Salts of dimer acid as polymer processing aid for polyethylene

Abstract

Embodiments of a formulation comprises at least 90 wt.% ethylene-based polymer and dimer acid salt, wherein the dimer acid salt is a polymer processing aid used to reduce melt fracture during extrusion.

Description

SALTS OF DIMER ACID AS POLYMER PROCESSING AID FORPOLYETHYLENECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 678,815 filed August 2, 2024, the contents of which are incorporated in their entirety herein.TECHNICAL FIELD

[0002] The present disclosure generally relates to formulations comprising ethylene-based polymer and dimer acid salts and are specifically related to the use of these formulations to reduce melt fracture during extrusion.BACKGROUND

[0003] Plastics are used for a wide range of industrial applications, including packaging, construction, and wire and cable. However, many plastics suffer from melt fracture during extrusion, which is a phenomenon wherein the surface of the plastic becomes distorted with undulations or irregularities. Some types of melt fracture, such as sharkskin melt fracture, impact the surface of the plastic by causing irregular and sometimes scaly surface texture, which may reduce the glossiness of the surface.

[0004] Conventional processes for preventing melt fracture in polyethylene include using polymer processing aids (PPA) comprising fluoropolymer-based polymer (PFA). However, environmental concerns with fluoropolymers have spurred restrictions on these materials. Accordingly, a need exists for improved PPA formulations that may reduce melt fracture while also alleviating environmental concerns.SUMMARY

[0005] Embodiments of the present disclosure address these and other needs by providing formulations for polymer processing aids comprising at least 90 wt.% ethylene-based polymer and dimer acid salts. Dimer acid is a compound that is primarily obtained from tall oil, a byproduct of the paper industry. The tall oil fatty acid undergoes a process known as dimerization, resultingin dimer acid. Dimerization is achieved through the reaction of unsaturations on the tall oil (ene reactions, Diels Alder reactions). The dimer acid with a small component of trimer acid, small component of remaining unreacted monomeric acid, and potentially small amount of polycyclic dimer acid can then optionally be hydrogenated to remove any remaining unsaturations.

[0006] In further embodiments, the formulation may also comprise a trimer acid. In further embodiments, the ethylene-based polymer may comprise linear low-density polyethylene, high- density polyethylene, or combinations thereof.

[0007] Additional features and advantages will be set forth in the detailed description that follows and, in part, will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description, which follows in addition to the claims.

[0008] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter.DETAILED DESCRIPTION

[0009] As used in this disclosure, the term “polymer” may refer to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer,” which refers to polymers prepared from two or more different monomers. The term “interpolymer,” as used herein, refers to a polymer prepared by the polymerization of at least two different types of monomers. The generic term interpolymer thus includes copolymers, and polymers prepared from more than two different types of monomers, such as terpolymers.

[0010] “Blend,” “polymer blend,” and like terms mean a composition of two or more polymers. Such a blend may or may not be miscible. Such a blend may or may not be phase separated. Such a blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and any other method knownin the art. Blends are not laminates, but one or more layers of a laminate may contain a blend. Such blends can be prepared as dry blends, formed in situ (e.g., in a reactor), melt blends, or using other techniques known to those of skill in the art.

[0011] As used in this disclosure, the term “polyethylene” or “ethylene -based polymer” may refer to polymers comprising greater than 50% by mole of units which have been derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of ethylene-based polymer known in the art include Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).

[0012] The term “LLDPE,” includes both resins made using the traditional Ziegler-Natta catalyst systems and chromium-based catalyst systems as well as single-site catalysts, including, but not limited to, bis -metallocene catalysts (sometimes referred to as “m- LLDPE”), constrained geometry catalysts (CGC), and molecular catalysts. Resins include linear, substantially linear, or heterogeneous polyethylene copolymers or homopolymers. LLDPEs contain less long chain branching than LDPEs and includes the substantially linear ethylene polymers which are further defined in U.S. Patent 5,272,236, U.S. Patent 5,278,272, U.S. Patent 5,582,923 and US Patent 5,733,155; the homogeneously branched linear ethylene polymer compositions such as those in U.S. Patent No. 3,645,992; the heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Patent No. 4,076,698; and / or blends thereof (such as those disclosed in US 3,914,342 or US 5,854,045). The LLDPEs can be made via gasphase, solution-phase or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0013] The term “HDPE” or “high density polyethylene” refers to ethylene-based polymers having densities greater than 0.935 g / cc, which are generally prepared with Ziegler-Natta catalysts, chrome catalysts or even metallocene catalysts.

[0014] As used herein “fluoropolymer” refers to polymeric compounds comprising fluorine, and is intended to be interpreted broadly so as to include what might be referred to as oligomeric species. As a non-limiting example, the fluoropolymer may comprise molecules containing at least three, at least four, at least five, or at least six fluorine containing units.

[0015] As used herein, “essentially free of” means comprising less than 50 ppmw.

[0016] As used herein, “melt fracture” refers to the formation of defects on a polymeric extrudate under various processing conditions. The defects may be any deviation from a smooth, glossy, regular extrudate.

[0017] As used herein, “parts per million” or “ppm” refers to parts per million by weight.

[0018] As used herein, “polymer melt” refers to polymers or polymer blends that are at temperatures above their glass transition temperature, i.e. the temperature below which the physical properties of the polymers change to those of a glassy or crystalline state, and usually above their melting temperature. The polymer melts may present as highly viscous liquids, and may possess non-Newtonian or viscoelastic natures.

[0019] As used herein, “dimer acid” refers to dicarboxylic acids that are prepared by dimerizing unsaturated fatty acids. Similarly, “trimer acid” refers to tricarboxylic acids prepared from unsaturated fatty acids. As used herein, “dimer acid salt” or “trimer acid salt” refers to the result of the neutralizing of dimer acids or trimer acids to form a salt.

[0020] Reference will now be made in detail to embodiments of formulations as described herein.

[0021] Embodiments of the formulation may include at least 90 wt.% ethylene-based polymer and dimer acid salt. In one or more embodiments, the dimer acid salt may be present in a mixture comprising dimer acid salts, and trimer acid salts. Dimer acid salts may be present in a greater amount than trimer acid salts. In one or more embodiments, the mixture comprising the dimer acid salts and trimer acid salts comprise from a minimum of 51 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, 90 wt.%, or 95 wt.% dimer acid salts to a maximum of 55 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, 90wt.%, 95 wt.%, or 100 wt.% dimer acid salts. Additionally, the mixture may also comprise some amount of the salt of monomeric acid (e.g., salt of non-dimerized or non-trimerized carboxylic acid) or salt produced therefrom addition to the dimer acid salt and trimer acid salt, for example, less than 5 wt.%, less than 2 wt.%, or less 1 wt.% monomeric acid.

[0022] In embodiments, the dimer acid salt may comprise the structure of Formula (I), Formula(II), Formula (III), or mixtures thereof.Formula (I) Formula (II) Formula (III)

[0023] As shown, Formula (II) is the hydrogenated dimer acid salt of Formula (I). In specific embodiments, Ri comprises a C4-C12 alkyl or a C4-C12 alkenyl when R4 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; R2 comprises a C4-C12 alkyl or a C4-C12 alkenyl when R3 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; R3 comprises a C4-C12 alkyl or a C4-C12 alkenyl when R2 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; R4 comprises a C4-C12 alkyl or a C4-C12 alkenyl when Ri comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; and R5 and Re independently comprise a hydrogen, C1-C12 alkyl, or a C1-C12 alkenyl.

[0024] In one embodiment, the dimer acid salt may be a salt of dimer acid composition having a CAS number of 61788-89-4. In one or more embodiments, the dimer acid salt comprises a dimer salt of oleic acid.

[0025] In other embodiments, a formulation comprises a dimer acid salt wherein the dimer acid salt comprises the structure of any one of Formula (I), Formula (II), or Formula (III).

[0026] In Formula (I), Formula (II), or both, Ri may comprise a C4-C12 alkyl or a C4-C12 alkenyl when R4 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; R2 may comprise a C4-C12 alkyl or a C4-C12 alkenyl when R3 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; R3 may comprise, independently or simultaneously, a C4-C12 alkyl or a C4-C12 alkenyl when R2 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; and R5 and Re independently comprise a hydrogen, C1-C12 alkyl, or a C1-C12 alkenyl.

[0027] In Formula (III), Ri may comprise a C4-C12 alkyl or a C4-C12 alkenyl when R4 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; R2 may comprise a C4-C12 alkyl or a C4-C12 alkenyl when R3 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid;

[0028] In other embodiments, the dimer acid salt is in a mixture having a majority of the structure of Formula (I). In embodiments, the dimer acid salt is in a mixture having a greater amount of the structure of Formula (I) than Formula (II), Formula (III), or mixtures thereof.Formula (IV) Formula (V)

[0029] In embodiments, the formulations described herein may further comprise a trimer acid. In embodiments, the trimer acid salt may comprise the structure of Formula (IV), Formula (V), or mixtures thereof. As shown, Formula (V) is the hydrogenated trimer acid salt of Formula (IV). In embodiments, Ri comprises a C4-C12 alkyl or a C4-C12 alkenyl when R4 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; R2 comprises a C4-C12 alkyl or a C4-C12 alkenyl when R3 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; R3 comprises a C4-C12 alkyl or a C4-C12alkenyl when R2 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; R4 comprises a C4-C12 alkyl or a C4-C12 alkenyl when Ri comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; R5, Re, R9, and Rio independently comprise a hydrogen, a C1-C12 alkyl, or a C1-C12 alkenyl; R7 comprises a C4- C12 alkyl or a C4-C12 alkenyl when Rs comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; and Rs comprises a C4-C12 alkyl or a C4-C12 alkenyl when R7 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid.

[0030] In embodiments, the formulations described herein may further comprise a monomeric fatty acid or salt produced therefrom.

[0031] As used herein, “neutralized” means that at least some of the acid units of the dimer acids and / or trimer acids are converted to salt form. While full neutralization is contemplated in some embodiments, the dimer acids and / or trimer acids of the present are partially neutralized in many embodiments. In one or more embodiments, at least 30 mole percent (mol%) of total acid units are neutralized with a metal cation. In one or more embodiments, from 35 to 50 mol%, from 45 to 70 mol%, from 60 to 80 mol%, or from 80 to 100 mol% of the total acid units are neutralized.

[0032] Various metal salts are considered suitable for the dimer acid salts or trimer acid salts. In embodiments, the formulation comprises, but not limited to aluminum, zirconium, lithium, potassium, calcium, magnesium, zinc, and sodium salts, or combinations thereof.

[0033] The dimer and trimer acid salts may be produced via various methods familiar to the skilled person. For example, these salts may be produced from acid-base neutralization of dimer acids or trimer acids. Moreover, further salts may be produced via salt metathesis.

[0034] Various compositions are considered suitable for the ethylene-based polymer in the formulations. In one or more embodiments, the ethylene-based polymer may comprise LLDPE, HDPE, or combinations thereof. In embodiments, the ethylene-based polymer may comprise a melt index (I2) of less than 4.0 dg / min as measured according to ASTM D-1238 (190° C, loadingof 2.16 kg). In embodiments, the ethylene-based polymer may comprise a melt index of from 0.05 to 4.0 dg / 10 min, from 0.05 to 3 dg / 10 min, or from 0.05 to 2.5 dg / 10 min. In further embodiments, the ethylene-based polymer may comprise a density from 0.850 to 0.980 g / cc, from 0.875 to 0.925 g / cc, from 0.890 to 0.920 g / cc.

[0035] In embodiments, the formulations described herein may comprise greater than 90 wt.%, greater than 92 wt.%, greater than 95 wt.%, greater than 97 wt.%, greater than 98 wt.%, or even greater than 99 wt.% ethylene-based polymer, based on the total weight of the formulation. In other embodiments, the formulations described herein may comprise less than 100 wt.%, less than 98 wt.%, less than 97 wt.%, less than 95 wt.%, less than 92 wt.%, or even less than 91 wt.% ethylene-based polymer, based on the total weight of the formulation. In one or more embodiments, the dimer acid salts may comprise less than or equal to 10 wt.% based on the total weight of the formulation. In specific embodiments, the dimer acid salts may be present in formulation from a minimum of 0.001 wt.%, 0.01 wt.%, 0.1 wt.%, 1 wt.%, 2 wt.%, or 5 wt.% to a maximum of 0.1 wt.%, 0.5 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, or 10 wt.% based on the total weight of the formulation.

[0036] In various embodiments, the formulation is used to reduce or completely eliminate melt fracture during extrusion. The polymer processing aid (PPA), i.e., the dimer acid salt may be delivered in many forms, for example, PPA masterbatch, or neat as a solid.

[0037] Further optional additives are contemplated for the PPA and / or the formulation encompassing the PPA. Non limiting examples of suitable other additives include antioxidants, antistatic agents, stabilizing agents, nucleating agents, colorants, pigments, ultraviolet (UV) absorbers or stabilizers, flame retardants, compatibilizers, plasticizers, fdlers, processing aids, antifog additive, crosslinking agents (e.g., peroxides), and combinations thereof.

[0038] Further optional additives are contemplated for the PPA and / or the formulation encompassing the PPA. For example, it is contemplated to add the PPA components in various orders. In some embodiments, the dimer acid salt may be melt blended directly into the ethylenebased polymer. In one or more embodiments, the dimer acid salt may be added to the ethylenebased polymer via a masterbatch. In embodiments, generating a masterbatch may comprise compounding a polyethylene resin with the dimer acid salt. The masterbatch may be combinedwith a base resin to reduce melt fracture in the base resin in an extruder to fabricate a finished article, for example, a tape extrudate, a blown film, cable, wire, tube, or pipe. The base resin may include ethylene-based polymer, for example, LLDPE, LDPE, EIDPE, or combinations thereof.

[0039] TEST METHODS

[0040] Density measurements were made in accordance with ASTM D792, Method B.

[0041] Melt Index (190 °C, 2.16 kg, “fc”) Test Method: ASTM D 1238-13, Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer, using conditions of 190 °C / 2.16 kilograms (kg). Results were reported in units of grams eluted per 10 minutes (dg / 10 min).EXAMPLES

[0042] The following examples are offered by way of illustration and are presented in a manner such that one skilled in the art should recognize are not meant to be limiting to the present disclosure as a whole or to the appended claims.

[0043] The following compositions were used in the Examples below.

[0044] All solvents including methyl isobutyl ketone, toluene, acetone, water are commercially available from Sigma-Aldrich.

[0045] The EEDPE Resin used as the base resin and PPA masterbatch carrier for the inventive examples had a melt index (I2) of 2.3 dg / 10 min and a density of 0.917 g / cc.

[0046] The dimer acid, which is commercially available from Cargill, was obtained from Sigma Aldrich, is hydrogenated dimer acid having a CAS Number of 68783-41-5. The hydrogenated dimer acid comprises greater than 98.0 % Dimer and less than 2 % trimer with small amount of monomeric fatty acids (about 1 wt.% or less).

[0047] Dynamar™ FX 5920 A is a fluoropolymer based PPA masterbatch available from 3M™.

[0048] Preparation of Dimer Acid Salts

[0049] Disodium Salt

[0050] To a 1000 mL 3 neck flask containing a dropping funnel, thermowell, and a stir paddle / shaft was charged 171 g of dimer acid, hydrogenated (Mn 570 average, 300 mmol). The mixture was placed under an atmosphere of nitrogen and stirred at 180 rpm. Then, 450 mT of acetone was added. The mixture heated to approximately 50 °C. Then, 600 mmol of NaOH (31.68 mT of a 50:50 w / w solution in water) was added over the course of approximately 30 min via the dropping funnel. After addition, the flask was cooled, and the filtrate was filtered off. The solids were placed in a blender with fresh acetone and blended. The resulting powder was filtered off, washed with water, and then dried at 70 °C under vacuum for 18 hrs. 181 g was isolated. 98% yield.

[0051] Calcium Salt

[0052] 50 g of the disodium salt of dimer acid was sieved in a 35-mesh sieve (< 560 microns) and then dissolved under stirring in 500 mT of water at 70 °C. This solution stirred for 40 minutes and was then removed from heating and cooled to room temperature, approximately 1 / 2 of the solution was placed in a blender. With the blender running on low, 10 mT of a solution of 8.92 g of CaCb in 20 mT water (1 :1 molar vs the disodium salt) was added. A precipitate immediately formed. The entire mixture was removed from the blender and the same protocol was performed with the remaining salt / water solution and CaCb solution. From the first solution, which had been poured into a 2T beaker, the precipitate was filtered off. Filtering was aided by adding and washing with acetone. For the material left in the blender, it was possible to scoop this material out into a beaker. The remaining solution was filtered. Then, the precipitate was placed back into the blender and blended with acetone. This helped break up agglomerations of precipitate and "dry" the mixture. The precipitate was filtered off. This protocol seemed to work better. All precipitates were pooled and dried at 70 °C under vacuum.

[0053] Next, a 100 g batch was run using the same protocol, except the solution was made at 20 wt.% salt (100 g salt in 500 g water). To better aide dissolution, the dimer acid Na salt was sieved through at 35 mesh screen. The same two step sequence was carried out, using twice theamount of CaCb. The raw material, floating to the top of the blender, was scooped out and blended with acetone to make a fine precipitate which could be filtered. All material was isolated and combined. This time, we attempted to remove some of the acetone by heating the material at 70 °C under a stream of nitrogen (prior to vacuum drying). This actually served to melt the material. Vacuum was then applied. The material was pooled with all other previous dimer acid (calcium salt) efforts to yield 151 g of material.

[0054] Zinc Salt

[0055] The same strategy (salt metathesis) was employed for the zinc salt. The first run was a 50 g batch. Tike done the last time with the Ca material, the dimer acid Na salt was sieved through a 35 mesh screen. 50 g of material was dissolved in 500 g water at 70 °C. Then the material was placed in a blender. The blender was run on “low.” Then, 23 g of ZnSCh heptahydrate (dissolved in approximately 20 g water) was added while the blender was running. The foamy solution immediately congealed into a mass around the blender impeller. This mass was removed from the blender and re-blended with acetone. The material seemed to still be sticky and unable to be “dried” or powderized by blending in acetone. The material was removed and dried under vacuum. 41.8 g of material was isolated.

[0056] A 113 g batch was then run in the same manner, except the material was dissolved at approximately 15 wt.% Na salt in water. The material was divided equally in two and then run in the blender. For each batch, 26 g of zinc sulfate heptahydrate was added in approximately 30 g water. The material was removed from the solution and reblended, again to no avail. The material was vacuum dried. 106 g of material isolated. Combined, this was 147 g of material (90% yield). The material was then shipped to plastics R&D for testing as a polymer processing aid, along with the Calcium and sodium salts.

[0057] Production of Dry Blended Examples IE1-IE3

[0058] Calculated amount of corresponding dimer acid salt was added neat to the polyethylene carrier resin (FFDPE) followed by shaking of FFDPE pellets with dimer acid salt together for 5 minutes.

[0059] Production of PPA Masterbatch Examples IE4-IE5

[0060] Masterbatches were made in a Micro 18 Twin Screw Extruder from Haake. The EEDPE base resin was fed into the main extruder dry-blended together with 4% of the dimer acid and together was fed into the main extruder. The flow rate was 10 Ibs / hr. The polymer melt was extruded using a Single Plate Die and was pelletized using MAAG GAEA Underwater Pelletizer. The process conditions are presented in Table 1.Table 1: Masterbatch Production Process Conditions

[0061] Melt Fracture Screening Method

[0062] Referring to the extruder conditions of Table 1 below, the base EEDPE resin was extruded via a single screw extruder into a 2 mm diameter capillary die. The flow rate was 0.5 kg / hr, which at a melt temperature of 212 °C, translates approximately to a shear rate of about 269 s'1. The resulting extrudate had melt fracture. After that, the PPA was introduced at loading levels listed in Table 3.Table 2: Extruder Conditions used in Melt Fracture Screening

[0063] A timer was started when each formulation was introduced in the extruder after the process was stabilized. If melt fracture was not cleared after a maximum observable timeframe of 120 minutes, the timer was stopped. The time to clear melt fracture, concentration of the PPA added and peak temperature is shown in Table 3. After every formulation, the extruder was purged with the base resin until the melt fracture was fully re-established; confirmed visually as well by the stabilization of the processing conditions (extruder torque, pressure).Table 3: Concentration of PPA, Peak Temperature, and Time to Clear Melt Fracture

[0064] As shown in Table 3, IE1-IE5 shows comparable or better performance in clearing melt fracture than CE1, (fluoropolymer PPA) for the time needed to clear melt fracture at about the same peak temperature.

[0065] The subject matter of the present disclosure has been described in detail and by reference to specific embodiments. It should be understood that any detailed description of a component or feature of an embodiment does not necessarily imply that the component or feature is essential to the particular embodiment or to any other embodiment. Further, it should be apparent to those skilled in the art that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

[0066] It is noted that one or more of the following claims utilize the term “wherein” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

[0067] It is also noted that recitations herein of “at least one” component, element, etc., should not be used to create an inference that the alternative use of the articles “a” or “an” should be limited to a single component, element, etc.

Claims

CLAIMS1. A formulation comprising: at least 90 wt.% ethylene-based polymer; and dimer acid salts.

2. The formulation of claim 1, wherein the dimer acid salts comprise the structure ofFormula (I), Formula (II), Formula (III), or mixtures thereof:Formula (I) Formula (II) Formula (III) whereinRi comprises a C4-C12 alkyl or a C4-C12 alkenyl when R4 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid;R2 comprises a C4-C12 alkyl or a C4-C12 alkenyl when R3 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid;R3 comprises a C4-C12 alkyl or a C4-C12 alkenyl when R2 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid;R4 comprises a C4-C12 alkyl or a C4-C12 alkenyl when Ri comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; andRs and Re independently comprise a hydrogen, a C1-C12 alkyl, or a C1-C12 alkenyl.

3. The formulation of claim 2, wherein the dimer acid salts comprise a mixture having a majority of the structure of Formula (I).

4. The formulation of claim 2, wherein the dimer acid salt comprises mixture having a majority of the structure of Formula (II).

5. The formulation of claim 2, wherein the dimer acid salt comprises a mixture having a majority of the structure of Formula (I) and Formula (II).

6. The formulation of any preceding claim, further comprising trimer acid salts having the structure of Formula (IV), Formula (V), or mixtures thereof:Formula (IV) Formula (V) whereinRi comprises a C4-C12 alkyl or a C4-C12 alkenyl when R4 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid;R2 comprises a C4-C12 alkyl or a C4-C12 alkenyl when R3 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid;R3 comprises a C4-C12 alkyl or a C4-C12 alkenyl when R2 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid;R4 comprises a C4-C12 alkyl or a C4-C12 alkenyl when Ri comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid;Rs, Re, R9, and Rio independently comprise a hydrogen, a C1-C12 alkyl, or a C1-C12 alkenyl;R7 comprises a C4-C12 alkyl or a C4-C12 alkenyl when Rs comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid; andRs comprises a C4-C12 alkyl or a C4-C12 alkenyl when R7 comprises a C4-C12 alkyl with a neutralized terminal carboxylic acid or a C4-C12 alkenyl with a neutralized terminal carboxylic acid.

7. The formulation of claim 5, wherein the formulation comprises more dimer acid salt than trimer acid salt.

8. The formulation of any preceding claim, wherein the dimer acid salts comprise calcium dimer salts, zinc dimer salts, sodium dimer salts, or combinations thereof.

9. The formulation of any preceding claim, wherein the formulation is essentially free of fluoropolymer.

10. The formulation of any preceding claim, wherein the ethylene-based polymer comprises Tinear Tow Density Polyethylene (EEDPE), High Density Polyethylene (HDPE), or combinations thereof.

11. The formulation of any preceding claim, wherein the formulation is a polymer processing aid masterbatch.

12. The formulation of any preceding claim, wherein the formulation is a pellet.

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