Polymer compositions and methods for eliminating melt fracture

Abstract

Processes for preparing ethylene polymer compositions include a step of melt processing a blend of an ethylene polymer and an additive composition through a pelletizing or strand die to produce the ethylene polymer composition. The ethylene polymer contains from 1 to 50 ppm of inorganic fluorine, the additive composition contains a polyethylene glycol at an amount from 100 to 10,000 ppm based on the weight of the ethylene polymer composition, and the ethylene polymer composition is substantially free of organic fluorine. Ethylene polymer compositions and methods of making films from the ethylene polymer compositions also are encompassed herein.

Description

[0001] POLYMER COMPOSITIONS AND METHODS FOR ELIMINATING MELT FRACTURE

[0002] REFERENCE TO RELATED APPLICATION

[0003] This application is being filed on June 20, 2025, as a PCT International Patent Application and claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 662,442, filed on June 21, 2024, the disclosure of which is incorporated herein by reference in its entirety.

[0004] TECHNICAL FIELD

[0005] This disclosure relates generally to ethylene-based polymer compositions that are substantially free of organic fluorine, yet can be processed on conventional blown film equipment at high throughput rates without melt fracture.

[0006] BACKGROUND

[0007] Many polyethylene resins require the addition of polymer processing aids (PPAs) to eliminate melt fracture during extrusion. Most traditional PPAs rely on fluoropolymers which have recently been grouped with other PFAS (poly and perfluorinated alkyl substances) that contain organic fluorine and are the subject of increased regulation. Thus, there is a greater demand for additives and polymer compositions that contain PFAS -free PPAs. Accordingly, it is to these ends that the present disclosure is generally directed.

[0008] SUMMARY

[0009] This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify required or essential features of the claimed subject matter. Nor is this summary intended to be used to limit the scope of the claimed subject matter.

[0010] Processes for preparing ethylene polymer compositions are disclosed herein, and such processes can comprise melt processing a blend (or mixture) of an ethylene polymer and an additive composition through a die (e.g.. a pelletizing or strand die) to produce the ethylene polymer composition. The ethylene polymer (or the ethylene polymer composition, or both) can comprise from 1 to 50 ppm of inorganic fluorine, the additive composition can comprise a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition, and the ethylene polymer composition can be substantially free of (or can contain less than 5 ppm of) organic fluorine. While not required, often the ethylene polymer is in the form of powder or fluff, and the ethylene polymer composition typically is in the form of pellets or beads.

[0011] Another process for preparing an ethylene polymer composition is disclosed herein, and this process can comprise combining an additive composition with an ethylene polymer to form a blend, and melt processing the blend through a die to produce the ethylene polymer composition. In this process, the additive composition can consist of a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition, and one or more active additives. The additive composition can be substantially free of binding agents and carrier resins, and the ethylene polymer composition can be substantially free of organic fluorine.

[0012] In another aspect, the present disclosure also is directed to ethylene polymer compositions that are substantially free of organic fluorine. These compositions can comprise an ethylene polymer comprising from 1 to 50 ppm of inorganic fluorine, and an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition.

[0013] Another ethylene polymer composition encompassed herein is substantially free of organic fluorine and can comprise an ethylene polymer substantially free of inorganic fluorine, and an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition, and an inorganic fluorine containing additive at an amount in a range from 1 to 10 ppm of fluorine (or from 2 to 10 ppm, from 3 to 10 ppm, from 3 to 9 ppm, or from 4 to 10 ppm of fluorine), based on the ethylene polymer composition.

[0014] A method of making a film is provided in yet another aspect of this disclosure. One such method of making a film (e.g., a film with no melt fracture) can comprise melt processing an ethylene polymer composition through a film die to produce the film. In this method, the ethylene polymer composition can be substantially free of organic fluorine, and can comprise an ethylene polymer comprising from 1 to 50 ppm of inorganic fluorine, and an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition.

[0015] Both the foregoing summary' and the following detailed description provide examples and are explanatory only. Accordingly, the foregoing summary and the following detailed description should not be considered to be restrictive. Further, features or variations may be provided in addition to those set forth herein. For example, certain aspects and embodiments may be directed to various feature combinations and sub-combinations described in the detailed description.

[0016] BRIEF DESCRIPTION OF THE FIGURES

[0017] The following figures form part of the present specification and are included to further demonstrate certain aspects of the disclosure, which may be better understood by reference to these figures in combination with the detailed description.

[0018] FIG. 1 presents a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 1-5 and Comparative Examples C1-C2.

[0019] FIG. 2 presents a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 6-8 and Comparative Examples Cl and C3.

[0020] FIG. 3 presents a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 9-12 and Comparative Examples C4-C5.

[0021] FIG. 4 presents a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 13-16 and Comparative Example C6.

[0022] FIG. 5 presents a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 17-21 and Comparative Example Cl .

[0023] FIG. 6 presents a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 22-24 and Comparative Examples C1-C2.

[0024] FIG. 7 presents a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 25-26 and Comparative Examples C1-C2.

[0025] While the disclosure is susceptible to various modifications and alternative forms, only a few specific aspects have been shown by way of example in the drawings and described in detail below. The figures and detailed description of specific aspects are not intended to limit the breadth or scope of the inventive concepts or the appended claims in any manner. Rather, the figures and detailed description are provided to illustrate the inventive concepts to a person of ordinary skill in the art and to enable such person to make and use the inventive concepts.

[0026] DEFINITIONS

[0027] To define more clearly the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology, 2ndEd (1997). can be applied, as long as that definition does not conflict with any other disclosure or definition applied herein, or render indefinite or non-enabled any claim to which that definition is applied. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.

[0028] Herein, features of the subject matter are described such that, within particular aspects, a combination of different features can be envisioned. For each and every aspect and / or feature disclosed herein, all combinations that do not detrimentally affect the compositions, processes and / or methods described herein are contemplated with or without explicit description of the particular combination. Additionally, unless explicitly recited otherwise, any aspect and / or feature disclosed herein can be combined to describe inventive compositions and processes / methods consistent with the present disclosure.

[0029] While compositions and processes / methods are described herein in terms of "‘comprising” various components or steps, the compositions and processes / methods also can “consist essentially of’ or “consist of’ the various components or steps, unless stated otherwise. The terms “a,” “an,” “the,” etc., are intended to include plural alternatives, e.g., at least one, unless otherwise specified. All “ppm” quantities disclosed herein refer to ppm by weight (or ppmw). unless specifically stated otherwise.

[0030] Generally, groups of elements are indicated using the numbering scheme indicated in the version of the periodic table of elements published in Chemical and Engineering News, 63(5), 27, 1985. In some instances, a group of elements can be indicated using a common name assigned to the group; for example, alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Group 3-12 elements, and halogens or halides for Group 17 elements. For any particular compound disclosed herein, the general structure or name presented is also intended to encompass all structural isomers, conformational isomers, and stereoisomers that can arise from a particular set of substituents, unless indicated otherwise. Thus, a general reference to a compound includes all structural isomers unless explicitly indicated otherwise; e.g., a general reference to pentane includes n-pentane, 2- methyl-butane, and 2,2-dimethylpropane, while a general reference to a butyl group includes an n-butyl group, a sec-buty l group, an iso-buty l group, and a tert-butyl group. Additionally, the reference to a general structure or name encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context permits or requires. For any particular formula or name that is presented, any general formula or name presented also encompasses all conformational isomers, regioisomers, and stereoisomers that can arise from a particular set of substituents.

[0031] The term “substituted” when used to describe a group, for example, when referring to a substituted analog of a particular group, is intended to describe any nonhydrogen moiety that formally replaces a hydrogen in that group, and is intended to be non-limiting. A group or groups can also be referred to herein as “unsubstituted” or byequivalent terms such as “non-substituted,” which refers to the original group in which a non-hydrogen moietys does not replace a hydrogen within that group. Unless otherwise specified, “substituted” is intended to be non-limiting and include inorganic substituents or organic substituents as understood by one of ordinary skill in the art.

[0032] The term “polymer” is used herein generically to include olefin homopolymers, copolymers, terpolymers, and the like, as well as alloys and blends thereof. The term “polymer” also includes impact, block, graft, random, and alternating copolymers. A copolymer is derived from an olefin monomer and one olefin comonomer, while a terpolymer is derived from an olefin monomer and two olefin comonomers. Accordingly, “polymer” encompasses copolymers and terpolymers derived from any olefin monomer and comonomer(s) disclosed herein. Similarly, the scope of the term “polymerization” includes homopolymerization, copolymerization, and terpolymerization. Therefore, an ethylene polymer includes ethylene homopolymers, ethylene copolymers (e.g., ethylene / a-olefin copolymers), ethylene terpolymers, and the like, as well as blends or mixtures thereof. Thus, an ethylene polymer encompasses polymers often referred to in the art as LLDPE (linear low density polyethylene) and HDPE (high density polyethylene). As an example, an olefin copolymer, such as an ethylene copolymer, can be derived from ethylene and a comonomer, such as 1-butene, 1 -hexene, or 1 -octene. If the monomer and comonomer were ethylene and 1 -hexene, respectively, the resulting polymer can be categorized an as ethylene / 1 -hexene copolymer. The term “polymer” also includes all possible geometrical configurations, unless stated otherwise, and such configurations can include isotactic, syndiotactic, and random symmetries. Moreover, unless stated otherwise, the term “polymer” also is meant to include all molecular weight polymers.

[0033] The term “co-catalyst” is used generally herein to refer to compounds such as aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, and the like, that can constitute one component of a catalyst composition, when used, for example, in addition to a fluorided silica-coated alumina. The term “co-catalyst” is used regardless of the actual function of the compound or any chemical mechanism by which the compound may operate.

[0034] The terms “chemically-treated solid oxide,” “treated solid oxide compound,” and the like, are used herein to indicate a solid, inorganic oxide of relatively high porosity, which can exhibit Lewis acidic or Bronsted acidic behavior, and which has been treated with an electron-withdraw ing component, typically an anion, and which is calcined. The electron-withdrawing component is typically an electron-withdrawing anion source compound. Thus, the chemically-treated solid oxide can comprise a calcined contact product of at least one solid oxide with at least one electron-withdrawing anion source compound. Typically, the chemically-treated solid oxide comprises at least one acidic solid oxide compound. The “activator-support” of this disclosure can be a chemically- treated solid oxide. The terms “support” and “activator-support” are not used to imply these components are inert, and such components should not be construed as an inert component of the catalyst composition. The term “activator,” as used herein, refers generally to a substance that is capable of converting a metallocene component into a catalyst that can polymerize olefins, or converting a contact product of a metallocene component and a component that provides an activatable ligand (e.g.. an alkyl, a hydride) to the metallocene, when the metallocene compound does not already comprise such a ligand, into a catalyst that can polymerize olefins. This term is used regardless of the actual activating mechanism. Illustrative activators include activator-supports, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, and the like. Aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds generally are referred to as activators if used in a catalyst composition in which an activator-support is not present. If the catalyst composition contains an activator-support, then the aluminoxane, organoboron or organoborate, and ionizing ionic materials are typically referred to as co-catalysts.

[0035] The term “metallocene” as used herein describes compounds comprising at least one r|3to r|5-cycloalkadienyl-type moiety, wherein r]3to p5-cycloalkadienyl moieties include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including partially saturated or substituted derivatives or analogs of any of these. Possible substituents on these ligands can include H, therefore encompassed herein are ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl, and the like. In some contexts, the metallocene is referred to simply as the “catalyst,” in much the same way the term “co-catalyst” is used herein to refer to, for example, an organoaluminum compound.

[0036] The terms “catalyst composition,” “catalyst mixture,” “catalyst system,” and the like, do not depend upon the actual product or composition resulting from the contact or reaction of the initial components of the disclosed or claimed catalyst composition / mixture / system, the nature of the active catalytic site, or the fate of the cocatalyst, the metallocene compound, or the fluorided silica-coated alumina, after combining these components. Therefore, the terms “catalyst composition,” “catalyst mixture.” “catalyst system,” and the like, encompass the initial starting components of the composition, as well as whatever product(s) may result from contacting these initial starting components, and this is inclusive of both heterogeneous and homogenous catalyst systems or compositions. The terms “catalyst composition,” “catalyst mixture,” “catalyst system,” and the like, can be used interchangeably throughout this disclosure.

[0037] The terms “contacting” and “combining” are used herein to describe compositions, processes, and methods in which the materials or components are contacted or combined together in any order, in any manner, and for any length of time, unless otherwise specified. For example, the materials or components can be blended, mixed, melt processed, extruded, slurried, dissolved, reacted, treated, compounded, or otherwise contacted or combined in some other manner or by any suitable method or technique.

[0038] Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosure, the typical methods, devices, and materials are herein described.

[0039] All publications and patents mentioned herein are incorporated herein by reference in their entirety for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications and patents, which might be used in connection with the present disclosure.

[0040] Several types of ranges are disclosed herein. When a range of any type is disclosed or claimed, the intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein. As a representative example, the ratio of Mw / Mn of the ethylene polymer can be in certain ranges in various aspects described herein. By a disclosure that the ratio of Mw / Mn can be in a range from 3 to 10, the intent is to recite that the ratio of Mw / Mn can be any number in the range and, for example, can include any range or combination of ranges from 3 to 10, such as from 3.5 to 8, from 3 to 6, or from 3.5 to 6, and so forth. Likewise, all other ranges disclosed herein should be interpreted in a manner similar to this example.

[0041] In general, an amount, size, formulation, parameter, range, or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. Whether or not modified by the term “about” or “approximately ,” the claims include equivalents to the quantities or characteristics.

[0042] DETAILED DESCRIPTION

[0043] The present disclosure is directed generally to ethylene polymer compositions, processes for preparing the ethylene polymer compositions, and methods of making films from the ethylene polymer compositions. In particular, the present disclosure relates to such ethylene polymer compositions that are substantially free of organic fluorine, i.e.. the ethylene polymer compositions are “substantially free” (contain less than 5 ppm by weight) of “organic fluorine” (encompassing any compound having a carbon-fluorine bond). In some aspects, the ethylene polymer compositions can contain less than 4 ppm, less than 3 ppm, less than 2 ppm, or less than 1 ppm (by weight) of the organic fluorine. The ppm by weight of organic fluorine is based on the elemental weight of fluorine present as organic fluorine divided by the total weight of the ethylene polymer composition. As those of skill in the art would recognize, fluorinated PPAs and fluoropolymers and PFAS are sources of organic fluorine (containing carbon-fluorine bonds).

[0044] In contrast, the ethylene polymer compositions of this disclosure contain an ethylene polymer that comprises from 1 to 50 ppm of inorganic fluorine (no carbon- fluorine bond). The fluorine content is based on the elemental weight of fluorine (F), and the fluorine is from an inorganic source used in the preparation of the activatorsupport or chemically-treated solid oxide (such as fluorided silica-coated alumina). Due to the high catalytic activity and catalyst productivity of the activator-support (e.g., fluorided silica-coated alumina), the resulting ethylene polymer has beneficially low amounts of catalyst residue. For instance, the ethylene polymer can contain less than 350 ppm solid oxide (such as silica-coated alumina) and less than 10 ppm of the residual metal (e.g., zirconium) from the metallocene component of the catalyst system.

[0045] An objective of this disclosure is to produce ethylene polymer compositions that comprise inorganic fluorine, but are substantially free of organic fluorine and fluorinated PPAs. and can be melt processed without melt fracture in blown film and other end-use applications.

[0046] ETHYLENE POLYMERS AND ETHYLENE POLYMER COMPOSITIONS

[0047] Herein, a first ethylene polymer composition can comprise (i) an ethylene polymer comprising from 1 to 50 ppm of inorganic fluorine, and (ii) an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the weight of the ethylene polymer composition. A second ethylene polymer composition can comprise (I) an ethylene polymer substantially free of inorganic fluorine, and (11) an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the weight of the ethylene polymer composition, and an inorganic fluorine containing additive at an amount in a range from 1 to 10 ppm of fluorine, based on weight of the ethylene polymer composition (or from 2 to 10 ppm, from 3 to 10 ppm, from 3 to 9 ppm, or from 4 to 10 ppm of fluorine). These ethylene polymer compositions can be substantially free of organic fluorine, and, while not limited thereto, the ethylene polymer can be in the form of fluff, granules, or powder, and the ethylene polymer composition can be in the form of pellets or beads.

[0048] Generally, the ethylene-based polymers, or ethylene polymers, encompass homopolymers of ethylene as well as copolymers, terpolymers, etc., of ethylene and at least one olefin comonomer. Comonomers that can be copolymerized with ethylene often can have from 3 to 20 carbon atoms in their molecular chain. For example, typical comonomers can include, but are not limited to, propylene, 1 -butene, 1 -pentene, 1- hexene, 1 -heptene, 1 -octene, and the like, or combinations thereof. In an aspect, the olefin comonomer can comprise a C3-C18 olefin; alternatively, the olefin comonomer can comprise a C3-C10 olefin; alternatively, the olefin comonomer can comprise a C4-C10 olefin; alternatively, the olefin comonomer can comprise a C3-C10 a-olefin; alternatively, the olefin comonomer can comprise a C4-C10 a-olefin; alternatively, the olefin comonomer can comprise 1 -butene, 1 -hexene, 1 -octene, or any combination thereof; or alternatively, the comonomer can comprise 1 -hexene. Typically, the amount of the comonomer, based on the total weight of monomer (ethylene) and comonomer, can be in a range from 0.01 to 20 wt. %, from 0.01 to 1 wt. %, from 0.5 to 15 wt. %, from 0.5 to 8 wt. %. or from 1 to 15 wt. %.

[0049] In one aspect, the ethylene polymer (or the ethylene polymer composition) can comprise an ethylene / a-olefin copolymer, while in another aspect, the ethylene polymer (or the ethylene polymer composition) can comprise an ethylene homopolymer, and in yet another aspect, the ethylene polymer (or the ethylene polymer composition) can comprise an ethylene / a-olefin copolymer and an ethylene homopolymer. For example, the ethylene polymer (or the ethylene polymer composition) can comprise an ethylene / 1- butene copolymer, an ethylene / 1 -hexene copolymer, an ethylene / 1 -octene copolymer, an ethylene homopolymer, or any combination thereof; alternatively, an ethylene / 1 -butene copolymer, an ethylene / 1 -hexene copolymer, an ethylene / 1 -octene copolymer, or any combination thereof; or alternatively, an ethylene / 1 -hexene copolymer. The ethylene polymer in the first ethylene polymer composition - regardless of comonomer type(s) - can be produced with a metallocene-based catalyst system, typically containing zirconium, discussed further below. Ziegler-Natta and chromium based catalysts systems are not required. Therefore, the ethylene polymer (e.g., the metallocene-catalyzed ethylene polymer) can contain no measurable amount of chromium or titanium or hafnium (catalyst residue), i.e., less than 0. 1 ppm by weight. In some aspects, the ethylene polymer in the first ethylene polymer composition can contain, independently, less than 0.08 ppm. less than 0.05 ppm, or less than 0.03 ppm, of chromium and titanium and hafnium.

[0050] However, the ethylene polymer in the second ethylene polymer composition can be produced with a Ziegler-Natta catalyst system, typically containing titanium and magnesium. Metallocene and chromium based catalysts systems are not required. Therefore, the ethylene polymer (e.g., the Ziegler-Natta catalyzed ethylene polymer) can contain no measurable amount of chromium or zirconium or hafnium (catalyst residue), i.e., less than 0.1 ppm by weight. In some aspects, the ethylene polymer in the second ethylene polymer composition can contain, independently, less than 0.08 ppm, less than 0.05 ppm. or less than 0.03 ppm, of chromium and zirconium and hafnium.

[0051] Ethylene polymers (and ethylene polymer compositions) consistent with certain aspects of this disclosure often can have a unimodal molecular weight distribution (as determined using gel permeation chromatography (GPC) or other related analytical technique). Often, in a unimodal molecular weight distribution, there is a single peak on a molecular weight distribution curve.

[0052] Additionally, the ethylene polymers described herein can be a reactor product (e.g., a single reactor product), for example, not a post-reactor blend of two polymers, for instance, having different molecular weight characteristics. As one of skill in the art would readily recognize, physical blends of two different polymer resins can be made, but this necessitates additional processing and complexity not required for a reactor product.

[0053] Ethylene polymers and ethylene polymer compositions consistent with this disclosure can have any of the polymer properties listed below and in any combination, unless indicated otherwise. The densities of ethylene-based polymers (and ethylene polymer compositions) disclosed herein often are greater than or equal to 0.90 g / cm3, and less than or equal to 0.96 g / cm3. In particular aspects, the density of the ethylene polymer (or the ethylene polymer composition) can be in a range from 0.91 to 0.94 g / cm3, from 0.912 to 0.935 g / cm3, or from 0.91 to 0.925 g / cm3.

[0054] The ethylene polymers (and ethylene polymer compositions) described herein often can have a melt index (MI) of less than or equal to 10 g / 10 min. Representative and non-limiting ranges for the melt index of the ethylene polymer (or the ethylene polymer composition) include from 0.2 to 10 g / 10 min, from 0.2 to 3 g / 10 min, from 0.3 to 2 g / 10 min, or from 0.5 to 1.5 g / 10 min.

[0055] While not being limited thereto, these ethylene polymers (and ethylene polymer compositions) can have a ratio of high load melt index to melt index (HLMI / MI) in a range from 10 to 60; alternatively, from 10 to 30; alternatively, from 12 to 50; or alternatively, from 12 to 20.

[0056] In an aspect, the ethylene polymers (and ethylene polymer compositions) can have a ratio of Mw / Mn, or the poly dispersity index, in a range from 3 to 10, such as from 3.5 to 8, from 3 to 6, or from 3.5 to 6. Additionally or alternatively, the ethylene polymers (and ethylene polymer compositions) described herein can have a weight-average molecular weight (Mw) in a range from 50,000 to 250,000 g / mol, from 70,000 to 200,000 g / mol, from 100,000 to 250,000 g / mol, or from 100,000 to 200,000 g / mol.

[0057] Moreover, these ethylene polymers (or ehtylene polymer compostiions) can have a CY-a parameter of from 0.5 to 0.7. from 0.5 to 0.65. from 0.55 to 0.7. or from 0.55 to 0.65, and the like. Additionally or alternatively, these ethylene polymers (or ethylene polymer compositions) can have a relaxation time (Tau(eta) or r(r|)) in a range from 0.001 to 0.15 sec, from 0.002 to 0.1 sec, from 0.002 to 0.05 sec, or from 0.005 to 0.02 sec, and the like. Additionally or alternatively, these ethylene polymers (or ethlylene polymer compositoins) can have a zero-shea viscosity at 190 °C in a range from 1,000 to 100,000 Pa-sec, from 1,000 to 50,000 Pa-sec, or from 2,000 to 10,000 Pa-sec, and the like. These rheological parameters are determined from viscosity data measured at 190 °C and using the Carreau-Yasuda (CY) empirical model described herein.

[0058] As disclosed herein, the ethylene polymer compositions can comprise (i) an ethylene polymer and (ii) an additive composition comprising a polyethylene glycol (PEG) at an amount in a range from 100 to 10,000 ppm, and this amount is based on the total weight of the ethylene polymer composition. The additive composition portion (PEG and any other additives) of the overall ethylene polymer composition is typically present at a very minor amount. Accordingly, the amount of the ethylene polymer in the ethylene polymer composition often can be at least 95 wt. %, at least 97 wt. %, or at least 98 wt. %, based on the total weight of the ethylene polymer composition. Representative ranges for the amount of ethylene polymer present in the overall ethylene polymer composition include from 95 to 99.9 wt. %, from 97 to 99.9 wt. %, from 95 to 99.5 wt. %, from 97 to 99.5 wt. %, from 95 to 99 wt. %, or from 97 to 99 wt. %, and so forth.

[0059] Referring now to the polyethylene glycol (PEG) in the additive composition, the PEG is present in the ethylene polymer composition at an amount in a range from 100 to 10,000 ppm, based on the total weight of the ethylene polymer composition. The ethylene polymer composition can contain other suitable amounts of the polyethylene glycol (PEG), and illustrative and non-limiting ranges include from 200 to 5,000 ppm, from 300 to 5,000 ppm, from 300 to 2,000 ppm, from 500 to 3,000 ppm, from 500 to 1,500 ppm, from 700 to 1,500 ppm, from 900 to 2,500 ppm, from 900 to 1,500 ppm, from 1,000 to 2,500 ppm, from 1,000 to 2,000 ppm, or from 1,000 ppm to 1,500 ppm of the PEG, based on the total weight of the ethylene polymer composition.

[0060] The molecular weight (Mw) of the PEG in the additive composition (and therefore, in the ethylene polymer composition) is not particularly limited. Nonetheless, typical values of Mw (weight-average molecular weight) for the PEG include from 2,000 to 50,000 g / mol in one aspect, from 3,000 to 20,000 g / mol in another aspect, from 5,000 to 15,000 g / mol in another aspect, from 5,000 to 10,000 g / mol in another aspect, from 5,000 to 9,000 g / mol in another aspect, from 6,000 to 9,000 g / mol in yet another aspect, and from 6,000 to 8,000 g / mol in still another aspect. While not limited thereto, the PEG in the additive composition can be dihydroxy terminated.

[0061] Optionally, the additive composition (or the ethylene polymer composition) can further contain a polysorbate, with suitable grades available under the Tween designation. Illustrative and non-limiting ranges for the amount of the polysorbate - when present - include from 100 to 10.000 ppm, from 300 to 5,000 ppm, or from 500 to 3,000 ppm of the polysorbate. These amounts are based on the total weight of the ethylene polymer composition. Likewise and optionally, the additive composition (or the ethylene polymer composition) can further contain a poly(oxyalkylene), which is different from the PEG described hereinabove. Suitable grades of poly(oxyalkylene) are available under the Pluronic and Poloxamer designations. Illustrative and non-limiting ranges for the amount of the poly (oxy alkylene) - when present - include from 100 to 10,000 ppm, from 300 to 5,000 ppm, or from 500 to 3,000 ppm of the poly(oxyalkylene). These amounts are based on the total weight of the ethylene polymer composition.

[0062] Another material that optionally be present in the additive composition (or the ethylene polymer composition) is zinc oxide. When the zinc oxide is present, illustrative and non-limiting ranges for the amount of zinc oxide include from 100 to 2,000 ppm, from 200 to 1,000 ppm, or from 200 to 800 ppm of zinc oxide. These amounts are based on the total weight of the ethylene polymer composition.

[0063] Conventional polyethylene additives such as slip additives, antiblock additives, and antioxidants at suitable loadings also can be present in the additive composition (or the ethylene polymer composition), depending upon the end-use application of the ethylene polymer composition. Illustrative and non-limiting ranges for the amount of slip additive include from 100 to 5,000 ppm, from 200 to 3,000 ppm, or from 500 to 1,500 ppm of the slip additive. Illustrative and non-limiting ranges for the amount of antiblock additive include from 200 to 10,000 ppm, from 500 to 6,000 ppm, or from 2,000 to 6,000 ppm of the antiblock additive. Illustrative and non-limiting ranges for the amount of a phenolic antioxidant and a phosphite antioxidant, independently, include from 100 to 5.000 ppm, from 200 to 2,000 ppm. or from 300 to 1,500 ppm of the phenolic antioxidant (or the phosphite antioxidant). These respective additive amounts are based on the total weight of the ethylene polymer composition.

[0064] Typical slip additives can be amide compounds such as erucamide, stearamide, oleamide, and the like. These slip additives bloom to the surface of a fabricated film and reduce the coefficient of friction (COF) of the film. An antiblock additive is a particle (e.g., talc, SiCh) that roughens the surface of a fabricated film. For instance, antiblock additives in a blown or cast film are designed to prevent adjacent film surfaces from sticking together, or blocking. In some instances, and depending upon overall talc loading in the ethylene polymer composition, talc can contribute a few ppm (e.g.. 4-7 ppm) of inorganic fluorine to the ethylene polymer composition. Nonetheless, the typical amount of inorganic fluorine in the ethylene polymer of the first ethylene polymer composition and in the first ethylene polymer composition is less than or equal to 50 ppm.

[0065] Illustrative and non-limiting examples of phenolic antioxidants can include IRGANOX™ 1010 (pentaerythritol tetrakis(3-(3.5-di-terl-butyl-4-hydroxyphenyl) propionate), IRGANOX™ 1076 (octadecyl-3-(3.5-di-tertbutyl-4-hydrox phenyl) propionate), IRGANOX™ 1330 (l,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4- hydroxybenzyl)benzene), IRGANOX™ 3114 (tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate). IRGANOX™ 129 (2.2’-ethylidenebis (4,6-di-tert-butylphenol)), IRGANOX™ MD 1024 (l,2-bis(3,5-di-tert-butyl-4-hydroxy hydrocinnamoyl) hydrazine), and the like. Illustrative and non-limiting examples of phosphite (monophosphite and diphosphite) antioxidants can include IRGAFOS™ 168 (tris(2,4,6- di-tert-butylphenyl) phosphite), HP-10 (2,2?-methylenebis(2,4-di-tert-butylphenyl) 2- ethylhexyl phosphite), ULTRANOX™ 627A (bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite plus stabilizer), ULTRANOX™ 626 (bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite), PEP-36 (bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate). DOVERPHOS™ 9228 (bis(2.4-dicumylphenyl) pentaerythritol diphosphate), DOVERPHOS™ S9228T (bis(2,4-dicumylphenyl) pentaerythritol diphosphite plus stabilizer), and the like.

[0066] In a particular aspect, the additive composition (or the ethylene polymer composition) optionally can contain any suitable processing aid synergist. While not limited thereto, the processing acid synergist can include citric acid, a polyanhydride resin, a polyacid resin, and the like, as well as mixtures or combinations thereof.

[0067] Referring now to the inorganic fluorine content of the ethylene polymer in the first ethylene polymer composition, the ethylene polymer ordinarily contains from 1 to 50 ppm of inorganic fluorine. As noted herein, inorganic fluorine (no carbon-fluorine bond) refers to the fluorine content based on the elemental weight of fluorine (F), and the fluorine is from an inorganic source used in the preparation of the activator-support (such as fluorided silica-coated alumina). More often, the inorganic fluorine content of the ethylene polymer can range from 2 to 50 ppm or from 2 to 45 ppm, and other illustrative ranges include, but are not limited to. from 4 to 35 ppm. from 5 to 50 ppm, from 5 to 45 ppm, from 5 to 35 ppm, from 10 to 50 ppm, from 10 to 45 ppm, from 10 to 35 ppm, from 15 to 50 ppm, from 15 to 45 ppm, from 15 to 35 ppm, from 20 to 50 ppm, or from 20 to 35 ppm of inorganic fluorine.

[0068] Further, due to the high catalytic activity and catalyst productivity of the activator-support (e.g., fluorided silica-coated alumina), the resulting ethylene polymer in the first ethylene polymer composition has beneficially low amounts of catalyst residue. The ethylene polymer typically contains from 50 to 350 ppm solid oxide (such as silica-coated alumina). Other illustrative ranges for the solid oxide content of the ethylene polymer include, but are not limited to, from 50 to 300 ppm, from 70 to 350 ppm, from 100 to 350 ppm. from 100 to 250 ppm, from 120 to 350 ppm, from 120 to 300 ppm, or from 120 to 200 ppm of solid oxide. The solid oxide content of the ethylene polymer is quantified by an ash test, discussed hereinbelow. While not required, the solid oxide can contain silica and alumina in any suitable relative amount, and illustrative weight ratios of silica: alumina can include from 20:80 to 80:20, from 20:80 to 60:40, from 25:75 to 55:45, or from 35:65 to 45:55, and so forth. While not being limited thereto, the fluorided silica-coated alumina can contain from 0.5 to 18 wt. % F, although any suitable amount can be used. In many instances, the fluorided silica-coated alumina of this disclosure contains from 1 to 13 wt. % F, from 2 to 9 wt. % F, from 3 to 16 wt. % F, or from 3 to 10 wt. % F, and the like. These weight percentages are based on the weight of the fluorided silica-coated alumina. The ethylene polymer also contains residual metal from the metallocene compound, typically zirconium. Generally, the ethylene polymer can contain from 0.5 to 10 ppm, from 0.5 to 7 ppm, from 0.5 to 5 ppm, from 0.6 to 10 ppm, from 0.6 to 5 ppm, from 0.6 to 3 ppm, from 0.7 to 7 ppm. or from 0.7 to 3 ppm of zirconium.

[0069] Referring now to the second ethylene polymer composition, the ethylene polymer in the second ethylene polymer composition is substantially free of inorganic fluorine. The additive composition in the second ethylene polymer composition comprises the PEG (at 100 to 10,000 ppm, based on the weight of the ethylene polymer composition), and an inorganic fluorine containing additive at an amount in a range from 1 to 10 ppm of fluorine, based on the weight of the ethylene polymer composition (or from 2 to 10 ppm, from 3 to 10 ppm. from 3 to 9 ppm. or from 4 to 10 ppm of fluorine).

[0070] In one aspect, the inorganic fluorine containing additive in the additive composition of the second ethylene polymer composition is an antiblock additive, while in another aspect, the inorganic fluorine containing additive in the additive composition of the second ethylene polymer composition is talc.

[0071] ARTICLES AND FILMS

[0072] Articles of manufacture can be formed from, and / or can comprise, the ethylene polymer compositions and, accordingly, are encompassed herein. For example, articles which can comprise the ethylene polymer compositions disclosed herein can include, but are not limited to, an agricultural film, an automobile part, a bottle, a container for chemicals, a drum, a fiber or fabric, a food packaging film or container, a food service article, a fuel tank, a geomembrane, a household container, a liner, a molded product, a medical device or material, an outdoor storage product (e.g., panels for walls of an outdoor shed), outdoor play equipment (e.g., kayaks, bases for basketball goals), a pipe, a sheet or tape, a toy, or a traffic barrier, and the like. V arious processes can be employed to form these articles. Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, and the like. In some aspects, an article of manufacture can comprise any of the ethylene polymer compositions described herein, and the article of manufacture can be or can compnse a film, such as a single layer or multilayer blown film or cast film.

[0073] Also contemplated herein is a method for making a film comprising any ethylene polymer composition disclosed herein. For instance, a method of making a film (e.g., a film with no melt fracture) can comprise melt processing the first ethylene polymer composition through a film die to produce the film. The first ethylene polymer composition can be substantially free of (or contain less than 5 ppm by weight) of organic fluorine, and can comprise an ethylene polymer comprising from 1 to 50 ppm of inorganic fluorine, and an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition.

[0074] Another method of making a film (e.g., a film with no melt fracture) can comprise melt processing the second ethylene polymer composition through a film die to produce the film. The second ethylene polymer composition can comprise an ethylene polymer substantially free of inorganic fluorine and an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition, and an inorganic fluorine containing additive at an amount in a range from 1 to 10 ppm of fluorine, based on the ethylene polymer composition (or from 2 to 10 ppm, from 3 to 10 ppm, from 3 to 9 ppm, or from 4 to 10 ppm of fluorine).

[0075] In this method of making a film, the ethylene polymer composition is melt processed through a film die to form the film. Suitably, the film die can be configured based on the film type to be produced, for example, a blown film die or an annular die to produce a blown film, or a cast film die or slot die to produce a cast film. Moreover, any suitable means of melt processing can be employed, although extrusion typically is utilized. While not a requirement, the melt processing of the ethylene polymer composition through the film die can be performed using a single screw extrusion system.

[0076] Melt processing (e.g., extrusion) of the ethylene polymer composition can be performed at any suitable melt processing temperature (e.g., extrusion melt temperature), such as, for example, a temperature in a range from 200 to 600 °C, a temperature in a range from 300 to 500 °C, a temperature in a range from 350 to 550 °C, and so forth.

[0077] The film produced, whether cast or blown, can be any thickness that is suitable for the particular end-use application, and often, the average film thickness can be in a range from 0.4 to 20 mils, or from 0.5 to 8 mils. For certain film applications, typical average thicknesses can be in a range from 0.8 to 5 mils, from 0.7 to 2 mils, or from 0.7 to 1.5 mils.

[0078] In reference to multilayer films, these same average film thicknesses can apply, however, a method of making a multilayer film (e.g., with no melt fracture) can comprise melt processing an ethylene polymer composition through at least one flow channel of a coextrusion film die to produce the multilayer film, wherein at least one layer of the multilayer film contains the ethylene polymer composition. The thickness of the layer containing the ethylene polymer composition can be any suitable percentage of the overall film thickness, such as from 5 to 80%, and more often, from 5 to 50%, from 5 to 25%, from 10 to 75%, from 10 to 25%, from 25 to 75%, or from 50 to 75%.

[0079] Beneficially, the films produced by the methods described herein can have substantially no melt fracture, such as when processed a shear rate of approximately 115 sec'1, as demonstrated in the examples that follow. PROCESS FOR PREPARING ETHYLENE POLYMER COMPOSITIONS

[0080] In accordance with aspects of the present disclosure, a first process for preparing an ethylene polymer composition is provided herein. In these aspects, the first process for preparing the ethylene polymer composition can comprise melt processing a blend (also referred to as a mixture) of an ethylene polymer and an additive composition through a die (e.g., a pelletizing or strand die) to produce the ethylene polymer composition. In this process, the ethylene polymer (or the ethylene polymer composition, or both) can comprise from 1 to 50 ppm of inorganic fluorine, the additive composition can comprise a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition, and the ethylene polymer composition can be substantially free of (or can contain less than 5 ppm of) organic fluorine.

[0081] In other aspects, a second process for preparing an ethylene polymer composition can comprise combining an additive composition with an ethylene polymer to form a blend, and melt processing the blend through a die to produce the ethylene polymer composition. In this process, the additive composition can consist of a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition, and one or more active additives. The additive composition can be substantially free of binding agents and carrier resins, and the ethylene polymer composition can be substantially free of (or can contain less than 5 ppm of) organic fluorine.

[0082] Combining of the polyethylene glycol, and other additives, and the ethylene polymer can be accomplished in any order or sequence. In one aspect, the polyethylene glycol can be introduced to the ethylene polymer in the form of fluff prior to the melt processing. Additionally or alternatively, the polyethylene glycol can be introduced to the ethylene polymer separately from at least one other additive of the additive composition. In another aspect, the polyethylene glycol can be introduced to the ethylene polymer together with at least one other additive of the additive composition.

[0083] Melt processing the blend (or mixture) of the ethylene polymer and the additive composition can be accomplished at any suitable melt processing temperature, such as, for example, a temperature in a range from 130 to 400 °C, a temperature in a range from 150 to 300 °C, a temperature in a range from 175 to 275 °C. and so forth. While not limited thereto, the ethylene polymer can be in the form of fluff, granules, or powder, the additive composition can be in the form of powder, pressed masterbatch pills, pellets, or beads, and the ethylene polymer composition can be in the form of pellets or beads.

[0084] Various methods of melt processing can be employed, as would be recognized by those of skill in the art. Ordinarily, however, the melt processing of the ethylene polymer and the additive composition to form the (first or second) ethylene polymer composition utilizes extrusion. For example, the melt processing of the ethylene polymer and the additive composition to form the ethylene polymer composition can be performed in a twin screw extrusion system (e.g., a counter-rotating mixer or a co-rotating twin screw extrusion system) or a multi-screw extrusion system. The twin screw extrusion system can include any combination of feeding, melting, mixing, and conveying elements. For instance, the twin screw extrusion system can contain all or a majority of mixing elements.

[0085] In an aspect, the additive composition - which can be in the form of pellets or beads - can be formed by compaction. Thus, the additive composition can be formed cold or without heat, and thus differs from a traditional polymer-based masterbatch. In this aspect, the various additives can be mixed together, then compacted beads or pellets can be formed, which can then be fed to the twin screw system described above.

[0086] Generally, the additive composition therefore is substantially free of polyolefins, i.e., contains less than or equal to 3 wt. % of a polyolefin, such as a polyethylene and / or a polypropylene. In some instances, the additive composition contains less than or equal to 2 wt. %, less than or equal to 1 wt. %, or less than or equal to 0.5 wt. % of the polyolefin. If desired, the additive composition can further contain, in addition to the mixture of additives, a binding agent. Suitable binding agents can include a mineral oil or a w ax.

[0087] Referring now to the second process for preparing an ethylene polymer composition, the additive composition can consist of the polyethylene glycol and one or more active additives, and therefore, the additive composition can be substantially free of binding agents and carrier resins (e.g., polyolefins). For instance, the polyethylene glycol can be utilized neat or without a carrier, and the other active additives (e.g., slip, antiblock, antioxidant, and the like) also can be utilized neat or without a carrier resin. The additive composition can be in the form of powder or compacted pills, pellets, or beads, and as discussed herein, can be substantially free of any binding agents or carrier resins.

[0088] Optionally, the processes for preparing ethylene polymer compositions can further comprise a step of determining an amount of a tracer in the ethylene polymer composition, in which one or more of the (active) additives comprises the tracer, and then adjusting an amount of the additive composition combined with the ethylene polymer based on the amount of tracer. As a non-limiting example, the amount of polyethylene glycol in the ethylene polymer composition can be controlled by determining the amount of the tracer in the ethylene polymer composition. Any suitable analytical technique and sampling frequency can be utilized, an illustrative example of which is to take a sample of the ethylene polymer composition and analyze the sample via FT-IR (or other suitable technique) for the amount of the tracer.

[0089] EXAMPLES

[0090] The disclosure is further illustrated by the following examples, which are not to be construed in any way as imposing limitations to the scope of this disclosure. Various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to one of ordinary skill in the art without departing from the spirit of the present disclosure or the scope of the appended claims.

[0091] Melt index (MI, g / 10 min) was determined in accordance with ASTM DI 238 at 190 °C with a 2,160 gram weight, and high load melt index (HLMI, g / 10 min) was determined in accordance with ASTM D1238 at 190 °C with a 21,600 gram weight. Density was determined in grams per cubic centimeter (g / cm3) on a compression molded sample, cooled at 15 °C per minute, and conditioned for 40 hr at room temperature in accordance with ASTM D1505 and ASTM D4703.

[0092] Molecular weights and molecular weight distributions were obtained using a PL- GPC 220 (Polymer Labs, an Agilent Company) system equipped with a IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA) running at 145 °C. The flow rate of the mobile phase 1 ,2,4-trichlorobenzene (TCB) containing 0.5 g / L 2.6-di-l-bul l-4-methylphenol (BHT) was set at 1 mL / min. and polymer solution concentrations were in the range of 1.0- 1.5 mg / mL, depending on the molecular weight. Sample preparation was conducted at 150 °C for nominally 4 hr with occasional and gentle agitation, before the solutions were transferred to sample vials for injection. An injection volume of about 200 pL was used. The integral calibration method was used to deduce molecular weights and molecular weight distributions using a Chevron Phillips Chemical Company’s HDPE polyethylene resin, MARLEX® BHB5003. as the broad standard. The integral table of the broad standard was pre-determined in a separate experiment with SEC-MALS. Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the z-average molecular weight, Mv is the viscosity-average molecular weight, and Mp is the peak molecular weight (location, in molecular weight, of the highest point of the molecular weight distribution curve).

[0093] Melt rheological characterizations were performed as follows. Small-strain (less than 10%) oscillator}' shear measurements were performed on an Anton Paar MCR rheometer using parallel-plate geometry. All rheological tests were performed at 190 °C. The complex viscosity versus frequency (co) data were then curve fitted using the modified three parameter Carreau-Yasuda (CY) empirical model to obtain the zero shear viscosity - ry. characteristic viscous relaxation time - cy. and the breadth parameter - a (CY-a parameter). The simplified Carreau-Yasuda (CY) empirical model is as follows. wherein: | rj*(co) | = magnitude of complex shear viscosity'; 0 = zero shear viscosity;

[0094] Tij = viscous relaxation time (Tau(r|)); a = “breadth” parameter (CY-a parameter); n = fixes the final power law slope, fixed at 2 / 11 ; and co = angular frequency of oscillatory shearing deformation.

[0095] Details of the significance and interpretation of the CY model and derived parameters can be found in: C. A. Hieber and H. H. Chiang, Rheol. Acta, 28, 321 (1989); C.A. Hieber and H.H. Chiang, Polym. Eng. Sci., 32, 931 (1992); and R. B. Bird. R. C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987); each of which is incorporated herein by reference in its entirety'. Herein, the ASTM ash content of the polymer (measured by ASTM D5630-13, procedure B) encompasses the amount of solid oxide (e.g., silica-coated alumina), metallocene transition metal, and fluorine. Since the metallocene transition metal and fluorine are minor portions of the ash content, the ash content is very close to the solid oxide content, but solid oxide content herein equals ash content minus metallocene transition metal content and minus fluorine content.

[0096] Metal content, such as from the transition metal of the metallocene compound, can be determined by ICP analysis on a PerkinElmer Optima 8300 instrument. Polymer or article samples can be ashed in a Thermolyne furnace with sulfuric acid overnight, followed by acid digestion in a HotBlock with HC1 and HNO3 (3: 1 v:v).

[0097] During manufacture, fluorine content was determined by direct weight of the fluorine compound added during catalyst preparation. Fluorine content of the ethylene polymer or ethylene polymer composition was determined by X-ray fluorescence, using calibrated samples of known fluorine content. The fluorided silica-coated alumina component of the catalyst system was prepared as generally described in U.S. Patent Nos. 7,884,163, 9,346,896. 9,670,296, 10,239,975, 10,676,553, 10,919,996, 11,208,514, and 11,912,809.

[0098] EXAMPLES 1-26 AND COMPARATIVE EXAMPLES C1-C6

[0099] Blown fdms were prepared on a LabTech 40 mm single screw' extruder (30: 1 L / D) with a mixing screw containing both a Maddock mixing element (dispersive mixer) at 22D and a pineapple head mixer (distributive mixer) at the screw tip. The 40 mm extruder had 5 heating zones with all heating zones set at the same temperature (380 °F), and the heating zones of the die and adapter / transfer tube also were set at the same temperature. The extruder was fitted with a weight loss hopper system for gravimetric calculation of extruder output, therefore the output (in Ib / hr) was set, and the screw speed (rpm) to achieve that output was recorded. For these evaluations, the extruder w as fitted with a 2” annular die and a 1.0 mm die pin for a 39.4 mil die gap. The small die gap was selected to bias higher shear rates at all outputs to ensure good melt fracture behavior, and standard run rates were 18 Ib / hr, corresponding to an approximate 115 sec’1shear rate. All films were maintained at 1.5 mil average thickness across the bubble. Frostline height (FLH) was held constant, and line speed and air speed were varied to maintain constant FLH and film thickness. During the evaluation period, film samples are cut off the line every 10 min and the extent of melt fracture was assessed. Melt fracture severity was rated on a scale of 1-10, with 10 being indicative of severe sharkskin / orange peel melt fracture, and 0 being no observable melt fracture. A rating of 1 was indicative of 1% or less of the film surface having observable melt fracture.

[0100] The base ethylene polymer was an ethylene / 1 -hexene copolymer having a nominal melt index of 0.8- 1.2 g / 10 min, HLMI / MI of approximately 16, and density of 0.916-0.920 g / cm3, and containing 400 ppm ZnO, 500 ppm of a phenolic antioxidant, and 1000 ppm of a phosphite antioxidant. It is believed that zinc oxide is an improvement over zinc stearate and other related stearates (e.g., calcium stearate), which are susceptible to significant plate-out on die surfaces. The base ethylene polymer had the following general properties: CY-a parameter of 0.56, relaxation time of 0.015 sec, zeroshear viscosity of 9700 Pa-sec, Mw of 165 kg / mol, and ratio of Mw / Mn of 3.5. The base ethylene polymer was produced with a single metallocene catalyst system. The base ethylene polymer contained inorganic fluorine.

[0101] Comparative Example Cl was this base ethylene polymer combined with a fluorinated polymer processing aid. Comparative Example C2 was this ethylene polymer combined with 650 ppm of fluorinated polymer processing aid. Comparative Example C3 was this ethylene polymer with no fluorinated polymer processing aid, Comparative Example C4 w as this ethylene polymer combined with a fluorinated polymer processing aid and 6000 ppm of talc, Comparative Example C5 was this ethylene polymer combined with 650 ppm of fluorinated polymer processing aid and 12000 ppm of talc, and Comparative Example C6 was this ethylene polymer combined with 650 ppm of fluorinated polymer processing aid and 1200 ppm of talc.

[0102] The ethylene polymer compositions of Examples 1-5 are summarized in Table 1, and these compositions contained either Poloxamer 188, a combination of Poloxamer 188 and Tween 20, or a combination of PEG 8000 (Mw of approximately 8000 g / mol) with either Tween 20 or Poloxamer 188. FIG. 1 is a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 1-5 and Comparative Examples C1-C2. FIG. 1 demonstrates that each of Examples 1-5 improved melt fracture comparable to that of the comparative examples, which utilized a fluorinated polymer processing aid. The ethylene polymer compositions of Examples 6-8 are summarized in Table 2, and these compositions contained Tween 20, Tween 40, or Tween 80 at a loading of 500 ppm. FIG. 2 is a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 6-8 and Comparative Examples Cl and C3. FIG. 2 demonstrates that each of Examples 6-8 performed similarly and improved melt fracture comparable to that of the Comparative Example Cl, which utilized a fluorinated polymer processing aid. As expected, Comparative Example C3 exhibited severe melt fracture throughout the 60 min test.

[0103] The ethylene polymer compositions of Examples 9-12 are summarized in Table

[0104] 3, FIG. 3 is a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 9-12 and Comparative Examples C4-C5. FIG. 3 demonstrates that Tween 20 had no effect on improving melt fracture when talc is present (Example 12), while Poloxamer improved melt fracture in the presence of talc (Example 11). Tween 20 and Poloxamer (Example 10) and Tween 20 and PEG 8000 (Example 9) appeared to work synergistically to improve melt fracture, even in the presence of the talc antiblock.

[0105] The ethylene polymer compositions of Examples 13-16 are summarized in Table

[0106] 4, and these compositions contained Tween 20, Tween 40, Tween 60, or Tween 80 at a loading of 500 ppm. FIG. 4 is a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 13-16 and Comparative Example C6. FIG. 4 demonstrates that (at equivalent concentrations) increasing the molecular weight of the Tween surfactant decreased its effectiveness in improving melt fracture in the presence of talc antiblock. Tween 20 (Example 13) performed the best.

[0107] The ethylene polymer compositions of Examples 17-21 are summarized in Table

[0108] 5, and these compositions contained either PEG, citric acid, or PA-18 LV (low viscosity polyanhydride from 1-octadecene and maleic anhydride), or combinations of PEG and the respective acid synergists. FIG. 5 is a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 17-21 and Comparative Example Cl . FIG. 5 demonstrates that citric acid individually and PA- 18 LV individually did not improve melt fracture, which remained severe throughout the test (Examples 19-20). While PEG 8000 at 350 ppm (Example 21) was slightly better, melt fracture was not improved significantly. Unexpectedly, however, PEG with either citric acid or PA- 18 LV worked synergistically, effectively eliminating melt fracture comparably to Comparative Example Cl, which utilized a fluorinated polymer processing aid.

[0109] The ethylene polymer compositions of Examples 22-24 are summarized in Table

[0110] 6, and these compositions contained PEG 8000 (Mw of approximately 8000 g / mol) at different loadings. FIG. 6 is a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 22-24 and Comparative Examples C 1-C2. FIG. 6 demonstrates that Example 22 had melt fracture comparable to that of the comparative examples, while the melt fracture in Examples 23-24 was eliminated more rapidly than that of the comparative examples, which utilized a fluorinated polymer processing aid. Even in the presence of high loadings of talc antiblock, 1200-1440 ppm of PEG 8000 (Examples 23-24) were sufficient to effectively eliminate melt fracture.

[0111] The ethylene polymer compositions of Examples 25-26 are summarized in Table

[0112] 7, and these compositions contained PEG 8000 (Mw of approximately 8000 g / mol) at different loadings. FIG. 7 is a plot of melt fracture severity versus time for the ethylene polymer compositions of Examples 25-26 and Comparative Examples C 1-C2. FIG. 7 demonstrates that Example 25 had melt fracture comparable to that of the comparative examples, while the melt fracture in Examples 26 was eliminated more rapidly than that of the comparative examples, which utilized a fluorinated polymer processing aid. Even in the presence of high loadings of talc antiblock, similar to Table 6 and FIG. 6, 1200 ppm of PEG 8000 (Example 26) was sufficient to effectively eliminate melt fracture.

[0113] EXAMPLES 27-68

[0114] Inorganic fluorine levels were determined by X-ray fluorescence (XRF) for the ethylene polymer compositions in Examples 27-68 and summarized in Table 8. Polymer composition A was the ethylene / 1 -hexene copolymer used in the melt fracture experiments discussed above (melt index of 0.8-1.2 g / 10 min. HLMI / MI of approximately 16, and density of 0.916-0.920 g / cm3) and contained nominally 400 ppm zinc stearate, 500 ppm of a phenolic antioxidant, and 1000 ppm of a phosphite antioxidant. Polymer composition B was the ethylene / l-hexene copolymer used in the melt fracture experiments discussed above (melt index of 0.8-1.2 g / 10 min, HLMI / MI of approximately 16, and density of 0.916-0.920 g / cm3) and contained nominally 400 ppm ZnO, 500 ppm of a phenolic antioxidant, 1000 ppm of a phosphite antioxidant, 1000 ppm of a slip additive, 5000 ppm of talc (which also contained some inorganic fluorine), and 1200 ppm of PEG 8000.

[0115] Polymer composition C was a metallocene-catalyzed ethylene / l-hexene copolymer (melt index of 1.2-1.6 g / 10 min and density’ of 0.914-0.918 g / cm3) and contained nominally 400 ppm zinc stearate, 500 ppm of a phenolic antioxidant, and 1000 ppm of a phosphite antioxidant. Polymer composition D was a metallocene-catalyzed ethylene / l-hexene copolymer (melt index of 0.8-1 g / 10 min and density of 0.920-0.924 g / cm3) and contained nominally 400 ppm zinc stearate, 500 ppm of a phenolic antioxidant. 1000 ppm of a phosphite antioxidant, and 5000 ppm of talc (which also contained some inorganic fluorine).

[0116] Polymer composition E was a Ziegler-Natta catalyzed ethylene / l-hexene copolymer (melt index of 0.65-0.95 g / 10 min and density of 0.924-0.927 g / cm3) and contained nominally 400 ppm ZnO, 800 ppm of a phenolic antioxidant, 1600 ppm of a phosphite antioxidant, and 3000 ppm of talc (which contained some inorganic fluorine). As a control sample, Polymer composition F was Polymer Composition E but with no talc additive, and therefore no inorganic fluorine. As shown in Table 8, the inorganic fluorine levels in Polymer Compositions A-E ranged from approximately 4 ppm to 47 ppm. Relatively more inorganic fluorine in the polymer was from the catalyst residue as compared to the talc additive.

[0117] Table 1. Examples 1-5 - Additive amounts in ppm by weight.

[0118] Table 2. Examples 6-8 - Additive amounts in ppm by weight.

[0119] Table 3. Examples 9-12 - Additive amounts in ppm by weight.

[0120] Table 4. Examples 13-16 - Additive amounts in ppm by weight.

[0121] Table 5. Examples 17-21 - Additive amounts in ppm by weight.

[0122] Table 6. Examples 22-24 - Additive amounts in ppm by weight.

[0123] Table 7. Examples 25-26 - Additive amounts in ppm by weight.

[0124] Table 8. Examples 27-68 - Inorganic Fluorine (ppm by weight). The disclosure provided above refers to numerous aspects and specific examples. Many variations will suggest themselves to those skilled in the art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims. Other aspects of the disclosure can include, but are not limited to, the following (aspects are described as “comprising” but, alternatively, can “consist essentially of’ or “consist of):

[0125] Aspect 1. A process for preparing an ethylene polymer composition, the process comprising: melt processing a blend (or mixture) of an ethylene polymer and an additive composition through a die (e g., a pelletizing or strand die) to produce the ethylene polymer composition, wherein the ethylene polymer and / or the ethylene polymer composition comprises from 1 to 50 ppm of inorganic fluorine (or from 2 to 50 ppm, from 2 to 45 ppm, from 4 to 35 ppm. from 5 to 50 ppm, from 5 to 45 ppm, from 5 to 35 ppm, from 10 to 50 ppm, from 10 to 45 ppm, from 10 to 35 ppm, from 15 to 50 ppm, from 15 to 45 ppm, from 15 to 35 ppm, from 20 to 50 ppm, or from 20 to 35 ppm of inorganic fluorine); the additive composition comprises a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition; and the ethylene polymer composition is substantially free of (contains less than 5 ppm of) organic fluorine (carbon-fluorine bonds).

[0126] Aspect 2. The process defined in aspect 1, wherein the ethylene polymer is in the form of fluff, granules, or powder.

[0127] Aspect 3. The process defined in aspect 1 or 2, wherein the polyethylene glycol is introduced to the ethylene polymer in the form of fluff prior to the melt processing.

[0128] Aspect 4. The process defined in any one of aspects 1-3, wherein the polyethylene glycol is introduced to the ethylene polymer separately from at least one other additive of the additive composition.

[0129] Aspect 5. The process defined in aspect 1 or 2, wherein the polyethylene glycol is introduced to the ethylene polymer together with at least one other additive of the additive composition.

[0130] Aspect 6. The process defined in any one of aspects 1-5, wherein the melt processing is performed at any suitable melt processing temperature, e.g., from 130 to 400 °C, from 150 to 300 °C, or from 175 to 275 °C. Aspect 7. The process defined in any one of aspects 1-6, wherein the melt processing comprises extrusion.

[0131] Aspect 8. The process defined in any one of aspects 1-7, wherein the melt processing is performed in a twin screw extrusion system or a multi-screw extrusion system.

[0132] Aspect 9. The process defined in any one of aspects 1-8, wherein the additive composition is in the form of powder, pressed masterbatch pills, pellets, or beads.

[0133] Aspect 10. The process defined in any one of aspects 1-9. wherein the additive composition is formed by compaction (e.g., cold, without heat).

[0134] Aspect 11. The process defined in any one of aspects 1-10, wherein the additive composition contains less than or equal to 3 wt. %, less than or equal to 2 wt. %, or less than or equal to 1 wt. %, of a polyolefin.

[0135] Aspect 12. The process defined in any one of aspects 1-11, wherein the additive composition further comprises a binding agent, e.g., a mineral oil or a wax.

[0136] Aspect 13. A method of making a film (with no melt fracture), the method comprising: melt processing an ethylene polymer composition through a film die to produce the film, wherein the ethylene polymer composition is substantially free of organic fluorine and comprises: an ethylene polymer comprising from 1 to 50 ppm of inorganic fluorine (or from 2 to 50 ppm, from 2 to 45 ppm, from 4 to 35 ppm, from 5 to 50 ppm, from 5 to 45 ppm, from 5 to 35 ppm, from 10 to 50 ppm, from 10 to 45 ppm, from 10 to 35 ppm, from 15 to 50 ppm. from 15 to 45 ppm, from 15 to 35 ppm, from 20 to 50 ppm, or from 20 to 35 ppm of inorganic fluorine); and an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition.

[0137] Aspect 14. The method defined in aspect 13, wherein the film die is a blown film die (annular die) and the film is a blown film.

[0138] Aspect 15. The method defined in aspect 13, wherein the film die is a cast film die (slot die) and the film is a cast film.

[0139] Aspect 16. The method defined in any one of aspects 13-15, wherein the melt processing is performed at any suitable melt processing temperature, e g., from 200 to 600 °C, from 300 to 500 °C, or from 350 to 550 °C. Aspect 17. The method defined in any one of aspects 13-16, wherein the melt processing comprises extrusion.

[0140] Aspect 18. The method defined in any one of aspects 13-17, wherein the melt processing is performed in a single screw extrusion system.

[0141] Aspect 19. The method defined in any one of aspects 13-18, wherein the film has any suitable average thickness, e.g., from 0.4 to 20 mils, from 0.5 to 8 mils, from 0.8 to 5 mils, from 0.7 to 2 mils, or from 0.7 to 1.5 mils.

[0142] Aspect 20. The method defined in any one of aspects 13-19, wherein the film has substantially no melt fracture when processed at a shear rate of approximately 115 sec-1.

[0143] Aspect 21. An ethylene polymer composition substantially free of organic fluorine and comprising: an ethylene polymer comprising from 1 to 50 ppm of inorganic fluorine (or from 2 to 50 ppm, from 2 to 45 ppm, from 4 to 35 ppm, from 5 to 50 ppm, from 5 to 45 ppm. from 5 to 35 ppm, from 10 to 50 ppm. from 10 to 45 ppm, from 10 to 35 ppm, from 15 to 50 ppm, from 15 to 45 ppm, from 15 to 35 ppm, from 20 to 50 ppm, or from 20 to 35 ppm of inorganic fluorine); and an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition.

[0144] Aspect 22. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer composition is in the form of pellets (or beads).

[0145] Aspect 23. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer is a metallocene-catalyzed ethylene polymer (or produced using a metallocene-based catalyst system).

[0146] Aspect 24. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) has a unimodal molecular weight distribution (single peak).

[0147] Aspect 25. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer is a single reactor product.

[0148] Aspect 26. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) comprises an ethylene / a-olefin copolymer and / or an ethylene homopolymer. Aspect 27. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) comprises an ethylene homopolymer, an ethylene / l-butene copolymer, an ethylene / 1- hexene copolymer, and / or an ethylene / 1 -octene copolymer.

[0149] Aspect 28. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) comprises an ethylene / 1 -hexene copolymer.

[0150] Aspect 29. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) contains, independently, less than 0.1 ppm, less than 0.08 ppm, less than 0.05 ppm, or less than 0.03 ppm of hafnium and titanium and chromium.

[0151] Aspect 30. The process, method, or composition defined in any one of the preceding aspects, wherein an amount of the ethylene polymer in the ethylene polymer composition is in any suitable range, e.g., at least 95 wt. %, at least 97 wt. %, at least 98 wt. %, from 95 to 99.9 wt. %, from 97 to 99.9 wt. %, from 95 to 99.5 wt. %, from 97 to 99.5 wt. %, from 95 to 99 wt. %, or from 97 to 99 wt. %, based on the total weight of the composition.

[0152] Aspect 31. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) has a density in any suitable range, e.g., from 0.90 to 0.96 g / cm3, from 0.91 to 0.94 g / cm3, from 0.912 to 0.935 g / cm3, or from 0.91 to 0.925 g / cm3.

[0153] Aspect 32. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) has a melt index (MI) in any suitable range, e.g., from 0.2 to 10 g / 10 min, from 0.2 to 3 g / 10 min, from 0.3 to 2 g / 10 min, or from 0.5 to 1.5 g / 10 min.

[0154] Aspect 33. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) has a ratio of HLMI / MI in any suitable range, e.g., from 10 to 60, from 10 to 30, from 12 to 50, or from 12 to 20.

[0155] Aspect 34. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) has a CY-a parameter in any suitable range, e g., from 0.5 to 0.7, from 0.5 to 0.65, from 0.55 to 0.7, or from 0.55 to 0.65.

[0156] Aspect 35. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) has a relaxation time in any suitable range, e.g., from 0.001 to 0.15 sec, from 0.002 to 0.1 sec, from 0.002 to 0.05 sec, or from 0.005 to 0.02 sec.

[0157] Aspect 36. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) has a zero-shear viscosity in any suitable range, e.g., from 1,000 to 100,000 Pa-sec, from 1,000 to 50,000 Pa-sec, or from 2,000 to 10,000 Pa-sec.

[0158] Aspect 37. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) has a Mw in any suitable range, e.g., from 50,000 to 250.000 g / mol, from 70,000 to 200,000 g / mol, from 100,000 to 250,000 g / mol, or from 100,000 to 200,000 g / mol.

[0159] Aspect 38. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer (or the ethylene polymer composition) has a ratio of Mw / Mn in any suitable range, e.g., from 3 to 10, from 3.5 to 8. from 3 to 6, or from 3.5 to 6.

[0160] Aspect 39. The process, method, or composition defined in any one of the preceding aspects, wherein the ethylene polymer composition contains any suitable amount of the polyethylene glycol (PEG), e.g., from 200 to 5,000 ppm, from 300 to 5,000 ppm, from 300 to 2.000 ppm. from 500 to 3,000 ppm, from 500 to 1,500 ppm, from 700 to 1 ,500 ppm, from 900 to 2,500 ppm, from 900 to 1 ,500 ppm, from 1 ,000 to 2,500 ppm, from 1,000 to 2,000 ppm, or from 1,000 ppm to 1,500 ppm.

[0161] Aspect 40. The process, method, or composition defined in any one of the preceding aspects, wherein the polyethylene glycol (PEG) has a Mw in any suitable range, e.g., from 2,000 to 50,000 g / mol, from 3,000 to 20,000 g / mol, from 5,000 to 15,000 g / mol, from 5,000 to 10,000 g / mol, from 5,000 to 9,000 g / mol, from 6,000 to 9,000 g / mol, or from 6,000 to 8,000 g / mol.

[0162] Aspect 41. The process, method, or composition defined in any one of the preceding aspects, wherein the additive composition (or the ethylene polymer composition) further comprises a polysorbate (e.g.. Tween) at any suitable amount, e.g.. from 100 to 10,000 ppm, from 300 to 5,000 ppm, or from 500 to 3,000 ppm, based on the total weight of the ethylene polymer composition.

[0163] Aspect 42. The process, method, or composition defined in any one of the preceding aspects, wherein the additive composition (or the ethylene polymer composition) further comprises apoly(oxyalkylene) (e.g., Pluronic or Poloxamer) at any suitable amount, e.g., from 100 to 10,000 ppm, from 300 to 5,000 ppm, or from 500 to 3,000 ppm, based on the total weight of the ethylene polymer composition.

[0164] Aspect 43. The process, method, or composition defined in any one of the preceding aspects, wherein the additive composition (or the ethylene polymer composition) further comprises zinc oxide at any suitable amount, e g., from 100 to 2,000 ppm, from 200 to 1,000 ppm, or from 200 to 800 ppm, based on the total weight of the ethylene polymer composition.

[0165] Aspect 44. The process, method, or composition defined in any one of the preceding aspects, wherein the additive composition (or the ethylene polymer composition) further comprises a slip additive at any suitable amount, e.g., from 100 to 5,000 ppm, from 200 to 3,000 ppm. or from 500 to 1,500 ppm, based on the total weight of the ethylene polymer composition.

[0166] Aspect 45. The process, method, or composition defined in any one of the preceding aspects, wherein the additive composition (or the ethylene polymer composition) further comprises an antiblock additive at any suitable amount, e.g., from 200 to 10.000 ppm. from 500 to 6,000 ppm, or from 2,000 to 6,000 ppm, based on the total weight of the ethylene polymer composition.

[0167] Aspect 46. The process, method, or composition defined in any one of the preceding aspects, wherein the additive composition (or the ethylene polymer composition) further comprises a phenolic antioxidant, a phosphite antioxidant, or both, at any suitable amount, e.g., independently from 100 to 5,000 ppm, from 200 to 2,000 ppm, or from 300 to 1,500 ppm, based on the total weight of the ethylene polymer composition.

[0168] Aspect 47. The process, method, or composition defined in any one of the preceding aspects, wherein the additive composition (or the ethylene polymer composition) further comprises any suitable processing aid synergist, e.g., citric acid, a polyanhydride resin, a polyacid resin, or a combination thereof. Aspect 48. An ethylene polymer composition substantially free of organic fluorine and comprising an ethylene polymer substantially free of inorganic fluorine, and an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition, and an inorganic fluorine containing additive at an amount in a range from 1 to 10 ppm of fluorine (or from 2 to 10 ppm, from 3 to 10 ppm, from 3 to 9 ppm, or from 4 to 10 ppm of fluorine), based on the ethylene polymer composition.

[0169] Aspect 49. The composition defined in aspect 48, wherein the ethylene polymer is a Ziegler-Natta-catalyzed ethylene polymer (or produced using a Ziegler-Natta-based catalyst system).

[0170] Aspect 50. The composition defined in aspect 47 or 48, wherein the ethylene polymer composition is in the form of pellets or beads.

[0171] Aspect 51. The composition defined in any one of aspects 48-50, wherein the ethylene polymer (or the ethylene polymer composition) contains, independently, less than 0.1 ppm, less than 0.08 ppm, less than 0.05 ppm, or less than 0.03 ppm of hafnium and zirconium and chromium.

[0172] Aspect 52. The composition defined in any one of aspects 48-51, wherein the ethylene polymer (or the ethylene polymer composition) is further defined by any one of aspects 24-28 or 30-46.

[0173] Aspect 53. The composition defined in any one of aspects 48-52, wherein the inorganic fluorine containing additive is an antiblock additive.

[0174] Aspect 54. A process for preparing an ethylene polymer composition, the process comprising combining an additive composition with an ethylene polymer to form a blend, the additive composition consisting of a polyethylene glycol at an amount in a range from 100 to 10.000 ppm, based on the ethylene polymer composition, and one or more active additives, wherein the additive composition is substantially free of binding agents and carrier resins, and melt processing the blend through a die to produce the ethylene polymer composition, wherein the ethylene polymer composition is substantially free of organic fluorine.

[0175] Aspect 55. The process defined in aspect 54, further comprising determining an amount of a tracer in the ethylene polymer composition, wherein the one or more active additives comprises the tracer, and adjusting an amount of the additive composition combined with the ethylene polymer based on the amount of tracer.

[0176] Aspect 56. The process defined in aspect 55, wherein the amount of polyethylene glycol in the ethylene polymer composition is controlled by determining the amount of the tracer in the ethylene polymer composition.

[0177] Aspect 57. The process defined in any one of aspects 54-56, wherein the additive composition is in the form of powder, pressed masterbatch pills, pellets, or beads, and the ethylene polymer is in the form of fluff, granules, or powder.

Claims

CLAIMS1. A process for preparing an ethylene polymer composition, the process comprising: melt processing a blend of an ethylene polymer and an additive composition through a die to produce the ethylene polymer composition, wherein: the ethylene polymer and / or the ethylene polymer composition comprise(s) from 1 to 50 ppm of inorganic fluorine (or from 2 to 50 ppm, from 2 to 45 ppm. from 4 to 35 ppm, from 5 to 50 ppm. from 5 to 45 ppm, from 5 to 35 ppm, from 10 to 50 ppm, from 10 to 45 ppm, from 10 to 35 ppm, from 15 to 50 ppm, from 15 to 45 ppm, from 15 to 35 ppm, from 20 to 50 ppm, or from 20 to 35 ppm of inorganic fluorine); the additive composition comprises a polyethylene glycol at an amount in a range from 100 to 10.000 ppm, based on the ethylene polymer composition; and the ethylene polymer composition is substantially free of organic fluorine.

2. The process of claim 1, wherein the ethylene polymer is in the form of fluff, granules, or powder.

3. The process of claim 1 or 2, wherein the polyethylene glycol is introduced to the ethylene polymer in the form of fluff prior to the melt processing.

4. The process of any one of claims 1-3. wherein the polyethylene glycol is introduced to the ethylene polymer separately from at least one other additive of the additive composition.

5. The process of claim 1 or 2. wherein the polyethylene glycol is introduced to the ethylene polymer together with at least one other additive of the additive composition.

6. The process of any of the preceding claims, wherein the melt processing is performed at a melt processing temperature from 130 to 400 °C. from 150 to 300 °C, or from 175 to 275 °C.

7. The process of any one of claims 1-6, wherein the melt processing comprises extrusion.

8. The process of any one of claims 1-7, wherein the melt processing is performed in a twin screw extrusion system or a multi-screw extrusion system.

9. The process of any one of claims 1-8. wherein the additive composition is in the form of powder, pressed masterbatch pills, pellets, or beads.

10. The process of any one of claims 1-9, wherein the additive composition is formed by compaction.

11. The process of any one of claims 1-10, wherein the additive composition contains less than or equal to 3 wt. %, less than or equal to 2 wt. %, or less than or equal to 1 wt. %, of a polyolefin.

12. The process of any one of claims 1-11, wherein the additive composition further comprises a binding agent.

13. A method of making a film, the method comprising: melt processing an ethylene polymer composition through a film die to produce the film, wherein the ethylene polymer composition is substantially free of organic fluorine and comprises: an ethylene polymer comprising from 1 to 50 ppm of inorganic fluorine (or from 2 to 50 ppm. from 2 to 45 ppm, from 4 to 35 ppm, from 5 to 50 ppm, from 5 to 45 ppm, from 5 to 35 ppm, from 10 to 50 ppm, from 10 to 45 ppm, from 10 to 35 ppm, from 15 to 50 ppm, from 15 to 45 ppm, from 15 to 35 ppm, from 20 to 50 ppm, or from 20 to 35 ppm of inorganic fluorine); and an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10.000 ppm. based on the ethylene polymer composition.

14. The method of claim 13, wherein the film die is a blown film die and the film is a blown film.

15. The method of claim 13, wherein the film die is a cast film die and the film is a cast film.

16. The method of any one of claims 13-15, wherein the melt processing is performed at a melt processing temperature from 200 to 600 °C, from 300 to 500 °C, or from 350 to 550 °C.

17. The method of any one of claims 13-16, wherein the melt processing comprises extrusion.

18. The method of any one of claims 13-17, wherein the melt processing is performed in a single screw extrusion system.

19. The method of any one of claims 13-18, wherein the film has an average thickness from 0.4 to 20 mils, from 0.5 to 8 mils, from 0.8 to 5 mils, from 0.7 to 2 mils, or from 0.7 to 1.5 mils.

20. The method of any one of claims 13-19, wherein the film has substantially no melt fracture when processed at a shear rate of approximately 115 sec'1.

21. An ethylene polymer composition substantially free of organic fluorine and comprising: an ethylene polymer comprising from 1 to 50 ppm of inorganic fluorine (or from 2 to 50 ppm, from 2 to 45 ppm, from 4 to 35 ppm, from 5 to 50 ppm, from 5 to 45 ppm, from 5 to 35 ppm, from 10 to 50 ppm, from 10 to 45 ppm, from 10 to 35 ppm, from 15 to 50 ppm, from 15 to 45 ppm, from 15 to 35 ppm, from 20 to 50 ppm, or from 20 to 35 ppm of inorganic fluorine); and an additive composition comprising a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition.

22. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer composition is in the form of pellets or beads.

23. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer is a metallocene-catalyzed ethylene polymer (or produced using a metallocene-based catalyst system).

24. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) has a unimodal molecular weight distribution.

25. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer is a single reactor product.

26. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) comprises an ethylene / a-olefm copolymer and / or an ethylene homopolymer.

27. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) comprises an ethylene homopolymer, an ethylene / 1 -butene copolymer, an ethylene / 1 -hexene copolymer, and / or an ethylene / 1 -octene copolymer.

28. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) comprises an ethylene / 1 -hexene copolymer.

29. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) contains, independently, less than 0.1 ppm. less than 0.08 ppm, less than 0.05 ppm, or less than 0.03 ppm of hafnium and titanium and chromium.

30. The process, method, or composition of any one of the preceding claims, wherein an amount of the ethylene polymer in the ethylene polymer composition is at least 95 wt. %, at least 97 wt. %, at least 98 wt. %, from 95 to 99.9 wt. %, from 97 to 99.9 wt. %, from 95 to 99.5 wt. %, from 97 to 99.5 wt. %, from 95 to 99 wt. %, or from 97 to 99 wt. %, based on a total weight of the ethylene polymer composition.

31. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) has a density in a range from 0.90 to 0.96 g / cnT, from 0.91 to 0.94 g / cnT, from 0.912 to 0.935 g / cm3, or from 0.91 to 0.925 g / cm3.

32. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) has a melt index (MI) in a range from 0.2 to 10 g / 10 min, from 0.2 to 3 g / 10 min, from 0.3 to 2 g / 10 min, or from 0.5 to 1.5 g / 10 min.

33. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) has a ratio of HLMI / MI in a range from 10 to 60, from 10 to 30, from 12 to 50, or from 12 to 20.

34. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) has a CY-a parameter in a range from 0.5 to 0.7, from 0.5 to 0.65, from 0.55 to 0.7, or from 0.55 to 0.65.

35. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) has a relaxation time in a range from 0.001 to 0.15 sec, from 0.002 to 0.1 sec, from 0.002 to 0.05 sec, or from 0.005 to 0.02 sec.

36. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) has a zero-shear viscosity' in a range from 1,000 to 100,000 Pa-sec, from 1,000 to 50,000 Pa-sec, or from 2,000 to 10.000 Pa-sec.

37. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) has a Mw in a range from 50,000 to 250,000 g / mol, from 70,000 to 200,000 g / mol. from 100,000 to 250.000 g / mol, or from 100,000 to 200,000 g / mol.

38. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer (or the ethylene polymer composition) has a ratio of Mw / Mn in a range from 3 to 10, from 3.5 to 8, from 3 to 6, or from 3.5 to 6.

39. The process, method, or composition of any one of the preceding claims, wherein the ethylene polymer composition contains from 200 to 5,000 ppm, from 300 to 5.000 ppm, from 300 to 2,000 ppm, from 500 to 3,000 ppm. from 500 to 1,500 ppm, from 700 to 1,500 ppm, from 900 to 2,500 ppm, from 900 to 1,500 ppm, from 1,000 to 2,500 ppm, from 1,000 to 2,000 ppm, or from 1,000 ppm to 1,500 ppm of the polyethylene glycol (PEG).

40. The process, method, or composition of any one of the preceding claims, wherein the polyethylene glycol (PEG) has a Mw in a range from 2,000 to 50,000 g / mol, from 3,000 to 20,000 g / mol, from 5,000 to 15,000 g / mol, from 5,000 to 10,000 g / mol. from 5,000 to 9,000 g / mol, from 6,000 to 9,000 g / mol, or from 6,000 to 8,000 g / mol.

41. The process, method, or composition of any one of the preceding claims, wherein the additive composition (or the ethylene polymer composition) further comprises from 100 to 10,000 ppm, from 300 to 5,000 ppm, or from 500 to 3,000 ppm of a polysorbate, based on a total weight of the ethylene polymer composition.

42. The process, method, or composition of any one of the preceding claims, wherein the additive composition (or the ethylene polymer composition) further comprises from 100 to 10,000 ppm, from 300 to 5,000 ppm, or from 500 to 3,000 ppm of a poly(oxyalkylene), based on a total weight of the ethylene polymer composition.

43. The process, method, or composition of any one of the preceding claims, wherein the additive composition (or the ethylene polymer composition) further comprises from 100 to 2,000 ppm, from 200 to 1,000 ppm, or from 200 to 800 ppm of zinc oxide, based on a total weight of the ethylene polymer composition.

44. The process, method, or composition of any one of the preceding claims, wherein the additive composition (or the ethylene polymer composition) further comprises from 100 to 5,000 ppm, from 200 to 3,000 ppm, or from 500 to 1,500 ppm of a slip additive, based on a total weight of the ethylene polymer composition.

45. The process, method, or composition of any one of the preceding claims, wherein the additive composition (or the ethylene polymer composition) further comprises from 200 to 10,000 ppm, from 500 to 6,000 ppm, or from 2,000 to 6,000 ppm of an antiblock additive, based on a total weight of the ethylene polymer composition.

46. The process, method, or composition of any one of the preceding claims, wherein the additive composition (or the ethylene polymer composition) further comprises from 100 to 5,000 ppm, from 200 to 2,000 ppm, or from 300 to 1,500 ppm, independently, of a phenolic antioxidant, a phosphite antioxidant, or both, based on a total weight of the ethylene polymer composition.

47. The process, method, or composition of any one of the preceding claims, wherein the additive composition (or the ethylene polymer composition) further comprises a processing aid synergist selected from citric acid, a polyanhydride resin, a polyacid resin, or a combination thereof.

48. An ethylene polymer composition substantially free of organic fluorine and comprising: an ethylene polymer substantially free of inorganic fluorine; and an additive composition comprising: a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition, and an inorganic fluorine containing additive at an amount in a range from 1 to 10 ppm of fluorine (or from 2 to 10 ppm, from 3 to 10 ppm, from 3 to 9 ppm, or from 4 to 10 ppm of fluorine), based on the ethylene polymer composition.

49. The composition of claim 48, wherein the ethylene polymer is a Ziegler-Natta- catalyzed ethylene polymer (or produced using aZiegler-Natta-based catalyst system).

50. The composition of claim 47 or 48, wherein the ethylene polymer composition is in the form of pellets or beads.

51. The composition of any one of claims 48-50, wherein the ethylene polymer (or the ethylene polymer composition) contains, independently, less than 0.1 ppm, less than 0.08 ppm, less than 0.05 ppm, or less than 0.03 ppm of hafnium and zirconium and chromium.

52. The composition of any one of claims 48-51. wherein the ethylene polymer (or the ethylene polymer composition) is further characterized by any one of claims 24-28 or 30-46.

53. The composition of any one of claims 48-52, wherein the inorganic fluorine containing additive is an antiblock additive.

54. A process for preparing an ethylene polymer composition, the process comprising: combining an additive composition with an ethylene polymer to form a blend, the additive composition consisting of:a polyethylene glycol at an amount in a range from 100 to 10,000 ppm, based on the ethylene polymer composition; and one or more active additives; wherein the additive composition is substantially free of binding agents and carrier resins; and melt processing the blend through a die to produce the ethylene polymer composition; wherein the ethylene polymer composition is substantially free of organic fluorine.

55. The process of claim 54, further comprising determining an amount of a tracer in the ethylene polymer composition, wherein the one or more active additives comprises the tracer; and adjusting an amount of the additive composition combined with the ethylene polymer based on the amount of tracer.

56. The process of claim 55, wherein the amount of polyethylene glycol in the ethylene polymer composition is controlled by determining the amount of the tracer in the ethylene polymer composition.

57. The process of any one of claims 54-56, wherein: the additive composition is in the form of powder, pressed masterbatch pills, pellets, or beads; and the ethylene polymer is in the form of fluff, granules, or powder.

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