Metal salts as polymer processing aids

Abstract

A polymer processing aid (PPA) reduces melt defects in extruded polyolefins in the absence of fluoropolymers. The polymer processing aid contains a monovalent metal salt of a carboxylic acid and effectively reduces melt defects in thermoplastic polyolefins such as linear low-density polyethylene (LLDPE).

Description

[Technical Field]

[0001] The present disclosure relates to processing aids for the extrusion of thermoplastic polyolefins that perform well in the absence of fluorinated alkene-based fluoropolymers. [Background technology]

[0002] During the extrusion of polyolefin polymers, surface defects, including those referred to as sharkskin, snakeskin, and orange peel, can occur, and each type of surface defect is generally related to the rheology of the polymer melt. One particularly serious surface defect that can occur is "melt fracture." This is believed to occur when the shear rate at the surface of the polyolefin polymer becomes high enough to cause the surface of the polymer to begin to fracture. That is, the surface of the extruded polymer slips relative to the main body of the polymer melt. This surface generally cannot flow fast enough to keep up with the main body of the extrudate, resulting in melt fracture, which significantly impairs the surface properties of the extrudate polymer.

[0003] US Patent No. 3,125,547 discloses a blend of polyethylene with a small amount of fluoropolymer that provides a smooth surface on polyethylene extrudates at high extrusion rates.

[0004] US Patent No. 3,222,314 discloses blends of polyethylene and low molecular weight polyethylene glycols that provide heat-sealable films suitable for printing.

[0005] U.S. Patent No. 4,013,622 teaches the use of low molecular weight polyethylene glycol to reduce the occurrence of "breakdown" during the manufacture of polyethylene film. Similarly, U.S. Patent No. 4,540,538 teaches that pinstriping during the extrusion of polyolefins into film can be reduced by using a combination of (i) polyethylene glycol, (ii) a hindered phenolic antioxidant, and (iii) a selected inorganic antiblock material.

[0006] Additionally, there are patents relating to the use of a combination of polyalkylene oxide and a fluorocarbon polymer as a processing aid in the extrusion of polyolefins. These patents include U.S. Pat. No. 4,855,360, which discloses and claims a composition containing a polyolefin and a processing aid, and U.S. Pat. No. 5,015,693, which claims the processing aid itself. These patents teach the use of a combination of relatively low molecular weight polyethylene glycols (e.g., having a molecular weight of about 400 Da to about 20,000 Da) and a fluorocarbon polymer as a polymer processing aid, and further demonstrate that in the absence of the fluoropolymer, these polyethylene glycols were not very effective in reducing melt defects.

[0007] US Patent No. 6,294,604 describes the use of a combination of fluoropolymer, polyethylene glycol, and magnesium oxide as a polymer processing additive package.

[0008] US Patent No. 5,986,005 describes the use of a combination of an elastomeric fluoropolymer and a polyamide / polyether block copolymer as a polymer processing aid.

[0009] U.S. Patent No. 11,359,079 describes the use of fluoropolymers or silicone-containing polymers in combination with polyethylene glycol and a metal salt of a carboxylic acid, sulfonic acid, or alkyl sulfate as a polymer processing aid. The metal salt of a carboxylic acid is used to increase the decomposition temperature of polyethylene glycol and has not been shown to be capable of being a polymer processing aid in its own right.

[0010] Because fluoroelastomers and fluoropolymers are expensive materials, there are economic incentives to avoid their use. Furthermore, it is becoming increasingly recognized that perfluorinated alkanes and perfluorinated surfactant compounds, such as perfluorooctanesulfonic acid and perfluorooctanoic acid, used during the production of fluoropolymers can have adverse environmental impacts.

[0011] In U.S. Patent Application Publication No. 2005 / 0070644, the inventors disclosed that high molecular weight polyethylene glycols, particularly PEGs with molecular weights greater than 20,000 g / mol, reduce melt fracture during extrusion of polyolefins in the absence of fluoropolymers.

[0012] U.S. Patent No. 10,982,079 also details the performance of a polymer processing aid in the absence of an added fluoropolymer. The polymer processing aid comprises a high molecular weight polyethylene glycol with improved thermal stability due to the inclusion of a metal salt of a carboxylic acid, sulfonic acid, or alkyl sulfate. However, the use of a metal salt of a carboxylic acid alone as a polymer processing aid has not been demonstrated.

[0013] Metal stearates, such as calcium stearate, are well-known polymer additives, primarily used as acid scavengers for polyethylene, but can also function as lubricants and mold release agents for some thermoplastics. It has been suggested that calcium stearate itself may play a role in reducing the load (i.e., pressure) required to extrude linear polyethylene with long chain branching produced using metallocene catalysts (see Hatsikiriakos, SG, Kazatchkov, IB, Vlassopoulos D., Journal of Rheology, vol. 41, 1997, p. 1299).

[0014] However, metal stearates, by themselves, are generally not known to be very effective as polymer processing aids that can significantly reduce melt fracture defects during the extrusion of linear polyethylene. Summary of the Invention

[0015] We report that monovalent metal salts of carboxylic acids, such as aliphatic carboxylic acids, used alone perform well as polymer processing aids during the extrusion of thermoplastic polyolefins, even in the absence of a fluoropolymer processing aid.

[0016] The present disclosure provides a useful alternative to fluorinated alkene-based polymer processing aids.

[0017] One embodiment is a process for preparing a thermoplastic composition extrudate, the process comprising extruding a thermoplastic composition in a melt extrusion process, the thermoplastic composition comprising a linear polyethylene and a monovalent metal salt of a carboxylic acid; The linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; The thermoplastic composition is substantially free of fluoropolymer and the melt extrusion process is carried out in the absence of fluoropolymer.

[0018] One embodiment is an extrudable thermoplastic composition comprising: i) a linear polyethylene; and ii) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal salt of a carboxylic acid, where the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof, and the extrudable thermoplastic composition is substantially free of fluoropolymer.

[0019] One embodiment is a method for reducing melt extrusion defects during extrusion of a thermoplastic composition comprising linear polyethylene, the method comprising the steps of adding at least one monovalent metal salt of a carboxylic acid to the linear polyethylene; extruding the thermoplastic composition in a melt extrusion process; Including, The linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof.

[0020] In one embodiment, the monovalent metal salt of a carboxylic acid is a monovalent metal salt of an aliphatic carboxylic acid.

[0021] In one embodiment, the monovalent metal salt of a carboxylic acid is a monovalent metal salt of an aromatic carboxylic acid.

[0022] In one embodiment, the thermoplastic composition comprises one or more of polyethylene glycol and a poly(ether block amide) copolymer, where the poly(ether block amide) copolymer comprises a polyamide block and a polyether block.

[0023] In one embodiment, the melt extrusion process is carried out at a shear rate that, when carried out with a thermoplastic composition consisting essentially of linear polyethylene, produces a thermoplastic composition extrudate having melt fracture defects.

[0024] In one embodiment, the linear polyethylene is LLDPE.

[0025] In one embodiment, the LLDPE has a melt index, I2, of 0.1 to 5.0 grams per 10 minutes.

[0026] In one embodiment, the LLDPE has a viscosity of 0.910 to 0.936 g / cm 3 It has a density of

[0027] In one embodiment, the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more alpha olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene. [Brief explanation of the drawings]

[0028] [Figure 1] The results of experiments (Examples 1A-1C) evaluating the ability of various polymer processing aids to eliminate melt extrusion defects when extruding a thermoplastic composition containing linear low-density polyethylene (LLDPE) in a blown film line melt extrusion process are presented. A monolayer blown film line equipped with a 3-inch diameter die was used in these experiments. [Figure 2] The results of experiments (Examples 2A-2E) evaluating the ability of various polymer processing aids to eliminate melt extrusion defects when extruding a thermoplastic composition containing linear low-density polyethylene (LLDPE) in a blown film line melt extrusion process are presented. A monolayer blown film line equipped with a 3-inch diameter die was used in these experiments. [Figure 3] The results of experiments (Examples 2A, 2F, and 2I) evaluating the ability of various polymer processing aids to eliminate melt extrusion defects when extruding a thermoplastic composition containing linear low-density polyethylene (LLDPE) in a blown film line melt extrusion process are presented. A monolayer blown film line equipped with a 3-inch diameter die was used in these experiments. [Figure 4]The results of a control experiment (Example 2L) and experiments (Examples 2J and 2K) evaluating the ability of various polymer processing aids to eliminate melt extrusion defects when extruding a thermoplastic composition containing linear low-density polyethylene (LLDPE) in a blown film line melt extrusion process are presented. A monolayer blown film line equipped with a 3-inch diameter die was used in these experiments. DETAILED DESCRIPTION OF THE INVENTION

[0029] As used herein, the term "monomer" refers to a small molecule that can chemically react and chemically bond with itself or other monomers to form a polymer.

[0030] As used herein, the term "α-olefin" or "alpha-olefin" is used to describe a monomer having a linear hydrocarbon chain containing 3 to 20 carbon atoms with a double bond at one end of the chain; an equivalent term is "linear α-olefin." Alpha-olefins are also referred to as comonomers.

[0031] As used herein, the terms "polyethylene" or "ethylene polymer" refer to a polymer produced from ethylene monomer and, optionally, one or more additional monomers, regardless of the specific catalyst or process used to make the ethylene polymer. In the polyethylene field, the one or more additional monomers are often referred to as "comonomers" and typically include an α-olefin. The term "homopolymer" generally refers to a polymer containing only one type of monomer. The term "copolymer" refers to a polymer containing two or more types of monomers. Common types of polyethylene include high-pressure low-density polyethylene (LDPE), high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), or very low-density polyethylene (ULDPE), also known as plastomers and elastomers. The term polyethylene also includes polyethylene terpolymers, which may contain two or more comonomers in addition to ethylene. The term polyethylene also includes combinations or blends of the above types of polyethylene.

[0032] The term "fluoropolymer" in this disclosure refers to homopolymers and copolymers of fluorinated olefins. The fluorinated olefins may have a fluorine atom to carbon ratio of at least 1:2, or in some embodiments, at least 1:1. Homopolymers include, for example, those derived from vinylidene fluoride and vinyl fluoride. Copolymers include, for example, those derived from vinylidene fluoride and one or more additional olefins, where the one or more additional olefins may be fluorinated, such as hexafluoropropylene, or may be non-fluorinated, such as propylene. Non-limiting examples of the term "fluoropolymer" as used in this disclosure include those described in, for example, U.S. Pat. Nos. 2,968,649; 3,051,677; 3,318,854; 5,015,693; 4,855,360; 5,710,217; 6,277,919; 7,375,157; ​​and U.S. Patent Application Publication No. 2010 / 0311906. Examples of commercially available fluoropolymers include copolymers of hexafluoropropylene and vinylidene fluoride available under the trade names "DYNAMAR® FX 9613" and "DYNAMAR FX 9614" and copolymers of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene available under the trade names "DYNAMAR FX 5911" and "DYNAMAR FX 5912." Other commercially available fluoropolymers include "VITON® A," "VITON® FREEFLOW™," "DAI-EL®," and "KYNAR®," all available in various grades.

[0033] In this disclosure, the terms polyalkylene oxide, poly(oxyalkylene), and polyalkylene glycol are used interchangeably. Thus, the terms polyethylene oxide, poly(oxyethylene), and polyethylene glycol are also used interchangeably; likewise, the terms polypropylene oxide, poly(oxypropylene), and polypropylene glycol.

[0034] The term "film" is used herein to mean a film having one or more layers formed by extrusion of a polymer through one or more die openings. The term "film structure" is used to mean that the film has multiple layers (film structures can have at least two layers, at least three layers, at least four layers, at least five layers, etc.).

[0035] The terms "alkyl group" and the prefix "alk-", unless otherwise specified, include both straight and branched chain groups and cyclic groups having up to 30 carbons. Cyclic groups can be monocyclic or polycyclic, and in some embodiments have from 3 to 10 ring carbon atoms.

[0036] For example, with respect to an alkyl, alkylene, or arylalkylene, the phrase "interrupted by one or more ether linkages" means having an alkyl, alkylene, or arylalkylene moiety on both sides of the functional group. An example of an alkylene interrupted by -O- is -CH-CH-O-CH-CH-.

[0037] The term "aryl" as used herein includes carbocyclic aromatic rings or ring systems, e.g., having one, two, or three rings, optionally containing at least one heteroatom (e.g., O, S, or N) in the ring, and optionally substituted with up to five substituents including one or more alkyl groups (e.g., methyl or ethyl) having up to four carbon atoms, alkoxy groups having up to four carbon atoms, halo (i.e., fluoro, chloro, bromo, or iodo), hydroxy, or nitro groups. Examples of aryl groups include phenyl, naphthyl, biphenyl, fluorenyl, and furyl, thienyl, oxazolyl, and thiazolyl. "Arylalkylene" refers to an "alkylene" moiety to which an aryl group is attached. "Alkylarylene" refers to an "arylene" moiety to which an alkyl group is attached.

[0038] The term "substituted" or similar terms (e.g., "substituent") means that one or more non-hydrogen radicals (or non-hydrogen moieties or groups) are replaced with one or more hydrogen radicals at any position within the referenced group.

[0039] In an embodiment of the present disclosure, the extrusion of thermoplastic polyolefins is improved (“assisted”) by the use of a polymer processing aid (PPA).

[0040] In embodiments of the present disclosure, one or more components of the polymer processing aid may be mixed (e.g., pre-mixed) or pre-blended (e.g., dry-blended or melt-blended) with the thermoplastic polyolefin, followed by extrusion of the polyolefin.

[0041] In embodiments of the present disclosure, one or more components of the polymer processing aid may be fed into the extruder along with the thermoplastic polyolefin.

[0042] In embodiments of the present disclosure, one or more components of a polymer processing aid can be added to a thermoplastic polyolefin to prepare a masterbatch of the polyolefin containing one or more components of the polymer processing aid. The resulting polyolefin masterbatch can then be used to conventionally introduce one or more components of the polymer processing aid into the thermoplastic polyolefin prior to extrusion of the polyolefin (e.g., dry blended or melt blended) or during extrusion of the polyolefin (e.g., fed into an extruder with the polyolefin).

[0043] <Polymer processing aid (PPA)> In one embodiment of the present disclosure, a polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins comprises a monovalent metal salt of a carboxylic acid ("metal salt").

[0044] In one embodiment of the present disclosure, a polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins comprises a monovalent metal salt ("metal salt") of an aliphatic carboxylic acid.

[0045] In one embodiment of the present disclosure, a polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins comprises a polymeric processing aid selected from the group consisting of: i) a monovalent metal salt of a carboxylic acid ("metal salt"); and ii) poly(oxyalkylene) polymers (also known as polyalkylene glycols (PAGs)); iii) poly(ether block amide) copolymers (the poly(ether block amide) copolymers contain polyamide blocks and polyether blocks); iv) polycaprolactone (PCL) polymer; and v) High-pressure low-density polyethylene (LDPE) and one or more of:

[0046] In one embodiment of the present disclosure, a polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins comprises i) a monovalent metal salt of a carboxylic acid ("metal salt") and ii) a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG)).

[0047] In one embodiment of the present disclosure, a polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins comprises i) a monovalent metal salt of a carboxylic acid ("metal salt") and ii) a poly(ether block amide) copolymer, the poly(ether block amide) copolymer comprising polyamide blocks and polyether blocks.

[0048] In one embodiment of the present disclosure, a polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins comprises a polymeric compound selected from the group consisting of: i) a monovalent metal salt of an aliphatic carboxylic acid ("metal salt"); and ii) poly(oxyalkylene) polymers (also known as polyalkylene glycols (PAGs)); iii) poly(ether block amide) copolymers (the poly(ether block amide) copolymers contain polyamide blocks and polyether blocks); iv) polycaprolactone (PCL) polymer; and v) High-pressure low-density polyethylene (LDPE) and one or more of:

[0049] In one embodiment of the present disclosure, a polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins comprises i) a monovalent metal salt ("metal salt") of an aliphatic carboxylic acid, and ii) a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG)).

[0050] In one embodiment of the present disclosure, a polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins comprises i) a monovalent metal salt of an aliphatic carboxylic acid ("metal salt") and ii) a poly(ether block amide) copolymer, the poly(ether block amide) copolymer comprising polyamide blocks and polyether blocks.

[0051] In one embodiment of the present disclosure, the polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polymers is further characterized by the substantial absence of perfluoroalkane compounds, fluoroelastomers, and fluoropolymers.

[0052] One embodiment of the present disclosure is characterized by the substantial absence of perfluoroalkane compounds, fluoroelastomers, and fluoropolymers in the extrudable thermoplastic composition.

[0053] One embodiment of the present disclosure is a process for preparing a thermoplastic composition extrudate, comprising melt extruding a thermoplastic composition in a melt extrusion process, wherein the thermoplastic composition is characterized by the substantial absence of perfluoroalkane compounds, fluoroelastomers, and fluoropolymers, and wherein the melt extrusion process is conducted in the absence of perfluoroalkane compounds, fluoroelastomers, and fluoropolymers.

[0054] In embodiments of the present disclosure, melt extrusion processes include film extrusion, extrusion blow molding, injection molding, pipe extrusion, wire extrusion, cable extrusion, and fiber extrusion, all of which are well known to those skilled in the art.

[0055] <Metal salts of carboxylic acids ("metal salts")> In one embodiment, the polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins comprises a monovalent metal salt of a carboxylic acid.

[0056] In one embodiment, the polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins comprises a monovalent metal salt of an aliphatic carboxylic acid.

[0057] The carboxylic acids used to provide the metal salts may be monofunctional or polyfunctional (e.g., bifunctional) and aliphatic or aromatic. In other words, the carbonyl carbon may be attached to an aliphatic group or an aromatic ring. The aliphatic carboxylic acids may be saturated or unsaturated. In addition to one or more -C(O)O anions (i.e., carboxylate groups, respectively), the aliphatic or aromatic groups may be substituted with other functional groups, including halogen (i.e., fluoro, chloro, bromo, and iodo) groups, hydroxyl groups, and alkoxy groups, and the aromatic rings may be substituted with alkyl groups. However, those skilled in the art will recognize that a monovalent metal salt of a carboxylic acid has only one -C(O)O anion (i.e., carboxylate group) and the counterion metal is M. + (i.e., the metal M has one valence electron, is "monovalent," and forms a positive cation upon reaching an octet state).

[0058] In an embodiment of the present disclosure, the carboxylic acid is monofunctional or difunctional and aliphatic, with no additional substituents on the aliphatic chain.

[0059] In an embodiment of the present disclosure, the carboxylic acid is monofunctional and aliphatic, with no additional substituents on the aliphatic chain.

[0060] In an embodiment of the present disclosure, the carboxylic acid is monofunctional and paraffinic (i.e., acyclic saturated aliphatic group) and has no further substituents on the paraffinic group (i.e., acyclic saturated aliphatic group).

[0061] In embodiments of the present disclosure, the carboxylic acid is monofunctional and aromatic and may optionally have additional substituents on the aromatic group, including functional groups or other aliphatic groups (e.g., saturated or unsaturated aliphatic groups such as alkyl, alkenyl, alkynyl groups, etc.).

[0062] In some embodiments, carboxylic acids useful for providing metal salts have the formula RCOOH, where R is an alkyl or alkenyl group. In some embodiments, carboxylic acids useful for providing metal salts have the formula RCOOH, where R is a straight chain alkyl group. In some embodiments, carboxylic acids useful for providing metal salts have the formula RCOOH, where R is an aromatic or substituted aromatic group.

[0063] In one embodiment, the carboxylic acid used to provide the metal salt is benzoic acid, hi one embodiment, the carboxylic acid used to provide the metal salt is benzoic acid further substituted with one or more aliphatic groups at the 2-, 3-, 4-, 5-, or 6-position of the phenyl ring.

[0064] In some embodiments, the carboxylic acid used to provide the metal salt is an aromatic carboxylic acid having from 7 to 30 carbon atoms.

[0065] In some embodiments, the carboxylic acid used to provide the metal salt is an aromatic carboxylic acid having from 7 to 20 carbon atoms.

[0066] In some embodiments, the carboxylic acid used to provide the metal salt is a carboxylic acid having an alkyl or alkenyl group having from 2 to 30 carbon atoms.

[0067] In some embodiments, the carboxylic acid used to provide the metal salt is an aliphatic carboxylic acid having from 2 to 30 carbon atoms.

[0068] In some embodiments, the carboxylic acid used to provide the metal salt is an aliphatic carboxylic acid having from 6 to 30 carbon atoms.

[0069] In some embodiments, the carboxylic acid used to provide the metal salt is an aliphatic carboxylic acid having from 6 to 26 carbon atoms.

[0070] In some embodiments, the carboxylic acid used to provide the metal salt is an aliphatic carboxylic acid having from 6 to 22 carbon atoms.

[0071] In one embodiment, the carboxylic acid used to provide the metal salt is acetic acid.

[0072] In some embodiments, the carboxylic acid used to provide the metal salt is a fatty acid, e.g., a carboxylic acid having an alkyl or alkenyl group, having 8 to 30 carbon atoms, in some embodiments, 8 to 26 carbon atoms, and in some embodiments, 8 to 22 carbon atoms. Common names for fatty acids having 8 to 26 carbon atoms that can be used to provide the metal salts used in embodiments of the present disclosure include caprylic acid (C8 carboxylic acid), capric acid (C8 carboxylic acid), and the like. 10 carboxylic acid), lauric acid (C 12 carboxylic acid), myristic acid (C 14 carboxylic acid), palmitic acid (C 16 carboxylic acid), stearic acid (C 18 carboxylic acid), arachidic acid (C 20 carboxylic acid), behenic acid (C 22 carboxylic acid), lignoceric acid (C 24 carboxylic acid), and cerotic acid (C 26 Fatty acid metal salts (including monovalent metal salts) of these fatty acids that can be used in embodiments of the present disclosure are metal caprylate, metal caprate, metal laurate, metal myristate, metal palmitate, metal stearate, metal arachidate, metal behenate, metal lignocerate, and metal cerotate, respectively.

[0073] In an embodiment of the present disclosure, the carboxylic acid used to provide the metal salt is stearic acid.

[0074] Examples of useful monovalent metals (which form the cation in the metal salt of a carboxylic acid) include rubidium (Rb), lithium (Li), sodium (Na), and potassium (K). In some embodiments, the metal salt is a sodium or potassium salt.

[0075] In an embodiment of the present disclosure, the metal salt is a potassium salt.

[0076] In an embodiment of the present disclosure, the metal salt is a sodium salt.

[0077] Many metal salts of carboxylic acids are available from various commercial sources, while others can be prepared by conventional methods. In some embodiments, the metal salt of a carboxylic acid can be formed in situ within the thermoplastic polyolefin. In these embodiments, typically, both a first component containing a metal cation and a second component containing a carboxylic acid can be added to an extrudable thermoplastic polyolefin. Metal salts of carboxylic acids that can be used in embodiments of the present disclosure include rubidium stearate, potassium stearate, sodium stearate, sodium acetate, sodium hexanoate, potassium hexanoate, sodium caprylate, sodium laurate, and sodium behenate.

[0078] In an embodiment of the present disclosure, the metal salt used as the PPA is selected from the group consisting of lithium acetate, sodium acetate, potassium acetate, lithium stearate, sodium stearate, potassium stearate, lithium hexanoate, sodium hexanoate, potassium hexanoate, and mixtures thereof.

[0079] In an embodiment of the present disclosure, the metal salt used as the PPA is selected from the group consisting of potassium stearate, sodium stearate, lithium stearate, and mixtures thereof.

[0080] In some embodiments of the present disclosure, the metal salt used as the PPA is potassium stearate. In some embodiments of the present disclosure, the metal salt used as the PPA is sodium stearate.

[0081] In an embodiment of the present disclosure, the metal salt used as the PPA is selected from the group consisting of potassium hexanoate, sodium hexanoate, lithium hexanoate, and mixtures thereof.

[0082] In some embodiments of the present disclosure, the metal salt used as the PPA is potassium hexanoate. In some embodiments of the present disclosure, the metal salt used as the PPA is sodium hexanoate.

[0083] In some embodiments of the present disclosure, the metal salt used as the PPA is potassium benzoate. In some embodiments of the present disclosure, the metal salt used as the PPA is sodium benzoate. In some embodiments of the present disclosure, the metal salt used as the PPA is lithium sodium benzoate.

[0084] In one embodiment of the present disclosure, the amount of metal salt (e.g., monovalent metal salt of an aliphatic carboxylic acid) used as a polymer processing aid (PPA) is 100 to 5,000 ppm by weight (based on the weight of the thermoplastic polyolefin), including any subranges and any value within the range. Further optimized PPA addition levels and ranges for a given extrusion process can be readily determined by one of ordinary skill in the art. For example, in certain embodiments, the amount of metal salt (e.g., monovalent metal salt of an aliphatic carboxylic acid) used as a polymer processing aid (PPA) is from 100 to 4,000 ppm by weight (based on the weight of the thermoplastic polyolefin), or from 200 to 4,000 ppm by weight, or from 100 to 3,000 ppm by weight, or from 200 to 3,000 ppm by weight, or from 100 to 2,000 ppm by weight, or from 200 to 2,500 ppm by weight, or from 300 to 2,500 ppm by weight, or from 300 to 2,500 ppm by weight, or from 400 to 2,500 ppm by weight, or from 500 to 2,500 ppm by weight. ,500 ppm, or 750 to 4,000 ppm by weight, or 750 to 3,000 ppm by weight, or 750 to 2,500 ppm by weight, or 1,000 to 4,000 ppm by weight, or 1,000 to 3,000 ppm by weight, or 1,000 to 2,500 ppm by weight, or 1,000 to 2,250 ppm by weight, or 1,000 to 2,000 ppm by weight, or 1,250 to 1,750 ppm by weight, or 500 to 2,250 ppm by weight, or 500 to 2,000 ppm by weight, or 300 to 2,000 ppm by weight, or 200 to 2,000 ppm by weight.

[0085] In embodiments of the present disclosure, the amount of metal salt (e.g., a monovalent metal salt of an aliphatic carboxylic acid) used as a polymer processing aid (PPA) is from 200 to 1,500 ppm by weight (based on the weight of the thermoplastic polyolefin), or from 300 to 1,500 ppm by weight, or from 400 to 1,500 ppm by weight, or from 500 to 1,500 ppm by weight, or from 750 to 1,500 ppm by weight, or from 300 to 1,250 ppm by weight, or from 400 to 1,250 ppm by weight, or from 500 to 1,250 ppm by weight, or from 750 to 1,250 ppm by weight, or from 200 to 1,000 ppm by weight, or from 300 to 1,000 ppm by weight, or from 500 to 1,000 ppm by weight, or from 750 to 1,000 ppm by weight (based on the weight of the thermoplastic polyolefin).

[0086] In one embodiment of the present disclosure, a metal salt (e.g., a monovalent metal salt of an aliphatic carboxylic acid) is added to a thermoplastic polyolefin (e.g., linear polyethylene) using a masterbatch formulation containing the metal salt (e.g., a monovalent metal salt of an aliphatic carboxylic acid). The term masterbatch is well known to those skilled in the art. In general, the term "masterbatch" refers to the initial melt-mixing of an additive, such as a metal salt (e.g., a monovalent metal salt of an aliphatic carboxylic acid), with a small amount of a given thermoplastic polyolefin (e.g., linear polyethylene), followed by blending (e.g., melt-mixing or dry-blending) of the resulting "masterbatch" with the remaining bulk of the thermoplastic polyolefin (e.g., linear polymer).

[0087] In embodiments of the present disclosure, from about 0.1 to about 15.0 weight percent, or from about 0.5 to about 15.0 weight percent, or from about 0.5 to about 10.0 weight percent, or from about 0.1 to about 10.0 weight percent, or from about 0.1 to about 7.5 weight percent, or from about 0.5 to about 7.5 weight percent, or from about 0.5 to about 5.0 weight percent, or from about 0.1 to about 5.0 weight percent, or from about 1.0 to about 15.0 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 1.0 to about 7.5 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 0.1 to about 2.5 weight percent, or from about 0.5 to about 2.5 weight percent of the masterbatch is used in the blend with the bulk polymer (the weight percent of the masterbatch is based on the combined weight of the masterbatch and the bulk polymer).

[0088] In embodiments of the present disclosure, a masterbatch (e.g., of linear polyethylene) may contain an amount of metal salt (e.g., a monovalent metal salt of an aliphatic carboxylic acid) in the range of 500 to 50,000 ppm by weight (based on the weight of the masterbatch), including subranges and any number within the range. For example, in further embodiments of the present disclosure, the masterbatch may contain 500 to 40,000 ppm by weight (based on the weight of the masterbatch), or 500 to 35,000 ppm, or 500 to 40,000 ppm, or 500 to 25,000 ppm, or 1,000 to 40,000 ppm, or 1,000 to 35,000 ppm, or 1,000 to 30,000 ppm. m, or 1,000 to 25,000 ppm, or 5,000 to 25,000 ppm, or 1,000 to 20,000 ppm, or 2,000 to 20,000 ppm, or 3,000 to 20,000, or 4,000 to 20,000 ppm, or 5,000 to 20,000 ppm, or 5,000 to 17,500, or 5,000 to 15,000, or 5,000 to 1 2,500 ppm, or 2,500 to 15,000 ppm, or 5,000 to 15,000 ppm, or 7,500 to 15,000 ppm, or 7,500 to 12,500 ppm, or 5,000 to 50,000 ppm, or 7,500 to 50,000 ppm, or 10,000 to 50,000 ppm, or 10,000 to 35,000 ppm, or 10 It may contain a metal salt (for example, a monovalent metal salt of an aliphatic carboxylic acid) in an amount ranging from 5,000 to 25,000 ppm, or 5,000 to 35,000 ppm, or 5,000 to 30,000 ppm, or 5,000 to 25,000 ppm, or 15,000 to 30,000 ppm, or 17,500 to 27,500 ppm, or 20,000 to 25,000 ppm.

[0089] Metal salts (eg, monovalent metal salts of aliphatic carboxylic acids) used as polymer processing aids (PPAs) may be used in the form of semi-solid or viscous liquids, or as powders, pellets, or granules.

[0090] <Poly(oxyalkylene) polymer> In one embodiment of the present disclosure, the polymer processing aid comprises a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG) or polyalkylene oxide).

[0091] In one embodiment of the present disclosure, the polymer processing aid comprises a poly(oxyethylene) polymer (also known as polyethylene glycol or polyethylene oxide).

[0092] In one embodiment of the present disclosure, the polymer processing aid comprises poly(oxypropylene) glycol (also known as polypropylene glycol or polypropylene oxide).

[0093] The poly(oxyalkylene) polymer, in embodiments of the present disclosure, has the formula A[(OR 1 ) x OR 2 ] y where A is typically an alkylene interrupted by one or more ether linkages, y is 2 or 3, and (OR 1 ) x is a number (x) of oxyalkylene groups OR 1 wherein each R 1 are independently C2-C5 alkylene, and in some embodiments C2-C3 alkylene; R 2 is hydrogen, alkyl, aryl, arylalkenyl, alkylarylenyl, —C(O)-alkyl, —C(O)-aryl, —C(O)-arylalkenyl, or —C(O)-alkylarylenyl, where —C(O)— is OR 2 is bonded to O.

[0094] In one embodiment of the present disclosure, the poly(oxyalkylene) polymer is 1 is —CHCH—, or a homopolymer such as a poly(oxyethylene) polymer (also referred to in this disclosure as polyethylene glycol) where each R 1 It can be a homopolymer such as a poly(oxypropylene) polymer where is —C3H6—.

[0095] In another embodiment of the present disclosure, the poly(oxyalkylene) polymer comprises chains of randomly distributed oxyalkylene groups (e.g., copolymers containing -OC2H4- and -OC3H6- units) or has alternating blocks of repeating oxyalkylene groups (e.g., (-OC2H4-) a and (-OC3H6-) b block, a+b=x), a copolymer, and a poly(oxyalkylene) polymer.

[0096] Poly(oxyalkylene) copolymers containing randomly distributed or alternating units of (-OC2H4-) and (-OC3H6-), or (-OC2H4-) a and (-OC3H6-) b Poly(oxyalkylene) copolymers containing blocks of the formula (I) are sometimes called "poloxamers" and are commercially available under the trade names PLURONIC®, KOLLIPHOR®, and SYNPERONIC®.

[0097] In some embodiments of the present disclosure, A is ethylene, —CH—CH(—)—CH— (derived from glycerol), CHCHC(CH—) (derived from 1,1,1-trimethylolpropane), poly(oxypropylene), —CHCH—O—CHCH—, or —CHCH—O—CHCH—O—CHCH—.

[0098] In some embodiments of the present disclosure, R 2 is hydrogen, methyl, butyl, phenyl, benzyl, acetyl, benzoyl, or stearyl.

[0099] In other embodiments of the present disclosure, the poly(oxyalkylene) polymer may be, for example, a dicarboxylic acid and a carboxylic acid represented by the formula A[(OR 1 ) x OR 2 ] y [In the formula, A, R 1 , and x are as defined above, and R 2is hydrogen and y is 2; and

[0100] In one embodiment of the present disclosure, a majority portion by weight of the poly(oxyalkylene) polymer is made up of repeating oxyalkylene groups (OR 1 )

[0101] In one embodiment of the present disclosure, the poly(oxyalkylene) polymer is polyethylene glycol (PEG). Polyethylene glycol (PEG) has the formula H(O—CH2CH2—) x OH. Many polyethylene glycols, as well as their ethers and esters, are commercially available, all of which are contemplated for use in embodiments of the present disclosure.

[0102] The weight average molecular weight (e.g., M) of polyalkylene glycols such as polyethylene glycol (PEG) n and M w ) can be measured by techniques known in the art, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using narrow molecular weight distribution poly(oxyalkylene) polymers (e.g., polyethylene glycol) as standards.

[0103] In an embodiment of the present disclosure, the polyalkylene glycol (PAG) has a weight average molecular weight M w is at least about 20,000 g / mol, or at least about 30,000 g / mol, or at least about 40,000 g / mol, or at least about 50,000 g / mol, or at least about 60,000 g / mol.

[0104] In an embodiment of the present disclosure, the polyalkylene glycol (PAG) has a weight average molecular weight M whas an upper limit of about 500,000 g / mol, or about 450,000 g / mol, or about 400,000 g / mol, or about 350,000 g / mol, or about 300,000 g / mol.

[0105] In an embodiment of the present disclosure, the polyalkylene glycol (PAG) is a polyethylene glycol polymer having a weight average molecular weight M w is about 60,000 g / mol to about 500,000 g / mol, or about 75,000 g / mol to about 500,000 g / mol, or about 60,000 g / mol to about 450,000 g / mol, or about 75,000 g / mol to about 450,000 g / mol, or about 80,000 g / mol to about 500,000 g / mol, or about 80,000 g / mol to about 450,000 g / mol, or about 85,000 g / mol to about 500,000 g / mol, or about 60,000 g / mol to about 400,000 g / mol g / mol, or about 60,000 g / mol to about 350,000 g / mol, or about 70,000 g / mol to about 400,000 g / mol, or about 70,000 g / mol to about 350,000 g / mol, or about 100,000 g / mol to about 350,000 g / mol, or about 150,000 g / mol to about 350,000 g / mol, or about 200,000 g / mol to about 350,000 g / mol, or about 250,000 g / mol to about 350,000 g / mol.

[0106] In an embodiment of the present disclosure, the polyalkylene glycol (PAG) has a weight average molecular weight M w is less than 20,000 g / mol, or less than 15,000 g / mol, or less than 10,000 g / mol, or less than 5,000 g / mol.

[0107] In an embodiment of the present disclosure, the polyalkylene glycol (PAG) has a weight average molecular weight M wis from about 200 g / mol to about 20,000 g / mol, or from about 400 g / mol to about 15,000 g / mol, or from about 400 g / mol to about 10,000 g / mol, or from about 400 g / mol to about 7,500 g / mol, or from about 400 g / mol to about 5,000 g / mol.

[0108] In an embodiment of the present disclosure, the polyalkylene glycol (PAG) has a weight average molecular weight M w is from about 1,000 g / mol to about 20,000 g / mol, or from about 2,000 g / mol to about 20,000 g / mol, or from about 1,000 g / mol to about 15,000 g / mol, or from about 2,000 g / mol to about 15,000 g / mol, or from about 1,000 g / mol to about 10,000 g / mol, or from about 2,000 g / mol to about 10,000 g / mol.

[0109] In an embodiment of the present disclosure, the polyalkylene glycol (PAG) has a weight average molecular weight M w is about 1,000 g / mol to about 8,000 g / mol, or about 2,000 g / mol to about 8,000 g / mol, or about 1,000 g / mol to about 7,000 g / mol, or about 2,000 g / mol to about 7,000 g / mol, or about 1,000 g / mol to about 6,500 g / mol, or about 2,000 g / mol to about 6,500 g / mol, or about 1,000 g / mol to about 6,000 g / mol, or about 2,000 g / mol to about 6,000 g / mol, or about 1,000 g / mol to about 5,000 g / mol, or about 2,000 g / mol to about 5,000 g / mol.

[0110] In an embodiment of the present disclosure, the polyalkylene glycol (PAG) has a weight average molecular weight M wis about 10,000 g / mol to about 50,000 g / mol, or about 15,000 g / mol to about 50,000 g / mol, or about 20,000 g / mol to about 50,000 g / mol, or about 25,000 g / mol to about 50,000 g / mol, or about 20,000 g / mol to about 40,000 g / mol, or about 25,000 g / mol to about 35,000 g / mol, or about 15,000 g / mol to about 35,000 g / mol, or about 15,000 g / mol to about 30,000 g / mol, or about 15,000 g / mol to about 25,000 g / mol.

[0111] In an embodiment of the present disclosure, the polyethylene glycol (PEG) is a polyethylene glycol polymer having a weight average molecular weight M w is at least about 20,000 g / mol, or at least about 30,000 g / mol, or at least about 40,000 g / mol, or at least about 50,000 g / mol, or at least about 60,000 g / mol.

[0112] In an embodiment of the present disclosure, the polyethylene glycol (PEG) is a polyethylene glycol polymer having a weight average molecular weight M w has an upper limit of about 500,000 g / mol, or about 450,000 g / mol, or about 400,000 g / mol, or about 350,000 g / mol, or about 300,000 g / mol.

[0113] In an embodiment of the present disclosure, the polyethylene glycol (PEG) is a polyethylene glycol polymer having a weight average molecular weight M wis about 60,000 g / mol to about 500,000 g / mol, or about 75,000 g / mol to about 500,000 g / mol, or about 60,000 g / mol to about 450,000 g / mol, or about 75,000 g / mol to about 450,000 g / mol, or about 80,000 g / mol to about 500,000 g / mol, or about 80,000 g / mol to about 450,000 g / mol, or about 85,000 g / mol to about 500,000 g / mol, or about 60,000 g / mol to about 400,000 g / mol g / mol, or about 60,000 g / mol to about 350,000 g / mol, or about 70,000 g / mol to about 400,000 g / mol, or about 70,000 g / mol to about 350,000 g / mol, or about 100,000 g / mol to about 350,000 g / mol, or about 150,000 g / mol to about 350,000 g / mol, or about 200,000 g / mol to about 350,000 g / mol, or about 250,000 g / mol to about 350,000 g / mol.

[0114] In an embodiment of the present disclosure, the polyethylene glycol (PEG) is a polyethylene glycol polymer having a weight average molecular weight M w is less than 20,000 g / mol, or less than 15,000 g / mol, or less than 10,000 g / mol, or less than 5,000 g / mol.

[0115] In an embodiment of the present disclosure, the polyethylene glycol (PEG) is a polyethylene glycol polymer having a weight average molecular weight M w is from about 200 g / mol to about 20,000 g / mol, or from about 400 g / mol to about 15,000 g / mol, or from about 400 g / mol to about 15,000 g / mol, or from about 400 g / mol to about 10,000 g / mol, or from about 400 g / mol to about 7,500 g / mol, or from about 400 g / mol to about 5,000 g / mol.

[0116] In an embodiment of the present disclosure, the polyethylene glycol (PEG) is a polyethylene glycol polymer having a weight average molecular weight M wis from about 1,000 g / mol to about 20,000 g / mol, or from about 2,000 g / mol to about 20,000 g / mol, or from about 1,000 g / mol to about 15,000 g / mol, or from about 2,000 g / mol to about 15,000 g / mol, or from about 1,000 g / mol to about 10,000 g / mol, or from about 2,000 g / mol to about 10,000 g / mol.

[0117] In an embodiment of the present disclosure, the polyethylene glycol (PEG) is a polyethylene glycol polymer having a weight average molecular weight M w is about 1,000 g / mol to about 8,000 g / mol, or about 2,000 g / mol to about 8,000 g / mol, or about 1,000 g / mol to about 7,000 g / mol, or about 2,000 g / mol to about 7,000 g / mol, or about 1,000 g / mol to about 6,500 g / mol, or about 2,000 g / mol to about 6,500 g / mol, or about 1,000 g / mol to about 6,000 g / mol, or about 2,000 g / mol to about 6,000 g / mol, or about 1,000 g / mol to about 5,000 g / mol, or about 2,000 g / mol to about 5,000 g / mol.

[0118] In an embodiment of the present disclosure, the polyethylene glycol (PEG) has a weight average molecular weight M of about 3,350 g / mol. w It has.

[0119] In an embodiment of the present disclosure, the polyethylene glycol (PEG) is a polyethylene glycol polymer having a weight average molecular weight M wis about 10,000 g / mol to about 50,000 g / mol, or about 15,000 g / mol to about 50,000 g / mol, or about 20,000 g / mol to about 50,000 g / mol, or about 25,000 g / mol to about 50,000 g / mol, or about 20,000 g / mol to about 40,000 g / mol, or about 25,000 g / mol to about 35,000 g / mol, or about 15,000 g / mol to about 35,000 g / mol, or about 15,000 g / mol to about 30,000 g / mol, or about 15,000 g / mol to about 25,000 g / mol.

[0120] In one embodiment of the present disclosure, the polyethylene glycol (PEG) has a weight average molecular weight M of at least 20,000 g / mol, or at least 25,000 g / mol. w It has.

[0121] In one embodiment of the present disclosure, the polyethylene glycol (PEG) has a weight average molecular weight M of about 20,000 g / mol to about 50,000 g / mol. w It has.

[0122] In an embodiment of the present disclosure, the polyethylene glycol (PEG) has a weight average molecular weight M of about 35,000 g / mol. w It has.

[0123] In embodiments of the present disclosure, the polyethylene glycol (PEG) has a weight average molecular weight M of about 100,000 g / mol to about 500,000 g / mol, or about 150,000 g / mol to about 450,000 g / mol, or about 200,000 g / mol to about 400,000 g / mol. w It has.

[0124] In an embodiment of the present disclosure, the polyethylene glycol (PEG) has a weight average molecular weight M of about 300,000 g / mol. w It has.

[0125] In one embodiment of the present disclosure, polyethylene glycol (PEG), commercially available under the trademark POLYGLYKOL™, is used as a polymer processing aid.

[0126] In one embodiment of the present disclosure, polyethylene glycol (PEG), commercially available under the trademarks CARBOWAX® or PLURIOL®, is used as a polymer processing aid.

[0127] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w The polyalkylene glycols include at least two of the following:

[0128] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w The polyethylene glycol compound contains at least two of the following:

[0129] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of less than 10,000 g / mol. w and the second polyethylene glycol has a weight average molecular weight M greater than 25,000 g / mol. w It has.

[0130] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of less than 25,000 g / mol. w and the second polyethylene glycol has a weight average molecular weight M of at least 25,000 g / mol. w It has.

[0131] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of less than 25,000 g / mol.w and the second polyethylene glycol has a weight average molecular weight M of at least 250,000 g / mol. w It has.

[0132] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of less than 10,000 g / mol. w and the second polyethylene glycol has a weight average molecular weight M of at least 250,000 g / mol. w It has.

[0133] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w The first polyethylene glycol has a weight average molecular weight M of about 2,000 to about 10,000 g / mol. w and the second polyethylene glycol has a weight average molecular weight M of about 25,000 to about 350,000 g / mol. w It has.

[0134] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w The first polyethylene glycol has a weight average molecular weight M of about 2,000 to about 10,000 g / mol. w and the second polyethylene glycol has a weight average molecular weight M of about 15,000 to about 50,000 g / mol. w It has.

[0135] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w The first polyethylene glycol has a weight average molecular weight M of about 2,000 to about 10,000 g / mol. w and the second polyethylene glycol has a weight average molecular weight M of about 15,000 to about 25,000 g / mol. w It has.

[0136] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w The first polyethylene glycol has a weight average molecular weight M of about 2,000 to about 10,000 g / mol. w and the second polyethylene glycol has a weight average molecular weight M of about 25,000 to about 50,000 g / mol. w It has.

[0137] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w The first polyethylene glycol has a weight average molecular weight M of about 2,000 to about 10,000 g / mol. w and the second polyethylene glycol has a weight average molecular weight M of about 250,000 to about 350,000 g / mol. w It has.

[0138] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of less than 10,000 g / mol. w and the second polyethylene glycol has a weight average molecular weight M greater than 10,000 g / mol. w It has.

[0139] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of less than about 10,000 g / mol. w and the second polyethylene glycol has a weight average molecular weight M of at least about 50,000 g / mol. w It has.

[0140] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M wThe first polyethylene glycol has a weight average molecular weight M of about 2,000 to 8,000 g / mol. w or the first polyethylene glycol has a weight average molecular weight M of about 2,000 to 5,000 g / mol w and the second polyethylene glycol has a weight average molecular weight M of about 25,000 to 50,000 g / mol. w or the second polyethylene glycol has a weight average molecular weight M of about 15,000 to 25,000 g / mol w It has.

[0141] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w and a weight average molecular weight M between the at least two polyethylene glycols. w The difference in weight average molecular weight M ranges from 2:1 to 100,000:1, including any subranges and any value within the range. For example, in embodiments of the present disclosure, the polymer processing aid may be a polymer having different weight average molecular weights M w and a weight average molecular weight M between the at least two polyethylene glycols. w The difference is in the range of 5:1 to 100,000:1, or 2:1 to 1,000:1, or 5:1 to 1,000:1, or 2:1 to 500:1, or 5:1 to 500:1, or 2:1 to 100:1, or 5:1 to 100:1.

[0142] In one embodiment of the present disclosure, the polymer processing aids are of different weight average molecular weights M w and at least two polyethylene glycols of different M w are present in a molar ratio of 1:99 to 99:1, including any subranges and any value within the range. For example, in embodiments of the present disclosure, the polymer processing aid may comprise at least two polyethylene glycols of different weight average molecular weights, M wat least two polyethylene glycols in a molar ratio of 5:95 to 95:5, or 10:90 to 90:10, or 20:80 to 80:20, or 25:75 to 75:25, or 35:65 to 65:35, or 40:60 to 60:40, or about 50:50.

[0143] In one embodiment of the present disclosure, the amount of polyalkylene glycol (PAG) or the amount of polyethylene glycol (PEG) used as a polymer processing aid (PPA) is 100 to 5,000 ppm by weight (based on the weight of the thermoplastic polyolefin, such as linear polyethylene), including any subranges and any value within the range. Further optimized PPA addition levels and ranges for a given extrusion process can be readily determined by one of ordinary skill in the art. For example, in certain embodiments, the amount of polyalkylene glycol (PAG) or the amount of polyethylene glycol (PEG) used as a polymer processing aid (PPA) is from 100 to 4,000 ppm by weight (based on the weight of the thermoplastic polyolefin such as linear polyethylene), or from 100 to 3,000 ppm by weight, or from 200 to 3,000 ppm by weight, or from 100 to 2,000 ppm by weight, or from 200 to 2,000 ppm by weight, or from 300 to 2,000 ppm by weight, or from 400 to 2,000 ppm by weight, or from 200 to 1,500 ppm by weight, or from 300 to 1,500 ppm by weight, or from 400 to 1,500 ppm by weight, or from 200 to 1,200 ppm by weight, or from 300 to 1,200 ppm by weight, or from 400 to 1,200 ppm by weight.

[0144] In one embodiment of the present disclosure, polyalkylene glycol (PAG) or polyethylene glycol (PEG) is added to a thermoplastic polyolefin (e.g., linear polyethylene) using a masterbatch formulation containing the PAG or PEG. The term masterbatch is well known to those skilled in the art. Generally, the term "masterbatch" refers to the initial melt mixing of an additive, such as PEG, with a small amount of a given thermoplastic polyolefin (e.g., linear polyethylene), followed by blending (e.g., melt mixing or dry blending) the resulting "masterbatch" with the remaining bulk of the thermoplastic polyolefin (e.g., linear polymer).

[0145] In embodiments of the present disclosure, from about 0.1 to about 15.0 weight percent, or from about 0.5 to about 15.0 weight percent, or from about 0.5 to about 10.0 weight percent, or from about 0.1 to about 10.0 weight percent, or from about 0.1 to about 7.5 weight percent, or from about 0.5 to about 7.5 weight percent, or from about 0.5 to about 5.0 weight percent, or from about 0.1 to about 5.0 weight percent, or from about 1.0 to about 15.0 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 1.0 to about 7.5 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 0.1 to about 2.5 weight percent, or from about 0.5 to about 2.5 weight percent of the masterbatch is used in the blend with the bulk polymer (the weight percent of the masterbatch is based on the combined weight of the masterbatch and the bulk polymer).

[0146] In embodiments of the present disclosure, a masterbatch (e.g., of linear polyethylene) may contain an amount of PAG or PEG by weight (based on the weight of the masterbatch) of 500 to 50,000 ppm, including subranges and any number within the ranges. For example, in further embodiments of the present disclosure, the masterbatch may contain 500 to 40,000 ppm by weight (based on the weight of the masterbatch), or 500 to 35,000 ppm, or 500 to 40,000 ppm, or 500 to 25,000 ppm, or 1,000 to 40,000 ppm, or 1,000 to 35,000 ppm, or 1,000 to 30,000 ppm. 00 ppm, or 1,000 to 25,000 ppm, or 5,000 to 25,000 ppm, or 1,000 to 20,000 ppm, or 2,000 to 20,000 ppm, or 3,000 to 20,000, or 4,000 to 20,000 ppm, or 5,000 to 20,000 ppm, or 5,000 to 17,500, or 5,000 to 15,000, or is 5,000 to 12,500 ppm, or 2,500 to 15,000 ppm, or 5,000 to 15,000 ppm, or 7,500 to 15,000 ppm, or 7,500 to 12,500 ppm, or 5,000 to 50,000 ppm, or 7,500 to 50,000 ppm, or 10,000 to 50,000 ppm, or 10,000 to 35, The composition may contain PAG or PEG in an amount ranging from 10,000 to 25,000 ppm, or from 5,000 to 35,000 ppm, or from 5,000 to 30,000 ppm, or from 5,000 to 25,000 ppm, or from 15,000 to 30,000 ppm, or from 17,500 to 27,500 ppm, or from 20,000 to 25,000 ppm.

[0147] The polyalkylene glycol or polyethylene glycol used as a polymer processing aid (PPA) may be used in the form of a semi-solid or viscous liquid, or as a powder, pellets, or granules.

[0148] Polyamide / polyether block copolymers (i.e., poly(ether block amide), PEBA) In one embodiment of the present disclosure, a polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins comprises a poly(ether block amide) copolymer having polyamide blocks and polyether blocks. In this disclosure, such block copolymers having polyamide blocks and polyether blocks are also referred to as "polyamide / polyether block copolymers." In this disclosure, the term "poly(ether block amide) copolymer" can be abbreviated as "PEBA copolymer," and similarly, the term "poly(ether block amide)" can be abbreviated as "PEBA."

[0149] In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula: [ka] In the formula, PA is a polyamide block, PE is a polyether block, and p indicates the length of the PEBA copolymer and the total number of polyamide blocks and polyether blocks.

[0150] In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula: [ka] where EG is a first unspecified terminal group, B is an unspecified bridging group, and EG * is the second unspecified end group, and EG, B, and EG * is determined by the synthesis method used to produce the PEBA copolymer, where n represents the length of the polyamide block, x represents the length of the amide moiety within the polyamide block, m represents the length of the poly(ether) block, y represents the length of the ether moiety within the poly(ether) block, and p represents the length of the PEBA copolymer and the total number of polyamide blocks and polyether blocks.

[0151] In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula: [ka] In the formula, n represents the length of the polyamide block, x represents the length of the amide component in the polyamide block, m represents the length of the poly(ether) block, y represents the length of the ether component in the poly(ether) block, and p represents the length of the PEBA copolymer and the total number of polyamide blocks and polyether blocks.

[0152] In an embodiment of the present disclosure, the poly(ether-block-amide) copolymer ("PEBA copolymer") comprises polyamide blocks and polyether blocks.

[0153] Poly(ether-block-amide) copolymers suitable for use in embodiments of the present disclosure are described in U.S. Patent No. 5,986,005, which is incorporated herein by reference in its entirety. Suitable PEBA copolymers for use in embodiments of the present disclosure, including methods for their preparation, are further described in Chapter 9, "Thermoplastic Poly(Ether-b-Amide) Elastomers: Synthesis," by Malet, FLG, The Handbook of Condensation Thermoplastic Elastomers, 2005, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, pp. 243-262, and Chapter 10, "Poly(Ether-b-Amide) Thermoplastic Elastomers: Structure, Properties, and Applications," by Eustache, RP, The Handbook of Condensation Thermoplastic Elastomers, 2005, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, pp. 263-281, both of which are incorporated herein by reference in their entireties.

[0154] In one embodiment, the poly(ether-block-amide) copolymer is the result of a copolycondensation reaction between one or more polyamides having reactive end groups and one or more poly(oxyalkylenes), such as poly(oxyethylene), having reactive end groups. The reactive end groups of the polyamides include, for example, diamine chain ends and dicarboxyl chain ends. The reactive end groups of the poly(oxyalkylenes) include, for example, dicarboxyl chain ends, diol chain ends, and diamine chain ends.

[0155] In embodiments, poly(oxyalkylenes) with diamine chain ends are obtained by cyanoethylation and hydrogenation of alpha-omega-dihydroxyaliphatic poly(oxyalkylenes), also known in the art as polyether diols.

[0156] In embodiments, polyamides with dicarboxylic acid chain ends are obtained by condensation of bifunctional monomers, such as lactams (e.g., laurolactam), with alpha-omega-aminocarboxylic acids, or by condensation of dicarboxylic acids with diamines. The condensation polymerization may be carried out in the presence of a chain-limiting dicarboxylic acid.

[0157] In embodiments, the polyamide blocks in the PEBA copolymer are derived from polyamide-12 (PA-12), or polyamide-11 (PA-11), or polyamide-6 (PA-6), or polyamide-66 (PA-66).

[0158] In embodiments, the polyamide blocks in the PEBA copolymer are derived from polyamide-12 (PA-12).

[0159] In embodiments, the polyamide blocks in the PEBA copolymer are derived from polyamide-11 (PA-11).

[0160] In embodiments, the polyamide blocks in the PEBA copolymer are derived from polyamide-6 (PA-6).

[0161] The weight average molecular weight (e.g., M w and M n ) can be measured by techniques known in the art, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using narrow molecular weight distribution polymer standards.

[0162] In embodiments, the number average molecular weight M of the polyamide blocks in the PEBA copolymer n is about 100 to about 15,000 g / mol, or about 300 to about 15,000 g / mol, or about 600 to about 10,000 g / mol, or about 600 to about 5,000 g / mol.

[0163] In embodiments, the number average molecular weight M of the polyether blocks in the PEBA copolymer n is about 100 to about 15,000 g / mol, or about 100 to about 10,000 g / mol, or about 100 to about 6,000 g / mol, or about 100 to about 3,000 g / mol, or about 200 to about 6,000 g / mol, or about 200 to about 3,000 g / mol, or about 250 to about 2,000 g / mol, or about 750 to about 3,500 g / mol, or about 1,000 to about 3,000 g / mol.

[0164] In embodiments, the number average molecular weight M of the PEBA copolymer n is from 10,000 to 500,000 g / mol, including subranges therein and any number within this range. For example, in embodiments of the present disclosure, the number average molecular weight M of the PEBA copolymer is nis 10,000 to 400,000 g / mol, or 10,000 to 300,000 g / mol, or 10,000 to 250,000 g / mol, or 15,000 to 300,000 g / mol, or 20,000 to 300,000 g / mol, or 15,000 to 200,000 g / mol, or 20,000 to 200,000 g / mol, or 30,000 to 250,000 g / mol, or about 25,000 to about 75,000 g / mol, or about 50,000 to about 75,000 g / mol, or about 100,000 to about 150,000 g / mol.

[0165] In embodiments, the number average molecular weight M of the PEBA copolymer n is at least 10,000 g / mol, or at least 20,000 g / mol, or at least 25,000 g / mol, or greater than 25,000 g / mol, or at least 30,000 g / mol, or greater than 30,000 g / mol, or at least 35,000 g / mol, or greater than 35,000 g / mol, or at least 50,000 g / mol, or greater than 50,000 g / mol.

[0166] In embodiments, the weight average molecular weight M of the PEBA copolymer w is 25,000 to 500,000 g / mol, including subranges therein and any numerical value therein. For example, in embodiments of the present disclosure, the weight average molecular weight M of the PEBA copolymer is w is about 100,000 to about 250,000 g / mol, or about 100,000 to about 150,000 g / mol, or about 125,000 to about 150,000 g / mol.

[0167] In embodiments, the polyamide and polyether blocks within the PEBA copolymer may be randomly distributed.

[0168] In embodiments, the PEBA copolymer comprises polyamide blocks and polyether blocks, wherein the polyamide blocks comprise at least 50% by weight of the copolymer. In embodiments, the PEBA copolymer comprises polyamide blocks and polyether blocks, wherein the polyether blocks comprise at least 50% by weight of the copolymer. In further embodiments, the PEBA copolymer comprises polyamide blocks and polyether blocks, wherein the molar ratio of polyamide blocks to polyether blocks is within the range of 1:3 to 3:1, or 1:2 to 2:1, or 3:2 to 1:3, or 2:3 to 3:1, or about 1:1.

[0169] In one embodiment, PEBA copolymers having polyamide and polyether blocks can be prepared by the reaction of polyamide and polyether block precursors, for example, a lactam, a polyether diol, and a chain-limiting diacid can be reacted in the presence of a small amount of water to yield PEBA copolymers having polyamide and polyether blocks of variable length and statistically randomly distributed within the block copolymer chain.

[0170] In embodiments, the polyether blocks may be derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, each in its native state, and co-polycondensed with the polyamide blocks containing carboxyl chain ends. A chain limiter may be present during the polycondensation reaction to obtain a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed within the block copolymer.

[0171] In embodiments, the polyether blocks may be derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycols, which are first converted to polyether diamines by amination and then copolycondensed with polyamide blocks containing carboxyl chain ends. A chain limiter may be present during the polycondensation reaction, resulting in a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed within the block copolymer.

[0172] PEBA copolymers suitable for use in embodiments of the present disclosure are described in U.S. Patent Nos. 4,331,786, 4,115,475, 4,195,015, 4,839,441, 4,864,014, 4,230,838, 4,332,920, and 5,986,005, each of which is incorporated by reference in its entirety. Additional PEBA copolymers that can be used in some embodiments of the present disclosure are described in U.S. Patent No. 8,231,950.

[0173] In embodiments of the present disclosure, the polyether blocks may be derived from poly(oxyethylene), also known as polyethylene glycol (PEG).

[0174] In embodiments of the present disclosure, the polyether blocks may be derived from poly(oxypropylene), also known as polypropylene glycol (PPG).

[0175] In embodiments of the present disclosure, the polyether blocks may be derived from poly(tetramethylene ether) glycol (PTMG), also known as polytetramethylene oxide (PTMEO) or polytetrahydrofuran (PTHF).

[0176] In an embodiment of the present disclosure, the PEBA copolymer comprises i) polyamide blocks selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or mixtures thereof, and ii) polyether blocks selected from polyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran (PTHF), or mixtures thereof.

[0177] In an embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or a mixture thereof, and ii) a polyether block that is polyethylene glycol (PEG).

[0178] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG).

[0179] In some embodiments of the present disclosure, the PEBA copolymer comprises 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

[0180] In some embodiments of the present disclosure, the PEBA copolymer includes only one type of polyamide block and only one type of polyether block.

[0181] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-12 block comprises about 30-70 weight percent of the copolymer and the polyethylene glycol block comprises about 70-30 weight percent of the copolymer.

[0182] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-12 block comprises about 40-50 weight percent of the copolymer and the polyethylene glycol block comprises about 60-40 weight percent of the copolymer.

[0183] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-12 block comprises about 45 weight percent of the copolymer and the polyethylene glycol block comprises about 55 weight percent of the copolymer.

[0184] In one embodiment of the present disclosure, the PEBA copolymer comprises i) 10 to 20 polyamide blocks that are polyamide-12 (PA-12) and ii) 10 to 20 polyether blocks that are polyethylene glycol (PEG).

[0185] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 25,000 to about 75,000 g / mol.

[0186] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 50,000 to about 75,000 g / mol.

[0187] In one embodiment of the present disclosure, the PEBA copolymer comprises i) polyamide blocks that are polyamide-12 (PA-12) and ii) polyether blocks that are polyethylene glycol (PEG), and has a number average molecular weight, Mn, of about 66,100 g / mol.

[0188] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 100,000 to about 150,000 g / mol.

[0189] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 125,000 to about 150,000 g / mol.

[0190] In one embodiment of the present disclosure, the PEBA copolymer comprises i) polyamide blocks that are polyamide-12 (PA-12) and ii) polyether blocks that are polyethylene glycol (PEG), and has a weight average molecular weight, Mw, of about 134,000 g / mol.

[0191] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polyethylene glycol (PEG).

[0192] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-6 block comprises about 30-60 weight percent of the copolymer and the polyethylene glycol block comprises about 70-40 weight percent of the copolymer.

[0193] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-6 block comprises about 50-35 weight percent of the copolymer and the polyethylene glycol block comprises about 50-65 weight percent of the copolymer.

[0194] In one embodiment of the present disclosure, the PEBA copolymer comprises i) 10 to 20 polyamide blocks that are polyamide-6 (PA-6) and ii) 10 to 20 polyether blocks that are polyethylene glycol (PEG).

[0195] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-11 (PA-11) and ii) a polyether block that is polyethylene glycol (PEG).

[0196] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0197] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), wherein the polyamide-12 block comprises about 75-10 weight percent of the copolymer and the polytetrahydrofuran block comprises about 25-90 weight percent of the copolymer.

[0198] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), wherein the polyamide-12 block comprises about 80-60 weight percent of the copolymer and the polytetrahydrofuran block comprises about 20-40 weight percent of the copolymer.

[0199] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), wherein the polyamide-12 block comprises about 40-60 weight percent of the copolymer and the polytetrahydrofuran block comprises about 60-40 weight percent of the copolymer.

[0200] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), wherein the polyamide-12 block comprises about 30-10 weight percent of the copolymer and the polytetrahydrofuran block comprises about 70-90 weight percent of the copolymer.

[0201] In one embodiment of the present disclosure, the PEBA copolymer comprises i) 10 to 20 polyamide blocks that are polyamide-12 (PA-12) and ii) 10 to 20 polyether blocks that are polytetrahydrofuran (PTHF).

[0202] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 25,000 to about 75,000 g / mol.

[0203] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 40,000 to about 60,000 g / mol.

[0204] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 50,000 g / mol.

[0205] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0206] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-11 (PA-11) and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0207] In one embodiment of the present disclosure, the PEBA copolymer is a commercially available elastomer sold under the trade name PEBAX®.

[0208] In further specific embodiments of the present disclosure, the PEBA copolymer is a commercially available elastomer selected from the group consisting of: PEBAX 2533 SA 01, PEBAX 2533 SA 01 MED, PEBAX 2533 SD 02, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP 01, PEBAX 4011, PEBAX 4033 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP 01, PEBAX 4533 SA 01, PEBAX 4533 SA 01 MED, PEBAX 4533 SP 01, PEBAX 5513 SA 01, PEBAX 5513 SP 01, PEBAX 5533 SA 01, PEBAX 5533 SA 01 MED, PEBAX 5533 SN 70 BLACK, PEBAX 5533 SP 01, PEBAX 6333 SA 01, PEBAX 6333 SA 01 MED, PEBAX 6333 SP01, PEBAX 7033 SA 01, PEBAX 7033 SA 01 MED, PEBAX 7033 SP 01, PEBAX 7233 SA 01, PEBAX 7233 SA 01 MED, PEBAX 7233 SP 01, PEBAX 7433 SA 01 MED, PEBAX Clear 1200, PEBAX ES 9002 UV, PEBAX MH 1657, PEBAX MH2030, PEBAX MV 1074 SA 01, PEBAX MV 1074 SA 01 MED, PEBAX MV 1074 SP 01, PEBAX MV 2080, PEBAX MV 3000 SP 01, PEBAX RNEW® 30R51 SA 01, PEBAX RNEW 35R53 SP 01, PEBAX RNEW 40 R53 SP 01, PEBAX RNEW 55R53 SP 01, PEBAX RNEW 63R53 SP 01, PEBAX RNEW 70R53 SP 01, PEBAX RNEW 72R53 SP 01, PEBAX RNEW 80R53 SP 02, and mixtures thereof.

[0209] In one embodiment of the present disclosure, the PEBA copolymer is a commercially available elastomer sold under the trade name VESTAMID® or VESTAMID E.

[0210] In further specific embodiments of the present disclosure, the PEBA copolymer is a commercially available elastomer selected from the group consisting of: VESTAMID D, VESTAMID DX, VESTAMID E, VESTAMID EX, VESTAMID Care, VESTAMID Care ML, VESTAMID Care ME, VESTAMID Care ME-B, VESTAMID L, VESTAMID LX, VESTAMID NRG, VESTAMID Terra, VESTAMID X, and mixtures thereof.

[0211] In one embodiment of the present disclosure, the polymer processing aids are of different number average molecular weights M n It contains two poly(ether-block-amide) copolymers.

[0212] In one embodiment of the present disclosure, the polymer processing aids are of different number average molecular weights M n Two poly(ether-block-amide) copolymers with different M n are present in a molar ratio of 1:99 to 99:1, including any subranges and any value within the range. For example, in embodiments of the present disclosure, the polymer processing aid may comprise two poly(ether-block-amide) copolymers having different number average molecular weights, M n The two poly(ether-block-amide) copolymers are in a molar ratio of 5:95 to 95:5, or 10:90 to 90:10, or 20:80 to 80:20, or 25:75 to 75:25, or 35:65 to 65:35, or 40:60 to 60:40, or about 50:50.

[0213] In one embodiment of the present disclosure, the amount of PEBA copolymer used as a polymer processing aid (PPA) is 100 to 5,000 ppm by weight (based on the weight of the thermoplastic polyolefin), including any subranges and any value within the range. Further optimized PPA addition levels and ranges for a given extrusion process can be readily determined by one of ordinary skill in the art. For example, in certain embodiments, the amount of PEBA copolymer used as a polymer processing aid (PPA) is (based on the weight of the thermoplastic polyolefin) 100 to 4,000 ppm by weight, or 200 to 4,000 ppm by weight, or 100 to 3,000 ppm by weight, or 200 to 3,000 ppm by weight, or 100 to 2,000 ppm by weight, or 200 to 2,500 ppm by weight, or 300 to 2,500 ppm by weight, or 300 to 2,500 ppm by weight, or 400 to 2,500 ppm by weight, or 500 to 2,500 ppm by weight , or 750 to 4,000 ppm by weight, or 750 to 3,000 ppm by weight, or 750 to 2,500 ppm by weight, or 1,000 to 4,000 ppm by weight, or 1,000 to 3,000 ppm by weight, or 1,000 to 2,500 ppm by weight, or 1,000 to 2,250 ppm by weight, or 1,000 to 2,000 ppm by weight, or 1,250 to 1,750 ppm by weight, or 500 to 2,250 ppm by weight, or 500 to 2,000 ppm by weight, or 300 to 2,000 ppm by weight, or 200 to 2,000 ppm by weight.

[0214] In embodiments of the present disclosure, the amount of PEBA copolymer used as a polymer processing aid (PPA) is 200 to 1,500 ppm by weight (based on the weight of the thermoplastic polyolefin), or 300 to 1,500 ppm by weight, or 400 to 1,500 ppm by weight, or 500 to 1,500 ppm by weight, or 750 to 1,500 ppm by weight, or 300 to 1,250 ppm by weight, or 400 to 1,250 ppm by weight, or 500 to 1,250 ppm by weight, or 750 to 1,250 ppm by weight, or 200 to 1,000 ppm by weight (based on the weight of the thermoplastic polyolefin), or 300 to 1,000 ppm by weight, or 500 to 1,000 ppm by weight, or 750 to 1,000 ppm by weight.

[0215] In one embodiment of the present disclosure, the PEBA copolymer is added to a thermoplastic polyolefin (e.g., linear polyethylene) using a masterbatch formulation containing the PEBA copolymer. The term masterbatch is well known to those skilled in the art. Generally, the term "masterbatch" refers to the initial melt mixing of an additive, such as a PEBA copolymer, with a small amount of a given thermoplastic polyolefin (e.g., linear polyethylene), followed by blending (e.g., melt mixing or dry blending) the resulting "masterbatch" with the remaining bulk of the thermoplastic polyolefin (e.g., linear polymer).

[0216] In embodiments of the present disclosure, from about 0.1 to about 15.0 weight percent, or from about 0.5 to about 15.0 weight percent, or from about 0.5 to about 10.0 weight percent, or from about 0.1 to about 10.0 weight percent, or from about 0.1 to about 7.5 weight percent, or from about 0.5 to about 7.5 weight percent, or from about 0.5 to about 5.0 weight percent, or from about 0.1 to about 5.0 weight percent, or from about 1.0 to about 15.0 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 1.0 to about 7.5 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 0.1 to about 2.5 weight percent, or from about 0.5 to about 2.5 weight percent of the masterbatch is used in the blend with the bulk polymer (the weight percent of the masterbatch is based on the combined weight of the masterbatch and the bulk polymer).

[0217] In embodiments of the present disclosure, a masterbatch (e.g., of linear polyethylene) may contain an amount of PEBA copolymer in the range of 500 to 50,000 ppm by weight (based on the weight of the masterbatch), including subranges and any number within the range. For example, in further embodiments of the present disclosure, the masterbatch may contain 500 to 40,000 ppm by weight (based on the weight of the masterbatch), or 500 to 35,000 ppm, or 500 to 40,000 ppm, or 500 to 25,000 ppm, or 1,000 to 40,000 ppm, or 1,000 to 35,000 ppm, or 1,000 to 30,000 ppm. 0 ppm, or 1,000 to 25,000 ppm, or 5,000 to 25,000 ppm, or 1,000 to 20,000 ppm, or 2,000 to 20,000 ppm, or 3,000 to 20,000, or 4,000 to 20,000 ppm, or 5,000 to 20,000 ppm, or 5,000 to 17,500, or 5,000 to 15,000, or 5,000 to 12,500 ppm, or 2,500 to 15,000 ppm, or 5,000 to 15,000 ppm, or 7,500 to 15,000 ppm, or 7,500 to 12,500 ppm, or 5,000 to 50,000 ppm, or 7,500 to 50,000 ppm, or 10,000 to 50,000 ppm, or 10,000 to 35,0 The composition may contain PEBA copolymer in an amount ranging from 10,000 to 25,000 ppm, or from 5,000 to 35,000 ppm, or from 5,000 to 30,000 ppm, or from 5,000 to 25,000 ppm, or from 15,000 to 30,000 ppm, or from 17,500 to 27,500 ppm, or from 20,000 to 25,000 ppm.

[0218] PEBA copolymers used as polymer processing aids (PPAs) may be used in the form of a semi-solid or viscous liquid, or as powders, pellets, or granules.

[0219] <Polycaprolactone (PCL) polymer> In one embodiment of the present disclosure, the polymer processing aid comprises a polycaprolactone polymer.

[0220] In this disclosure, the term "polycaprolactone" or its abbreviation "PCL" is used to mean a polycaprolactone polymer, which is a polymer containing as repeat units i) an ester derived from the polycondensation of a hydroxycarboxylic acid, 6-hydroxyhexanoic acid, or ii) an ester derived from the ring-opening polymerization of epsilon-caprolactone (a cyclic ester containing a seven-membered ring) or its substituted derivatives (see, e.g., Labet M, Thielemans W., "Synthesis of Polycaprolactone: A Review," Chemical Society Reviews, December 2009, 38(12):3484-3504).

[0221] Thus, in this disclosure, the term "polycaprolactone" refers to a compound having the following general formula as repeating units: [ka] The polycaprolactone polymer has the formula:

[0222] A catalyst such as stannous octoate (ie, stannous (II) 2-ethylhexanoate) can be used to catalyze the ring-opening polymerization reaction.

[0223] It is also well known to those skilled in the art that polycaprolactone polymers can be prepared by ring-opening polymerization of epsilon-caprolactone using suitable hydroxyl-functionalized organic compounds as initiators. For example, the monools methanol, ethanol, and isopropanol, or the diols diethylene glycol and 1,4-butanediol can be used as initiators for the polymerization of epsilon-caprolactone.

[0224] In embodiments of the present disclosure, the polycaprolactone polymer may be a polycaprolactone monol, a polycaprolactone diol, a polycaprolactone triol, a polycaprolactone tetrol, or a mixture thereof. For example, in embodiments of the present disclosure, the polycaprolactone polymer may be a polycaprolactone having the general formula: [ka] or a polycaprolactone monol having the general formula: [ka] or a polycaprolactone diol having the general formula: [ka] or a polycaprolactone triol having the general formula: [ka] is a polycaprolactone tetrol having the formula wherein m, n, p, and q each represent a plurality of caprolactone units, and R is an organic group corresponding to the organic alcohol compound used to initiate the ring-opening polymerization of epsilon-caprolactone.

[0225] As noted above, the R group is a specific monol, diol, triol, tetrol, or polyol compound R—(OH) used as an initiator for the ring-opening polymerization of caprolactone. r For example, ethanol has an R group of -CH2CH2 where r is 1, diethylene glycol has an R group of -CH2CH2-O-CH2CH2- where r is 2, and 1,4-butanediol has an R group of -CH2CH2CH2CH2- where r is 2.

[0226] The present disclosure also contemplates the use of either unsubstituted or substituted polycaprolactone polymers, or both, as polymer processing aids. Such unsubstituted or substituted polycaprolactone polymers have the general formula: [ka] It can be expressed as wherein R is defined as above, R' is hydrogen, alkyl, alkoxy, aryl, cycloalkyl, alkylaryl, or arylalkyl moiety, each moiety having up to 20 carbon atoms; m is an integer representing the average number of repeating ester units, and r represents the number of hydroxy groups. In one embodiment, r is 1. In one embodiment, r is 2-8. In one embodiment, at least six of the R' moieties are hydrogen. In one embodiment, each R' is hydrogen. In one embodiment, r is 2-4.

[0227] Further specific examples of polycaprolactone polymers, including those derived from polyols and polyalkylene glycols, that can be used in embodiments of the present disclosure, and methods for their preparation are described in U.S. Pat. Nos. 3,169,945 and 4,751,112.

[0228] In one embodiment of the present disclosure, the polycaprolactone polymer is not a block copolymer. In one embodiment of the present disclosure, the polycaprolactone polymer is not a block copolymer that includes units that make up a polyoxyalkylene polymer.

[0229] In one embodiment of the present disclosure, the polycaprolactone polymer is a commercially available polyester sold under the trade name CAPA®.

[0230] In one embodiment of the present disclosure, the polycaprolactone polymer is a commercially available polyester sold under the trade names TONE®, CAPROMER®, and PLACCEL®.

[0231] In an embodiment of the present disclosure, the polycaprolactone polymer is made from the ring-opening polymerization of epsilon-caprolactone using an initiator selected from the group consisting of butanediol, diethylene glycol, hexanediol, monoethylene glycol, pentaerythritol, trimethylolpropane, neopentyl glycol, and butylethylpropanediol.

[0232] The weight average molecular weight (e.g., M w and M n ) can be measured by techniques known in the art, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using narrow molecular weight distribution polymer standards.

[0233] In an embodiment, the number average molecular weight M of the polycaprolactone polymer n is 100 to 32,000 g / mol, or 100 to 25,000 g / mol, or 100 to 20,000 g / mol, or 100 to 15,000 g / mol, or 100 to 12,500 g / mol, or 100 to 10,000 g / mol, or 200 to 15,000 g / mol, or 200 to 12,500 g / mol, or 200 to 10,000 g / mol, or 200 to 9,000 g / mol, or 200 to 8,000 g / mol, or 200 to 7,000 g / mol, or 200 to 6,000 g / mol, or 200 to 5, 000 g / mol, or 200 to about 4,500 g / mol, or 200 to 4,000 g / mol, or 200 to 3,000 g / mol, or 200 to 2,000 g / mol, or 1,000 to 10,000 g / mol, or 1,500 to 10,000 g / mol, or 2,000 to 10,000 g / mol, or 2,000 to 8,000 g / mol, or 2,000 to 6,000 g / mol, or 2,000 to 4,000 g / mol, or 1,000 to 32,000 g / mol, or 2,000 to 32,000 g / mol.

[0234] In an embodiment, the number average molecular weight M of the polycaprolactone polymer nFor example, in embodiments of the present disclosure, the number average molecular weight M of the polycaprolactone polymer is n is 30,000 to 100,000 g / mol, or 30,000 to 90,000 g / mol, or 35,000 to 90,000 g / mol, or 35,000 to 85,000 g / mol.

[0235] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 400 g / mol and derived from epsilon-caprolactone using a diol (e.g., 1,4 butane) as an initiator.

[0236] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 1,000 g / mol and derived from epsilon-caprolactone using a diol (e.g., 1,4 butane) as an initiator.

[0237] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 2,000 g / mol and derived from epsilon-caprolactone using a diol (e.g., 1,4 butane) as an initiator.

[0238] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 4,000 g / mol and derived from epsilon-caprolactone using a diol (e.g., 1,4 butanediol) as an initiator.

[0239] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 32,000 g / mol and derived from epsilon-caprolactone using a diol (e.g., 1,4 butanediol) as an initiator.

[0240] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 32,000 g / mol and derived from epsilon-caprolactone using a diol (e.g., 1,4 butanediol) as an initiator.

[0241] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 200 g / mol to about 10,000 g / mol, derived from epsilon-caprolactone using a linear monol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 400 g / mol to about 8,000 g / mol, derived from epsilon-caprolactone using a linear monol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 500 g / mol to about 6,000 g / mol, derived from epsilon-caprolactone using a linear monol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 750 g / mol to about 4,000 g / mol, derived from epsilon-caprolactone using a linear monol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 750 g / mol to about 2,000 g / mol, derived from epsilon-caprolactone using a linear monol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 500 g / mol to about 1,500 g / mol, derived from epsilon-caprolactone using a linear monol (e.g., cetyl alcohol) as an initiator.

[0242] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 200 g / mol to about 10,000 g / mol, derived from epsilon-caprolactone using a branched monol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 400 g / mol to about 8,000 g / mol, derived from epsilon-caprolactone using a branched monol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 500 g / mol to about 6,000 g / mol, derived from epsilon-caprolactone using a branched monol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 750 g / mol to about 4,000 g / mol, derived from epsilon-caprolactone using a branched monol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 750 g / mol to about 2,000 g / mol, derived from epsilon-caprolactone using a branched monol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monol polymer having a number average molecular weight Mn of about 500 g / mol to about 1,500 g / mol, derived from epsilon-caprolactone using a branched monol as an initiator.

[0243] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 200 g / mol to about 10,000 g / mol derived from epsilon-caprolactone using a linear diol (e.g., 1,4-butanediol, hexanediol, diethylene glycol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 400 g / mol to about 8,000 g / mol derived from epsilon-caprolactone using a linear diol (e.g., 1,4-butanediol, hexanediol, diethylene glycol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 500 g / mol to about 6,000 g / mol, derived from epsilon-caprolactone using a linear diol (e.g., 1,4-butanediol, hexanediol, diethylene glycol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 750 g / mol to about 4,000 g / mol, derived from epsilon-caprolactone using a linear diol (e.g., 1,4-butanediol, hexanediol, diethylene glycol) as an initiator.

[0244] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 200 g / mol to about 10,000 g / mol, derived from epsilon-caprolactone using a branched diol (e.g., neopentyl diol or butyl ethyl propane diol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 400 g / mol to about 8,000 g / mol, derived from epsilon-caprolactone using a branched diol (e.g., neopentyl diol or butyl ethyl propane diol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 500 g / mol to about 6,000 g / mol, derived from epsilon-caprolactone using a branched diol (e.g., neopentyl diol or butyl ethyl propane diol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 750 g / mol to about 4,000 g / mol, derived from epsilon-caprolactone using a branched diol (e.g., neopentyl diol or butyl ethyl propane diol) as an initiator.

[0245] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 100 g / mol to about 8,000 g / mol, derived from epsilon-caprolactone using a linear triol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 6,000 g / mol, derived from epsilon-caprolactone using a linear triol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 4,000 g / mol, derived from epsilon-caprolactone using a linear triol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 3,000 g / mol, derived from epsilon-caprolactone using a linear triol as an initiator.

[0246] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 100 g / mol to about 8,000 g / mol, derived from epsilon-caprolactone using a branched triol (e.g., trimethylolpropane) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 6,000 g / mol, derived from epsilon-caprolactone using a branched triol (e.g., trimethylolpropane) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 4,000 g / mol, derived from epsilon-caprolactone using a branched triol (e.g., trimethylolpropane) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 3,000 g / mol, derived from epsilon-caprolactone using a branched triol (e.g., trimethylolpropane) as an initiator.

[0247] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone tetrol polymer having a number average molecular weight Mn of about 100 g / mol to about 15,000 g / mol, derived from epsilon-caprolactone using a tetrol (e.g., pentaerythritol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone tetrol polymer having a number average molecular weight Mn of about 200 g / mol to about 10,000 g / mol, derived from epsilon-caprolactone using a tetrol (e.g., pentaerythritol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone tetrol polymer having a number average molecular weight Mn of about 200 g / mol to about 8,000 g / mol, derived from epsilon-caprolactone using a tetrol (e.g., pentaerythritol) as an initiator.

[0248] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone copolymer derived from epsilon-caprolactone using a polyalkylene glycol (e.g., polytetramethylene ether glycol, also known as polytetrahydrofuran) as an initiator.

[0249] In one embodiment of the present disclosure, the amount of polycaprolactone polymer used as a polymer processing aid (PPA) is 100 to 5,000 ppm by weight (based on the weight of the thermoplastic polyolefin), including any subranges and any value within the range. Further optimized PPA addition levels and ranges for a given extrusion process can be readily determined by one of ordinary skill in the art. For example, in certain embodiments, the amount of polycaprolactone polymer used as a polymer processing aid (PPA) is from 100 to 4,000 ppm by weight (based on the weight of the thermoplastic polyolefin), or from 200 to 4,000 ppm by weight, or from 100 to 3,000 ppm by weight, or from 200 to 3,000 ppm by weight, or from 100 to 2,000 ppm by weight, or from 200 to 2,500 ppm by weight, or from 300 to 2,500 ppm by weight, or from 300 to 2,500 ppm by weight, or from 400 to 2,500 ppm by weight, or from 500 to 2,500 ppm by weight. pm, or 750 to 4,000 ppm by weight, or 750 to 3,000 ppm by weight, or 750 to 2,500 ppm by weight, or 1,000 to 4,000 ppm by weight, or 1,000 to 3,000 ppm by weight, or 1,000 to 2,500 ppm by weight, or 1,000 to 2,250 ppm by weight, or 1,000 to 2,000 ppm by weight, or 1,250 to 1,750 ppm by weight, or 500 to 2,250 ppm by weight, or 500 to 2,000 ppm by weight, or 300 to 2,000 ppm by weight, or 200 to 2,000 ppm by weight.

[0250] In one embodiment of the present disclosure, the polycaprolactone polymer is added to a thermoplastic polyolefin (e.g., linear polyethylene) using a masterbatch formulation containing the polycaprolactone polymer. The term masterbatch is well known to those skilled in the art. In general, the term "masterbatch" refers to the initial melt mixing of an additive, such as a polycaprolactone polymer, with a small amount of a given thermoplastic polyolefin (e.g., linear polyethylene), followed by blending (e.g., melt mixing or dry blending) the resulting "masterbatch" with the remaining bulk of the thermoplastic polyolefin (e.g., linear polymer).

[0251] In embodiments of the present disclosure, from about 0.1 to about 15.0 weight percent, or from about 0.5 to about 15.0 weight percent, or from about 0.5 to about 10.0 weight percent, or from about 0.1 to about 10.0 weight percent, or from about 0.1 to about 7.5 weight percent, or from about 0.5 to about 7.5 weight percent, or from about 0.5 to about 5.0 weight percent, or from about 0.1 to about 5.0 weight percent, or from about 1.0 to about 15.0 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 1.0 to about 7.5 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 0.1 to about 2.5 weight percent, or from about 0.5 to about 2.5 weight percent of the masterbatch is used in the blend with the bulk polymer (the weight percent of the masterbatch is based on the combined weight of the masterbatch and the bulk polymer).

[0252] In embodiments of the present disclosure, a masterbatch (e.g., of linear polyethylene) may contain an amount of polycaprolactone polymer in the range of 500 to 50,000 ppm by weight (based on the weight of the masterbatch), including subranges and any number within the range. For example, in further embodiments of the present disclosure, the masterbatch may contain 500 to 40,000 ppm by weight (based on the weight of the masterbatch), or 500 to 35,000 ppm, or 500 to 40,000 ppm, or 500 to 25,000 ppm, or 1,000 to 40,000 ppm, or 1,000 to 35,000 ppm, or 1,000 to 30,000 ppm. ppm, or 1,000 to 25,000 ppm, or 5,000 to 25,000 ppm, or 1,000 to 20,000 ppm, or 2,000 to 20,000 ppm, or 3,000 to 20,000, or 4,000 to 20,000 ppm, or 5,000 to 20,000 ppm, or 5,000 to 17,500, or 5,000 to 15,000, or 5, 000 to 12,500 ppm, or 2,500 to 15,000 ppm, or 5,000 to 15,000 ppm, or 7,500 to 15,000 ppm, or 7,500 to 12,500 ppm, or 5,000 to 50,000 ppm, or 7,500 to 50,000 ppm, or 10,000 to 50,000 ppm, or 10,000 to 35,000 ppm pm, or 10,000 to 25,000 ppm, or 5,000 to 35,000 ppm, or 5,000 to 30,000 ppm, or 5,000 to 25,000 ppm, or 15,000 to 30,000 ppm, or 17,500 to 27,500 ppm, or 20,000 to 25,000 ppm.

[0253] Polycaprolactone (PCL) polymers used as polymer processing aids (PPAs) may be used in the form of semi-solid or viscous liquids, or as powders, pellets, or granules.

[0254] <High-pressure low-density polyethylene (LDPE)> In one embodiment of the present disclosure, the polymer processing aid comprises high pressure low density polyethylene LDPE.

[0255] In this disclosure, high pressure low density polyethylene (LDPE) is an ethylene homopolymer and is prepared by the free radical homopolymerization of ethylene.

[0256] While not wishing to be bound by theory, LDPE has a high degree of so-called long-chain branching (which can be as long as the main polymer backbone), which gives LDPE a non-linear microstructure. Thus, high-pressure low-density polyethylene (LDPE) is distinguished from linear polyethylene, which is made using an ethylene polymerization catalyst and has a linear polymer microstructure, as further described below. Further description of high-pressure low-density polyethylene LDPE as used in this disclosure can be found in the chapter entitled "Polyethylene, Low Density" by Norma Maraschin in the Kirk-Othmer Encyclopedia of Chemical Technology, first published March 18, 2005, which is incorporated herein by reference in its entirety.

[0257] In an embodiment of the present disclosure, high pressure low density polyethylene (LDPE) is prepared in either a tubular reactor or an autoclave reactor.

[0258] Tubular reactors operate at high pressures and temperatures in continuous mode. Typical operating pressures for tubular reactors are 2,000 to 3,500 bar. Operating temperatures can range from 140 to 340°C. Reactors are designed with large length-to-diameter ratios (e.g., 400 to 40,000) and may have multiple reaction zones in the form of elongated coils. High gas velocities (at least 10 m / s) are used to provide optimal heat transfer. Conversion rates in multizone systems are typically 22 to 30% per pass, but can reach 36 to 40%. Tubular reactors may have multiple injection points for adding monomer or initiator to different reaction zones at different temperatures.

[0259] Autoclave reactors may have a length-to-diameter ratio of 2 to 20 and may be single- or multi-stage. Typically, cold ethylene is passed through a hot reaction zone, and conversion can be controlled by the temperature difference between the incoming ethylene gas and the temperature of the autoclave reactor. Conversion rates are typically lower in autoclave reactors than in tubular reactors, which have a greater ability to remove the heat of polymerization, and are up to 23% per pass. Typical operating pressures for autoclave reactors are 1,100 to 2,000 bar. Average operating temperatures are 220 to 300°C, but temperatures can reach 340°C.

[0260] Various initiators may be used in each type of reactor to initiate the free radical polymerization of ethylene. Initiators include, but are not limited to, oxygen or one or more organic peroxides, such as di-tert-butyl peroxide, cumuyl peroxide, tert-butyl peroxypivalate, tert-butyl hydroperoxide, benzoyl peroxide, tert-amyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, and decanoyl peroxide. Chain transfer agents may also be used in each type of reactor to control the polymer melt index. Chain transfer agents include, but are not limited to, propane, n-butane, n-hexane, cyclohexane, propylene, 1-butene, and isobutylene.

[0261] In an embodiment of the present disclosure, the LDPE has a viscosity of about 0.910 g / cm, including any subrange or value within the range. 3 ~Approx. 0.940g / cm 3 For example, in an embodiment of the present disclosure, LDPE has a density of about 0.914 g / cm 3 ~Approx. 0.930g / cm 3 , or about 0.916 g / cm 3 ~Approx. 0.930g / cm 3 , or about 0.920 g / cm 3 ~Approx. 0.940g / cm 3 , or about 0.920 g / cm 3~Approx. 0.930g / cm 3 It has a density of

[0262] In an embodiment, the LDPE used in this disclosure has a melt index I2 of 0.1 to 20.0 g / 10 min, or 0.1 to 15.0 g / 10 min, or 0.1 to 10.0 g / 10 min.

[0263] In an embodiment, the LDPE used in this disclosure has a melt index, I2, of at least 1.0 g / 10 min, or at least 2.0 g / 10 min, or at least 2.5 g / 10 min, or at least 3.0 g / 10 min.

[0264] In an embodiment, the LDPE used in this disclosure has a viscosity of 1.0 to 10.0 g / 10 min, or 1.5 to 10.0 g / 10 min, or 2.0 to 10 g / 10 min, or 2.5 to 10.0 g / 10 min, or 3.0 to 10.0 g / 10 min, or 3.5 to 10.0 g / 10 min, or 4.0 to 10.0 g / 10 min, or 2.5 to 9.0 g / 10 min, or 2.5 to 8.5 g / 10 min, or It has a melt index I2 of 2.5 to 8.0 g / 10 min, or 3.0 to 9.0 g / 10 min, or 3.0 to 8.5 g / 10 min, or 3.0 to 8.0 g / 10 min, or 3.5 to 9.0 g / 10 min, or 3.5 to 8.5 g / 10 min, or 3.5 to 8.0 g / 10 min, or 4.0 to 9.0 g / 10 min, or 4.0 to 8.5 g / 10 min, or 4.0 to 8.0 g / 10 min.

[0265] In an embodiment, the LDPE used in this disclosure has a melt index, I2, of less than 1.0 g / 10 min. Such LDPE is sometimes referred to as a "frac melt" LDPE material. In a further embodiment, the LDPE used in this disclosure has a melt index, I2, of 0.01 to 1.0 g / 10 min, or 0.01 to less than 1.0 g / 10 min.

[0266] In an embodiment of the present disclosure, the high pressure low density polyethylene (LDPE) is a blend of LDPE materials having different densities and / or different melt indices I2.

[0267] In one embodiment, the low density polyethylene LDPE is a blend of tubular reactor made LDPE and autoclave reactor made LDPE.

[0268] In one embodiment, LDPE polymer blends are prepared by physically blending different high-pressure LDPEs (e.g., tubular reactor-produced LDPE and autoclave reactor-produced LDPE). Physical blending is intended to include processes in which two or more individual ethylene homopolymers are mixed after they are removed from the polymerization reaction zone. Physical blending of the individual LDPEs may be achieved by dry blending (e.g., tumble blending), extrusion blending (coextrusion), solution blending, melt blending, or other similar blending techniques known to those skilled in the art.

[0269] Polydispersity M w / M n is also called molecular weight distribution (MWD), and the weight average molecular weight M w The number average molecular weight M n The MWD of LDPE is defined as the intrinsic viscosity divided by the viscosity of the polymer. In embodiments of the present disclosure, the MWD of LDPE can be determined by gel permeation chromatography (GPC)-viscosity measurement. The GPC-viscosity measurement technique is based on the method of ASTM D6474-99 and analyzes polymer samples using a dual refractometer / viscometer detector system. This approach allows for online measurement of intrinsic viscosity and is well known to those skilled in the art.

[0270] In an embodiment of the present disclosure, the LDPE has an MWD greater than about 5.0. In an embodiment of the present disclosure, the LDPE has an MWD of about 8.0 to about 30.0.

[0271] The molecular weight of LDPE or its blends can be further described as unimodal, bimodal, or multimodal. By using the term "unimodal," we mean that the molecular weight distribution can be said to have only one maximum in the molecular weight distribution curve. The molecular weight distribution curve can be generated according to the method of ASTM D6474-99. By using the term "bimodal," we mean that the molecular weight distribution can be said to have two maxima in the molecular weight distribution curve. The term "multimodal" means that there are more than two maxima in such a curve.

[0272] In an embodiment of the present disclosure, the LDPE used has a unimodal, bimodal or multimodal molecular weight distribution.

[0273] In one embodiment of the present disclosure, the LDPE used is made in a tubular reactor and has a multimodal molecular weight distribution.

[0274] In an embodiment of the present disclosure, the LDPE used is made in an autoclave reactor and has a bimodal or multimodal molecular weight distribution.

[0275] In one embodiment of the present disclosure, a blend of LDPEs is used, the blend having a multimodal molecular weight distribution.

[0276] Antioxidant packages for stabilizing LDPE in embodiments of the present disclosure are well known in the art and may include phenolic and phosphite compounds. Two non-limiting examples of phenolic and phosphite stabilizers that may be added to LDPE in embodiments of the present disclosure are sold under the trade names IRGANOX® 1076 and IRGAFOS® 168, respectively. Phenolic compounds are sometimes referred to as "primary" antioxidants. Phosphite compounds are sometimes referred to as "secondary" antioxidants.

[0277] In embodiments of the present disclosure, the level of antioxidant present in the LDPE is from 0 to 2,000 ppm by weight (based on the weight of the LDPE). In further embodiments, the amount of antioxidant present in the LDPE is from 0 to 1,000 ppm, or from 0 to 500 ppm, or from 0 to 300 ppm by weight (based on the weight of the LDPE).

[0278] In embodiments of the present disclosure, the LDPE may be used in the form of a powder, pellets, granules, or other extrudable form.

[0279] In the present disclosure, the amount of LDPE used as a polymer processing aid is relatively low compared to the weight of the bulk thermoplastic polyolefin material (e.g., linear polyethylene). Thus, in embodiments of the present disclosure, LDPE is used in an amount of 1.0 to 25.0 weight percent of the total weight of LDPE and bulk thermoplastic polyolefin (e.g., linear polyolefin), inclusive of any subranges and any value within the range. For example, in embodiments of the present disclosure, the amount of LDPE comprises 1.0 to 20.0 weight percent, or 3.0 to 20.0 weight percent, or 5.0 to 20.0 weight percent, or 5.0 to 15.0 weight percent, or 5.0 to 12.5 weight percent, or 7.5 to 12.5 weight percent, or 7.5 to 15.0 weight percent, or 7.5 to 20.0 weight percent, or 3.0 to 17.5 weight percent, or 3.0 to 15.0 weight percent, or 2.5 to 20.0 weight percent, or 2.5 to 15.0 weight percent, or 2.5 to 12.5 weight percent, or 3.0 to 12.5 weight percent, or greater than 0 to 20.0 weight percent, or greater than 0 to 15.0 weight percent, or greater than 0 to 12.5 weight percent of the total weight of LDPE and thermoplastic polyolefin (e.g., linear polyethylene).

[0280] <Thermoplastic polyolefin (e.g., linear polyethylene)> While the present disclosure is generally useful for extrudable thermoplastic polyolefins, in one embodiment the present disclosure is particularly suited to improving the extrusion of linear polyethylene.

[0281] In one embodiment of the present disclosure, the extrudable or extruded thermoplastic composition (“extrudate”) comprises linear polyethylene and a monovalent metal salt of a carboxylic acid, but is substantially free of fluoroelastomers, fluoropolymers, and other perfluorinated alkane derivatives.

[0282] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") comprises linear polyethylene and a monovalent metal salt of an aliphatic carboxylic acid, but is substantially free of fluoroelastomers, fluoropolymers, and other perfluorinated alkane derivatives.

[0283] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") is a thermoplastic composition comprising a linear polyethylene and a monovalent metal salt of a carboxylic acid, poly(oxyalkylene) polymers (also known as polyalkylene glycols (PAGs)); poly(ether block amide) copolymers (the poly(ether block amide) copolymers comprising polyamide blocks and polyether blocks); Polycaprolactone (PCL) polymer; and High-pressure low-density polyethylene (LDPE) and one or more of It is substantially free of fluoroelastomers, fluoropolymers, and other perfluorinated alkane derivatives.

[0284] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") is a thermoplastic composition comprising a linear polyethylene and a monovalent metal salt of an aliphatic carboxylic acid, poly(oxyalkylene) polymers (also known as polyalkylene glycols (PAGs)); poly(ether block amide) copolymers (the poly(ether block amide) copolymers comprising polyamide blocks and polyether blocks); Polycaprolactone (PCL) polymer; and High-pressure low-density polyethylene (LDPE) and one or more of It is substantially free of fluoroelastomers, fluoropolymers, and other perfluorinated alkane derivatives.

[0285] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition (“extrudate”) comprises a linear polyethylene, a monovalent metal salt of a carboxylic acid, and a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG)), It is substantially free of fluoroelastomers, fluoropolymers, and other perfluorinated alkane derivatives.

[0286] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition (“extrudate”) comprises a linear polyethylene, a monovalent metal salt of an aliphatic carboxylic acid, and a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG)), It is substantially free of fluoroelastomers, fluoropolymers, and other perfluorinated alkane derivatives.

[0287] By "substantially free," it is meant that fluoroelastomers, fluoropolymers, and other perfluorinated alkane derivatives are present in an amount less than that which would improve the melt defect (e.g., melt fracture) performance of the thermoplastic composition during a melt extrusion process. In embodiments of the present disclosure, fluoroelastomers, fluoropolymers, and other perfluorinated alkane derivatives are less than about 1 weight percent, or less than about 0.5 weight percent, or less than 0.1 weight percent, or less than 500 ppm, or less than 100 ppm, or less than 90 ppm, or less than 75 ppm, or less than 50 ppm, or less than 25 ppm, or less than 10 ppm, or about 0 weight percent, or about 0 ppm, of the extrudable or extruded thermoplastic composition.

[0288] In one embodiment of the present disclosure, the primary or predominant component in the extrudable or extruded thermoplastic composition ("extrudate") is linear polyethylene. In embodiments, such "extrudate" comprises linear polyethylene in an amount of at least about 70%, or at least about 75%, or at least about 80%, or at least about 85% by weight of the extrudate composition.

[0289] The extrudable or extruded thermoplastic composition ("extrudate"), in embodiments of the present disclosure, may comprise a mixture of more than one different types of linear polyethylene.

[0290] Unlike high-pressure low-density polyethylene (LDPE), which has a branched polymer microstructure (due to the presence of a large amount of long-chain branching), linear polyethylene is made in a high-pressure free-radical polymerization process. Linear polyethylene is made using transition metal-based olefin polymerization catalysts and has a linear polymer microstructure.

[0291] Olefin polymerization catalysts used to prepare linear polyethylene are well known in the art: linear polyethylene can be made using so-called single-site or multi-site polymerization catalysts. Multi-site polymerization catalysts, such as Ziegler-Natta catalysts and Phillips (chromium-based) catalysts, are well known to those skilled in the art. Single-site catalysts, such as metallocene catalysts, constrained geometry catalysts, phosphinimine catalysts, and catalysts with tetradentate ligands, are also well known to those skilled in the art.

[0292] Linear polyethylene includes homogeneously branched linear ethylene polymers such as those described in U.S. Pat. No. 3,645,992; heterogeneously branched linear ethylene polymers such as those described in U.S. Pat. No. 4,076,698; and homogeneously branched linear ethylene polymers containing long chain branching (less long chain branching than LDPE), sometimes referred to as "substantially linear ethylene polymers," as described in U.S. Pat. Nos. 5,272,236, 5,278,272, 5,582,923, and 5,733,155; and / or blends thereof.

[0293] The term "homogeneously branched" refers to a linear ethylene copolymer in which the α-olefin comonomer is randomly distributed within the copolymer molecules, with substantially all of the copolymer molecules having the same ethylene to α-olefin monomer ratio, such as a composition distribution index (CDBI) greater than about 50 weight percent, or in some embodiments greater than about 75 weight percent, or greater than about 80 weight percent, or greater than about 90 weight percent. 50 They are characterized by a relatively narrow short chain branching distribution, as indicated by: Homogeneously branched ethylene copolymers are generally prepared using single-site olefin polymerization catalysts.

[0294] The term "heterogeneously branched" as used herein refers to a composition distribution index (CDBI) of less than about 75 weight percent, or in some embodiments, less than about 50 weight percent. 50 It is used to refer to linear ethylene copolymers characterized by a relatively broad short chain branching distribution, as indicated by: Heterogeneously branched ethylene copolymers are generally prepared using multi-site olefin polymerization catalysts.

[0295] In an embodiment of the present disclosure, the linear polyethylene has the general formula CH=CHR 3 [R in the formula 3is hydrogen or an alkyl group. 3 is a hydrocarbon group having up to 10 carbon atoms. In another embodiment of the present disclosure, R 3 is a hydrocarbon group having 1 to 6 carbon atoms, and may be, for example, an aromatic group such as a phenyl group (i.e., styrene as an alpha olefin) or an n-hexyl group (i.e., 1-octene as an alpha olefin).

[0296] In an embodiment of the present disclosure, the linear polyethylene is an ethylene homopolymer or an ethylene copolymer.

[0297] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and a C3-C 12 and one or more polymerized alpha olefins selected from the group consisting of alpha olefins.

[0298] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and a C3-C 12 and one or more polymerized alpha olefins selected from the group consisting of alpha olefins, wherein the polymerized ethylene comprises at least 85 weight percent of the ethylene copolymer.

[0299] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and a C3-C 12 and one or more polymerized alpha olefins selected from the group consisting of alpha olefins, wherein the polymerized ethylene comprises at least 90 weight percent of the ethylene copolymer.

[0300] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more polymerized alpha olefins selected from the group comprising propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and 1-octadecene.

[0301] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more polymerized alpha olefins selected from the group comprising 1-butene, 1-hexene, and 1-octene.

[0302] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more alpha olefins selected from the group comprising 1-butene, 1-hexene, and 1-octene, wherein the polymerized ethylene comprises at least 85 weight percent of the ethylene copolymer.

[0303] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more polymerized alpha-olefins selected from the group comprising 1-butene, 1-hexene, and 1-octene, wherein the polymerized ethylene comprises at least 90 weight percent of the ethylene copolymer.

[0304] Linear polyethylene can be prepared by any conventional process known in the art, such as gas phase, slurry phase, or solution phase polymerization, using one or more olefin polymerization catalysts.

[0305] In gas-phase polymerization processes, transition metal polymerization catalysts can be immobilized on a suitable support material, and the resulting particulate catalyst can be used in a fluidized-bed polymerization process. Generally, fluidized-bed gas-phase polymerization reactors use a "bed" of polymer and catalyst particles fluidized by a stream of at least partially gaseous monomer and other optional components. Heat is generated by the enthalpy of polymerization of the monomer (and optional comonomer(s)) flowing through the bed. Unreacted monomer and other optional gaseous components exit the fluidized bed and contact a cooling system to remove this heat. The cooled gas stream containing monomer and optional other components (such as condensable liquids) is then recycled through the polymerization zone, along with "make-up" monomer, to replace that polymerized in the previous pass. Simultaneously, polymer product is removed from the reactor. As will be appreciated by those skilled in the art, the "fluidized" nature of the polymerization bed helps minimize the formation of localized temperature gradients by evenly distributing / mixing the heat of reaction.

[0306] In embodiments, reactor pressure for gas phase processes can vary from about atmospheric to about 600 psig. In another embodiment, the pressure can range from about 100 psig (690 kPa) to about 500 psig (3448 kPa). In yet another embodiment, the pressure can range from about 200 psig (1379 kPa) to about 400 psig (2759 kPa). In yet another embodiment, the pressure can range from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).

[0307] In a slurry-phase polymerization process, a transition metal polymerization catalyst is immobilized on a suitable support material, and the resulting particulate catalyst can be used in a slurry-phase polymerization process. The slurry-phase polymerization process is carried out in the presence of a hydrocarbon diluent, such as an alkane (including, for example, an isoalkane), an aromatic, or a cycloalkane. The diluent may be an alpha-olefin comonomer used in the copolymerization. Some non-limiting alkane diluents include propane, butane (i.e., normal butane and / or isobutane), pentane, hexane, heptane, and octane. The monomer may be soluble (or miscible) in the diluent, but the polymer (under polymerization conditions) is not. In embodiments, the polymerization temperature is from about 5°C to about 200°C, or less than about 120°C, or from about 10°C to about 100°C. The reaction temperature is selected so that ethylene or alpha-olefin homopolymers or copolymers are produced in the form of solid particles. The reaction pressure is influenced by the selection of the diluent and reaction temperature. For example, in embodiments, pressures can range from 15-45 atmospheres (about 220-660 psi or about 1,500-4,600 kPa) when using isobutane as the diluent to about twice that when using propane (i.e., 30-90 atmospheres - about 440-1,300 psi or about 3,000-9,100 kPa). Pressure in a slurry process must be maintained high enough so that at least a portion of the ethylene and / or alpha-olefins are polymerized in the liquid phase. The reaction is typically carried out in a jacketed, closed-loop reactor equipped with an internal agitator (e.g., an impeller) and at least one settling leg. Catalyst, monomer, and diluent are fed to the reactor as a liquid or suspension. The slurry circulates through the reactor, and the jacket is used to control the reactor temperature. The slurry enters the settling leg through a series of pressure-reducing valves, where the pressure is reduced to flash the diluent and unreacted monomers, and the polymer is recovered, usually in a cyclone. The diluent and unreacted monomer are recovered and recycled back to the reactor.

[0308] Solution polymerization processes for the polymerization or copolymerization of olefins, such as ethylene and alpha-olefins, are well known in the art. Solution processes are generally carried out in the presence of an inert hydrocarbon solvent in which the resulting polyolefin is soluble under the polymerization conditions used. In one embodiment of the present disclosure, the solvent used in the solution phase polymerization process is either unsubstituted or C 1-4 C optionally substituted with an alkyl group 5-12 The solvent is selected from the group consisting of hydrocarbons, including hydrocarbon solvents such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, and hydrogenated naphtha. Another example of a commercially available solvent suitable for use in embodiments of the present disclosure is "Isopar E" (C 8-12 Aliphatic solvents (Exxon Chemical Co.) are examples of suitable polymerization solvents. The polymerization temperature in a conventional solution process can be from about 80°C to about 300°C. In one embodiment of the present disclosure, the polymerization temperature in a solution process is from about 120°C to about 250°C. The polymerization pressure in a solution process is a "medium-pressure process," meaning that the pressure in the reactor is less than about 6,000 psi (about 42,000 kilopascals or kPa). In one embodiment of the present disclosure, the polymerization pressure in a solution process can be from about 10,000 to about 40,000 kPa, or from about 14,000 to about 22,000 kPa (i.e., from about 2,000 psi to about 3,000 psi).

[0309] In solution polymerization, the monomers are dissolved / dispersed in a solvent before being fed to the reactor (or in the case of gaseous monomers, the monomers can be fed to the reactor so that they dissolve in the reaction mixture). Before mixing, the solvent and monomers are generally purified to remove potential catalyst poisons such as water, oxygen, or metal impurities. Purification of the feedstock is carried out according to standard practices in the art; for example, molecular sieves, alumina beds, and oxygen removal catalysts are used to purify the monomers. The solvent itself (e.g., methylpentane, cyclohexane, hexane, or toluene) can also be treated similarly.

[0310] The feedstock may be heated or cooled before being fed to the reactor.

[0311] Generally, the olefin polymerization catalyst components (e.g., olefin polymerization catalyst molecule, ionic activator, and optionally alkylaluminoxane) may be premixed in a solvent for reaction or fed as separate streams to a solution-phase polymerization reactor. In some cases, premixing may be desirable to allow time for the catalyst components to react before entering the reaction. Such "in-line mixing" techniques are described in U.S. Pat. No. 5,589,555.

[0312] The solution phase polymerization process can be carried out in one or more stirred tank reactors (eg, continuous stirred tank reactors), loop reactors, etc., which can be configured in series or parallel with one another.

[0313] Examples of well-known linear polyethylenes that may be used in embodiments of the present disclosure include linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and very low density polyethylene (VLDPE).

[0314] In this disclosure, high density polyethylene (HDPE) is an ethylene homopolymer or an ethylene copolymer with another alpha olefin (e.g., 1-butene, 1-hexene, and / or 1-octene), with a density of about 0.949 g / cm 3 In an embodiment, the HDPE has a density of at least 0.950 g / cm 3 , or at least 0.951 g / cm 3 , or at least 0.952 g / cm 3 , or at least 0.953 g / cm 3 In an embodiment, HDPE is an ethylene homopolymer or an ethylene copolymer with another alpha olefin (such as 1-butene, 1-hexene, and / or 1-octene) having a density of about 0.950 g / cm. 3 ~Approx. 0.970g / cm 3 , or about 0.950 g / cm 3 ~Approx. 0.965g / cm 3The polymer is an ethylene homopolymer or an ethylene copolymer with another alpha olefin (such as, for example, 1-butene, 1-hexene, and / or 1-octene) having a density of 0.1 to 1.0 MPa.

[0315] In this disclosure, linear low density polyethylene (LLDPE) is an ethylene homopolymer or an ethylene copolymer with another alpha olefin (e.g., 1-butene, 1-hexene, and / or 1-octene) having a viscosity of about 0.910 g / cm, including any subrange or value within the range. 3 ~Approx. 0.940g / cm 3 In an embodiment of the present disclosure, the LLDPE has a density of 0.910 to 0.936 g / cm 3 , or 0.912 to 0.936 g / cm 3 , or 0.910 to 0.932 g / cm 3 , or 0.912 to 0.932 g / cm 3 It has a density of

[0316] In this disclosure, medium density polyethylene (MDPE) is an ethylene copolymer with another alpha olefin (e.g., 1-butene, 1-hexene, and / or 1-octene, etc.) having a viscosity of about 0.940 g / cm, including any subrange or value within the range. 3 ~Approx. 0.949g / cm 3 It has a density of

[0317] In this disclosure, very low density polyethylene is an ethylene copolymer with another alpha olefin (such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and / or 1-octene) and has a density of about 0.910 g / cm 3 In embodiments, VLDPE is a copolymer of ethylene with another alpha olefin (such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and / or 1-octene) and has a density of less than about 0.880 g / cm. 3 ~Approx. 0.910g / cm 3 , or about 0.880 g / cm 3~Approx. 0.905g / cm 3 , or about 0.880 g / cm 3 ~Approx. 0.902g / cm 3 It has a density of

[0318] In an embodiment of the present disclosure, the linear polyethylene has a viscosity of 0.900 to 0.955 g / cm 3 , or 0.900 to 0.950 g / cm 3 It has a density of

[0319] In one embodiment of the present disclosure, the linear polyethylene is selected from the group consisting of linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), very low density polyethylene (VLDPE), and mixtures thereof.

[0320] Depending on the polymerization process and type of olefin polymerization catalyst used, in embodiments of the present disclosure, the linear polyethylene may have a weight average molecular weight M of at least about 10,000 g / mol and up to about 1,500,000 g / mol, including any subrange or value within the range. w For example, in further embodiments, the linear polyethylene may have a molecular weight of from about 50,000 to about 1,000,000 g / mol, or from about 100,000 to about 1,000,000 g / mol, or from about 75,000 to about 750,000 g / mol, or from about 100,000 to about 750,000 g / mol, or from about 75,000 to about 500,000 g / mol, or from about 100,000 to about 500,000 g / mol, or from about 50,000 to about 350,000 g / mol, or A weight average molecular weight M of about 75,000 to about 350,000 g / mol, or about 100,000 to about 350,000 g / mol, or about 50,000 to about 300,000 g / mol, or about 75,000 to about 300,000 g / mol, or about 100,000 to about 300,000 g / mol, or about 50,000 to about 250,000 g / mol, or about 75,000 to about 250,000 g / mol, or about 100,000 to about 250,000 g / mol. w It has.

[0321] In embodiments of the present disclosure, the linear polyethylene has a molecular weight distribution M of about 2.0 to about 12.0, including any subrange or value within the range. w / M n For example, in embodiments of the present disclosure, the linear polyethylene has an M of about 2.0 to about 10.0, or about 2.0 to about 8.0, or about 2.0 to about 5.0. w / M n It has a value.

[0322] In embodiments of the present disclosure, the linear polyethylene is characterized by a melt index, I2, determined according to ASTM D1238, Condition E, at 190°C. In embodiments of the present disclosure, the linear polyethylene has a melt index, I2, of 0.1 to 20.0 g / 10 min, including any subrange within the range or any value within the range. For example, in embodiments of the present disclosure, the linear polyethylene has a melt index, I2, of 0.1 to 15.0 g / 10 min, or 0.1 to 10.0 g / 10 min, or 0.3 to 15.0 g / 10 min, or 0.3 to 10.0 g / 10 min, or 0.1 to 5.0 g / 10 min, or 0.3 to 5.0 g / 10 min, or 0.5 to 15.0 g / 10 min, or 0.5 to 10.0 g / 10 min, or 0.5 to 5.0 g / 10 min.

[0323] In embodiments of the present disclosure, the linear polyethylene selected from the group consisting of LLDPE, MDPE, HDPE, VLPDE, and mixtures thereof can be used in the form of powder, pellets, granules, or other extrudable form.

[0324] In an embodiment of the present disclosure, the linear polyethylene is LLDPE.

[0325] In an embodiment of the present disclosure, the linear polyethylene is an LLDPE having a melt index I2 of 0.1 to 10.0 g / 10 min, or 0.5 to 5.0 g / 10 min.

[0326] In one embodiment of the present disclosure, the linear polyethylene has a molecular weight of about 0.910 g / cm 3 ~Approx. 0.936g / cm 3and a melt index I2 of 0.1 to 10.0 g / 10 min.

[0327] In one embodiment of the present disclosure, the linear polyethylene has a molecular weight of about 0.910 g / cm 3 ~Approx. 0.936g / cm 3 and a melt index I2 of 0.1 to 5.0 g / 10 min.

[0328] In embodiments of the present disclosure, the linear polyethylene has a molecular weight distribution M of about 2.0 to about 12.0, including any subrange or value within the range. w / M n For example, in an embodiment of the present disclosure, the LLDPE has an M of about 2.0 to about 10.0, or about 2.0 to about 8.0, or about 2.0 to about 5.0. w / M n It has a value.

[0329] In some embodiments of the present disclosure, the linear polyethylene comprises a minor amount, defined as less than 3.0 weight percent (wt%, based on the total weight of the linear polymer and LDPE), of high-pressure low-density polyethylene (LDPE) having a melt index of less than about 1.0 g / 10 min. In some embodiments of the present disclosure, the homogeneously branched linear polyethylene comprises a minor amount, defined as less than 3.0 weight percent (wt%, based on the total weight of the linear polymer and LDPE), of high-pressure low-density polyethylene (LDPE) having a melt index of less than about 1.0 g / 10 min. While not wishing to be bound by theory, the presence of a minor amount of LDPE having a melt index of less than about 1.0 g / 10 min may be useful in various end uses.

[0330] This disclosure relates to the extrusion of thermoplastic compositions in a wide range of extrusion processes, including profile extrusion, in which extruded parts such as pipes or profile parts are prepared by extruding molten plastic through a shaping die, and film extrusion, in which plastic films are prepared by extruding molten plastic through a slit or annular die.

[0331] In one embodiment of the present disclosure, a film extrusion process is used, such as, for example, a "blown film" extrusion process, which is described in more detail in the Examples section below.

[0332] For film applications, in one embodiment of the present disclosure, it is preferred that no pigments or fillers be added to the polyolefin (e.g., linear polyethylene) to produce a clear or relatively clear extruded film. For other applications, such as wire and cable (electrical or optical), in one embodiment of the present disclosure, the polyolefin (e.g., linear polyethylene) may include pigments / fillers and other adjuvants, such as carbon black.

[0333] The thermoplastic polyolefins, such as linear polyethylene, used in the present disclosure may further comprise fillers, antioxidants (such as primary antioxidants and, optionally, secondary antioxidants), pigments, opacifying agents, static control agents such as glycerol monostearate, lubricants such as fatty acid esters, light stabilizers (such as hindered amine light stabilizers), zinc oxide, antiblocking agents, and other adjuvants. Care should be taken when using antiblocking agents (such as silica or talc) and / or hindered amine light stabilizers, as they can adversely affect the surface appearance of extruded compositions containing the polyolefin, as is known to those skilled in the art.

[0334] In embodiments of the present disclosure, an antioxidant (either a primary antioxidant alone or, optionally, a combination of a primary antioxidant and a secondary antioxidant) is added to a polyolefin (e.g., linear polyethylene) in an amount of from about 0.01 to about 2 weight percent, or from about 0.01 to about 1 weight percent.

[0335] In one embodiment, the linear polyethylene includes a primary antioxidant and a secondary antioxidant.

[0336] In one embodiment, the linear polyethylene comprises a hindered phenol primary antioxidant and a phosphorus-containing secondary antioxidant.

[0337] In embodiments, further description of additives that may be added to thermoplastic polyolefins such as linear polyethylene is set forth below, including primary antioxidants; secondary antioxidants; UV absorbers and light stabilizers; polyamide stabilizers; basic co-stabilizers; nucleating agents; slip agents; fillers, anti-blocking agents, and reinforcing agents, as well as various additional additives.

[0338] In embodiments of the present disclosure, additives added to thermoplastic polyolefins (e.g., linear polyethylene) may be used in amounts of 100 to 5,000 ppm, or 100 to 3,000 ppm, or 200 to 3,000 ppm, or 200 to 2,000 ppm, or 300 to 1,500 ppm, or 400 to 1,200 ppm (based on the weight of the thermoplastic polyolefin).

[0339] <Primary antioxidant> In an embodiment of the present disclosure, the primary antioxidant is selected from alkylated mono-phenols (also referred to herein as "hindered phenol primary antioxidants"), such as 2,6-di-tert-butyl-4-methylphenol; 2-tert-butyl-4,6-dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol; 2,6-di-tert-butyl-4-isobutylphenol; 2,6-dicyclopentyl-4-methylphenol; 2-(alpha-methylcyclohexyl)-4,6 dimethylphenol; 2,6-di-octadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol; and 2,6-di-tert-butyl-4-methoxymethylphenol. Suitable hindered phenolic antioxidants that can be used in embodiments of the present disclosure are sold by BASF Corporation under the trademarks IRGANOX 1010 (CAS Registry Number 6683-19-8) and IRGANOX 1076 (CAS Registry Number 2082-79-3).

[0340] In an embodiment of the present disclosure, the primary antioxidant is selected from alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol; 2,5-di-tert-butylhydroquinone; 2,5-di-tert-amyl-hydroquinone; and 2,6-diphenyl-4-octadecyloxyphenol.

[0341] In an embodiment of the present disclosure, the primary antioxidant is selected from hydroxylated thiodiphenyl ethers such as 2,2′-thio-bis-(6-tert-butyl-4-methylphenol); 2,2′-thio-bis-(4-octylphenol); 4,4′-thio-bis-(6-tert-butyl-3-methylphenol); and 4,4′-thio-bis-(6-tert-butyl-2-methylphenol).

[0342] In an embodiment of the present disclosure, the primary antioxidant is selected from alkylidene bisphenols, such as, for example: 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol); 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol); 2,2'-methylene-bis-(4-methyl-6-(alpha-methylcyclohexyl)phenol); 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol); 2,2'-methylene-bis-(6-nonyl-4-methylphenol). 2,2'-methylene-bis-(6-nonyl-4-methylphenol); 2,2'-methylene-bis-(6-(alpha-methylbenzyl)-4-nonylphenol); 2,2'-methylene-bis-(6-(alpha,alpha-dimethylbenzyl)-4-nonyl-phenol); 2,2'-methylene-bis-(4,6-di-tert-butylphenol); 2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol); 4,4'-methylene-bis-(2,6-di-tert-butylphenol) 4,4'-Methylene-bis-(6-tert-butyl-2-methylphenol);1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenol)butane 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol;1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecyl-mercaptobutane;Ethylene glycol di-(2-(3'-tert-butyl-2'hydroxy-5'methylbenzyl)-6-tert-butyl-4-methylphenyl)terephthalate; and other phenols such as monoacrylate esters of bisphenols such as ethylidenebis-2,4-di-t-butylphenol monoacrylate.

[0343] In an embodiment of the present disclosure, the primary antioxidant is a benzyl compound, such as 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene; bis-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate; bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol-terephthalate; 1,3,5-tris-(3,5-di-tert-butyl-4,10 hydroxybenzyl)isocyanurate; 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate; dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate; monoethyl The calcium salt of 3,5-di-tertbutyl-4-hydroxybenzylphosphonate; and 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0344] In an embodiment of the present disclosure, the primary antioxidant is selected from acylaminophenols such as 4-hydroxy-lauric acid anilide; 4-hydroxy-stearic acid anilide; 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine; and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

[0345] In an embodiment of the present disclosure, the primary antioxidant is selected from esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with mono- or polyhydric alcohols such as, for example, methanol; diethylene glycol; octadecanol; triethylene glycol; 1,6-hexanediol; pentaerythritol; neopentyl glycol; tris-hydroxyethyl isocyanurate; thidiethyleneglycol; and dihydroxyethyl oxalic acid diamide.

[0346] In an embodiment of the present disclosure, the primary antioxidant is selected from amides of beta-(3,5-di-tert-butyl-4-hydroxyphenol)-propionic acid, such as N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine; N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine; and N,N'-di(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

[0347] In embodiments of the present disclosure, the primary antioxidant may be used in an amount of 100 to 5,000 ppm, or 100 to 3,000 ppm, or 200 to 3,000 ppm, or 200 to 2,000 ppm, or 300 to 1,500 ppm, or 400 to 1,200 ppm (based on the weight of the thermoplastic polyolefin).

[0348] <Secondary antioxidant> In embodiments of the present disclosure, the secondary antioxidants are phosphites and phosphonites (also referred to herein as "phosphorus-containing secondary antioxidants"), such as triphenyl phosphite; diphenyl alkyl phosphites; dialkyl phenyl phosphites; tris(nonyl-phenyl)phosphite [WESTON® 399, available from SI Group]; phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester [WESTON 705, CAS Reg. No. 939402-02-5, available from SI Group]; trilauryl phosphite; trioctadecyl phosphite; distearyl pentaerythritol diphosphite; tris(2,4-di-tert-butylphenyl)phosphite [IRGAFOS 168, available from BASF]; diisodecylpentaerythritol diphosphite; 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite; bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite [IRGAFOS 38, available from BASF]; 2,2',2"-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite [IRGAFOS 12, available from BASF]; bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite tristearyl sorbitol triphosphite; tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonate; 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphospepin [SUMILIZER® GP]; bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphate; bis(2,4-dicumylphenyl)pentaerythritol diphosphate; distearyl pentaerythritol diphosphate; diisodecyl pentaerythritol diphosphate;Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite [ULTRANOX® 626, available from SI Group]; bis(2,6-di-tert-butyl-4-methylpenyl)pentaerythritol diphosphite; bisisodecyloxy-pentaerythritol diphosphite; bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite; bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite; tetrakis(2,4-di-tert-butylphenyl)4,4'-bipheylene-diphosphonite [IRGAFOS P-EPQ, available from BASF]; bis(2,4-dicumylphenyl)pentaerythritol diphosphite [DOVERPHOS® S9228-T or DOVERPHOS S9228-CT] and PEPQ® (CAS Reg. No. 119345-01-06), a commercially available diphosphonate; or mixtures thereof. In an embodiment of the present disclosure, the secondary antioxidant is selected from DOVERPHOS LGP-11, DOVERPHOS LGP-12, and DOVERPHOS LGP-12LV.

[0349] In an embodiment of the present disclosure, the secondary antioxidant is selected from alkylphenol-free polymeric polyphosphites, examples of which are disclosed in U.S. Pat. No. 8,563,637.

[0350] In embodiments of the present disclosure, the secondary antioxidant is selected from peroxide scavengers such as esters of beta-thiodipropionic acid. The beta-thiodipropionic acid esters can be selected from the group consisting of lauryl, stearyl, myristyl, or tridecyl esters. In certain embodiments, other peroxide scavengers used as secondary antioxidants can be selected from the group consisting of mercaptobenzimidazole; or the zinc salt of 2-mercaptobenzimidazole; zinc-dibutyldithiocarbamate; dioctadecyl disulfide; and pentaerythrityltetrakis-(beta-dodecylmercapto)-propionate.

[0351] In embodiments of the present disclosure, the secondary antioxidant is selected from hydroxylamines and amine oxides, such as, for example, N,N-dibenzylhydroxylamine; N,N-diethylhydroxylamine; N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N-ditetradecylhydroxylamine; N,N-dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine; N-hexadecyl-N-octadecylhydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; and N,N-dialkylhydroxylamines derived from hydrogenated tallow amine. Similar amine oxides are also suitable. A commercially available example of a hydroxylamine that can be used in embodiments of the present disclosure is the N,N-di(alkyl)hydroxylamine sold as IRGASTAB® 042 (BASF), which is reported to be prepared by direct oxidation of N,N-di(hydrogenated) tallow amine.

[0352] In embodiments of the present disclosure, the secondary antioxidant is selected from nitrones such as, for example, N-benzyl-alpha-phenyl nitrone; N-ethyl-alpha-methyl nitrone; N-octyl-alpha-heptyl nitrone; N-lauryl-alpha-undecyl nitrone; N-tetradecyl-alpha-tridecyl nitrone; N-hexadecyl-alpha-pentadecyl nitrone; N-octadecyl-alpha-heptadecyl nitrone; N-hexadecyl-alpha-heptadecyl nitrone; N-octadecyl-alpha-pentadecyl nitrone; N-heptadecyl-alpha-heptadecyl nitrone; N-octadecyl-alpha-hexadecyl nitrone; and nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

[0353] In embodiments of the present disclosure, secondary antioxidants may also be used in amounts of 100 to 5,000 ppm, or 100 to 3,000 ppm, or 200 to 3,000 ppm, or 200 to 2,000 ppm, or 300 to 1,500 ppm, or 400 to 1,200 ppm (based on the weight of the thermoplastic polyolefin).

[0354] <UV absorbers and light stabilizers> In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from 2-(2'-hydroxyphenyl)-benzotriazoles, such as, for example, 5'-methyl-; 3',5'-di-tert-butyl-; 5'-tert-butyl-; 5'(1,1,3,3-tetramethylbutyl)-; 5-chloro-3',5'-di-tert-butyl-; 5-chloro-3'-tert-butyl-5'-methyl-; 3'-sec-butyl-5'-tert-butyl-; 4'-octoxy,3',5'-ditert-amyl-; and 3',5'-bis-(alpha,alpha-dimethylbenzyl)-derivatives.

[0355] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from 2-hydroxy-benzophenones such as, for example, 4-hydroxy-; 4-methoxy-; 4-octoxy-; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4,2',4'-trihydroxy-; and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0356] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from sterically hindered amines such as, for example: bis(2,2,6,6-tetramethylpiperidyl)-sebacate; bis-5(1,2,2,6,6-pentamethylpiperidyl)-sebacate; n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid bis(1,2,2,6,6-pentamethylpiperidyl)ester; 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid. Condensation products of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine; tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarbonic acid; and 1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone). These amines are typically called HALS (Hindered Amines Light Stabilizing) and include butanetetracarboxylic acid 2,2,6,6-tetramethylpiperidinol ester. Such amines include hydroxylamines derived from hindered amines. For example, di(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 1-hydroxy-2,2,6,6-tetramethyl-4-benzoxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-piperidine; and N-(1-hydroxy-2,2,6,6-tetramethyl-piperidin-4-yl)-ε-caprolactam.Commercially available HALS suitable for use in embodiments of the present disclosure include those sold by BASF under the trademarks CHIMASSORB® 119; CHIMASSORB 944; CHIMASSORB 2020; TINUVIN® 622, and TINUVIN 770, and those sold by Solvay under the trademarks CYASORB® UV3346, CYASORB UV3529, CYASORB UV4801, and CYASORB UV4802. Other embodiments of the present disclosure also contemplate the use of mixtures of two or more HALS.

[0357] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from esters of substituted and unsubstituted benzoic acid, such as, for example, phenyl salicylate; 4-tert-butylphenyl-salicylate; octylphenyl salicylate; dibenzoylresorcinol; bis-(4-tert-butylbenzoyl)-resorcinol; benzoylresorcinol; 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoate; and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.

[0358] In embodiments of the present disclosure, the UV absorber or light stabilizer is selected from acrylates such as, for example, alpha-cyano-beta,beta-diphenylacrylic acid-ethyl ester or isooctyl ester; alpha-carbomethoxy-cinnamic acid methyl ester; alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester; alpha-carbomethoxy-p-methoxy-cinnamic acid methyl ester; and N-(beta-carbomethoxy-beta-cyano-vinyl)-2-methyl-indoline.

[0359] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from nickel compounds, such as nickel complexes of 2,2′-thio-bis(4-(1,1,1,3-tetramethylbutyl)-phenol) (e.g., 1:1 or 1:2 complexes, optionally containing additional ligands such as n-butylamine, triethanolamine, or N-cyclohexyl-diethanolamine); nickel dibutyldithiocarbamate; nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, e.g., methyl, ethyl, or butyl ester; nickel complexes of ketoximes, such as 2-hydroxy-4-methyl-phenylundecylketoxime; and nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole (optionally containing additional ligands).

[0360] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from oxalic acid diamides, such as 4,4'-dioctyloxy-oxanilide; 2,2'-dioctyloxy-5',5'-ditert-butyloxanilide; 2,2'-di-dodecyloxy-5',5'di-tert-butyl-oxanilide; 2-ethoxy-2'-ethyl-oxanilide; N,N'-bis(3-dimethylaminopropyl)-oxalamide; 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4-di-tert-butyloxanilide; and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

[0361] In an embodiment of the present disclosure, the UV absorber or light stabilizer is a hydroxyphenyl-s-triazine, such as 2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4 octyloxyphenyl)-s-triazine; 2,6-bis(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine; 5,2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis(2-hydroxy4-(2-hydroxyethoxy)phenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis(2-hydroxy4-(2-hydroxyethoxy)phenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis(2-hydroxy4-(2-hydroxyethoxy)phenyl)-6-phenyl-s-triazine; 2,4-bis(2-hydroxy4-(2-hydroxyethoxy)phenyl)-6-(2,4-dimethylphenyl)-s-triazine; 2,4-bis(2-hydroxy4-(2-hydroxyethoxy)phenyl)-6-(4-bromo-phenyl)-s-triazine; 2,4-bis(2-hydroxy4-(2-acetoxyethoxy)phenyl)-6-(4-chlorophenyl)-s-triazine; and 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-1-s-triazine.

[0362] <Polyamide stabilizer> In an embodiment of the present disclosure, the polyamide stabilizer is selected from, for example, copper salts in combination with iodides and / or phosphorus compounds, and salts of divalent manganese.

[0363] <Basic co-stabilizer> In embodiments of the present disclosure, basic co-stabilizers are selected from, for example, melamine; polyvinylpyrrolidone; dicyandiamide; triallyl cyanurate; urea derivatives; hydrazine derivatives; amines; polyamides; polyurethanes; alkali metal and alkaline earth metal salts of higher fatty acids, such as Ca stearate, calcium stearoyl lactylate, calcium lactate, Zn stearate, Mg stearate, Na ricinoleate, and K palmitate; antimony pyrocatecholate or zinc pyrocatecholate (including neutralizers such as zinc oxide, hydrotalcite, and synthetic hydrotalcite), and Li, Na, Mg, Ca, Al hydroxycarbonates.

[0364] In an embodiment, the hydrotalcite has the formula: [M 2+ 1-x M 3+ x (OH)2] x+ [(A n- ) x / n mH2O] x- [In the formula, M 2+ is divalent Mg, Ni, Zn, Cu, or Mn, and M 3+ is trivalent Al, Fe, or Cr, and A n- For example, CO3 2- , or SO4 2- , NO3 2- , Cl 1- , or OH 1- and the like, where x is between 0.1 and 0.5. In one embodiment, the hydrotalcite has the formula: MgAl(OH) 16 CO₃·nH₂O. In one embodiment, the hydrotalcite is the mineral hydrotalcite (Mg₆Al₂(OH) 16 Hydrotalcites that may be used in embodiments of the present disclosure include materials commercially available under the general trade names DHT®-4 (A, C, or V), ZHT®-4V HYCITE® 713, and AC-207™.

[0365] <Nucleating agent> The term "nucleating agent" as used herein is intended to convey its conventional meaning to those skilled in the art of preparing nucleated polyolefin compositions, namely, an additive that alters the crystallization behavior of a polymer as the polymer melt cools.

[0366] A review of nucleating agents is provided in US Pat. Nos. 5,981,636, 6,465,551 and 6,599,971, the disclosures of which are incorporated herein by reference.

[0367] Nucleating agents that are commercially available and can be added to thermoplastic polyolefins (eg, linear polyethylene) are dibenzylidene sorbital esters. Further examples of nucleating agents that can be added to thermoplastic polyolefins (e.g., linear polyethylene) include the cyclic organic structures disclosed in U.S. Pat. No. 5,981,636 (and salts thereof, such as disodium bicyclo[2.2.1]heptenedicarboxylate); saturated versions of the structures disclosed in U.S. Pat. No. 5,981,636 (such as those disclosed in U.S. Pat. No. 6,465,551; Zhao et al. to Milliken); salts of certain cyclic dicarboxylic acids having a hexahydrophthalic acid structure (or "HHPA" structure) disclosed in U.S. Pat. No. 6,599,971 (Dotson et al. to Milliken); and cyclic dicarboxylic acid salts and salts thereof, such as phosphate esters such as those disclosed in U.S. Pat. No. 5,342,868 and sold by Asahi Denka Kogyo under the trade names NA-11 and NA-21, and divalent metal or metalloid salts (especially calcium salts) of the HHPA structure disclosed in U.S. Pat. No. 6,599,971. For clarity, the HHPA structure includes a ring structure having six carbon atoms in the ring and two carboxylic acid groups that are substituents on adjacent atoms of the ring structure. As disclosed in U.S. Pat. No. 6,599,971, the other four carbon atoms in the ring may be substituted. One example is 1,2-cyclohexanedicarboxylic acid calcium salt (CAS Registry Number 491589-22-1). Further examples of nucleating agents that can be added to thermoplastic polyolefins (e.g., linear polyethylene) include those disclosed in WO 2015 / 042561, WO 2015 / 042563, WO 2015 / 042562, and WO 2011 / 050042.

[0368] In one embodiment of the present disclosure, the amount of nucleating agent used is relatively small, between 100 and 3,000 ppm by weight (based on the weight of the thermoplastic polyolefin), and care must be taken to ensure good dispersion of the nucleating agent, as will be appreciated by those skilled in the art. In one embodiment of the present disclosure, the nucleating agent is added to the thermoplastic polyolefin (e.g., linear polyethylene) in a finely divided form (less than 50 microns, particularly less than 10 microns) to facilitate mixing. This type of "physical blend" (i.e., a solid-state mixture of nucleating agent and resin) is preferred in some embodiments over using a "masterbatch" of the nucleating agent (wherein the term "masterbatch" refers to an embodiment in which the additive (in this case, the nucleating agent) is first melt-mixed with a small amount of the thermoplastic polyolefin and then the "masterbatch" is melt-mixed with the remaining bulk of the thermoplastic polyolefin).

[0369] In one embodiment of the present disclosure, additives such as nucleating agents may be added to the thermoplastic polyolefin by means of a "masterbatch," where the term "masterbatch" refers to an embodiment in which the additive (e.g., nucleating agent) is first melt-mixed with a small amount of the thermoplastic polyolefin, and then the "masterbatch" is melt-mixed with the remaining bulk of the thermoplastic polyolefin.

[0370] In embodiments, the nucleating agent or mixture of nucleating agents is added in an amount of 50 to 5,000 ppm, or 100 to 4,000 ppm, or 200 to 4,000 ppm, or 100 to 3,000 ppm, or 200 to 3,000 ppm, or 100 to 2,000 ppm, or 200 to 2,000 ppm, or 500 to 5,000 ppm, or 500 to 4,000 ppm, or 500 to 3,000 ppm, or 500 to 2,000 ppm, or 500 to 1,500 ppm, based on the weight of the thermoplastic polyolefin.

[0371] <Slip agent> In an embodiment of the present disclosure, the slip agent is selected from oleamide, erucamide, stearamide, and behenamide.

[0372] <Fillers, anti-blocking agents, and reinforcing agents> In embodiments of the present disclosure, the filler, anti-blocking, or reinforcing agent is selected from calcium carbonate, diatomaceous earth, natural and synthetic silica, silicates, glass fiber, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, and graphite.

[0373] When present, in some embodiments of the present disclosure, the filler may be incorporated into the thermoplastic polyolefin (e.g., linear polyethylene) in an amount of up to about 50 weight percent, or up to about 30 weight percent, or up to about 20 weight percent, or up to about 10 weight percent (based on the weight of the thermoplastic polyolefin).

[0374] <Other additives> In an embodiment of the present disclosure, the other additives are selected from plasticizers, epoxidized vegetable oils such as epoxidized soybean oil, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, antifog agents, foaming agents, and thiosynergists such as dilauryl thiodipropionate or distearyl thiodipropionate.

[0375] <Melt extrusion> Extrudable thermoplastic compositions according to the present disclosure can be prepared by any one or a variety of processes. In one embodiment, the polymer processing aid components can be mixed with the thermoplastic polyolefin during the melt extrusion process. In an alternative embodiment, one or more polymer processing aid components can be compounded with the polyolefin in a so-called "masterbatch." Such masterbatches can be used to provide a useful dilution amount of one or more polymer processing aid components. The masterbatch can be added to bulk thermoplastic polyolefin for extrusion during the melt extrusion process into an extrudate.

[0376] The thermoplastic polyolefin to be extruded and the polymer processing aid component can be combined using any blending means known to those skilled in the art, such as a compounding mill, a Banbury mixer, or a mixing extruder that uniformly distributes the polymer processing aid component within the thermoplastic polyolefin. Such mixing may be carried out at a temperature above the melting or softening point of the polyolefin, or such mixing may simply be by dry blending the solid thermoplastic polyolefin with the polymer processing aid component.

[0377] In one embodiment, the extrudable thermoplastic composition of the present disclosure is prepared by melt blending a thermoplastic polyolefin (e.g., linear polyethylene) with a polymer processing aid prior to final extrusion in a melt extrusion process (e.g., a blown film extrusion process, etc.).

[0378] Several methods can be used to make the extrudable thermoplastic composition of the present disclosure. In one embodiment, all components are dry-blended in a suitable device, such as a tumble blender, in the desired weight ratio. The resulting dry blend is then melted in a suitable device, such as an extruder. In an alternative embodiment, a masterbatch can be prepared using a portion of the thermoplastic polyolefin and other components, including polymer processing aids or other additives. In one such embodiment, the thermoplastic polyolefin masterbatch is then fed into an extruder and melt-blended, as needed, with other components, including, for example, bulk polyolefin, polymer processing aids, or other additives. In yet another embodiment, each component used to make the extrudable thermoplastic composition can be metered directly into the extruder used in the melt-extrusion process.

[0379] Melt extrusion processes are well known to those skilled in the art, non-limiting examples of which include cast film extrusion, blown film extrusion, extrusion blow molding, injection molding, pipe extrusion, wire extrusion, cable extrusion, and fiber extrusion. The extruder used in embodiments of the present disclosure may be a twin-screw or single-screw extruder. When a twin-screw extruder is used, it may be operated in a co-rotating mode (i.e., both screws rotate in the same direction) or a counter-rotating mode (i.e., the screws rotate in opposite directions).

[0380] The specific operating conditions of an extruder in a melt extrusion process differ from those of other extruders. Variations between extruders can usually be resolved through routine optimization methods well known to those skilled in the art. In one embodiment of the present disclosure, a laboratory-scale twin-screw extruder operates within the following range of conditions: the barrel is heated to a temperature of about 180-210°C, or about 190-200°C; and the screw speed is operated at about 50 to about 150 rpm, or about 100 to about 130 rpm. The specific operating conditions of a particular extruder can be easily determined by one skilled in the art through routine experimentation, taking into account the aforementioned conditions. The extruder typically extrudes the thermoplastic composition as a strand, which is then cooled and cut into pellets for further use, such as film extrusion. The extruder used for final extrusion can also be a single-screw or twin-screw extruder. In blown film extrusion, the die can be a slot die or an annular ring die, which extrudes a polyolefin film around a stable air bubble. In blown film extrusion, the film is collapsed after passing over or around the bubbles.

[0381] Specific details of extruders and their operation are known to those skilled in the art. A typical extruder contains one (or two) flighted screws that rotate within a cylinder or "barrel." The thermoplastic polyolefin is sheared between the barrel and the screws due to stresses created by the rotation of the screws. In addition, the barrel of the extruder may be heated. The shear and / or heat melt the thermoplastic polyolefin and transport it along the length of the extruder by the action of the flighted screws. The molten thermoplastic polyolefin extrudate is then forced through a die to form the desired plastic part.

[0382] In an embodiment of the present disclosure, the melt extrusion process is a blown film melt extrusion process.

[0383] In the blown film melt extrusion process, an extruder heats, melts, mixes, and conveys a thermoplastic polyolefin composition. The molten thermoplastic composition is forced into an annular die to produce a thermoplastic tube. In coextrusion, multiple extruders are used to produce multilayer thermoplastic tubes. The temperature of the extrusion process is primarily determined by the melting point or glass transition temperature of the thermoplastic polyolefin composition being processed, e.g., the melting point or glass transition temperature of the thermoplastic polyolefin composition, and the desired viscosity of the melt. For thermoplastic polyolefins, typical extrusion temperatures are 330°F to 550°F (166°C to 288°C). Upon exiting the annular die, the thermoplastic tube is inflated with air, cooled, solidified, and drawn through a pair of nip rollers. The expansion by the air increases the diameter of the tube, forming cells of the desired size. The pulling action of the nip rollers stretches the cells in the machine direction. Thus, the cells are stretched in two directions: in the transverse direction (TD), the expanding air increases the cell diameter, and in the machine direction (MD), the nip rollers stretch the cells. In the blown film process, as the thermoplastic polyolefin exits the annular die, air is blown around the outer periphery of the bubbles to cool them. The final width of the film is determined by controlling the expanding air or internal bubble pressure, which in turn increases or decreases the bubble diameter. The thickness of the film is primarily controlled by increasing or decreasing the speed of the nip rollers to control the drawdown rate. After exiting the nip rollers, the bubbles or tubes are collapsed and slit in the machine direction to create sheets. Each sheet is wound into a roll of film. Each roll is further slit to create a film of the desired width. Each film roll is further processed into various consumer products.

[0384] The cast film process is similar in that it can use single or multiple extruders, but various thermoplastic materials are metered into a flat die and extruded into a single or multilayer sheet rather than a tube. In the cast film process, the extruded sheet is solidified on a chill roll.

[0385] In an embodiment of the present disclosure, a polymer processing aid is used during melt extrusion of a thermoplastic polyolefin into a thermoplastic polyolefin extrudate.

[0386] In an embodiment of the present disclosure, melt defects during extrusion of thermoplastic polyolefins are reduced by using a polymer processing aid when melt extruding the thermoplastic polyolefin into a thermoplastic polyolefin extrudate.

[0387] In one embodiment of the present disclosure, the use of a polymer processing aid during melt extrusion of a thermoplastic polyolefin into a thermoplastic polyolefin extrudate increases the shear rate at which the melt extrusion process can be operated without the occurrence of melt defects in the thermoplastic polyolefin extrudate, compared to the shear rate at which melt defects in the thermoplastic polyolefin extrudate occur in the absence of the polymer processing aid.

[0388] In embodiments of the present disclosure, the use of a polymer processing aid during melt extrusion of a thermoplastic polyolefin into a thermoplastic polyolefin extrudate increases the shear rate at which the melt extrusion process can be operated without the occurrence of melt defects in the thermoplastic polyolefin extrudate by at least 10 percent, or at least 25 percent, or at least 50 percent, or at least 75 percent, or at least 100 percent, or at least 200 percent, or at least 300 percent, or at least 400 percent, or at least 500 percent, compared to the shear rate at which melt defects occur in the thermoplastic polyolefin extrudate in the absence of the polymer processing aid.

[0389] One embodiment of the present disclosure is a method for reducing melt defects during extrusion of a thermoplastic composition comprising linear polyethylene, the method comprising: combining a linear polyethylene with a monovalent metal salt of a carboxylic acid; extruding a thermoplastic polyolefin; Includes:

[0390] One embodiment of the present disclosure is a method for reducing melt defects during extrusion of a thermoplastic composition comprising linear polyethylene, the method comprising: combining linear polyethylene with one or more of: a monovalent metal salt of a carboxylic acid; a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG)); a poly(ether-block-amide) copolymer (comprising a polyamide block and a polyether block); a polycaprolactone (PCL) polymer; and a high-pressure low-density polyethylene (LDPE); extruding the thermoplastic composition; Includes:

[0391] One embodiment of the present disclosure is a method for reducing melt defects during extrusion of a thermoplastic composition comprising linear polyethylene, the method comprising: combining a linear polyethylene with one or more of: a monovalent metal salt of a carboxylic acid; and a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG)); extruding the thermoplastic composition; Includes:

[0392] In some embodiments of the present disclosure, the use of a polymer processing aid comprising a monovalent metal salt of a carboxylic acid and one or more of: a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG)); a poly(ether-block-amide) copolymer (comprising a polyamide block and a polyether block); a polycaprolactone (PCL) polymer; and a high-pressure low-density polyethylene (LDPE) also helps reduce extruder die lip buildup (DLBU) during melt extrusion of a thermoplastic polyolefin (e.g., linear polyethylene) into a thermoplastic polyolefin extrudate.

[0393] In some embodiments of the present disclosure, the use of a polymer processing aid comprising a monovalent metal salt of a carboxylic acid and a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG)) during melt extrusion of a thermoplastic polyolefin (e.g., linear polyethylene) into a thermoplastic polyolefin extrudate also helps reduce extruder die lip buildup (DLBU).

[0394] One embodiment of the present disclosure is a method for reducing melt defects during extrusion of a thermoplastic composition comprising linear polyethylene, the method comprising: combining a linear polyethylene with a monovalent metal salt of an aliphatic carboxylic acid; extruding a thermoplastic polyolefin; Includes:

[0395] One embodiment of the present disclosure is a method for reducing melt defects during extrusion of a thermoplastic composition comprising linear polyethylene, the method comprising: combining linear polyethylene with one or more of: a monovalent metal salt of an aliphatic carboxylic acid; a poly(oxyalkylene) polymer (also known as polyalkylene glycol (PAG)); a poly(ether-block-amide) copolymer (comprising a polyamide block and a polyether block); a polycaprolactone (PCL) polymer; and a high-pressure low-density polyethylene (LDPE); extruding the thermoplastic composition; Includes:

[0396] One embodiment of the present disclosure is a method for reducing melt defects during extrusion of a thermoplastic composition comprising linear polyethylene, the method comprising: combining linear polyethylene with one or more of a monovalent metal salt of an aliphatic carboxylic acid and a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG)); extruding the thermoplastic composition; Includes:

[0397] In some embodiments of the present disclosure, the use of a polymer processing aid comprising a monovalent metal salt of an aliphatic carboxylic acid and one or more of: a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG)); a poly(ether-block-amide) copolymer (comprising a polyamide block and a polyether block); a polycaprolactone (PCL) polymer; and a high-pressure low-density polyethylene (LDPE) also helps reduce extruder die lip buildup (DLBU) during melt extrusion of a thermoplastic polyolefin (e.g., linear polyethylene) into a thermoplastic polyolefin extrudate.

[0398] In some embodiments of the present disclosure, the use of a polymer processing aid comprising a monovalent metal salt of an aliphatic carboxylic acid and a poly(oxyalkylene) polymer (also known as a polyalkylene glycol (PAG)) during melt extrusion of a thermoplastic polyolefin (e.g., linear polyethylene) into a thermoplastic polyolefin extrudate also helps reduce extruder die lip buildup (DLBU).

[0399] The following examples are presented for the purpose of illustrating selected embodiments of the present disclosure, and it is understood that the presented examples do not limit the scope of the presented claims. [Example]

[0400] <Polymer characteristic evaluation and test methods> Prior to testing, each polymer specimen was conditioned at 23±2°C and 50±10% relative humidity for at least 24 hours, with subsequent testing being performed at 23±2°C and 50±10% relative humidity. As used herein, the term "ASTM conditions" refers to a laboratory maintained at 23±2°C and 50±10% relative humidity, and the specimens to be tested were conditioned in this laboratory for at least 24 hours prior to testing. ASTM refers to American Society for Testing and Materials.

[0401] <density> The density of the polymer (e.g., linear polyethylene) was determined using ASTM D792-13 (November 1, 2013).

[0402] <Melt index> The melt index of polyethylene was determined using ASTM D1238 (August 1, 2013). Melt index, I2, I6, I 10 , and I 21 were measured at 190°C using weights of 2.16 kg, 6.48 kg, 10 kg, and 21.6 kg, respectively.

[0403] <Gel Permeation Chromatography (GPC)> Polyethylene sample (polymer) solutions (1–3 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating it on a wheel in an oven at 150 °C for 4 hours. To stabilize the polymer against oxidative degradation, an antioxidant (2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture. The BHT concentration was 250 ppm. The polymer solution was chromatographed in a PL220 high-temperature chromatography unit equipped with four SHODEX® columns (HT803, HT804, HT805, and HT806) using TCB as the mobile phase at a flow rate of 1.0 mL / min at 140 °C, with differential refractive index (DRI) as the concentration detector. To protect the GPC column from oxidative degradation, BHT was added to the mobile phase at a concentration of 250 ppm. The sample injection volume was 200 μL. The GPC column was calibrated with narrow-distribution polystyrene standards. Polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation as described in ASTM Standard Test Method D6474-12 (December 2012). Raw GPC data were processed with CIRRUS® GPC software to obtain molar mass averages (M n , M w , M z ) and molar mass distribution (e.g., polydispersity M w / M nIn the polyethylene art, the commonly used term equivalent to GPC is SEC, or size exclusion chromatography.

[0404] <Melt extrusion> It has been observed that the performance of polymer processing aids ("PPAs") in reducing melt defects in polyolefin extrudates is affected by the shear rate at the extruder die. A commonly accepted equation for estimating the shear rate at the die is Equation 1: (1) γ=2Q(S+2) / ρπd 2 D [Where γ = reciprocal of shear rate (s -1 ); ρ = density of polymer melt; S = 1 / power exponent; d = die gap width; D = die diameter; Q = polymer mass flow rate] It is shown as follows.

[0405] A commonly accepted estimate for the density of molten polyethylene is 0.76 grams per cubic centimeter (g / cm 3 ), and this value was used for all calculations. The commonly accepted value for the power exponent is 0.5, and this value was used for all calculations.

[0406] <Example: Set 1> Extrudable thermoplastic polyolefin compositions for blown film extrusion were prepared by melt compounding linear polyethylene with polymer processing aids and other additives in a Leistritz twin-screw pelletizer under mild conditions with a nitrogen purge (see Table 1 for conditions).

[0407] [Table 1]

[0408] The monovalent metal salt of an aliphatic carboxylic acid used as a PPA was potassium stearate, commercially available from PMC Crystal as Potassium Stearate PSV-10.The divalent metal salt of an aliphatic carboxylic acid used in the comparative examples to determine its effectiveness as a PPA was calcium stearate, commercially available from Baerlocher as CEASIT™ AV FI VEG.

[0409] The linear polyethylene used in these experiments was 0.920 g / cm 3It is a linear low-density polyethylene (LLDPE) with a density of 1.0 g / 10 min and a melt index I2 of approximately 1.0 g / 10 min, sold by NOVA Chemicals under the trade name FP120. FP120 is also available in various formulations as FP120-A, FB120-AS, and FP120-C. FP120, FP120-A, FB120-AS, and FP120-C are copolymers of ethylene and 1-octene and are produced by a solution-phase polymerization process using a Ziegler-Natta catalyst. The linear polyethylene FP120 contained a conventional primary antioxidant (hindered phenol = 500 ppm IRGANOX 1076); a conventional secondary antioxidant (phosphite = 500 ppm IRGAFOS 168); and hydrotalcite (800 ppm). Here, ppm is based on the weight of the linear polyethylene. The linear polyethylene FP120-C contained a conventional primary antioxidant (hindered phenol = 500 ppm IRGANOX 1076); a conventional secondary antioxidant (phosphite = 500 ppm IRGAFOS 168); hydrotalcite (800 ppm); and 650 ppm VITON Z110 (a PPA comprising an elastomeric fluoropolymer and polyethylene glycol, where ppm is based on the weight of the linear polyethylene). The linear polyethylene FP120-AS contained two conventional primary antioxidants (hindered phenol = IRGANOX 1076 at 500 ppm and hindered phenol = IRGANOX 1010 at 250 ppm); a conventional secondary antioxidant (phosphite = IRGAFOS 168 at 1,000 ppm); hydrotalcite (800 ppm); and calcium stearate (lubricant = 1,250 ppm CEASIT AV FI VEG).

[0410] Blown films were prepared on a 3-inch Macro blown film line. The line had a standard output of greater than 60 pounds per hour and was equipped with a 15-horsepower motor. The feed screw had a 1.5-inch diameter and a length / diameter (L / D) ratio of 24 / 1. The feed screw was of barrier design and equipped with a mixing element at the end of the screw. The film bubble was air cooled using chilled air, and the line was operated at a blow-up ratio (BUR) of 2 / 1 to 4 / 1. The blown film line was equipped with a 3-inch diameter annular die. Two die pins were utilized to create a die gap of 35 or 85 mils for the experiments.

[0411] In Example 1A, linear polyethylene FP120-C containing an elastomeric fluoropolymer (VITON Z110) as the PPA was melt extruded on a blown film line.

[0412] In Example 1B, linear polyethylene FP120 was pre-compounded (e.g., melt-compounded in an extruder / pelletizer) with 1,500 ppm (by weight based on the weight of the linear polyethylene) potassium stearate (PSV-10) and then melt-extruded on a blown film line.

[0413] In Example 1C, linear polyethylene FP120 was blended with 0.125 wt% of a masterbatch containing 20 wt% calcium stearate (CEASIT AV FI VEG), 4 wt% IRGANOX 1076, and 4 wt% IRGANOX 1010, and then melt extruded on a blown film line.

[0414] During melt fracture elimination experiments on a blown film line, the extruder was operated at approximately 65 pounds per hour (approximately 460 s -1The film was operated at a mass flow rate "target point" of 100 rpm (corresponding to a shear rate of 100 rpm). The term "melt fracture" is well known to those skilled in the art and generally refers to a film that has visible signs of surface imperfections that manifest as die lines, haze bands, or small bands of soft melt fracture (orange peel) or hard melt fracture (sharkskin). The phrase "clear of melt fracture" means that the film has a clear, defect-free surface.

[0415] The ingredients used in the extrudable thermoplastic compositions and details of the melt extrusion process are shown in Table 2.

[0416] [Table 2]

[0417] Prior to adding the target thermoplastic composition, the blown film line was purged with LLDPE or LDPE containing 30-40% diatomaceous earth without polymer processing aids to abrade the die. Following the purge, a density of approximately 0.92 g / cm3 was obtained. 3A PPA-free LLDPE with a melt index of 0.8 g / 10 min was introduced to produce an extrudate with 100% hard melt fracture across the entire width of the film (e.g., producing a film with rough surface defects similar in appearance to sharkskin). The target thermoplastic composition was then introduced, which was recorded as time zero. The target thermoplastic composition was extruded under constant conditions, and samples of the extruded film were collected every 10 minutes. Melt fracture defects were measured as a percentage of the sample width. The melt extrusion process continued for 60–90 minutes for each experiment, and the melt fracture percentage was recorded at 10-minute intervals. The extrudate was considered melt fracture-free once the melt fracture percentage reached zero. As a general, non-limiting guideline, a polymer processing aid (PPA) can be considered to be performing well if melt fracture is eliminated within approximately 60 minutes of starting the extruder. The results of the melt fracture elimination experiment are shown in Figure 1.

[0418] Those skilled in the art will note from the data presented in Figure 1 that a thermoplastic composition comprising linear polyethylene and only potassium stearate as a PPA (e.g., 1,500 ppm PSV-10) completely eliminated melt fracture within about 30 minutes (see Example 1B), as did a thermoplastic composition comprising linear polyethylene, an elastomeric fluoropolymer, and polyethylene glycol (e.g., Viton Z110, see Example 1A).

[0419] The data in Figure 1 also show that thermoplastic compositions containing only linear polyethylene and the divalent stearate calcium stearate as the PPA (e.g., 1,500 ppm CEASIT AV FI VEG) failed to eliminate melt fracture after 90 minutes of extrusion (see Example 1C). Furthermore, during extrusion of the thermoplastic composition containing linear polyethylene and calcium stearate, the extrudate became unstable and the cells collapsed after about 30 minutes, resulting in undesirable results for commercial operations.

[0420] The data presented in Figure 1 demonstrate that monovalent metal salts of aliphatic carboxylic acids alone can be used as effective polymer processing aids for linear polyethylene, even in the absence of fluoropolymer and polyethylene glycol.

[0421] <Example: Set 2> Extrudable thermoplastic polyolefin compositions for blown film extrusion were prepared by melt compounding linear polyethylene with polymer processing aids and other additives in a Leistritz twin-screw pelletizer under mild conditions with a nitrogen purge (see Table 3 for conditions).

[0422] [Table 3]

[0423] The monovalent metal salts of aliphatic carboxylic acids used as PPAs were potassium stearate (commercially available from PMC Crystal as Potassium Stearate PSV-10), sodium stearate (commercially available from Thermo Fisher Scientific as Sodium stearate), sodium hexanoate (commercially available from MilliporeSigma as Sodium Hexanoate), potassium benzoate, and potassium acetate (both commercially available from Sigma-Aldrich). The sodium hexanoate, potassium benzoate, and potassium acetate were dried in a vacuum oven at 70°C before melt compounding.

[0424] The polyamide / polyether block copolymer used in the blend with linear polyethylene was PEBAX MV 1074, available from Arkema.

[0425] The PEG used in the blend with linear polyethylene was PEG 3350, having a weight average molecular weight Mw of about 3,350 g / mol, or a 1:1 blend of PEG 3350, having a weight average molecular weight Mw of about 3,350 g / mol, and PEG 35000, having a weight average molecular weight Mw of about 35,000 g / mol. PEG 3350 and PEG 35000 are commercially available from Clariant and sold under the trade names POLYGLYKOL 3350 and POLYGLYKOL 35000, respectively.

[0426] In the comparative example, the PPA used in the blend with the linear polyethylene was a blend of elastomeric fluoropolymer and polyethylene glycol commercially available as VITON Z110 from The Chemours Company.

[0427] The linear polyethylene used in the experiment was 0.914 g / cm 3 It is a linear low-density polyethylene (LLDPE) with a density of 1000 MPa and a melt index I2 of approximately 0.85 g / 10 min, sold under the trade name VPsK914. VPsK914 is available in various formulations as VPsK914-A, VPsK914-A04, and VPsK914-C. VPsK914 is a copolymer of ethylene and 1-octene, made in a solution-phase polymerization process using dual-reactor single-site catalyst and Ziegler-Natta catalyst technology.

[0428] The linear polyethylene (VPsK914-A) used in the experiments contained a conventional primary antioxidant (hindered phenol = IRGANOX 1076 at 350 ppm), a conventional secondary antioxidant (phosphite = IRGAFOS 168 at 750 ppm), a specialty antioxidant (SUMILIZER GP at 500 ppm), and hydrotalcite (800 ppm), where ppm (parts per million) is based on the weight of the linear polyethylene.

[0429] Blown films were prepared on a 3-inch Macro blown film line. The line had a standard output of greater than 60 pounds per hour and was equipped with a 15-horsepower motor. The feed screw had a 1.5-inch diameter and a length / diameter (L / D) ratio of 24 / 1. The feed screw was of barrier design and equipped with a mixing element at the end of the screw. The film bubble was air cooled using chilled air, and the line was operated at a blow-up ratio (BUR) of 2 / 1 to 4 / 1. The blown film line was equipped with a 3-inch diameter annular die. Two die pins were utilized to create a die gap of 35 or 85 mils for the experiments.

[0430] In Example 2A, linear polyethylene VPsK914-A was pre-compounded (e.g., melt compounded in an extruder / pelletizer) with a blend of elastomeric fluoropolymer and 1,000 ppm (by weight based on the weight of linear polyethylene) polyethylene glycol (Viton® Z110) and then melt extruded on a blown film line.

[0431] In Example 2B, linear polyethylene VPsK914-A was pre-compounded (e.g., melt compounded in an extruder / pelletizer) with 500 ppm (by weight based on the weight of the linear polyethylene) potassium stearate (PSV-10) and then melt extruded on a blown film line.

[0432] In Example 2C, linear polyethylene VPsK914-A was pre-blended (e.g., melt-blended in an extruder / pelletizer) with 500 ppm (by weight based on the weight of the linear polyethylene) potassium stearate (PSV-10) and 1,000 ppm (by weight based on the weight of the linear polyethylene) polyethylene glycol (PEG3350) and then melt-extruded on a blown film line.

[0433] In Example 2D, linear polyethylene VPsK914-A was pre-compounded (e.g., melt-compounded in an extruder / pelletizer) with 500 ppm (by weight based on the weight of the linear polyethylene) potassium stearate (PSV-10), 500 ppm (by weight based on the weight of the linear polyethylene) PEG 3350, and 500 ppm (by weight based on the weight of the linear polyethylene) PEG 35000, and then melt-extruded on a blown film line.

[0434] In Example 2E, linear polyethylene VPsK914-A was pre-compounded (e.g., melt-compounded in an extruder / pelletizer) with 500 ppm (by weight based on the weight of the linear polyethylene) potassium stearate (PSV-10) and 1,000 ppm (by weight based on the weight of the linear polyethylene) polyamide / polyether block copolymer (PEBAX MV 1074), and then melt-extruded on a blown film line.

[0435] In Example 2F, linear polyethylene VPsK914-A was pre-compounded (e.g., melt compounded in an extruder / pelletizer) with 1,500 ppm (by weight based on the weight of the linear polyethylene) sodium stearate and then melt extruded on a blown film line.

[0436] In Example 2G, linear polyethylene VPsK914-A was pre-blended (e.g., melt-blended in an extruder / pelletizer) with 500 ppm (by weight based on the weight of the linear polyethylene) sodium stearate and 1,000 ppm (by weight based on the weight of the linear polyethylene) polyethylene glycol (PEG 3350) and then melt-extruded on a blown film line.

[0437] In Example 2H, linear polyethylene VPsK914-A was pre-compounded (e.g., melt compounded in an extruder / pelletizer) with 1,500 ppm (by weight based on the weight of the linear polyethylene) of sodium hexanoate and then melt extruded on a blown film line.

[0438] In Example 2I, linear polyethylene VPsK914-A was pre-blended (e.g., melt-blended in an extruder / pelletizer) with 500 ppm (by weight based on the weight of the linear polyethylene) sodium hexanoate and 1,000 ppm (by weight based on the weight of the linear polyethylene) polyethylene glycol (PEG 3350) and then melt-extruded on a blown film line.

[0439] In Example 2J, linear polyethylene VPsK914-A was pre-blended (e.g., melt-blended in an extruder / pelletizer) with 500 ppm (by weight based on the weight of the linear polyethylene) potassium benzoate and 1,000 ppm (by weight based on the weight of the linear polyethylene) polyethylene glycol (PEG3350) and then melt-extruded on a blown film line.

[0440] In Example 2K, linear polyethylene VPsK914-A was pre-blended (e.g., melt-blended in an extruder / pelletizer) with 500 ppm (by weight based on the weight of the linear polyethylene) potassium acetate and 1,000 ppm (by weight based on the weight of the linear polyethylene) polyethylene glycol (PEG 3350) and then melt-extruded on a blown film line.

[0441] During melt fracture elimination experiments on a blown film line, the extruder was operated at approximately 65 pounds per hour (approximately 460 s -1 The film was operated at a mass flow rate "target point" of 100 rpm (corresponding to a shear rate of 100 rpm). The term "melt fracture" is well known to those skilled in the art and generally refers to a film that has visible signs of surface imperfections that manifest as die lines, haze bands, or small bands of soft melt fracture (orange peel) or hard melt fracture (sharkskin). The phrase "clear of melt fracture" means that the film has a clear, defect-free surface.

[0442] The ingredients used in the extrudable thermoplastic compositions and details of the melt extrusion process are shown in Table 4.

[0443] [Table 4-1] [Table 4-2] [Table 4-3]

[0444] Prior to adding the target thermoplastic composition, the film line was purged with LLDPE or LDPE containing 30-40% diatomaceous earth without polymer processing aids to abrade the die. Following the purge, a film with a density of approximately 0.92 g / cm3 was obtained. 3 A PPA-free LLDPE with a melt index of approximately 0.8 g / 10 min was introduced to produce an extrudate with 100% hard melt fracture across the entire width of the film (e.g., producing a film with rough surface defects similar in appearance to sharkskin). The target thermoplastic composition was then introduced, which was recorded as time zero. The target thermoplastic composition was extruded under constant conditions, and samples of the extruded film were collected every 10 minutes to measure melt fracture defects as a percentage of the sample width. The melt extrusion process was continued for up to 90 minutes, with the melt fracture percentage recorded at 10-minute intervals. The extrudate was considered melt fracture-free once the melt fracture percentage reached zero. As a general, non-limiting guideline, a polymer processing aid (PPA) can be considered to be performing well if melt fracture is eliminated within approximately 60 minutes of starting the extruder. The results of the melt fracture elimination experiment are shown in Figures 2, 3, and 4.

[0445] Those skilled in the art will recognize from the data presented in Figures 2 and 3 that thermoplastic compositions containing linear polyethylene and only a monovalent metal stearate (potassium stearate in Example 2B; sodium stearate in Example 2F) as the PPA were able to significantly reduce melt fracture (up to about 20%) within about 20-40 minutes. Surprisingly, the onset of melt fracture elimination occurred sooner for linear polyethylene containing potassium stearate or sodium stearate as the PPA (see Examples 2B and 2F) than for linear polyethylene containing an elastomeric fluoropolymer (Viton Z110) as the PPA (see Example 2A in Figures 2 and 3). Figures 2 and 3 further show that when 500 ppm potassium stearate or 500 ppm sodium stearate was added to linear polyethylene and used in combination with polyethylene glycol (e.g., PEG 3350, or PEG 3350 and PEG 35000) as a PPA, the thermoplastic composition was able to completely eliminate melt fracture in about 60 to 70 minutes or less (see Examples 2C, 2D, and 2G). The data in Figure 2 also show that when 500 ppm potassium stearate was added to linear polyethylene and used in combination with a polyamide / polyether block copolymer (e.g., PEBAX MV 1074) as a PPA, the thermoplastic composition was able to completely eliminate melt fracture in about 40 to 50 minutes. Finally, the data in Figure 3 show that monovalent metal salts of hexanoic acid (e.g., sodium hexanoate) perform very well as PPAs when added to linear polyethylene alone (see Example 2H) or in combination with polyethylene glycol (e.g., PEG3350) (see Example 2I). Indeed, in both scenarios, melt fracture was completely eliminated within 60 minutes.

[0446] The data presented in Figure 4 demonstrate that using a combination of a monovalent metal salt (e.g., potassium benzoate or potassium acetate) and polyethylene glycol (e.g., PEG335) as a PPA in linear polyethylene significantly improved melt fracture removal compared to the baseline example where no PPA was added (compare Examples 2J and 2K with Example 2L).

[0447] This data demonstrates that monovalent metal salts of aliphatic carboxylic acids can be used as effective polymer processing aids for linear polyethylene, either alone or optionally with polyethylene glycol or polyamide / polyether block copolymers, even in the absence of fluoropolymers.

[0448] Non-limiting embodiments of the present disclosure include the following:

[0449] Embodiment 1. A process for preparing a thermoplastic composition extrudate, comprising extruding a thermoplastic composition by a melt extrusion process, the thermoplastic composition comprising: i) a linear polyethylene; and ii) 200 to 4000 ppm (based on the weight of the linear polyethylene) of a monovalent metal salt of a carboxylic acid; the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; the thermoplastic composition is substantially free of fluoropolymers; The melt extrusion process is carried out in the absence of fluoropolymer; The above process.

[0450] Embodiment 2. The process of embodiment 1, wherein the monovalent metal salt of a carboxylic acid is a monovalent metal salt of an aliphatic carboxylic acid.

[0451] Embodiment 3. The process of embodiment 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 2 to 30 carbon atoms.

[0452] Embodiment 4. The process of embodiment 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 30 carbon atoms.

[0453] Embodiment 5. The process of embodiment 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 26 carbon atoms.

[0454] Embodiment 6. The process of embodiment 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having 6 to 22 carbon atoms.

[0455] Embodiment 7. The process of embodiment 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid selected from the group consisting of hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof.

[0456] Embodiment 8. The process of embodiment 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is selected from the group consisting of lithium acetate, sodium acetate, potassium acetate, lithium stearate, sodium stearate, potassium stearate, lithium hexanoate, sodium hexanoate, potassium hexanoate, and mixtures thereof.

[0457] Embodiment 9 The process of embodiment 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is potassium stearate.

[0458] Embodiment 10 The process of embodiment 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium stearate.

[0459] Embodiment 11. The process of embodiment 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium hexanoate or potassium hexanoate.

[0460] Embodiment 12 The process of embodiment 1, wherein the monovalent metal salt of a carboxylic acid is a monovalent metal salt of an aromatic carboxylic acid.

[0461] Embodiment 13 The process of embodiment 12, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 30 carbon atoms.

[0462] Embodiment 14. The process of embodiment 12, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 20 carbon atoms.

[0463] Embodiment 15. The process of embodiment 12, wherein the monovalent metal salt of an aromatic carboxylic acid is potassium benzoate or sodium benzoate.

[0464] Embodiment 16. The process of any one of embodiments 1-15, wherein the thermoplastic composition comprises: iii) 200 to 4,000 ppm polyethylene glycol (based on the weight of the linear polyethylene); and iv) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a poly(ether block amide) copolymer comprising polyamide blocks and polyether blocks; The above process further comprising one or more of:

[0465] Embodiment 17 The process of any one of embodiments 1 to 16, wherein the linear polyethylene is LLDPE.

[0466] Embodiment 18. The process of embodiment 17, wherein the LLDPE has a melt index, I2, of 0.1 to 5.0 grams per 10 minutes.

[0467] Embodiment 19: The LLDPE has a viscosity of 0.910 to 0.936 g / cm 3 19. The process of embodiment 17 or 18, wherein the density is

[0468] Embodiment 20. The process of any one of embodiments 17-19, wherein the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more alpha olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

[0469] Embodiment 21. The process of any one of embodiments 1-20, wherein the melt extrusion process is carried out at a shear rate that, when carried out with a thermoplastic composition consisting essentially of linear polyethylene, produces a thermoplastic composition extrudate having melt fracture defects.

[0470] Embodiment 22. The process of any one of embodiments 1 to 21, wherein the thermoplastic composition comprises 200 to 2,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal salt of a carboxylic acid.

[0471] Embodiment 23. An extrudable thermoplastic composition comprising: i) a linear polyethylene; and ii) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal salt of a carboxylic acid; the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; the extrudable thermoplastic composition is substantially free of fluoropolymers; The extrudable thermoplastic composition.

[0472] Embodiment 24. The extrudable thermoplastic composition of embodiment 23, wherein the monovalent metal salt of a carboxylic acid is a monovalent metal salt of an aliphatic carboxylic acid.

[0473] Embodiment 25. The extrudable thermoplastic composition of embodiment 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 2 to 30 carbon atoms.

[0474] Embodiment 26. The extrudable thermoplastic composition of embodiment 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 30 carbon atoms.

[0475] Embodiment 27. The extrudable thermoplastic composition of embodiment 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 26 carbon atoms.

[0476] Embodiment 28. The extrudable thermoplastic composition of embodiment 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 22 carbon atoms.

[0477] Embodiment 29. The extrudable thermoplastic composition of embodiment 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid selected from the group consisting of hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof.

[0478] Embodiment 30. The extrudable thermoplastic composition of embodiment 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is selected from the group consisting of lithium acetate, sodium acetate, potassium acetate, lithium stearate, sodium stearate, potassium stearate, lithium hexanoate, sodium hexanoate, potassium hexanoate, and mixtures thereof.

[0479] Embodiment 31. The extrudable thermoplastic composition of embodiment 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is potassium stearate.

[0480] Embodiment 32. The extrudable thermoplastic composition of embodiment 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium stearate.

[0481] Embodiment 33. The extrudable thermoplastic composition of embodiment 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium hexanoate or potassium hexanoate.

[0482] Embodiment 34. The extrudable thermoplastic composition of embodiment 23, wherein the monovalent metal salt of a carboxylic acid is a monovalent metal salt of an aromatic carboxylic acid.

[0483] Embodiment 35. The extrudable thermoplastic composition of embodiment 34, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 30 carbon atoms.

[0484] Embodiment 36. The extrudable thermoplastic composition of embodiment 34, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 20 carbon atoms.

[0485] Embodiment 37. The extrudable thermoplastic composition of embodiment 34, wherein the monovalent metal salt of an aromatic carboxylic acid is potassium benzoate or sodium benzoate.

[0486] Embodiment 38. The extrudable thermoplastic composition of any one of Embodiments 23-37, wherein the thermoplastic composition comprises: iii) 200 to 4,000 ppm polyethylene glycol (based on the weight of the linear polyethylene); and iv) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a poly(ether block amide) copolymer comprising polyamide blocks and polyether blocks; The extrudable thermoplastic composition further comprising one or more of:

[0487] Embodiment 39. The extrudable thermoplastic composition of any one of embodiments 23 to 38, wherein the linear polyethylene is LLDPE.

[0488] Embodiment 40. The extrudable thermoplastic composition of embodiment 39, wherein the LLDPE has a melt index, I2, of 0.1 to 5.0 grams per 10 minutes.

[0489] Embodiment 41. LLDPE has a viscosity of 0.910 to 0.936 g / cm 3 41. The extrudable thermoplastic composition of embodiment 39 or 40, having a density of

[0490] Embodiment 42. The extrudable thermoplastic composition of any one of embodiments 39-41, wherein the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more alpha olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

[0491] Embodiment 43. The extrudable thermoplastic composition of any one of embodiments 23 to 42, wherein the thermoplastic composition comprises 200 to 2,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal salt of a carboxylic acid.

[0492] Embodiment 44. A method for reducing melt extrusion defects during extrusion of a thermoplastic composition comprising linear polyethylene, comprising: adding at least one monovalent metal salt of a carboxylic acid to a linear polyethylene; extruding the thermoplastic composition in a melt extrusion process; Including, The linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; The above method.

[0493] Embodiment 45 The method of embodiment 44, wherein the thermoplastic composition is: iii) 200 to 4,000 ppm polyethylene glycol (based on the weight of the linear polyethylene); and iv) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a poly(ether block amide) copolymer comprising polyamide blocks and polyether blocks; The above method further comprising one or more of:

[0494] Embodiment 46. The method of embodiment 44 or 45, wherein the thermoplastic composition is substantially free of fluoropolymers.

[0495] Embodiment 47. The method of any one of embodiments 44-46, wherein the melt extrusion process is carried out in the absence of a fluoropolymer.

[0496] Embodiment 48. The method of any one of embodiments 44-47, wherein the at least one monovalent metal salt of a carboxylic acid comprises a monovalent metal salt of an aliphatic carboxylic acid.

[0497] Embodiment 49 The method of embodiment 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 2 to 30 carbon atoms.

[0498] Embodiment 50 The method of embodiment 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 30 carbon atoms.

[0499] Embodiment 51 The method of embodiment 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having 6 to 26 carbon atoms.

[0500] Embodiment 52 The method of embodiment 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having 6 to 22 carbon atoms.

[0501] Embodiment 53. The method of embodiment 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid selected from the group consisting of hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof.

[0502] Embodiment 54. The method of embodiment 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is selected from the group consisting of lithium acetate, sodium acetate, potassium acetate, lithium stearate, sodium stearate, potassium stearate, lithium hexanoate, sodium hexanoate, potassium hexanoate, and mixtures thereof.

[0503] Embodiment 55 The method of embodiment 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is potassium stearate.

[0504] Embodiment 56 The method of embodiment 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium stearate.

[0505] Embodiment 57 The method of embodiment 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium hexanoate or potassium hexanoate.

[0506] Embodiment 58 The method of any one of embodiments 44-47, wherein the at least one monovalent metal salt of a carboxylic acid comprises a monovalent metal salt of an aromatic carboxylic acid.

[0507] Embodiment 59 The method of embodiment 58, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 30 carbon atoms.

[0508] Embodiment 60 The method of embodiment 58, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 20 carbon atoms.

[0509] Embodiment 61 The method of embodiment 58, wherein the monovalent metal salt of an aromatic carboxylic acid is potassium benzoate or sodium benzoate.

[0510] Embodiment 62 The method of any one of embodiments 44 to 61, wherein the linear polyethylene is LLDPE.

[0511] Embodiment 63 The method of embodiment 62, wherein the LLDPE has a melt index, I2, of 0.1 to 5.0 grams per 10 minutes.

[0512] Embodiment 64: The LLDPE has a viscosity of 0.910 to 0.936 g / cm 3 64. The method of embodiment 62 or 63, wherein the density is

[0513] Embodiment 65. The method of any one of embodiments 62-64, wherein the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more alpha olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

[0514] Embodiment 66. The method of any one of embodiments 44 to 65, wherein the thermoplastic composition comprises 200 to 2,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal salt of a carboxylic acid. [Industrial Applicability]

[0515] A polymer processing aid (PPA) is provided that reduces melt fracture defects in extruded polyolefins in the absence of fluoropolymers.

Claims

1. 1. A process for preparing a thermoplastic composition extrudate, comprising the step of extruding a thermoplastic composition by a melt extrusion process, the thermoplastic composition comprising: i) a linear polyethylene; and ii) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal salt of a carboxylic acid; the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; the thermoplastic composition is substantially free of fluoropolymers; The melt extrusion process is carried out in the absence of fluoropolymer; The above process.

2. 2. The process of claim 1, wherein the monovalent metal salt of a carboxylic acid is a monovalent metal salt of an aliphatic carboxylic acid.

3. 3. The process of claim 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 2 to 30 carbon atoms.

4. 3. The process of claim 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 30 carbon atoms.

5. 3. The process of claim 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 26 carbon atoms.

6. 3. The process of claim 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 22 carbon atoms.

7. 3. The process of claim 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid selected from the group consisting of hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof.

8. 3. The process of claim 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is selected from the group consisting of lithium acetate, sodium acetate, potassium acetate, lithium stearate, sodium stearate, potassium stearate, lithium hexanoate, sodium hexanoate, potassium hexanoate, and mixtures thereof.

9. 3. The process of claim 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is potassium stearate.

10. 3. The process of claim 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium stearate.

11. 3. The process of claim 2, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium hexanoate or potassium hexanoate.

12. 2. The process of claim 1, wherein the monovalent metal salt of a carboxylic acid is a monovalent metal salt of an aromatic carboxylic acid.

13. 13. The process of claim 12, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 30 carbon atoms.

14. 13. The process of claim 12, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 20 carbon atoms.

15. 13. The process of claim 12, wherein the monovalent metal salt of an aromatic carboxylic acid is potassium benzoate or sodium benzoate.

16. The process according to any one of claims 1 to 15, wherein the thermoplastic composition is iii) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of polyethylene glycol; and iv) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a poly(ether block amide) copolymer comprising polyamide blocks and polyether blocks; The above process further comprising one or more of:

17. The process of any one of claims 1 to 16, wherein the linear polyethylene is LLDPE.

18. The LLDPE has a melt index I of 0.1 to 5.0 grams per 10 minutes. ２ 18. The process of claim 17, comprising:

19. LLDPE is 0.910 to 0.936 g / cm ３ 19. The process of claim 17 or 18, wherein the granules have a density of

20. 20. The process of any one of claims 17 to 19, wherein the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more alpha olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

21. 21. The process of any one of claims 1 to 20, wherein the melt extrusion process is carried out at a shear rate that, when carried out with a thermoplastic composition consisting essentially of linear polyethylene, produces a thermoplastic composition extrudate having melt fracture defects.

22. The process of any one of claims 1 to 21, wherein the thermoplastic composition comprises 200 to 2,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal salt of a carboxylic acid.

23. An extrudable thermoplastic composition comprising: i) a linear polyethylene; and ii) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal salt of a carboxylic acid; the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; the extrudable thermoplastic composition is substantially free of fluoropolymers; The extrudable thermoplastic composition.

24. 24. The extrudable thermoplastic composition of claim 23, wherein the monovalent metal salt of a carboxylic acid is a monovalent metal salt of an aliphatic carboxylic acid.

25. 25. The extrudable thermoplastic composition of claim 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 2 to 30 carbon atoms.

26. 25. The extrudable thermoplastic composition of claim 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 30 carbon atoms.

27. 25. The extrudable thermoplastic composition of claim 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 26 carbon atoms.

28. 25. The extrudable thermoplastic composition of claim 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 22 carbon atoms.

29. 25. The extrudable thermoplastic composition of claim 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid selected from the group consisting of hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof.

30. 25. The extrudable thermoplastic composition of claim 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is selected from the group consisting of lithium acetate, sodium acetate, potassium acetate, lithium stearate, sodium stearate, potassium stearate, lithium hexanoate, sodium hexanoate, potassium hexanoate, and mixtures thereof.

31. 25. The extrudable thermoplastic composition of claim 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is potassium stearate.

32. 25. The extrudable thermoplastic composition of claim 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium stearate.

33. 25. The extrudable thermoplastic composition of claim 24, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium hexanoate or potassium hexanoate.

34. 24. The extrudable thermoplastic composition of claim 23, wherein the monovalent metal salt of a carboxylic acid is a monovalent metal salt of an aromatic carboxylic acid.

35. 35. The extrudable thermoplastic composition of claim 34, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 30 carbon atoms.

36. 35. The extrudable thermoplastic composition of claim 34, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 20 carbon atoms.

37. 35. The extrudable thermoplastic composition of claim 34, wherein the monovalent metal salt of an aromatic carboxylic acid is potassium benzoate or sodium benzoate.

38. 38. The extrudable thermoplastic composition of any one of claims 23 to 37, wherein the thermoplastic composition comprises: iii) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of polyethylene glycol; and iv) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a poly(ether block amide) copolymer comprising polyamide blocks and polyether blocks; The extrudable thermoplastic composition further comprising one or more of:

39. 39. The extrudable thermoplastic composition of any one of claims 23 to 38, wherein the linear polyethylene is LLDPE.

40. The LLDPE has a melt index I of 0.1 to 5.0 grams per 10 minutes. ２ 40. The extrudable thermoplastic composition of claim 39, having

41. LLDPE is 0.910 to 0.936 g / cm ３ 41. The extrudable thermoplastic composition of claim 39 or 40, having a density of

42. 42. The extrudable thermoplastic composition of any one of claims 39 to 41, wherein the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more alpha olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

43. 43. The extrudable thermoplastic composition of any one of claims 23 to 42, wherein the thermoplastic composition comprises 200 to 2,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal salt of a carboxylic acid.

44. 1. A method for reducing melt extrusion defects during extrusion of a thermoplastic composition comprising linear polyethylene, comprising: adding at least one monovalent metal salt of a carboxylic acid to a linear polyethylene; extruding the thermoplastic composition in a melt extrusion process; Including, The linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; The above method.

45. 45. The method of claim 44, wherein the thermoplastic composition comprises: iii) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of polyethylene glycol; and iv) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a poly(ether block amide) copolymer comprising polyamide blocks and polyether blocks; The above method further comprising one or more of:

46. 46. ​​The method of claim 44 or 45, wherein the thermoplastic composition is substantially free of fluoropolymers.

47. The method of any one of claims 44 to 46, wherein the melt extrusion process is carried out in the absence of a fluoropolymer.

48. 48. The method of any one of claims 44 to 47, wherein the at least one monovalent metal salt of a carboxylic acid comprises a monovalent metal salt of an aliphatic carboxylic acid.

49. 49. The method of claim 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 2 to 30 carbon atoms.

50. 49. The method of claim 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 30 carbon atoms.

51. 49. The method of claim 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 26 carbon atoms.

52. 49. The method of claim 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid having from 6 to 22 carbon atoms.

53. 49. The method of claim 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is derived from an aliphatic carboxylic acid selected from the group consisting of hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof.

54. 49. The method of claim 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is selected from the group consisting of lithium acetate, sodium acetate, potassium acetate, lithium stearate, sodium stearate, potassium stearate, lithium hexanoate, sodium hexanoate, potassium hexanoate, and mixtures thereof.

55. 49. The method of claim 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is potassium stearate.

56. 49. The method of claim 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium stearate.

57. 49. The method of claim 48, wherein the monovalent metal salt of an aliphatic carboxylic acid is sodium hexanoate or potassium hexanoate.

58. 48. The method of any one of claims 44 to 47, wherein the at least one monovalent metal salt of a carboxylic acid comprises a monovalent metal salt of an aromatic carboxylic acid.

59. 59. The method of claim 58, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 30 carbon atoms.

60. 59. The method of claim 58, wherein the monovalent metal salt of an aromatic carboxylic acid is derived from an aromatic carboxylic acid having from 7 to 20 carbon atoms.

61. 59. The method of claim 58, wherein the monovalent metal salt of an aromatic carboxylic acid is potassium benzoate or sodium benzoate.

62. 62. The method of any one of claims 44 to 61, wherein the linear polyethylene is LLDPE.

63. The LLDPE has a melt index I of 0.1 to 5.0 grams per 10 minutes. ２ 63. The method of claim 62, comprising:

64. LLDPE is 0.910 to 0.936 g / cm ３ 64. The method of claim 62 or 63, wherein the density is

65. 65. The method of any one of claims 62 to 64, wherein the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more alpha olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

66. 66. The method of any one of claims 44 to 65, wherein the thermoplastic composition comprises 200 to 2,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal salt of a carboxylic acid.

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