets for use in the production of a second or subsequent product. rPET could be either post-industrial streams, such as manufacturing scrap, runners, or off-spec parts generated during primary processing, or post-consumer streams such as bottles, films, and packaging collected after consumer end use.

[0033] In some aspects, rPET is produced via mechanical recycling. Mechanical recycling encompasses physical processing steps that collect, sort, and clean used or previously formed PETPT-2269-WO-PCTproducts. These materials are then remelted without depolymerizing the polymer backbone and are processed into rPET pellets, which can be used to manufacture new products. In other aspects, rPET is produced via chemical recycling. Chemical recycling involves processes that convert PET to its monomeric or oligomeric building blocks, or to intermediates, which are then purified and re-polymerized to form renewed PET resin. Representative chemical recycling routes include depolymerization by glycolysis (reaction with glycols, such as ethylene glycol, to form bis(2-hydroxyethyl) terephthalate and oligomers), methanolysis (reaction with methanol to form dimethyl terephthalate and ethylene glycol), hydrolysis (reaction with water under neutral, acidic, or basic conditions to form terephthalic acid and ethylene glycol), and. in some aspects, aminolysis or ammonolysis to form corresponding terephthalate derivatives. Chemical recycling generally includes purification steps such as crystallization, distillation, filtration, and ion exchange to remove dyes, additives, and non-PET contaminants. The purified monomers or intermediates are then subjected to esterification and / or polycondensation to produce PET with target intrinsic viscosity and molecular weight suitable for the intended application. Chemical recycling may be applied to mixed or contaminated waste streams for which mechanical methods are less effective, and can yield PET resin with properties comparable to virgin PET. The PET produced by chemical recycling can be pelletized.

[0034] These processes cannot be performed indefinitely as the repeated melting and forming of products from rPET will degrade the polymeric structure over time. This degradation typically leads to a decrease in melt viscosity requiring additional temperatures, pressure, and energy to form subsequent generation products which in itself further stresses the polymer. The additives of the present disclosure dramatically improve the processability of rPET and allow additional cost-effective recycling of the material.

[0035] Not all products that utilize rPET are manufactured from 100% rPET. Some manufacturers utilize blends of rPET and virgin PET in their processes for a variety of reasons. As used herein, rPET encompasses materials made by mechanical recycling, chemical recycling, or combinations thereof, including hybrid processes in which mechanically recycled flakes or pellets are partially depolymerized and re-polymerized, or chemically recycled monomers are blended with mechanically recycled or virgin PET. rPET may be provided as flakes, pellets, or preforms, and may be blended at any ratio with virgin PET depending on application requirements.

[0036] The additive of the present disclosure is useful for the manufacture of PET articles that include any percentage of rPET up to 100% rPET.PT-2269-WO-PCTMethod Of Preparing Compounds of Formula 1Formula 1

[0037] The compounds of Formula 1 described herein may be commercially available from a variety of sources including from Cargill, Incorporated. Alternatively, they may be prepared by methods well known in the art such as through dehydration of a starting material acid and alcohol. In some aspects, the catalyst is selected from the group of bases, acids, metals, or combinations thereof. In some aspects, the catalyst is an acid catalyst or combination of acid catalysts.

[0038] Methods for such dehydration are well known in art. such as those described in WO 2005 / 0853340 Al, the disclosure of which is incorporated in its entirety herein. In addition, a representative example is set out below.

[0039] To cany' out a chemical esterification, a catalyst can be added at an amount of about 0.1 wt% relative to the reaction mixture of the acid and alcohol ingredients. Example catalysts can be acids such methanesulfonic acid or bases such as sodium hydroxide and calcium hydroxide, or metal catalysts. In some aspects, methanesulfonic acid is the catalyst. Hypophosphoric acid can optionally be added to the reaction mixture to prevent formation of off colors. The reaction temperature can then be increased to about 140°-250°C. Typically, a reaction temperature of approximately 160°C is utilized. This reaction temperature is maintained for a period of time and the reaction vessel is subjected to vacuum to achieve a pressure of between 20 and 50 torr until a desired endpoint or steady state is reached. In some aspects, to an acid value of less than 15 or less than 10 or less than 5 is achieved. For example a mineral base such as sodium hydroxide or calcium hydroxide, can be added at an amount of about 0.2 wt% to neutralize the catalyst with a slight excess. The reaction mixture can then be cooled to a temperature ranging from about 60°-80°C. A filter media, for example acid activated beaching clay such as B80 neutral or Trisyl® silica, can be added to the reaction mixture in an amount of about 2 wt% or less relative to the reaction mixture to remove impurities. The final product ester is then filtered to remove the salts, silica, or clay mixture.

[0040] Alternatively, esterification can be performed without a catalyst. A reaction mixture of an acid and an alcohol are pre-melted (if necessary) and heated to a temperature rangingPT-2269-WO-PCTfrom 60°-80°C before adding to a reaction vessel along with a nitrogen sparge to prevent oxidation. A vacuum is applied to the reaction vessel to achieve a pressure of between 20 and 50 torr and the temperature increased to 180°-250°C. Lower pressures and / or temperatures may also be utilized depending on the equipment chosen for the reaction. The acid value of the reaction is monitored, and the reaction temperature and vacuum are maintained until an acid value of less than 20 (or other endpoint) is achieved. The product is isolated after cooling the reaction mixture to 60°-80°C and fdtering (such as through a sock fdter) to remove any particulates.

[0041] The compounds of Formula 1 may be prepared by esterification of a single acid with a single alcohol. Alternatively, the esterification can be performed on a mixture of acids with a single alcohol, or on a single acid with a mixture of alcohols, or on a mixture of acids with a mixture of alcohols.

[0042] Optionally, the compounds of Formula 1 may be formed by mixing (or blending) together two or more esters, prepared as described above. This mixing (or blending) of preproduced esters allows for more control over the ester mixture and may result in a more predictable performance.

[0043] In some aspects, Ri is a C14-C18 alkyl group.

[0044] In some aspects, Ri is C14-C16 alkyl group.

[0045] In some aspects, Ri is a mixture of C14-C16 alkyl groups.

[0046] In some aspects, R2 is a C14-C18 alkyl group.

[0047] In some aspects, R2 is a mixture of C14-C18 alkyl groups.

[0048] In some aspects, Ri is C14-C16 alkyl group and R2 is C14-C18 alkyl group.

[0049] In some aspects, Ri a mixture of C14-C16 alkyl groups and R2 is a mixture of C14- Cis alkyl groups.

[0050] In some aspects, the compounds of Formula 1 are purchased as Incomax 100®. Incromax 100® is a commercially available mixture of esters prepared from C14-C16 fatty acids and a mixture of C14-C18 alcohols available from Cargill, Incorporated.

[0051] In some aspects, the compound(s) of Formula 1 will have an acid value of < I mg KOH / g and / or a hydroxyl value less than 2 mg KOH / g. In some aspects, the compound(s) of Formula 1 will have an acid value of between 0.1 and 1 mg KOH / g and / or a hydroxyl value between 0.1 and 10 mg KOH / g. In some aspects, the compound(s) of Formula 1 will have an acid value of between 0.1 and 1 mg KOH / g and / or a hydroxyl value between 0.1 and 10 mg KOH / g. In some aspects, the compound(s) of Formula 1 will have an acid value of between 0.1 and 1 mg KOH / g and / or a hydroxyl value between 0.1 and 5 mg KOH / g.PT-2269-WO-PCTMethod Of Preparing PET Compositions

[0052] PET compositions of the present disclosure can be prepared by any method known in the art for combining polymer additives into a resin composition to be extruded. For example, methods include but are not limited to the following: the compounds of Formula 1 may be blended with the PET, coated onto the polyolefin, co-injected into an extruder at an appropriate dosage, or prepared in a master batch. Method of preparation of the PET is not critical and those skilled in the art employing additives similar to the compounds of Formula 1 of the present disclosure will choose among these and other methods depending upon their particular circumstances and equipment.

[0053] In some aspects, the PET compositions may comprise of a blend of virgin PET and recycled PET.

[0054] In some aspects, the PET compositions comprise greater than 10% by weight rPET.

[0055] In some aspects, the PET compositions compnse greater than 50% by weight rPET.

[0056] In some aspects, the PET compositions comprise greater than 80% by weight rPET.

[0057] In some aspects, the PET compositions comprise greater than 95% by weight rPET.

[0058] In some aspects, PET compositions may further comprise any additional additive desired by the ultimate user including uv protectants, antioxidants, colorants (such as TiCh), plasticizers, antiblocking, agents, slip agents, and the like.

[0059] Colorants, and in particular TiCh, are important PET additives for compositions used in the preparation of bottles for light sensitive liquids such as milk. The white PET (i.e., PET+TiCh) bottle market comprises approximately 5% of the global PET bottle market, which has an estimated value of $42bn in 2022 and expected to reach $54bn by 2028. TiCh acts as a UV light barrier, protecting daily' products such as milk, yogurt drinks, etc. from degradation. Its use is very' well established and regulated. For example, new regulations are in place by the European Union with regards to the permitted addition level and particle size of TiCh in PET compositions.

[0060] In some aspects, the PET composition will comprise greater than 100 ppm of one or more esters of Formula 1 disclosed herein.

[0061] In some aspects, the PET will comprise between 100 ppm and 3000 ppm of one or more esters of Formula 1 disclosed herein. In some aspects, the PET composition will comprise between 200 ppm and 1000 ppm of one or more esters Formula 1 disclosed herein.

[0062] In some aspects, the PET composition is a master batch which contains between 5% and 50% by weight of one or more esters of Formula 1 disclosed herein.PT-2269-WO-PCT

[0063] In some aspects, the present disclosure is related to a polyethylene terephthalate (PET) composition comprising PET and from 0.1% to 2.0% by weight, based on the weight of the PET composition, of a processing aid comprising one or more esters of Formula 1 disclosed herein wherein Ri and R2are independently a C12-C22 branched or linear alkyl group, wherein the PET composition is a blend of recycled PET and virgin PET.PET Processing

[0064] In bottle production, a preform is first prepared by drying and heating the PET resin. The heated PET resin pellets are fed into an injection molding machine, where they are heated to a molten state at around 280°C. The molten PET is then injected into preform molds under high pressure. These molds are designed to create the initial shape of the preform, which resembles a test tube with a threaded neck. A typical preform is shown in Figure 1.

[0065] There are various types of injection molding machines used in the production of PET preforms, each with its own capabilities and features.Hydraulic Injection Molding Machines: These machines use hydraulic power to inject the molten PET into the molds.Electric Injection Molding Machines: These machines use electric motors for precise control and energy efficiency.Hybrid Injection Molding Machines: These combine hydraulic and electric technologies for optimal performance.

[0066] Several parameters influence the quality and consistency of the PET preforms produced.Temperature: The temperature of the molten PET must be carefully controlled to ensure proper flow and filling of the molds.Pressure: High pressure is required to inj ect the molten PET into the molds and ensure it fills every part of the cavity.Cooling Rates: The cooling rate affects the crystallinity and clarity of the preforms.

[0067] In normal production operations, bottle preforms (and bottles) are produced at very fast speeds with very short cycles. To improve efficiency and costs, it is preferable to operate the preform and blowing lines as fast as possible. However, as cycle time is shortened, quality of the preforms and bottles can suffer, and other problems can arise. The most time-consuming stage in injection molding is cooling and as bottle preforms are quite thick, around 3-3.5mm wall thickness, relatively long cooling times are needed to allow the material to solidify sufficientlyPT-2269-WO-PCTbefore being ejected. If preforms are not sufficiently cooled, they can stick together or create issues in packing because the preforms do not easily slide over one another into boxes. Some preform manufacturers, address this failure of packing by employing vibrating / shaking equipment as preforms are being boxed. This creates and extra complication and expense to the process.

[0068] Proper cooling time is not only a major factor in the end quality of a part but it is the most time-consuming component of an injection molding cycle. Cooling typically makes up 80 to 85 percent of the overall cycle time. When you consider that the cooling part of the cycle is the counterpart to the immense amount of heat required to liquefy the plastic resin during the injection process, this 85 percent figure is consistent with what a skilled person would expect. Any reduction in heat required, or lowering of cooling time, is of immense value to the producer. For example, even a modest savings of 1 second cooling time per preform would save over 250 hours of production time over the course of each 1 million preforms manufactured.

[0069] Before the preforms can be blown into their final shapes, they must be reheated to make them pliable. This is done using infrared heaters that evenly heat the preforms to around 110°C which is above the PET’s glass transition temperature but below its cold crystallization temperature. The preforms are then blow molded. There are two main types of blow molding used in the production of PET bottles:Stretch Blow Molding: This process involves stretching the preform both axially and radially while blowing it into the final shape. It is commonly used for producing beverage bottles.Extrusion Blow Molding: This process involves extruding a tube of molten plastic and then blowing it into the final shape. It is used for larger containers and nonbeverage applications.

[0070] The glass transition temperature (Tg) of Polyethylene Terephthalate (PET) is a critical thermal property7. It typically ranges between 65°C and 80°C depending on the particular PET formulation. This temperature marks the point where PET transitions from a hard, glassy material to a viscoelastic one, i.e., a material with a softer, more rubbery, state in which it can be stretched or molded but does not lose structural integrity. This is contrast to the melt point of PET where the material becomes a free flowing fluid. The Tg is a well-known, studied and understood parameter in PET performance. Skilled artisans have a knowledge of how Tg is determined and represented by producers.

[0071] Placement in the Blow Molding Machine: The heated preforms are placed in the blow molding machine, where they are held in place by a mold.PT-2269-WO-PCT

[0072] Inflation to Final Container Shape: Compressed air is used to inflate the preforms, stretching them to fit the mold and form the final container shape.

[0073] Several parameters influence the blow molding process.Temperature: The temperature of the preforms must be carefully controlled to ensure proper stretching and inflation.Pressure: High pressure is required to inflate the preforms and ensure they take the shape of the mold.Mold Design: The design of the mold affects the final shape and quality of the containers.

[0074] Advantageously, use of the compounds of Formula 1 allows processing of the PET polymer matrix to be carried out at a lower process temperature and / or pressure and / or mechanical stress, than would be possible in the absence of such compounds. Preferably, the use of the compounds of Formula 1 allows processing of the PET polymer matrix to be carried out at a lower process temperature or pressure. The reduction in process temperature and / or pressure parameters has cost and other benefits. Additionally, reductions in processing temperatures, more especially, can have highly beneficial energy and associated cost reductions; even a slight reduction in process operating temperature can be dramatically beneficial.

[0075] These advantages in the use of compounds of Formula 1, allow for dramatically less sticking and seizing of preforms together as well as lessening or eliminating the need for shaking in the packaging or boxing of preforms.

[0076] The compounds of Formula 1 allow for improved stretchability of recycled PET. Using an ester additive can help by homogenizing the flow behaviors differences between virgin and recycle PET. This helps to eliminate issues with streaks and other mixing issues that can limit the amount of recycled PET that can be used.

[0077] In evaluating the benefits of the inclusion of compounds of Formula 1. The skilled artisan can perform a comparison in any mechanical process or production process of the performance of a PET composition including the compounds of Formula 1 versus the same composition that only differs by the absence of the compounds of Formulal . The two samples can be then evaluated side by side in the test or process in question to compare performance.

[0078] Furthermore, use of the compounds of Formula 1 of the present invention does not have any adverse effect on the physical or chemical properties of the final polyester product formed. More especially, the rigidity and strength of the final PET product obtained is not compromised.PT-2269-WO-PCT

[0079] In addition, use of the compounds of Formula 1 of the present invention does not adversely affect PET clarity or gas barrier properties. More especially, use of the compounds of Formula 1 of the present invention does not adversely affect the taste or food safety of any consumable product to be stored in (or in contact with) the final PET product.

[0080] Suitably, the compounds of Formula 1 may be used in any of the following processes: thermoforming, injection molding, extrusion, cast film extrusion, blown film extrusion, extrusion blow molding, injection stretch blow molding, stretch blow molding, and biaxial film orientation.

[0081] In some aspects, the final PET product produced is a container, for example product packaging and in particular a bottle. In another aspect, the final PET product produced is a bottle. The stretch blow molding processes typically employed to produce PET bottles from preform components subject the preform components to biaxial stresses to provide the final bottle shape. The preform components react to the stress in each axial direction differently, and it has advantageously been found that the compounds of Formula 1 of the present invention aid internal functioning of the polyester matrix in both the x and y axis of the biaxial stress applied.

[0082] In another aspect, the final PET product is a film, for example, product packaging and, in particular, a food contact film. Most preferably, in this case, the final polyester product is a biaxially-orientated polyethylene terephthalate (BOPET) film. The compounds of Formula 1 of the present invention aid internal functioning of the PET matrix in both the x and y axis of the biaxial stress applied to such BOPET materials.

[0083] Further aspects and / or exemplary embodiments include but are not limited to: A polyethylene terephthalate (PET) composition comprising PET and from 100 ppm to 3000 ppm by weight, based on the weight of the PET composition, of a processing aid comprising one or more esters of Formula 1, wherein Formula 1 is an ester in which Ri and R2 are independently a C12-C22 branched or linear alkyl group.

[0084] In another aspect, the PET composition of any of the described aspects herein, wherein the PET comprises recycled PET.

[0085] In another aspect, the PET composition of any of the described aspects herein, wherein the PET composition comprises of a blend of virgin PET and recycled PET.

[0086] In another aspect, the PET composition of any of the described aspects herein, wherein the recycled PET constitutes greater than 10% by weight of the PET.

[0087] In another aspect, the PET composition of any of the described aspects herein, wherein the recycled PET constitutes greater than 50% by weight of the PET.PT-2269-WO-PCT

[0088] In another aspect, the PET composition of any of the described aspects herein, wherein the recycled PET constitutes greater than 70% by weight of the PET.

[0089] In another aspect, the PET composition of any of the described aspects herein, wherein the recycled PET constitutes greater than 80% by weight of the PET.

[0090] In another aspect, the PET composition of any of the described aspects herein, wherein the recycled PET constitutes greater than 95% by weight of the PET.

[0091] In another aspect, the PET composition of any of the described aspects herein, wherein the processing aid is present in an amount from 200 ppm to 1000 ppm by weight.

[0092] In another aspect, the PET composition of any of the described aspects herein, wherein Ri is a C14-C16 alkyl group and R2 is a C14-C18 alkyl group.

[0093] In another aspect, the PET composition of any of the described aspects herein, wherein Ri is a mixture of C14-C16 alkyl groups and R2 is a mixture of C14-C18 alkyl groups.

[0094] In another aspect, the PET composition of any of the described aspects herein, wherein the one or more esters of Formula 1 have an acid value of less than 1 mg KOH / g and a hydroxyl value of less than 5 mg KOH / g.

[0095] In another aspect, the PET composition of any of the described aspects herein, wherein the one or more esters of Formula 1 comprise a mixture of esters prepared from C14-C16 fatty acids and C14-C18 alcohols.

[0096] In another aspect, the PET composition of any of the described aspects herein, further comprising titanium dioxide.

[0097] In another aspect, the PET composition of any of the described aspects herein, wherein the titanium dioxide is present in an amount from 1% to 10% by weight, based on the weight of the PET composition.

[0098] In another aspect, the PET composition of any of the described aspects herein, further comprises of one or more colorants, toners, ultraviolet light stabilizers, antioxidants, plasticizers, anti-blocking agents, slip agents, chain extenders, and acetaldehyde scavengers.

[0099] In another aspect the disclosure is related to a masterbatch composition comprising from 5% to 50% by weight, based on the weight of the masterbatch, of the one or more esters of Formula 1 of dispersed in a PET carrier resin.

[0100] In another aspect, the masterbatch composition comprises from 10% to 40% by weight, based on the weight of the masterbatch, of the one or more esters of Formula 1 of dispersed in a PET carrier resin.PT-2269-WO-PCT

[0101] In another aspect, the masterbatch composition comprises from 10% to 30% by weight, based on the weight of the masterbatch, of the one or more esters of Formula 1 of dispersed in a PET carrier resin.

[0102] In another aspect, the PET carrier resin is a virgin PET. In yet another aspect the PET carrier resin is a rPET.

[0103] In still other aspect, the PET carrier is a blend of virgin PET and rPET.

[0104] In another aspect, the disclosure is related to a preform comprising the PET composition of any of the described aspects herein. In another aspect, the disclosure is related to a blow-molded article comprising the PET composition of any of the described aspects herein.

[0105] In another aspect, the blow-molded article of any of the described aspects herein, wherein the article is a bottle.

[0106] In another aspect, the disclosure is related to a method of producing a PET article comprising providing a PET formulation comprising PET and from 100 ppm to 3000 ppm by weight of a processing aid comprising one or more esters of Formula 1 wherein Ri and R2 are independently a C12-C22 branched or linear alkyl group, heating the PET formulation to a temperature above the glass transition temperature of the PET formulation, and stretching the heated PET formulation to form the PET article.

[0107] In another aspect, the disclosure is related to a method of any of the described aspects herein, wherein forming the PET article requires a lower stretching force, a lower processing temperature, a lower air pressure, a shorter residence time, or any combination thereof, relative to forming the same article under the same conditions from a second PET formulation that differs only in that the processing aid is absent.

[0108] In another aspect, the disclosure is related to a method of any of the described aspects herein, wherein the stretching force is reduced by at least 5% relative to the second PET formulation.

[0109] In another aspect, the disclosure is related to a method of any of the described aspects herein, wherein the processing temperature during reheating prior to stretch blow molding is reduced by at least 5°C relative to the second PET formulation.

[0110] In another aspect, the disclosure is related to a method of any of the described aspects herein, further comprising injection molding the PET formulation to form a preform and cooling the preform, wherein the preform exhibits reduced stickiness to other preforms and improved mold release relative to a preform made from a second PET formulation that differs only in that the processing aid is absent.PT-2269-WO-PCT

[0111] In another aspect, the disclosure is related to a method of any of the described aspects herein, wherein a cooling time during injection molding is decreased by at least 1 second relative to the second PET formulation while maintaining separability of preforms without sticking.

[0112] In another aspect, the disclosure is related to a method of any of the described aspects herein, wherein preforms collected in a container exhibit increased natural settling such that a container holds at least 10% more preforms before requiring mechanical vibration relative to the second PET formulation.

[0113] In another aspect, the disclosure is related to the method of any of the described aspects herein, wherein the PET article is a biaxially oriented film.

[0114] In another aspect, the disclosure is related to a method of any of the described aspects herein, wherein the PET formulation further comprises titanium dioxide.

[0115] In another aspect, the disclosure is related to use of the one or more esters of Formula 1 defined in any of the described aspects herein as a processing aid in PET to improve stretchability at a temperature above the glass transition temperature, to reduce preform-to-preform sticking upon ejection from an injection mold, to improve mold release, to increase natural settling of preforms in a collection container, to reduce cooling time during injection molding, or any combination thereof.

[0116] In another aspect, the disclosure is related to a process comprising compounding PET with from 100 ppm to 3000 ppm by weight of the one or more esters of Formula 1, pelletizing the compounded PET to form a ready -to-mold resin, and injecting, extruding, or thermoforming the resin into an article, wherein the article exhibits rigidity' and gas barrier properties within ±10% of an otherwise identical article made from PET free of the one or more esters of Formula 1.

[0117] In another aspect, the disclosure is related to a PET composition of any of the described aspects herein, wherein the PET is a blend comprising virgin PET and recycled PET and the one or more esters of Formula 1 homogenize flow behavior differences between the virgin PET and recycled PET during molding so as to reduce visual streaks relative to a corresponding blend lacking the one or more esters of Formula 1.

[0118] In another aspect, the disclosure is related to a method of any of the described aspects herein, wherein free-blown volume of a preform blown at a fixed pressure and time is increased by at least 10% relative to a corresponding preform lacking the processing aid.PT-2269-WO-PCT

[0119] In another aspect, the disclosure is related to a masterbatch composition of any of the described aspects herein, wherein the one or more esters of Formula 1 have an acid value between 0.1 and 1 mg KOH / g and a hydroxyl value between 0.1 and 5 mg KOH / g.

[0120] In another aspect, the disclosure is related to a PET composition of any of the described aspects herein, wherein the one or more esters of Formula 1 comprise products of esterification of a mixture of C14-C16 fatty acids with a mixture of C14-C18 fatty alcohols.

[0121] In another aspect, the disclosure is related to a method of any of the described aspects herein, wherein the PET formulation is processed on hydraulic, electric, or hybrid injection molding equipment and the presence of the one or more esters of Formula 1 allows operation at a reduced clamp-open cooling time while maintaining part quality.

[0122] In another aspect, the disclosure is related to a PET composition of any of the described aspects herein, wherein the PET composition is free of petroleum-derived slip agents.

[0123] In another aspect, the disclosure is related to a blow-molded article of any of the described aspects herein, wherein the article is a dairy bottle compnsing titanium dioxide and exhibits reduced energy consumption during blowing due to lower required preform reheat temperature as compared to an otherwise identical article lacking the one or more esters of Formula 1.

[0124] In another aspect, the disclosure is related to a preform package comprising a plurality of preforms according to any of the described aspects herein in a container, wherein the preforms settle without mechanical vibration to a packing density at least 5% greater than preforms made from a corresponding PET composition lacking the one or more esters of Formula 1.EXAMPLESTable 1.PT-2269-WO-PCTExample 1. Preform manufacturing study

[0125] A comparative study was performed during production of bottle preforms. Preforms (23 grams as shown in Figure 1) were prepared on standard equipment according to the parameters in Table 2. The conditions were chosen to maximize production rate and to stress performance of the preforms.Table 2.

[0126] The tests showed that short cooling times of 3.5 seconds had a detrimental effect on all different types of PET, 100% virgin, partially recycled, or 100% recycled. Specifically, all preforms got substantially stuck / frozen (as shown in Figure 2) with each other to the point where they created a continuous amorphous mass within the box or container used to collect them after forming. In an actual production site, these preforms would be considered scrap.

[0127] With the addition of only as little as 0.15% to 0.25% IncroMax 100, the sticking phenomenon was eliminated almost completely. Preforms made from all three different PET resins could all be separated easily, despite using short cooling times of up to 3.5 seconds.

[0128] To overcome the adhesion problem without an additive, the preform producer would have to increase the cooling time, and by extension the overall cycle time, to produce more solidified preforms which would not stick to each other. Additional testing showed, that forPT-2269-WO-PCTreference PET, 10 seconds of cooling time, (i.e., more than double) was required to stop preforms getting stuck with each other after ejection. Therefore, the inclusion of IncroMax 100 esters could reduce the overall cycle time of preform molding by more than 50%, as cooling time accounts for approximately 80% of cycle time.[0129j But even with a 10 second cooling time, an additional process problem remains. While blank PET preforms could be produced without sticking to one another, they would not “settle” in the loadout box or container. These preforms would occupy a large volume resulting in bulky packing and inefficient filling of the boxes. To overcome this well-known “settling” problem, the current solution used by industry is a vibrating stage which shakes the collected preforms to make them settle as they are produced. In this way, they can be more tightly stacked to better fill the box / container. Unfortunately, this process often causes scratches on the preform surface yielding rejects and therefore more scrap. In addition, this process has the additional cost of the equipment and its maintenance. With the addition of only as little as 0.15% to 0.25% IncroMax 100 esters, packing volume was significantly reduced without the need for shaking or vibrating the load out box (as shown in Figure 3). If the vibrating stage is not available in a production site, then a box with blank PET preforms would occupy at least 10% more volume compared to a box with PET+esters disclosed herein for the same amount of preforms. This result highlights how the preform production and transportation can be done much more efficiently and sustainably through use of the ester additives of Formula 1.Example 2, White PET preforms evaluation

[0130] The effects demonstrated in Example 1 were also evaluated in PET formulations containing TiO2 as a colorant. To maximize the output rate of preform molding, the cooling time was intentionally set at a very low value, only 2.5 seconds (as seen in Table 3 below). Under these conditions, all formulations would be challenged to perform, and would face problems, e.g., stickiness of preforms or producing short shots. The effect of the addition of esters of the invention could then be assessed and determined if these problems would be solved, and shorter cycle times would be enabled. The mold release effect and stickiness of preforms were evaluated the same way it was done Example 1.P T-2269-WO-PCTTable 3.

[0131] The tests showed that the reduced cooling time had a detrimental effect on thepreforms. Specifically, blank PET and rPET preforms were sticking with each other, as shown inFigure 4, because the material did not have adequate time to solidify. While white preforms aretypically not as sticky as the colorless counterparts, it is clear that this problem can still occur.Increasing cooling times and hence cycle times, or expensive take-off units w ould be required to avoid this problem.

[0132] With the addition of only as little as 0.15% to 0.30% IncroMax 100. th e sticking phenomenon was eliminated almost completely. Preforms made from both virgin and re cycled PET could all be separated easily, despite using short cooling times of up to 2.5 seconds. T he cooling time was then increased to 10 seconds to eliminate the problem with stickiness of blank preforms. The rest of the processing conditions remained the same. New preforms were made and collected in a metallic container, where they were allow ed to settle naturally and pile up until the first preform touched a metallic bar laying on top of the container, as shown in Figure 5. At that point, the test stopped because it was assumed that shaking or rattling would be needed to settle the preforms, so more could be added on top.

[0133] Examples 2A-F were evaluated in this manner. The amount of molded preforms was then measured to find out if the effects the esters of the invention could allow more preforms to pile up naturally in the container.

[0134] The results in Table 4 show- that with 0.3% IncroMax 100, 17% more virgin white PET preforms could fit inside the container, before touching the bar. i.e., without the need of rattling, and 24% more white rPET preforms could be included. These results also revalidate thePT-2269-WO-PCTdata of Example 1 conducted on clear PET. It is surprising that the effect is dramatically increased with recycled PET.Table 4. Max number of molded white PET preforms inside the same container.

[0135] This is an important result / benefit because it shows the potential of IncroMax 100 to minimize, if not eliminate, the need for a rattling stage in the injection molding site / facility. Elimination of rattling would be an enormous bonus for bottle preform manufacturers because they would avoid the cost of purchasing the equipment, operation and maintenance. It would reduce the overall footprint of the facility. Even if the rattling stage is already installed and required, its use would be minimized and therefore any scratches and wear on the preform surface due to rattling would also be minimized, i.e., reduced scrap and waste.Example 3, Free form stretching of white PET preforms

[0136] Typically preforms are heated and blown / stretched within the confines of a mold. This allows the blow n form to take the appearance, shape, and volume of the mold. In order to investigate the performance of the compounds of Formula 1, a test system was utilized where the heated preforms were blown under consistent pressure normally utilized in the system but unconstrained by a mold. The volume of the resulting form is a function of the ease of the PETPT-2269-WO-PCTformulation’s stretchability where a stiffer less pliable formulation will result in a lower volume than a formulation with a better performance. In this experiment the preforms were prepared by injection molding and immediately blown into bottles. A virgin and a 100% recycled PET resin were used and the amount of TiCh was the same in all formulations. The only two variables were the amount of IncroMax 100 and the blowing conditions, specifically the cooling time of the preforms after injection molding and before stretching, as well as the blowing time. The full set of conditions is show' in Table 5 below'.Table 5.*Blowing Temperature in the table above refers to the settings on the infrared heaters used in the equipment to heat the preforms asthey are blown.PT-2269-WO-PCT

[0137] It is clear from Figure 6 that rPET is much more difficult to stretch compared to virgin PET, as shown when comparing 3A(i) vs 3D(i). Both Examples were prepared and tested under the same conditions. The rPET [example 3D(i)] was only slightly deformed.

[0100] The addition of the esters of the invention had a dramatic effect on the stretchability of the rPET formulations. As shown in Figure 7 addition of 0.15% or 0.3% additive dramatically improved the volume of the blown article.Table 6.

[0138] The bottles [3D(i), 3E(i), and 3 F(i)] were then filled with water to record their mass and by extension their volume. The increase in the bottles volume is shown in Figure 2. While appreciating that the test conditions are designed to be extremely challenging, the bottles preforms including the additives of the present invention exhibited up to 20% more volume than the control. Given the inherent challenges in stretching rPET this is a highly valuable effect to the bottle producer.Example 4, Free form stretching of PET preforms

[0139] The effects of the esters of the invention shown in Example 3 were also tested in PET compositions without TiCh. Free blow n molding tests of PET bottles were conducted in the same manner and using the same SBM machine, as they were for white PET bottles. The aim was to determine if the effects of Example 3 could be confirmed for TiCh free formulations. Preforms (23 grams) were prepared in a standard fashion using the materials described in Table 7. Virgin PET, Virgin PET / rPET blend, andl00% rPET formulations were compared with and without the inclusion of IncroMax 100 ester blend. Preforms were prepared as in Example 3. The headed preforms were then blown at the normal constant pressure of the equipment without the presence of any mold. The resulting bottle shape forms were filled with water, capped and weighed. The weight in water in grams is a surrogate measure of volume (1g water = 1ml volume).PT-2269-WO-PCTTable 7.

[0140] The inclusion of Incromax 100 dramatically improved the volume of the blown article. The effect is noticeable at 0.15% inclusion rate but 10% or greater improvement is seen at inclusion rate of 0.25%. The effect is even more dramatic for composition comprising fully recycled PET. Given that recycled PET typically experiences a loss in melt viscosity relative to virgin PET, the fact that inclusion of esters of the present disclosure can create better performance than virgin PET or virgin PET with equivalent levels of ester additives is a genuine surprise.Example 5: Acetaldehyde Testing:

[0141] Acetaldehyde (AA) is an important consideration for the PET water bottle industry, because it is a byproduct of PET production that can migrate into water even at very low concentrations (parts per billion), causing an undesirable sweetish, fruity off-flavor, especially in plain or carbonated water, where taste neutrality is key. While generally considered harmless at typical trace levels, its presence affects product quality, leading manufacturers to use special resins and additives called AA scavengers, e.g. 2-aminobenzamide, to minimize its formation and migration for consumer satisfaction.PT-2269-WO-PCT

[0142] Acetaldehyde is formed during the thermal processing (melting) of PET resin, especially at high temperatures used during injection molding of preforms. Also, cycle times affect the production of AA. Shorter cycles times, not only offer increased output rate and reduced energy consumption, but they also reduce the AA production. Recycled PET exhibits much higher AA levels than virgin PET, as it has been subjected to more thermal cycles. Therefore, the need for AA scavengers is higher and the use of 100% rPET in still and carbonated water bottles is very challenging.

[0143] Manufacturers attempt to mitigate the presence of AA by using high-quality PET resins inherently designed to produce less AA, Adding agents like 2-aminobenzamide to the PET melt to chemically "mop up" AA, and optimizing processing such as Lowering melt temperatures, improving drying, and efficient cooling during molding. Manufactures monitor AA levels using techniques like Headspace Gas Chromatography (GC).

[0144] Although these mitigation techniques can be successful in lowering concentrations of AA to levels below concentrations that cause significant health concerns, Individual molecules can migrate through the PET of a bottle wall and enter the packaged liquid, as AA is miscible in water. A higher concentration of the substance is undesirable, particularly in water packaged in PET bottles, as a change in taste occurs after a certain storage time, the threshold of which is 0.01-0.025 ppm. The beverage is then in breach of European Framework Regulation No. 1935 / 2004 or the US Federal Food, Drug and Cosmetic Act. Both regulations ensure that the organoleptic quality of food remains the same. This is why some water bottlers have set limits for AA in preforms and bottles. The EU sets a specific migration limit (SML) in PET preforms of 4 ppm*, with some countries, e g. Germany selecting even stricter limits of even 2 ppm.

[0145] Accordingly, the effect of the claimed additives on the production of AA in 100% rPET bottles was determined.

[0146] A 100% rPET resin, with an IV of 0.8dL / g (bottle grade) was used to produce the specimens required to assess the effect of IncroMax 100 additive on AA production. The additive was added via a 10% loaded masterbatch, made using virgin PET as the earner. Preforms and bottles were produced using Injection Moulding and Injection Stretch Blow Moulding (ISBM), respectively.

[0147] Injection molded preforms were made using 2 different barrel temperatures. Ahigh barrel temperature of 285°C and a low barrel temperature of 260°C. The injection speed, packing speed and pressure, as well as hot runner temperature remained constant for all formulations. It is worth noting that the blank rPET preforms molded at 260°C had defects, specifically they werePT-2269-WO-PCTshort and hazy. It can be concluded that blank rPET preforms without IncroMax 100 additive cannot be produced at that temperature. Nevertheless, the Acetaldehyde content was still measured in these preforms too. The exact formulations and conditions are show below in Table 8.Table 8. Acetaldehyde results for rPET preforms, with and without IncroMax™ 100&

[0148] From Table 8 it can be concluded that IncroMax 100 additive has a profound effect on the production of AA of rPET preforms. Even at the standard processing conditions used for blank rPET (sample Al - barrel temp of 285°C), IncroMax 100 reduces AA by 33% due to its internal lubrication / processing aid effect. However, by allowing a lower barrel temperature to be used. IncroMax 100 can further reduce AA to 81% compared to blank rPET preforms molded at the standard high temperature of 285°C.

[0149] Table 9 shows the effect of IncroMax 100 on AA levels of SBM bottles. A very similar and significant reduction of 79% is observed with the addition of 0.3% of the additive. The slightly different AA value of the blank rPET bottles is most likely due to the fact that a different rPET (bottle) grade was used for the production of the SBM bottles, plus that fact that the barrel temperature was 280°C instead of 285°C. The fact that we get almost the same reduction as a percentage in both rPET resins is also very reassuring as far as the effect of IncroMax 100.PT-2269-WO-PCTTable 9. Acetaldehyde results for rPET SBM bottles, with and without IncroMax™ 100

[0150] The AA assessment was conducted at Intertek Research Centre in the Netherlands. The content of acetaldehyde (CAS 75-07-0) was determined by Headspace GC-FID analysis according to ASTM F2013-10 (2016). The analysis was conducted in duplicate on each sample. Acetaldehyde standards were freshly prepared and used as external standard.

Claims

PT-2269-WO-PCTCLAIMS1. A polyethylene terephthalate (PET) composition comprising:a) PET; andb) from 0.1% to 2.0% by weight, based on the weight of the PET composition, of a processing aid comprising one or more esters of Formula 1 :wherein Ri and R2 are independently a C12-C22 branched or linear alkyl group.

2. The PET composition of claim 1, wherein the PET further comprises of: a blend of virgin PET and recycled PET.

3. The PET composition of claim 2, wherein the recycled PET constitutes greater than 10% by weight of the PET.

4. The PET composition of claim 2, wherein the recycled PET constitutes greater than 50% by weight of the PET.

5. The PET composition of claim 2, wherein the recycled PET constitutes greater than 80% by weight of the PET.

6. The PET composition of claim 2, wherein the recycled PET constitutes greater than 95% by weight of the PET.

7. The PET composition of claim 1, wherein the processing aid is present in an amount from 0.2% to 1.0% by weight.

8. The PET composition of claim 1, wherein Ri is a C14-C16 alkyl group and R2is a C14-C18 alkyl group.PT-2269-WO-PCT9. The PET composition of claim 1, wherein Ri is a mixture of C14-C16 alkyl groups and R2 is a mixture of C14-C18 alkyl groups.

10. The PET composition of claim 1, wherein the one or more esters of Formula 1 have an acid value of less than 1 mg KOH / g and a hydroxyl value of less than 5 mg KOH / g.

11. The PET composition of claim 1, wherein the one or more esters of Formula 1 comprise products of esterification of a mixture of C14-C16 fatty acids with a mixture of C14-C18 fatty alcohols.

12. The PET composition of claim 1, further comprising titanium dioxide.

13. A method of producing a PET article comprising providing a PET formulation comprising PET and from 0.1% to 2.0% by weight of a processing aid comprising one or more esters of Formula 1 wherein Ri and R2 are independently a C12-C22 branched or linear alkyl group, heating the PET formulation to a temperature above a glass transition temperature of the PET formulation, and stretching the heated PET formulation to form the PET article, wherein forming the PET article requires a lower stretching force, a lower processing temperature, a lower air pressure, a shorter residence time, or any combination thereof, relative to forming the same article under the same conditions from a second PET formulation that differs only in that the processing aid is absent.

14. The method of claim 13, wherein the PET formulation comprises recycled PET.

15. The method of claim 13, wherein the stretching comprises stretch blow molding.

16. The method of claim 13, wherein the stretching force is reduced by at least 5% relative to the second PET formulation.

17. The method of claim 13, wherein a reheating temperature prior to stretching is reduced by at least 5°C relative to the second PET formulation.PT-2269-WO-PCT18. The method of claim 13, further comprising injection molding the PET formulation to form a preform and cooling the preform, wherein a cooling time during injection molding is decreased by at least 1 second relative to the second PET formulation while maintaining separability of preforms without sticking.

19. The method of claim 18, wherein preforms collected in a container exhibit increased natural settling such that the container holds at least 10% more preforms before requiring mechanical vibration relative to the second PET formulation.

20. A masterbatch composition comprising from 5% to 50% by weight, based on the weight of the masterbatch, of the one or more esters of Formula 1 dispersed in a PET carrier resin.

21. The masterbatch composition of claim 20, wherein the one or more esters of Formula 1 have an acid value between 0.1 and 1 mg KOH / g and a hydroxyl value between 0.1 and 5 mg KOH / g.

22. The masterbatch composition of claim 20, wherein the one or more esters of Formula 1 comprise IncroMax 100.

23. The masterbatch composition of claim 20, wherein the one or more esters of Formula 1 compnses a blend of two or more preformed esters.

24. An article comprising the PET composition of claim 1, wherein the article is selected from a preform, a blow-molded bottle, and a biaxially oriented film.

25. The masterbatch composition of claim 20, wherein the PET carrier resin comprises recycled PET.

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