Metal salts as polymer processing aids

Abstract

A polymer processing aid (PPA) reduces melt defects in extruded polyolefins in the absence of fluoropolymers. The polymeric processing aid comprises a monovalent metal carboxylate and well 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 olefin-based fluoropolymers. Background Art

[0002] During the extrusion of polyolefin polymers, surface defects, including those known as sharkskin, snakeskin, and orange peel, can develop. Each of these surface defects is generally related to the rheology of the polymer melt. One particularly severe form of surface defect that can occur is "melt fracture," which is believed to occur when the shear rate at the surface of a polyolefin polymer is high enough to cause the polymer surface to begin to fracture. That is, the surface of the extruded polymer slips relative to the bulk of the polymer melt. The surface often cannot flow fast enough to keep up with the bulk of the extrudate, and melt fracture occurs, resulting in a significant loss of surface properties in the extruded polymer.

[0003] US Patent No. 3,125,547 discloses blends of polyethylene with small amounts of fluoropolymers to provide a smooth surface on polyethylene extrudates at high extrusion speeds.

[0004] US Patent No. 3,222,314 discloses blends of polyethylene with low molecular weight polyethylene glycol to 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 incidence of "failures" during the polyethylene film manufacturing process. Similarly, U.S. Patent No. 4,540,538 teaches that the use of a combination of (i) polyethylene glycol; (ii) a hindered phenolic antioxidant; and (iii) a selected inorganic antiblocking material can reduce fine streaking during polyolefin extrusion film formation.

[0006] More patents relate to the use of combinations of polyalkylene oxides and fluorocarbon polymers as processing aids in the extrusion of polyolefins. These patents include U.S. Patent No. 4,855,360, which discloses and claims a composition of matter comprising a polyolefin and a processing aid, and U.S. Patent No. 5,015,693, which claims the processing aid itself. These patents demonstrate the use of relatively low molecular weight polyethylene glycols (e.g., having a molecular weight of about 400 Da to about 20,000 Da) in combination with fluorocarbon polymers as polymer processing aids, and further, in the absence of fluoropolymers, these polyethylene glycols are not very effective in reducing melt defects.

[0007] US Patent No. 6,294,604 describes the use of a combination of fluoropolymers, 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 as polymer processing aids in combination with polyethylene glycol and a metal salt of a carboxylic acid, sulfonic acid, or alkyl sulfate. The metal carboxylates are used to increase the decomposition temperature of the polyethylene glycol, but are not shown to have the ability to act as polymer processing aids themselves.

[0010] Fluoroelastomers and fluoropolymers are expensive materials, so there is an economic incentive to avoid their use. In addition, the perfluoroalkanes and perfluorosurfactant compounds (e.g., perfluorooctane sulfonate and perfluorooctanoic acid) used in the production of fluoropolymers are increasingly recognized to have negative environmental impacts.

[0011] In US Patent Application No. 2005 / 0070644, we disclosed that high molecular weight polyethylene glycol (particularly PEG having a molecular weight greater than 20,000 g / mol) reduces melt fracture during polyolefin extrusion in the absence of fluoropolymers.

[0012] U.S. Patent No. 10,982,079 also details the performance of a polymer processing aid without the addition of a fluoropolymer. The polymer processing aid comprises a high molecular weight polyethylene glycol, enhanced in thermal stability by the inclusion of a metal salt of a carboxylic acid, sulfonic acid, or alkyl sulfate. However, the use of a metal carboxylate alone as a polymer processing aid is not demonstrated.

[0013] Metal stearates (such as calcium stearate) are well-known polymer additives, primarily used as acid scavengers in polyethylene, but can also serve as lubricants and release agents for certain thermoplastics. Studies have shown that calcium stearate may play a role in reducing the load (i.e., pressure) required to extrude linear polyethylene with long-chain branches and produced using metallocene catalysts (see Hatzikiriakos, SG; Kazatchkov, IB; Vlassopoulos D. in Journal of Rheology, Vol. 41, 1997, p. 1299).

[0014] However, metallic stearates are not generally considered to be highly effective polymer processing aids per se that are capable of significantly reducing melt fracture defects in linear polyethylene extrusion. Summary of the Invention

[0015] We now report that monovalent metal carboxylic acid (eg, aliphatic carboxylic acid) salts, when used alone as polymer processing aids, perform well in the extrusion of thermoplastic polyolefins in the absence of fluoropolymer processing aids.

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

[0017] One embodiment is a method of preparing an extrudate of a thermoplastic composition, the method comprising extruding a thermoplastic composition in a melt extrusion process; the thermoplastic composition comprising: a linear polyethylene; and a monovalent metal carboxylate;

[0018] wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE and mixtures thereof;

[0019] wherein the thermoplastic composition is substantially free of fluoropolymer; and wherein the melt extrusion process is performed in the absence of a fluoropolymer.

[0020] One embodiment is an extrudable thermoplastic composition comprising: i) a linear polyethylene; and ii) from 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal carboxylate; wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; and wherein the extrudable thermoplastic composition is substantially free of fluoropolymer.

[0021] A method of reducing melt extrusion defects during extrusion of a thermoplastic composition comprising a linear polyethylene, the method comprising: adding at least one monovalent metal carboxylate to the linear polyethylene; and

[0022] extruding the thermoplastic composition in a melt extrusion process;

[0023] The linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE and mixtures thereof.

[0024] In one embodiment, the monovalent metal carboxylate is a monovalent metal aliphatic carboxylate.

[0025] In one embodiment, the monovalent metal carboxylate is a monovalent metal aromatic carboxylate.

[0026] In one embodiment, the thermoplastic composition further comprises one or more of: polyethylene glycol; and a polyether block amide copolymer, wherein the polyether block amide copolymer comprises polyamide blocks and polyether blocks.

[0027] In one embodiment, the melt extrusion process is conducted at a shear rate that, when conducted with a thermoplastic composition consisting essentially of linear polyethylene, would produce an extrudate of the thermoplastic composition having melt fracture defects.

[0028] In one embodiment, the linear polyethylene is LLDPE.

[0029] In one embodiment, the LLDPE has a melt index I2 of 0.1 to 5.0 g / 10 min.

[0030] In one embodiment, the density of the LLDPE is from 0.910 to 0.936 g / cm 3 .

[0031] In one embodiment, the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more α-olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 Results are shown for experiments (Examples 1A-1C) evaluating the ability of various polymer processing aids to remove melt extrusion defects during melt extrusion of a thermoplastic composition comprising linear low density polyethylene (LLDPE) on a blown film line. In these experiments, a monolayer blown film line equipped with a 3-inch diameter die was used.

[0033] Figure 2 and Figure 3 Results are shown for experiments (Examples 2A-2I) evaluating the ability of various polymer processing aids to remove melt extrusion defects during melt extrusion of a thermoplastic composition comprising linear low density polyethylene (LLDPE) on a blown film line. In these experiments, a monolayer blown film line equipped with a 3-inch diameter die was used.

[0034] Figure 4 Shown are 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 during melt extrusion of a thermoplastic composition comprising linear low density polyethylene (LLDPE) on a blown film line. In these experiments, a monolayer blown film line equipped with a 3-inch diameter die was used. DETAILED DESCRIPTION

[0035] As used herein, the term "monomer" refers to a small molecule that can chemically react with itself or other monomers to form chemical bonds, thereby forming a polymer.

[0036] As used herein, the term "α-olefin" or "alpha-olefin" is used to describe a monomer having a linear hydrocarbon chain of 3 to 20 carbon atoms with a double bond at one end of the chain; an equivalent term is "linear α-olefin." α-olefins may also be referred to as comonomers.

[0037] As used herein, the term "polyethylene" or "ethylene polymer" refers to a macromolecule made from ethylene monomer and, optionally, one or more additional monomers; regardless of the specific catalyst or specific process used to make the ethylene polymer. In the polyethylene field, the one or more additional monomers are typically referred to as "comonomers," typically including α-olefins. The term "homopolymer" typically refers to a polymer that contains only one type of monomer. The term "copolymer" refers to a polymer that contains two or more types of monomers. Common polyethylene types include high pressure low density polyethylene (LDPE), high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE) or ultra low density polyethylene (ULDPE), which are 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 of the above polyethylene types or blends thereof.

[0038] In the present disclosure, the term "fluoropolymer" refers to homopolymers and copolymers of fluorinated olefins. The ratio of fluorine atoms to carbon atoms of fluorinated olefins can be at least 1:2, or in some embodiments at least 1:1. Homopolymers include those derived from, for example, vinylidene fluoride and vinyl fluoride. Copolymers include those derived from, for example, vinylidene fluoride and one or more other olefins, and the other olefins can be fluorinated (for example, hexafluoropropylene) or non-fluorinated (for example, propylene). Non-limiting examples of the term "fluoropolymer" used in the present disclosure include, for example, U.S. Patent Nos. 2,968,649, 3,051,677, 3,318,854, 5,015,693, 4,855,360, U.S. Patent No. 5,710,217, U.S. Patent No. 6,277,919, U.S. Patent No. 7,375,157, and those described in U.S. Patent Application Publication No. 2010 / 0311906. Some commercially available examples of fluoropolymers include, for example, copolymers of hexafluoropropylene and vinylidene fluoride, which are marketed under the trade name " FX 9613" and "DYNAMAR FX 9614" are available; and copolymers of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene are available under the trade names "DYNAMAR FX 5911" and "DYNAMAR FX 5912". Other commercially available fluoropolymers include " A", " FREEFLOW TM ”、 and All of these are available in various grades.

[0039] In this disclosure, the terms polyalkylene oxide, polyoxyalkylene and polyalkylene glycol are used interchangeably. Thus, the terms polyethylene oxide, polyoxyethylene and polyethylene glycol are also used interchangeably; the same is true for the terms polypropylene oxide, polyoxypropylene and polypropylene glycol.

[0040] The term "film" is used herein to refer to a film having one or more layers formed by extruding a polymer through one or more die openings. The term "film structure" is used to indicate that the film has more than one layer (i.e., the film structure may have at least two layers, at least three layers, at least four layers, at least five layers, etc.).

[0041] "Alkyl" and the prefix "alk-" include straight and branched chain groups, as well as cyclic groups, having up to 30 carbons, unless otherwise specified. Cyclic groups can be monocyclic or polycyclic, and in some embodiments have 3 to 10 ring carbon atoms.

[0042] For example, with respect to an alkyl, alkylene, or arylalkylene group, the phrase "interrupted by one or more ether linkages" means having a moiety of an alkyl, alkylene, or arylalkylene group on both sides of the functional group. An example of an alkylene group interrupted by —O— is —CH2—CH2—O—CH2—CH2—.

[0043] As used herein, the term "aryl" includes carbocyclic aromatic rings or ring systems, for example, having 1, 2, or 3 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) with up to 4 carbon atoms, alkoxy groups with up to 4 carbon atoms, halogens (i.e., fluorine, chlorine, bromine, or iodine), hydroxyl groups, or nitro groups. Examples of aryl groups include phenyl, naphthyl, biphenyl, fluorenyl, and furyl, thienyl, oxazolyl, and thiazolyl. "Arylalkylene" refers to an "alkylene" portion to which an aryl group is attached. "Alkylarylene" refers to an "arylene" portion to which an alkyl group is attached.

[0044] The term "substituted" or similar terms (eg, "substituent") means that one or more non-hydrogen groups (or non-hydrogen moieties or non-hydrogen groups) have replaced one or more hydrogen groups at any position in the referenced group.

[0045] In embodiments of the present disclosure, the extrusion of thermoplastic polyolefins is improved ("assisted") by the use of polymer processing aids (PPAs).

[0046] In embodiments of the present disclosure, one or more components of the polymer processing aid may be mixed (eg, pre-blended) or pre-compounded (eg, dry blended or melt blended) with the thermoplastic polyolefin prior to extrusion of the polyolefin.

[0047] In embodiments of the present disclosure, one or more components of the polymer processing aid may be co-fed with the thermoplastic polyolefin into the extruder.

[0048] In embodiments of the present disclosure, one or more components of the polymer processing aid can be added to a thermoplastic polyolefin to prepare a polyolefin masterbatch comprising one or more components of the polymer processing aid. The resulting polyolefin masterbatch can then be used to introduce one or more components of the polymer processing aid into the thermoplastic polyolefin in any conventional manner prior to polyolefin extrusion (e.g., dry blending or melt blending) or during polyolefin extrusion (e.g., co-feeding with the polyolefin into the extruder).

[0049] Polymer Processing Aids (PPA)

[0050] In one embodiment of the present disclosure, a polymer processing aid (PPA) for aiding in the extrusion of thermoplastic polyolefins comprises a monovalent metal carboxylate ("metal salt").

[0051] In one embodiment of the present disclosure, a polymer processing aid (PPA) for aiding in the extrusion of thermoplastic polyolefins comprises a monovalent metal aliphatic carboxylate ("metal salt").

[0052] In one embodiment of the present disclosure, a polymer processing aid (PPA) for aiding in the extrusion of thermoplastic polyolefins comprises: i) a monovalent metal carboxylate ("metal salt"), and one or more of:

[0053] ii) polyoxyalkylene polymers, also known as polyalkylene glycols (PAGs);

[0054] iii) a polyether block amide copolymer, wherein the polyether block amide copolymer comprises a polyamide block and a polyether block;

[0055] iv) polycaprolactone (PCL) polymers; and

[0056] v) High pressure low density polyethylene (LDPE).

[0057] In one embodiment of the present disclosure, a polymer processing aid (PPA) for aiding in the extrusion of thermoplastic polyolefins comprises: i) a monovalent metal carboxylate ("metal salt"), and ii) a polyoxyalkylene polymer, also known as a polyalkylene glycol (PAG).

[0058] In one embodiment of the present disclosure, a polymer processing aid (PPA) for aiding in the extrusion of thermoplastic polyolefins comprises: i) a monovalent metal carboxylate ("metal salt"), and ii) a polyether block amide copolymer, wherein the polyether block amide copolymer comprises polyamide blocks and polyether blocks.

[0059] In one embodiment of the present disclosure, a polymer processing aid (PPA) for aiding in the extrusion of thermoplastic polyolefins comprises: i) a monovalent metal aliphatic carboxylate ("metal salt"), and one or more of:

[0060] ii) polyoxyalkylene polymers, also known as polyalkylene glycols (PAGs);

[0061] iii) a polyether block amide copolymer, wherein the polyether block amide copolymer comprises a polyamide block and a polyether block;

[0062] iv) polycaprolactone (PCL) polymers; and

[0063] v) High pressure low density polyethylene (LDPE).

[0064] In one embodiment of the present disclosure, a polymer processing aid (PPA) for aiding in the extrusion of thermoplastic polyolefins comprises: i) a monovalent metal aliphatic carboxylate ("metal salt"), and ii) a polyoxyalkylene polymer, also known as a polyalkylene glycol (PAG).

[0065] In one embodiment of the present disclosure, a polymer processing aid (PPA) for aiding in the extrusion of thermoplastic polyolefins comprises: i) a monovalent metal aliphatic carboxylate ("metal salt"), and ii) a polyether block amide copolymer, wherein the polyether block amide copolymer comprises polyamide blocks and polyether blocks.

[0066] In one embodiment of the present disclosure, a polymer processing aid (PPA) for aiding in the extrusion of thermoplastic polymers is further characterized as being substantially free of perfluoroalkane compounds, fluoroelastomers, and fluoropolymers.

[0067] One embodiment of the present disclosure is characterized by an extrudable thermoplastic composition that is substantially free of perfluoroalkane compounds, fluoroelastomers, and fluoropolymers.

[0068] One embodiment of the present disclosure is a method of making an extrudate of a thermoplastic composition, comprising melt extruding the thermoplastic composition in a melt extrusion process; wherein the thermoplastic composition is characterized as being substantially free of perfluoroalkane compounds, fluoroelastomers, and fluoropolymers, and wherein the melt extrusion process is conducted in the absence of perfluoroalkane compounds, fluoroelastomers, and fluoropolymers.

[0069] In the embodiments of the present disclosure, the melt extrusion process includes film extrusion, extrusion blow molding, injection molding, pipe extrusion, wire extrusion, cable extrusion and fiber extrusion, which are well known to those skilled in the art.

[0070] Metal carboxylates ("metal salts")

[0071] In one embodiment, the polymer processing aid (PPA) used to aid in the extrusion of thermoplastic polyolefins comprises a monovalent metal carboxylate.

[0072] In one embodiment, a polymer processing aid (PPA) for aiding in the extrusion of thermoplastic polyolefins comprises a monovalent metal aliphatic carboxylate.

[0073] The carboxylic acid used to provide the metal salt can be monofunctional or polyfunctional (e.g., difunctional) and can be aliphatic or aromatic. In other words, the carbonyl carbon can be attached to an aliphatic group or an aromatic ring. The aliphatic carboxylic acid can be saturated or unsaturated. In addition to one or more -C(O)O anions (i.e., carboxylate groups, respectively), the aliphatic or aromatic group can also be substituted with other functional groups, including halogens (i.e., fluorine, chlorine, bromine and iodine), hydroxyl groups and alkoxy groups, and the aromatic rings can also be substituted with alkyl groups. However, those skilled in the art will recognize that a monovalent metal carboxylate will have only one -C(O)O anion (i.e., one carboxylate group), and the counterion metal can be represented as M + (ie, the metal M has one valence electron, is "monovalent," and forms a positive cation upon reaching its eight-electron state).

[0074] In an embodiment of the present disclosure, the carboxylic acid is a monofunctional or difunctional aliphatic carboxylic acid without any other substituents on the aliphatic chain.

[0075] In an embodiment of the present disclosure, the carboxylic acid is a monofunctional aliphatic carboxylic acid without any other substituents on the aliphatic chain.

[0076] In an embodiment of the present disclosure, the carboxylic acid is a monofunctional alkanoic acid (ie, an acyclic saturated aliphatic group), and the alkyl group (ie, the acyclic saturated aliphatic group) does not have any other substituents.

[0077] In embodiments of the present disclosure, the carboxylic acid is a monofunctional aromatic carboxylic acid, and the aromatic group may optionally have other substituents, including functional groups or other aliphatic groups (e.g., saturated or unsaturated aliphatic groups, such as alkyl, alkenyl, alkynyl).

[0078] In some embodiments, the carboxylic acid that can be used to provide the metal salt is represented by the formula RCOOH, wherein R is an alkyl or alkenyl group. In some embodiments, the carboxylic acid that can be used to provide the metal salt is represented by the formula RCOOH, wherein R is a linear alkyl group. In some embodiments, the carboxylic acid that can be used to provide the metal salt is represented by the formula RCOOH, wherein R is an aromatic group or a substituted aromatic group.

[0079] In one embodiment, the carboxylic acid used to provide the metal salt is benzoic acid. In one embodiment, the carboxylic acid used to provide the metal salt is benzoic acid, further substituted with one or more aliphatic groups at positions 2, 3, 4, 5 or 6 of the phenyl ring.

[0080] In some embodiments, the carboxylic acid used to provide the metal salt is an aromatic carboxylic acid having 7 to 30 carbon atoms.

[0081] In some embodiments, the carboxylic acid used to provide the metal salt is an aromatic carboxylic acid having 7 to 20 carbon atoms.

[0082] In some embodiments, the carboxylic acid used to provide the metal salt is a carboxylic acid having an alkyl or alkenyl group having 2 to 30 carbon atoms.

[0083] In some embodiments, the carboxylic acid used to provide the metal salt is an aliphatic carboxylic acid having from 2 to 30 carbon atoms.

[0084] In some embodiments, the carboxylic acid used to provide the metal salt is an aliphatic carboxylic acid having 6 to 30 carbon atoms.

[0085] In some embodiments, the carboxylic acid used to provide the metal salt is an aliphatic carboxylic acid having from 6 to 26 carbon atoms.

[0086] In some embodiments, the carboxylic acid used to provide the metal salt is an aliphatic carboxylic acid having 6 to 22 carbon atoms.

[0087] In one embodiment, the carboxylic acid used to provide the metal salt is acetic acid.

[0088] In some embodiments, the carboxylic acid used to provide the metal salt is a fatty acid, such as a carboxylic acid having an alkyl or alkenyl group with 8 to 30 carbon atoms, or in some embodiments, 8 to 26 carbon atoms, or 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 salt used in embodiments of the present disclosure include: octanoic acid (C8 carboxylic acid), decanoic acid (C8 carboxylic acid), ...decanoic acid (C8 carboxylic acid), decanoic acid (C8 carboxylic acid), decanoic acid (C8 carboxylic acid), octanoic acid (C8 carboxylic 10 Carboxylic acid), lauric acid (C 12 Carboxylic acid), myristic acid (C 14 Carboxylic acid), palmitic acid (C 16 Carboxylic acid), stearic acid (C 18Carboxylic acid), arachidic acid (C 20 Carboxylic acid), behenic acid (C 22 Carboxylic acid), lignoceric acid (C 24 Carboxylic acid) and cerotic acid (C 26 Carboxylic acids). Fatty acid metal salts of these fatty acids useful in embodiments of the present disclosure include monovalent metal salts, namely, caprylate, caprate, laurate, myristate, palmitate, stearate, arachidate, behenate, lignocerate, and cerate metal salts.

[0089] In an embodiment of the present disclosure, the carboxylic acid used to provide the metal salt is stearic acid.

[0090] Examples of useful monovalent metals (those that form cations in metal carboxylates) include rubidium (Rb), lithium (Li), sodium (Na), and potassium (K). In some embodiments, the metal salt is a sodium salt or a potassium salt.

[0091] In an embodiment of the present disclosure, the metal salt is a potassium salt.

[0092] In an embodiment of the present disclosure, the metal salt is a sodium salt.

[0093] Many metal carboxylates are available from a variety of commercial sources, and other metal salts can be prepared by conventional methods. In some embodiments, the metal carboxylates can be formed in situ in the thermoplastic polyolefin. In these embodiments, both a first component containing a metal cation and a second component containing a carboxylic acid are typically added to the extrudable thermoplastic polyolefin. Metal carboxylates that can be used in embodiments of the present disclosure include rubidium stearate, potassium stearate, sodium stearate, sodium acetate, sodium hexanoate, potassium hexanoate, sodium octanoate, sodium laurate, and sodium behenate.

[0094] In an embodiment of the present disclosure, the metal salt used as 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.

[0095] In an embodiment of the present disclosure, the metal salt used as PPA is selected from the group consisting of potassium stearate, sodium stearate, lithium stearate, and mixtures thereof.

[0096] In some embodiments of the present disclosure, the metal salt used as PPA is potassium stearate. In some embodiments of the present disclosure, the metal salt used as PPA is sodium stearate.

[0097] In an embodiment of the present disclosure, the metal salt used as PPA is selected from the group consisting of potassium hexanoate, sodium hexanoate, lithium hexanoate, and mixtures thereof.

[0098] In some embodiments of the present disclosure, the metal salt used as PPA is potassium hexanoate. In some embodiments of the present disclosure, the metal salt used as PPA is sodium hexanoate.

[0099] In some embodiments of the present disclosure, the metal salt used as PPA is potassium benzoate. In some embodiments of the present disclosure, the metal salt used as PPA is sodium benzoate. In some embodiments of the present disclosure, the metal salt used as PPA is sodium lithium benzoate.

[0100] In one embodiment of the present disclosure, the amount of metal salt (e.g., monovalent metal aliphatic carboxylate) used as a polymer processing aid (PPA) is from 100 to 5,000 ppm by weight (based on the weight of the thermoplastic polyolefin), including any subranges within that range and any values ​​within that range. One skilled in the art can readily determine further optimized PPA addition levels and ranges for a given extrusion process. For example, in certain embodiments, the amount of metal salt (e.g., monovalent metal aliphatic carboxylate) used as a polymer processing aid (PPA) is 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 (based on the weight of the thermoplastic polyolefin).

[0101] In embodiments of the present disclosure, the amount of metal salt (e.g., monovalent metal aliphatic carboxylate) 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, 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, or 500 to 1,000 ppm by weight, or 750 to 1,000 ppm by weight.

[0102] In one embodiment of the present disclosure, a metal salt (e.g., a monovalent metal aliphatic carboxylate) is added to a thermoplastic polyolefin (e.g., a linear polyethylene) using a masterbatch formulation containing the metal salt (e.g., a monovalent metal aliphatic carboxylate). The term "masterbatch" is well known to those skilled in the art. Generally, the term "masterbatch" refers to the practice of first melt mixing an additive (e.g., a metal salt, such as a monovalent metal aliphatic carboxylate) with a small amount of a given thermoplastic polyolefin (e.g., a linear polyethylene), and then blending the resulting "masterbatch" with the remainder of the thermoplastic polyolefin (e.g., a linear polymer) (e.g., by melt mixing or dry blending).

[0103] In embodiments of the present disclosure, about 0.1 to about 15.0 wt%, or about 0.5 to about 15.0 wt%, or about 0.5 to about 10.0 wt%, or about 0.1 to about 10.0 wt%, or about 0.1 to about 7.5 wt%, or about 0.5 to about 7.5 wt%, or about 0.5 to about 5.0 wt%, or about 0.1 to about 5.0 wt%, or about 1.0 to about 15.0 wt%, or about 1.0 to about 5.0 wt%, or about 1.0 to about 7.5 wt%, or about 1.0 to about 5.0 wt%, or about 0.1 to about 2.5 wt%, or about 0.5 to about 2.5 wt% of a masterbatch is used in a blend with a host polymer (wherein the weight percentages of the masterbatch are based on the total weight of the masterbatch and the host polymer).

[0104] In embodiments of the present disclosure, a masterbatch (e.g., a linear polyethylene masterbatch) may comprise a metal salt (e.g., a monovalent metal aliphatic carboxylate) in an amount ranging from 500 to 50,000 ppm by weight (based on the weight of the masterbatch), including subranges therein and any value therein. For example, in further embodiments of the present disclosure, the masterbatch may comprise from 500 to 40,000 ppm, or from 500 to 35,000 ppm, or from 500 to 40,000 ppm, or from 500 to 25,000 ppm, or from 1,000 to 40,000 ppm, or from 1,000 to 35,000 ppm, or from 1,000 to 30,000 ppm, or from 1,000 to 25,000 ppm by weight. ppm) (based on the weight of the masterbatch), 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 ppm, or 4,000 to 20,000 ppm, or 5,000 to 20,000 ppm, or 5,000 to 17,500 ppm, or 5,000 to 15,000 ppm, 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 0 ppm, 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.

[0105] Metal salts (eg, monovalent metal aliphatic carboxylates) used as polymer processing aids (PPAs) can be used in the form of a semisolid or viscous liquid, or as a powder, pellets, or granules.

[0106] Polyoxyalkylene polymers

[0107] In one embodiment of the present disclosure, the polymer processing aid will comprise a polyoxyalkylene polymer, also known as a polyalkylene glycol (PAG) or polyalkylene oxide.

[0108] In one embodiment of the present disclosure, the polymeric processing aid will comprise a polyoxyethylene polymer, also known as polyethylene glycol or polyethylene oxide.

[0109] In one embodiment of the present disclosure, the polymer processing aid will comprise polyoxypropylene glycol, also known as polypropylene glycol or polypropylene oxide.

[0110] In an embodiment of the present disclosure, the polyoxyalkylene polymer may be represented by the formula A[(OR 1 ) x OR 2 ] y , wherein A is typically an alkylene group interrupted by one or more ether bonds, y is 2 or 3, (OR 1 ) x is a compound having multiple (x) oxyalkylene groups OR 1 polyoxyalkylene chain, where each R 1 are independently C2 to C5 alkylene, in some embodiments C2 to C3 alkylene, R 2 is hydrogen, alkyl, aryl, arylalkylene, alkylarylene, —C(O)-alkyl, —C(O)-aryl, —C(O)-arylalkylene or —C(O)-alkylarylene, wherein —C(O)— is the same as OR 2 O bonding.

[0111] In one embodiment of the present disclosure, the polyoxyalkylene polymer may be a homopolymer, such as a polyoxyethylene polymer (also referred to as polyethylene glycol in the present disclosure), wherein each R 1 is —CH2CH2—, or a homopolymer, such as a polyoxypropylene polymer, wherein each R 1 It is —C3H6—.

[0112] In another embodiment of the present disclosure, the polyoxyalkylene polymer is a polyoxyalkylene polymer comprising chains of randomly distributed oxyalkylene groups (e.g., a copolymer comprising —OC2H4— and —OC3H6— units), or a polyoxyalkylene polymer having alternating blocks of repeating oxyalkylene groups (e.g., a copolymer comprising (—OC2H4—) a and (—OC3H6—) b A block copolymer wherein a+b is x).

[0113] Contains randomly distributed or alternating (—OC2H4—) and (—OC3H6—) units or (—OC2H4—) a and (—OC3H6—) b Block polyoxyalkylene copolymers are sometimes called "poloxamers" and are sold under the trade name and Commercially available.

[0114] In some embodiments of the present disclosure, A is ethylene, —CH2—CH(—)—CH2— (derived from glycerol), CH3CH2C(CH2—)3 (derived from 1,1,1-trimethylolpropane), polyoxypropylene, —CH2CH2—O—CH2CH2—, or —CH2CH2—O—CH2CH2—O—CH2CH2—.

[0115] In some embodiments of the present disclosure, R 2 is hydrogen, methyl, butyl, phenyl, benzyl, acetyl, benzoyl or stearyl.

[0116] In other embodiments of the present disclosure, the polyoxyalkylene polymer is, for example, a polymer composed of a dicarboxylic acid and a compound of formula A[(OR 1 ) x OR 2 ] y The polyester prepared from the polyoxyalkylene polymer represented by 1 and x are defined as above, R 2 is hydrogen, and y is 2.

[0117] In one embodiment of the present disclosure, the major portion by weight of the polyoxyalkylene polymer is repeating oxyalkylene groups (OR 1 ).

[0118] In one embodiment of the present disclosure, the polyoxyalkylene polymer is polyethylene glycol (PEG). Polyethylene glycol (PEG) can be represented by the formula H(O—CH2CH2—) x Many polyethylene glycols and their ethers and esters are commercially available and are contemplated for use in embodiments of the present disclosure.

[0119] The weight average molecular weight (e.g. M n and M w ) can be measured, for example, by gel permeation chromatography (ie, size exclusion chromatography) using a narrow molecular weight distribution polyoxyalkylene polymer (eg, polyethylene glycol) as a standard, using techniques known in the art.

[0120] In an embodiment of the present disclosure, the value of x of the polyalkylene glycol (PAG) is such that the weight average molecular weight M of the polyalkylene glycol polymer is w 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.

[0121] In an embodiment of the present disclosure, the value of x of the polyalkylene glycol (PAG) is such that the weight average molecular weight M of the polyalkylene glycol polymer is wThe upper limit is 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.

[0122] In an embodiment of the present disclosure, the value of x of the polyalkylene glycol (PAG) is such that the weight average molecular weight M of the polyethylene glycol polymer is w From about 60,000 g / mol to about 500,000 g / mol, or from about 75,000 g / mol to about 500,000 g / mol, or from about 60,000 g / mol to about 450,000 g / mol, or from about 75,000 g / mol to about 450,000 g / mol, or from about 80,000 g / mol to about 500,000 g / mol, or from about 80,000 g / mol to about 450,000 g / mol, or from about 85,000 g / mol to about 500,000 g / mol, or from about 60,000 g / mol to about 4 00,000 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.

[0123] In an embodiment of the present disclosure, the value of x of the polyalkylene glycol (PAG) is such that the weight average molecular weight M of the polyalkylene glycol polymer is w 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.

[0124] In an embodiment of the present disclosure, the value of x of the polyalkylene glycol (PAG) is such that the weight average molecular weight M of the polyalkylene glycol polymer is w 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.

[0125] In an embodiment of the present disclosure, the value of x of the polyalkylene glycol (PAG) is such that the weight average molecular weight M of the polyalkylene glycol polymer isw 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.

[0126] In an embodiment of the present disclosure, the value of x of the polyalkylene glycol (PAG) is such that the weight average molecular weight M of the polyalkylene glycol polymer is w From about 1,000 g / mol to about 8,000 g / mol, or from about 2,000 g / mol to about 8,000 g / mol, or from about 1,000 g / mol to about 7,000 g / mol, or from about 2,000 g / mol to about 7,000 g / mol, or from about 1,000 g / mol to about 6,500 g / mol, or from about 2,000 g / mol to about 6,500 g / mol, or from about 1,000 g / mol to about 6,000 g / mol, or from about 2,000 g / mol to about 6,000 g / mol, or from about 1,000 g / mol to about 5,000 g / mol, or from about 2,000 g / mol to about 5,000 g / mol.

[0127] In an embodiment of the present disclosure, the value of x of the polyalkylene glycol (PAG) is such that the weight average molecular weight M of the polyalkylene glycol polymer is w From about 10,000 g / mol to about 50,000 g / mol, or from about 15,000 g / mol to about 50,000 g / mol, or from about 20,000 g / mol to about 50,000 g / mol, or from about 25,000 g / mol to about 50,000 g / mol, or from about 20,000 g / mol to about 40,000 g / mol, or from about 25,000 g / mol to about 35,000 g / mol, or from about 15,000 g / mol to about 35,000 g / mol, or from about 15,000 g / mol to about 30,000 g / mol, or from about 15,000 g / mol to about 25,000 g / mol.

[0128] In the embodiments of the present disclosure, the value of x of polyethylene glycol (PEG) is such that the weight average molecular weight M of the polyethylene glycol polymer is w 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.

[0129] In the embodiments of the present disclosure, the value of x of polyethylene glycol (PEG) is such that the weight average molecular weight M of the polyethylene glycol polymer is w The upper limit is 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.

[0130] In the embodiments of the present disclosure, the value of x of polyethylene glycol (PEG) is such that the weight average molecular weight M of the polyethylene glycol polymer is w From about 60,000 g / mol to about 500,000 g / mol, or from about 75,000 g / mol to about 500,000 g / mol, or from about 60,000 g / mol to about 450,000 g / mol, or from about 75,000 g / mol to about 450,000 g / mol, or from about 80,000 g / mol to about 500,000 g / mol, or from about 80,000 g / mol to about 450,000 g / mol, or from about 85,000 g / mol to about 500,000 g / mol, or from about 60,000 g / mol to about 4 00,000 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.

[0131] In the embodiments of the present disclosure, the value of x of polyethylene glycol (PEG) is such that the weight average molecular weight M of the polyethylene glycol polymer is w 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.

[0132] In the embodiments of the present disclosure, the value of x of polyethylene glycol (PEG) is such that the weight average molecular weight M of the polyethylene glycol polymer is w 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.

[0133] In the embodiments of the present disclosure, the value of x of polyethylene glycol (PEG) is such that the weight average molecular weight M of the polyethylene glycol polymer is w 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.

[0134] In the embodiments of the present disclosure, the value of x of polyethylene glycol (PEG) is such that the weight average molecular weight M of the polyethylene glycol polymer is w From about 1,000 g / mol to about 8,000 g / mol, or from about 2,000 g / mol to about 8,000 g / mol, or from about 1,000 g / mol to about 7,000 g / mol, or from about 2,000 g / mol to about 7,000 g / mol, or from about 1,000 g / mol to about 6,500 g / mol, or from about 2,000 g / mol to about 6,500 g / mol, or from about 1,000 g / mol to about 6,000 g / mol, or from about 2,000 g / mol to about 6,000 g / mol, or from about 1,000 g / mol to about 5,000 g / mol, or from about 2,000 g / mol to about 5,000 g / mol.

[0135] In an embodiment of the present disclosure, the weight average molecular weight M of polyethylene glycol (PEG) is w About 3,350g / mol.

[0136] In the embodiments of the present disclosure, the value of x of polyethylene glycol (PEG) is such that the weight average molecular weight M of the polyethylene glycol polymer is w From about 10,000 g / mol to about 50,000 g / mol, or from about 15,000 g / mol to about 50,000 g / mol, or from about 20,000 g / mol to about 50,000 g / mol, or from about 25,000 g / mol to about 50,000 g / mol, or from about 20,000 g / mol to about 40,000 g / mol, or from about 25,000 g / mol to about 35,000 g / mol, or from about 15,000 g / mol to about 35,000 g / mol, or from about 15,000 g / mol to about 30,000 g / mol, or from about 15,000 g / mol to about 25,000 g / mol.

[0137] In one embodiment of the present disclosure, the weight average molecular weight M of polyethylene glycol (PEG) is w At least 20,000 g / mol, or at least 25,000 g / mol.

[0138] In one embodiment of the present disclosure, the weight average molecular weight M of polyethylene glycol (PEG) is w From about 20,000 g / mol to about 50,000 g / mol.

[0139] In an embodiment of the present disclosure, the weight average molecular weight M of polyethylene glycol (PEG) is w About 35,000 g / mol.

[0140] In an embodiment of the present disclosure, the weight average molecular weight M of polyethylene glycol (PEG) is w From about 100,000 g / mol to about 500,000 g / mol, or from about 150,000 g / mol to about 450,000 g / mol, or from about 200,000 g / mol to about 400,000 g / mol.

[0141] In an embodiment of the present disclosure, the weight average molecular weight M of polyethylene glycol (PEG) is w About 300,000 g / mol.

[0142] In one embodiment of the present disclosure, the polyols sold under the trademark POLYGLYKOL are used. TM Commercially available polyethylene glycol (PEG) was used as a polymer processing aid.

[0143] In the embodiments of the present disclosure, the trademark or Commercially available polyethylene glycol (PEG) was used as a polymer processing aid.

[0144] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w of polyalkylene glycol.

[0145] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w of polyethylene glycol.

[0146] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol w The weight average molecular weight M of the second polyethylene glycol is less than 10,000 g / mol. w Greater than 25,000 g / mol.

[0147] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol w The weight average molecular weight M of the second polyethylene glycol is less than 25,000 g / mol. w At least 25,000 g / mol.

[0148] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol w The weight average molecular weight M of the second polyethylene glycol is less than 25,000 g / mol. w At least 250,000 g / mol.

[0149] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol w The weight average molecular weight M of the second polyethylene glycol is less than 10,000 g / mol. w At least 250,000 g / mol.

[0150] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol w The weight average molecular weight M of the second polyethylene glycol is about 2,000 to about 10,000 g / mol. w From about 25,000 to about 350,000 g / mol.

[0151] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol w The weight average molecular weight M of the second polyethylene glycol is about 2,000 to about 10,000 g / mol. w From about 15,000 to about 50,000 g / mol.

[0152] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol wThe weight average molecular weight M of the second polyethylene glycol is about 2,000 to about 10,000 g / mol. w From about 15,000 to about 25,000 g / mol.

[0153] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol w The weight average molecular weight M of the second polyethylene glycol is about 2,000 to about 10,000 g / mol. w From about 25,000 to about 50,000 g / mol.

[0154] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol w The weight average molecular weight M of the second polyethylene glycol is about 2,000 to about 10,000 g / mol. w From about 250,000 to about 350,000 g / mol.

[0155] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol w The weight average molecular weight M of the second polyethylene glycol is less than 10,000 g / mol. w Greater than 10,000 g / mol.

[0156] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol w The weight average molecular weight M of the second polyethylene glycol is less than about 10,000 g / mol. w At least about 50,000 g / mol.

[0157] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, wherein the weight average molecular weight M of the first polyethylene glycol w The weight average molecular weight M of the first polyethylene glycol is about 2,000 to about 8,000 g / mol, or w The weight average molecular weight of the second polyethylene glycol is 2,000 to 5,000 g / mol; wThe weight average molecular weight M of the second polyethylene glycol is about 25,000 to about 50,000 g / mol, or w 15,000 to 25,000 g / mol.

[0158] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The weight average molecular weight M of the at least two polyethylene glycols is w The difference is in the range of 2:1 to 100,000:1, including any subranges encompassed within that range and any value within that range. For example, in an embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M w The weight average molecular weight M of at least two polyethylene glycols is w The difference is in the range of 5:1 to 100,000:1, or 2:1 to 1000:1, or 5:1 to 1000:1, or 2:1 to 500:1, or 5:1 to 500:1, or 2:1 to 100:1, or 5:1 to 100:1.

[0159] In one embodiment of the present disclosure, the polymer processing aid will comprise at least two polymers having different weight average molecular weights M. w The polyethylene glycol, and the at least two different M w The polyethylene glycol is present in a molar ratio of 1:99 to 99:1, including any subranges encompassed within that range and any values ​​within that range. For example, in an embodiment of the present disclosure, the polymer processing aid will include at least two different weight average molecular weights M w The polyethylene glycol has 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.

[0160] In one embodiment of the present disclosure, the amount of polyalkylene glycol (PAG) or polyethylene glycol (PEG) used as a polymer processing aid (PPA) is from 100 to 5,000 ppm by weight (based on the weight of the thermoplastic polyolefin, such as linear polyethylene), including any subranges within that range and any values ​​within that range. Further optimized PPA addition levels and ranges for a given extrusion process can be readily determined by one skilled in the art. For example, in certain embodiments, the amount of polyalkylene glycol (PAG) or polyethylene glycol (PEG) used as a polymer processing aid (PPA) is from 100 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 2,000 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 (based on the weight of the thermoplastic polyolefin, such as linear polyethylene).

[0161] 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 practice of first melt-mixing an additive (e.g., PEG) with a small amount of a given thermoplastic polyolefin (e.g., linear polyethylene) and then blending the resulting "masterbatch" with the bulk of the remaining thermoplastic polyolefin (e.g., linear polymer) (e.g., by melt mixing or dry blending).

[0162] In embodiments of the present disclosure, about 0.1 to about 15.0 wt%, or about 0.5 to about 15.0 wt%, or about 0.5 to about 10.0 wt%, or about 0.1 to about 10.0 wt%, or about 0.1 to about 7.5 wt%, or about 0.5 to about 7.5 wt%, or about 0.5 to about 5.0 wt%, or about 0.1 to about 5.0 wt%, or about 1.0 to about 15.0 wt%, or about 1.0 to about 5.0 wt%, or about 1.0 to about 7.5 wt%, or about 1.0 to about 5.0 wt%, or about 0.1 to about 2.5 wt%, or about 0.5 to about 2.5 wt% of a masterbatch is used in a blend with a host polymer (wherein the weight percentages of the masterbatch are based on the total weight of the masterbatch and the host polymer).

[0163] In embodiments of the present disclosure, a masterbatch (e.g., a linear polyethylene masterbatch) may contain PAG or PEG in an amount ranging from 500 to 50,000 ppm by weight (based on the weight of the masterbatch), including subranges therein and any value therein. For example, in further embodiments of the present disclosure, the masterbatch may contain 500 to 40,000 ppm, 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, or 1,000 to 25,000 ppm. m (by weight) (based on the weight of the masterbatch), 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 ppm, or 4,000 to 20,000 ppm, or 5,000 to 20,000 ppm, or 5,000 to 17,500 ppm, or 5,000 to 15,000 ppm ppm, 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 0 to 35,000 ppm, 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 of PAG or PEG.

[0164] The polyalkylene glycol or polyethylene glycol used as polymer processing aid (PPA) can be used in the form of a semisolid or viscous liquid, or as a powder, pellets or granules.

[0165] Polyamide / polyether block copolymer (i.e. polyether block amide, PEBA)

[0166] In one embodiment of the present disclosure, a polymer processing aid (PPA) for assisting in the extrusion of thermoplastic polyolefins comprises a polyether block amide copolymer having polyamide blocks and polyether blocks. In the present disclosure, such a block copolymer having polyamide blocks and polyether blocks may also be referred to as a "polyamide / polyether block copolymer." In the present disclosure, the term "polyether block amide copolymer" may be abbreviated as "PEBA copolymer," and similarly, the term "polyether block amide" may be abbreviated as "PEBA."

[0167] In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula:

[0168]

[0169] where PA is the polyamide block, PE is the polyether block, and p represents the length of the PEBA copolymer and indicates the total number of polyamide and polyether blocks.

[0170] In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula:

[0171]

[0172] wherein EG is the first unspecified terminal group, B is an unspecified bridging group, EG* is the second unspecified terminal group, and EG, B, and EG* are determined by the synthesis method used to prepare the PEBA copolymer; wherein 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 polyether block, y represents the length of the ether component in the polyether block, and p represents the length of the PEBA copolymer and indicates the total number of polyamide and polyether blocks.

[0173] In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula:

[0174]

[0175] wherein 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 polyether block, y represents the length of the ether component in the polyether block, p represents the length of the PEBA copolymer, and indicates the total number of polyamide and polyether blocks.

[0176] In one embodiment of the present disclosure, a polyether block amide copolymer ("PEBA copolymer") comprises polyamide blocks and polyether blocks.

[0177] Polyether block amide copolymers suitable for use in embodiments of the present disclosure are described in US Pat. No. 5,986,005, which is incorporated herein by reference in its entirety. PEBA copolymers suitable for use in embodiments of the present disclosure, including methods for their preparation, are further described in Malet, FLG, The Handbook of Condensation Thermoplastic Elastomers, Chapter 9 ("Thermoplastic Poly(Ether-b-Amide) Elastomers: Synthesis", 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, pp. 243-262) and Eustache, RP, The Handbook of Condensation Thermoplastic Elastomers, Chapter 10 "Poly(Ether-b-Amide) Thermoplastic Elastomers: Structure, Properties, and Applications", 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, pp. 263-281), both of which are incorporated herein by reference in their entirety.

[0178] In one embodiment, the polyether block amide copolymer is obtained by the co-condensation reaction of one or more polyamides having reactive end groups and one or more polyoxyalkylenes having reactive end groups (e.g., polyoxyethylene). The reactive end groups of the polyamide include, for example, diamine chain ends and dicarboxylic acid chain ends. The reactive end groups of the polyoxyalkylene include, for example, dicarboxylic acid chain ends, diol chain ends, and diamine chain ends.

[0179] In an embodiment, the polyoxyalkylene having diamine chain ends is obtained by cyanoethylation and hydrogenation of α,ω-dihydroxy aliphatic polyoxyalkylenes (also known in the art as polyether diols).

[0180] In an embodiment, the polyamide having dicarboxylic acid chain ends is obtained by condensation of α,ω-aminocarboxylic acid (which is a bifunctional monomer) with a lactam (e.g., laurolactam), or by condensation of a dicarboxylic acid with a diamine. The polycondensation reaction may be carried out in the presence of a chain-limiting dicarboxylic acid.

[0181] In an embodiment, 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).

[0182] In an embodiment, the polyamide blocks in the PEBA copolymer are derived from polyamide-12 (PA-12).

[0183] In an embodiment, the polyamide blocks in the PEBA copolymer are derived from polyamide-11 (PA-11).

[0184] In an embodiment, the polyamide blocks in the PEBA copolymer are derived from polyamide-6 (PA-6).

[0185] The weight average molecular weight of the PEBA copolymer (e.g. M w and M n ) can be measured, for example, by gel permeation chromatography (ie, size exclusion chromatography) using narrow molecular weight polymer standards using techniques known in the art.

[0186] In an embodiment, the number average molecular weight M of the polyamide block in the PEBA copolymer is n From about 100 to about 15,000 g / mol, or from about 300 to about 15,000 g / mol, or from about 600 to about 10,000 g / mol, or from about 600 to about 5,000 g / mol.

[0187] In an embodiment, the number average molecular weight M of the polyether block in the PEBA copolymer is n From about 100 to about 15,000 g / mol, or from about 100 to about 10,000 g / mol, or from about 100 to about 6,000 g / mol, or from about 100 to about 3,000 g / mol, or from about 200 to about 6,000 g / mol, or from about 200 to about 3,000 g / mol, or from about 250 to about 2,000 g / mol, or from about 750 to about 3,500 g / mol, or from about 1,000 to about 3,000 g / mol.

[0188] In an embodiment, the number average molecular weight M of the PEBA copolymer is n 10,000 to 500,000 g / mol, including subranges therein and any value therein. For example, in an embodiment of the present disclosure, the number average molecular weight M of the PEBA copolymer is nmol, or about 50,000 to about 75,000 g / mol, or about 100,000 to about 150,000 g / mol.

[0189] In an embodiment, the number average molecular weight M of the PEBA copolymer is n 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.

[0190] In an embodiment, the weight average molecular weight M of the PEBA copolymer is w 25,000 to 500,000 g / mol, including subranges therein and any value therein. For example, in an embodiment of the present disclosure, the weight average molecular weight M of the PEBA copolymer is w From about 100,000 to about 250,000 g / mol, or from about 100,000 to about 150,000 g / mol, or from about 125,000 to about 150,000 g / mol.

[0191] In embodiments, the polyamide blocks and polyether blocks in the PEBA copolymer may be randomly distributed.

[0192] In an embodiment, the PEBA copolymer comprises polyamide blocks and polyether blocks, with the polyamide blocks comprising at least 50% by weight of the copolymer. In an embodiment, the PEBA copolymer comprises polyamide blocks and polyether blocks, with the polyether blocks comprising at least 50% by weight of the copolymer. In a further embodiment, the PEBA copolymer comprises polyamide blocks and polyether blocks, with the molar ratio of polyamide blocks to polyether blocks being from 1:3 to 3:1, or from 1:2 to 2:1, or from 3:2 to 1:3, or from 2:3 to 3:1, or about 1:1.

[0193] In one embodiment, PEBA copolymers having polyamide blocks and polyether blocks can be prepared by reacting polyamide and polyether block precursors. For example, a lactam, a polyether diol, and a chain-limiting diacid can be reacted together in the presence of a small amount of water to produce PEBA copolymers having polyamide and polyether blocks of variable lengths and a statistically random distribution within the block copolymer chain.

[0194] In an embodiment, the polyether blocks may be derived from polyoxyethylene, polyoxypropylene, or poly(tetramethylene ether) glycol, which are co-condensed in their native state with polyamide blocks containing carboxylic acid chain ends. A chain limiter may also be present during the polycondensation reaction to produce a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed in the block copolymer.

[0195] In an embodiment, the polyether blocks may be derived from polyoxyethylene, polyoxypropylene, or poly(tetramethylene ether) glycol, which are first converted to polyetherdiamines by amination and then co-condensed with polyamide blocks containing carboxylic acid chain ends. A chain limiter may also be present during the polycondensation reaction to produce a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed in the block copolymer.

[0196] 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, all of which are incorporated herein by reference in their entirety. Additional PEBA copolymers useful in some embodiments of the present disclosure are described in U.S. Patent No. 8,231,950.

[0197] In embodiments of the present disclosure, the polyether blocks may be derived from polyethylene oxide, also known as polyethylene glycol (PEG).

[0198] In embodiments of the present disclosure, the polyether blocks may be derived from polyoxypropylene, also known as polypropylene glycol (PPG).

[0199] 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).

[0200] 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 selected from polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTHF), or a mixture thereof.

[0201] 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, wherein the polyether block is polyethylene glycol (PEG).

[0202] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, the polyamide block being polyamide-12 (PA-12); and ii) a polyether block, the polyether block being polyethylene glycol (PEG).

[0203] In some embodiments of the present disclosure, the PEBA copolymer comprises 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

[0204] In some embodiments of the present disclosure, the PEBA copolymer comprises only one type of polyamide block and only one type of polyether block.

[0205] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-12 (PA-12); and ii) a polyether block, which is polyethylene glycol (PEG), wherein the polyamide-12 block comprises about 30% to 70% by weight of the copolymer and the polyethylene glycol block comprises about 70% to 30% by weight of the copolymer.

[0206] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-12 (PA-12); and ii) a polyether block, which is polyethylene glycol (PEG), wherein the polyamide-12 block comprises about 40% to 50% by weight of the copolymer and the polyethylene glycol block comprises about 60% to 40% by weight of the copolymer.

[0207] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-12 (PA-12); and ii) a polyether block, which is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 45% by weight of the copolymer and the polyethylene glycol block accounts for about 55% by weight of the copolymer.

[0208] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) 10 to 20 polyamide blocks, which are polyamide-12 (PA-12); and ii) 10 to 20 polyether blocks, which are polyethylene glycol (PEG).

[0209] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, wherein the polyamide block is polyamide-12 (PA-12); and ii) a polyether block, wherein the polyether block is polyethylene glycol (PEG), and the number average molecular weight M of the copolymer is n From about 25,000 to about 75,000 g / mol.

[0210] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, wherein the polyamide block is polyamide-12 (PA-12); and ii) a polyether block, wherein the polyether block is polyethylene glycol (PEG), and the number average molecular weight M of the copolymer is n From about 50,000 to about 75,000 g / mol.

[0211] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, wherein the polyamide block is polyamide-12 (PA-12); and ii) a polyether block, wherein the polyether block is polyethylene glycol (PEG), and the number average molecular weight M of the copolymer is n About 66,100 g / mol.

[0212] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, wherein the polyamide block is polyamide-12 (PA-12); and ii) a polyether block, wherein the polyether block is polyethylene glycol (PEG), and the weight average molecular weight M of the copolymer is w From about 100,000 to about 150,000 g / mol.

[0213] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, wherein the polyamide block is polyamide-12 (PA-12); and ii) a polyether block, wherein the polyether block is polyethylene glycol (PEG), and the weight average molecular weight M of the copolymer is w From about 125,000 to about 150,000 g / mol.

[0214] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, wherein the polyamide block is polyamide-12 (PA-12); and ii) a polyether block, wherein the polyether block is polyethylene glycol (PEG), and the weight average molecular weight M of the copolymer is w About 134,000 g / mol.

[0215] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-6 (PA-6); and ii) a polyether block, which is polyethylene glycol (PEG).

[0216] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-6 (PA-6); and ii) a polyether block, which is polyethylene glycol (PEG), wherein the polyamide-6 block accounts for about 30% to 60% by weight of the copolymer and the polyethylene glycol block accounts for about 70% to 40% by weight of the copolymer.

[0217] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-6 (PA-6); and ii) a polyether block, which is polyethylene glycol (PEG), wherein the polyamide-6 block accounts for about 50% to 35% by weight of the copolymer and the polyethylene glycol block accounts for about 50% to 65% by weight of the copolymer.

[0218] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) 10 to 20 polyamide blocks, the polyamide blocks being polyamide-6 (PA-6); and ii) 10 to 20 polyether blocks, the polyether blocks being polyethylene glycol (PEG).

[0219] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-11 (PA-11); and ii) a polyether block, which is polyethylene glycol (PEG).

[0220] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, the polyamide block being polyamide-12 (PA-12); and ii) a polyether block, the polyether block being polytetrahydrofuran (PTHF).

[0221] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-12 (PA-12); and ii) a polyether block, which is polytetramethyleneimine (PTHF), wherein the polyamide-12 block accounts for about 75% to 10% by weight of the copolymer and the polytetramethyleneimine block accounts for about 25% to 90% by weight of the copolymer.

[0222] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-12 (PA-12); and ii) a polyether block, which is polytetramethyleneimine (PTHF), wherein the polyamide-12 block accounts for about 80% to 60% by weight of the copolymer and the polytetramethyleneimine block accounts for about 20% to 40% by weight of the copolymer.

[0223] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-12 (PA-12); and ii) a polyether block, which is polytetramethyleneimine (PTHF), wherein the polyamide-12 block accounts for about 40% to 60% by weight of the copolymer and the polytetramethyleneimine block accounts for about 60% to 40% by weight of the copolymer.

[0224] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-12 (PA-12); and ii) a polyether block, which is polytetramethyleneimine (PTHF), wherein the polyamide-12 block accounts for about 30% to 10% by weight of the copolymer and the polytetramethyleneimine block accounts for about 70% to 90% by weight of the copolymer.

[0225] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) 10 to 20 polyamide blocks, the polyamide blocks being polyamide-12 (PA-12); and ii) 10 to 20 polyether blocks, the polyether blocks being polytetrahydrofuran (PTHF).

[0226] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, wherein the polyamide block is polyamide-12 (PA-12); and ii) a polyether block, wherein the polyether block is polytetrahydrofuran (PTHF), and the number average molecular weight M of the copolymer is n From about 25,000 to about 75,000 g / mol.

[0227] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, wherein the polyamide block is polyamide-12 (PA-12); and ii) a polyether block, wherein the polyether block is polytetrahydrofuran (PTHF), and the number average molecular weight M of the copolymer is n From about 40,000 to about 60,000 g / mol.

[0228] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, wherein the polyamide block is polyamide-12 (PA-12); and ii) a polyether block, wherein the polyether block is polytetrahydrofuran (PTHF), and the number average molecular weight M of the copolymer is n About 50,000 g / mol.

[0229] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, the polyamide block being polyamide-6 (PA-6); and ii) a polyether block, the polyether block being polytetrahydrofuran (PTHF).

[0230] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block, which is polyamide-11 (PA-11); and ii) a polyether block, which is polytetrahydrofuran (PTHF).

[0231] In one embodiment of the present disclosure, PEBA copolymer is a commercially available elastomer known under the trade name Sale.

[0232] In a further embodiment 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 3533SA 01 MED, PEBAX 3533 SP 01, PEBAX 4011, PEBAX 4033 SA 01, PEBAX 4033 SA 01MED, PEBAX 4033 SP 01, PEBAX 4533 SA 01, PEBAX 4533 SA 01MED, PEBAX 4533 SP 01, PEBAX 5513 SA 01, PEBAX 5513 SP 01, PEBAX 5533 SA 01, PEBAX 5533 SA 01 MED, PEBAX 5533SN 70BLACK, PEBAX 5533 SP 01, PEBAX 6333 SA 01, PEBAX 6333 SA 01MED, PEBAX 6333SP01, 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 9002UV, PEBAX MH 1657, PEBAX MH2030, PEBAX MV 1074SA 01, PEBAX MV 1074SA01MED、PEBAX MV 1074SP 01, PEBAX MV 2080, PEBAX MV 3000SP 01, PEBAX 30R51SA 01, PEBAX RNEW 35R53 SP 01, PEBAX RNEW 40R53 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.

[0233] In one embodiment of the present disclosure, PEBA copolymer is a commercially available elastomer known under the trade name Or VESTAMID E sales.

[0234] In a further embodiment 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.

[0235] In one embodiment of the present disclosure, the polymer processing aid will comprise two polymers having different number average molecular weights M n Polyether block amide copolymer.

[0236] In one embodiment of the present disclosure, the polymer processing aid will comprise two polymers having different number average molecular weights M n Polyether block amide copolymers, and these two have different M n The polyether block amide copolymer will be present in a molar ratio of 1:99 to 99:1, including any subranges encompassed within that range and any value within that range. For example, in an embodiment of the present disclosure, the polymer processing aid will comprise two polymers having different number average molecular weights M n The polyether block amide copolymer has 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.

[0237] In one embodiment of the present disclosure, the amount of PEBA copolymer used as a polymer processing aid (PPA) is from 100 to 5,000 ppm by weight (based on the weight of the thermoplastic polyolefin), including any subranges therein and any values ​​therein. Further optimized PPA addition levels and ranges for a given extrusion process can be readily determined by one skilled in the art. For example, in certain embodiments, the amount of PEBA copolymer used as a polymer processing aid (PPA) is from 100 to 4,000 ppm by weight, 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, or from 750 to 4,000 ppm by weight, or from 750 to 4,000 ppm by weight. 0 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 (based on the weight of the thermoplastic polyolefin).

[0238] In embodiments of the present disclosure, the amount of PEBA copolymer 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, 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 (based on the weight of the thermoplastic polyolefin), or from 300 to 1,000 ppm, or from 500 to 1,000 ppm by weight, or from 750 to 1,000 ppm by weight.

[0239] In one embodiment of the present disclosure, a 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 practice of first melt-mixing an additive (e.g., a PEBA copolymer) with a small amount of a given thermoplastic polyolefin (e.g., linear polyethylene), and then blending the resulting "masterbatch" with the remainder of the thermoplastic polyolefin (e.g., linear polymer) (e.g., by melt mixing or dry blending).

[0240] In embodiments of the present disclosure, from about 0.1% to about 15.0% by weight, or from about 0.5% to about 15.0% by weight, or from about 0.5% to about 10.0% by weight, or from about 0.1% to about 10.0% by weight, or from about 0.1% to about 7.5% by weight, or from about 0.5% to about 7.5% by weight, or from about 0.5% to about 5.0% by weight, or from about 0.1% to about 5.0% by weight, or from about 1.0% to about 15.0% by weight, or from about 1.0% to about 5.0% by weight, or from about 1.0% to about 7.5% by weight, or from about 1.0% to about 5.0% by weight, or from about 0.1% to about 2.5% by weight, or from about 0.5% to about 2.5% by weight of a masterbatch is used in a blend with a host polymer (wherein the weight percentages of the masterbatch are based on the total weight of the masterbatch and the host polymer).

[0241] In embodiments of the present disclosure, a masterbatch (e.g., a linear polyethylene masterbatch) may contain PEBA copolymer in an amount ranging from 500 to 50,000 ppm by weight (based on the weight of the masterbatch), including subranges therein and any value therein. For example, in further embodiments of the present disclosure, the masterbatch may contain 500 to 40,000 ppm, 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, or 1,000 to 25,000 ppm. m (by weight) (based on the weight of the masterbatch), 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 ppm, or 4,000 to 20,000 ppm, or 5,000 to 20,000 ppm, or 5,000 to 17,500 ppm, or 5,000 to 15,000 ppm ppm, 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 0 to 35,000 ppm, 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 of the PEBA copolymer.

[0242] The PEBA copolymers used as polymer processing aids (PPAs) can be used in the form of a semisolid or viscous liquid, or as powders, pellets or granules.

[0243] Polycaprolactone (PCL) polymer

[0244] In one embodiment of the present disclosure, the polymer processing aid will comprise a polycaprolactone polymer.

[0245] In the present disclosure, the term "polycaprolactone" or its abbreviation "PCL" is used to refer to polycaprolactone polymers, which are polymers comprising as repeating units an ester derived from i) the polycondensation of a hydroxycarboxylic acid, 6-hydroxyhexanoic acid, or from ii) the ring-opening polymerization of ε-caprolactone (a cyclic ester comprising a seven-membered ring) or a substituted derivative thereof (see, for example, Labet M, Thielemans W. in "Synthesis of polycaprolactone: a review". Chemical Society Reviews, December 2009, 38(12):3484–504).

[0246] Thus, in this disclosure, the term "polycaprolactone" includes polycaprolactone polymers having as repeating units the following general formula:

[0247]

[0248] A catalyst such as stannous octoate (ie, tin(II) 2-ethylhexanoate) can be used to catalyze the ring-opening polymerization reaction.

[0249] It is also well known to those skilled in the art that polycaprolactone polymers can be prepared by ring-opening polymerization of ε-caprolactone using a suitable hydroxyl-functionalized organic compound as an initiator. For example, methanol, ethanol, and isopropanol (which are monohydric alcohols), or diethylene glycol and 1,4-butanediol (which are diols), can be used as initiators for the polymerization of ε-caprolactone.

[0250] In embodiments of the present disclosure, the polycaprolactone polymer can be a polycaprolactone monool, a polycaprolactone diol, a polycaprolactone triol, a polycaprolactone tetraol, or a mixture thereof. For example, in embodiments of the present disclosure, the polycaprolactone polymer is a polycaprolactone monool having the general formula:

[0251]

[0252] Polycaprolactone diol having the general formula:

[0253]

[0254] Polycaprolactone triol having the general formula:

[0255]

[0256] or polycaprolactone tetraol having the general formula:

[0257]

[0258] wherein m, n, p and q each represent a plurality of caprolactone units, and R is an organic group corresponding to an organic alcohol compound for initiating the ring-opening polymerization of ε-caprolactone.

[0259] As discussed above, the above R groups will reflect the specific monool, diol, triol, tetraol or polyol compound R-(OH) used as the initiator for the ring-opening polymerization of caprolactone. r For example, ethanol would provide an R group of -CH2CH2 and r would be 1, diethylene glycol would provide an R group of -CH2CH2-O-CH2CH2- and r would be 2, and 1,4-butanediol would provide an R group of -CH2CH2CH2CH2- and r would be 2.

[0260] The present disclosure also contemplates the use of either or both unsubstituted polycaprolactone polymers and substituted polycaprolactone polymers as polymer processing aids. Such unsubstituted or substituted polycaprolactone polymers can be represented by the following general formula:

[0261]

[0262] wherein R is as defined 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 hydroxyl groups.

[0263] In one embodiment, r is 1.

[0264] In one embodiment, r is 2-8.

[0265] In one embodiment, at least 6 of the R' moieties are hydrogen.

[0266] In one embodiment, each R' is hydrogen.

[0267] In one embodiment, r is 2-4.

[0268] 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 provided in US Pat. No. 3,169,945 and US Pat. No. 4,751,112.

[0269] 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 comprising units constituting a polyoxyalkylene polymer.

[0270] In one embodiment of the present disclosure, the polycaprolactone polymer is a commercially available polyester known under the trade name Sale.

[0271] In one embodiment of the present disclosure, the polycaprolactone polymer is a commercially available polyester known under the trade name and Sale.

[0272] In an embodiment of the present disclosure, the polycaprolactone polymer is prepared by ring-opening polymerization of ε-caprolactone using an initiator selected from the group consisting of butanediol, diethylene glycol, hexanediol, monoethylene glycol, pentaerythritol, trimethylolpropane, neopentyl glycol, and butylethylpropylene glycol.

[0273] The weight average molecular weight of the polycaprolactone polymer (e.g., M w and M n ) can be measured, for example, by gel permeation chromatography (ie, size exclusion chromatography) using narrow molecular weight polymer standards using techniques known in the art.

[0274] In an embodiment, the number average molecular weight M of the polycaprolactone polymer is n 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.

[0275] In an embodiment, the number average molecular weight M of the polycaprolactone polymer is n Greater than 30,000 g / mol. For example, in an embodiment of the present disclosure, the number average molecular weight M of the polycaprolactone polymer is n30,000 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.

[0276] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M n It is approximately 400 g / mol and is derived from ε-caprolactone using a diol (such as 1,4-butanediol) as an initiator.

[0277] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M n It is approximately 1,000 g / mol and is derived from ε-caprolactone using a diol (such as 1,4-butanediol) as an initiator.

[0278] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M n It is approximately 2,000 g / mol and is derived from ε-caprolactone using a diol (such as 1,4-butanediol) as an initiator.

[0279] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M n It is approximately 4,000 g / mol and is derived from ε-caprolactone using a diol (such as 1,4-butanediol) as an initiator.

[0280] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M n It is approximately 32,000 g / mol and is derived from ε-caprolactone using a diol (such as 1,4-butanediol) as an initiator.

[0281] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M n It is approximately 32,000 g / mol and is derived from ε-caprolactone using a diol (such as 1,4-butanediol) as an initiator.

[0282] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monool polymer having a number average molecular weight M nThe polycaprolactone polymer is about 200 g / mol to about 10,000 g / mol and is derived from ε-caprolactone using a linear monohydric alcohol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monohydric alcohol polymer having a number average molecular weight M n The polycaprolactone polymer is about 400 g / mol to about 8,000 g / mol and is derived from ε-caprolactone using a linear monohydric alcohol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monool polymer having a number average molecular weight M n The polycaprolactone polymer is about 500 g / mol to about 6,000 g / mol and is derived from ε-caprolactone using a linear monohydric alcohol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monohydric alcohol polymer having a number average molecular weight M n The polycaprolactone polymer is about 750 g / mol to about 4,000 g / mol and is derived from ε-caprolactone using a linear monohydric alcohol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monohydric alcohol polymer having a number average molecular weight M n The polycaprolactone polymer is about 750 g / mol to about 2,000 g / mol and is derived from ε-caprolactone using a linear monohydric alcohol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monool polymer having a number average molecular weight M n The range is from about 500 g / mol to about 1,500 g / mol and is derived from ε-caprolactone using a linear monohydric alcohol (such as cetyl alcohol) as an initiator.

[0283] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monool polymer having a number average molecular weight M n The polycaprolactone polymer is a polycaprolactone monool polymer having a number average molecular weight M of about 200 g / mol to about 10,000 g / mol and is derived from ε-caprolactone using a branched monool as an initiator. n The polycaprolactone polymer is a polycaprolactone monool polymer having a number average molecular weight M of about 400 g / mol to about 8,000 g / mol and is derived from ε-caprolactone using a branched monool as an initiator. n The polycaprolactone polymer is a polycaprolactone monool polymer having a number average molecular weight M of about 500 g / mol to about 6,000 g / mol and is derived from ε-caprolactone using a branched monool as an initiator. nThe polycaprolactone polymer is a polycaprolactone monool polymer having a number average molecular weight M of about 750 g / mol to about 4,000 g / mol and is derived from ε-caprolactone using a branched monool as an initiator. n The polycaprolactone polymer is a polycaprolactone monool polymer having a number average molecular weight M of about 750 g / mol to about 2,000 g / mol and is derived from ε-caprolactone using a branched monool as an initiator. n It is about 500 g / mol to about 1,500 g / mol and is derived from ε-caprolactone using a branched monohydric alcohol as an initiator.

[0284] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M n The polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M of about 200 g / mol to about 10,000 g / mol and is derived from ε-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 M of about 100 g / mol to about 10,000 g / mol and is derived from ε-caprolactone using a linear diol (e.g., 1,4-butanediol, hexanediol, diethylene glycol) as an initiator. n The polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M of about 400 g / mol to about 8,000 g / mol and is derived from ε-caprolactone using a linear diol (e.g., 1,4-butanediol, hexanediol, or diethylene glycol) as an initiator. n The polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M of about 500 g / mol to about 6,000 g / mol and is derived from ε-caprolactone using a linear diol (e.g., 1,4-butanediol, hexanediol, or diethylene glycol) as an initiator. n The initiator is about 750 g / mol to about 4,000 g / mol and is derived from ε-caprolactone using a linear diol such as 1,4-butanediol, hexanediol, or diethylene glycol as an initiator.

[0285] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M n The polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M of about 200 g / mol to about 10,000 g / mol and is derived from ε-caprolactone using a branched diol (e.g., neopentyl glycol or butyl ethyl propylene 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 M of about 100 g / mol to about 10,000 g / mol and is derived from ε-caprolactone using a branched diol (e.g., neopentyl glycol or butyl ethyl propylene glycol) as an initiator. nThe polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M of about 400 g / mol to about 8,000 g / mol and is derived from ε-caprolactone using a branched diol (e.g., neopentyl glycol or butyl ethyl propylene 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 M of about 400 g / mol to about 8,000 g / mol and is derived from ε-caprolactone using a branched diol (e.g., neopentyl glycol or butyl ethyl propylene glycol) as an initiator. n The polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight M of about 500 g / mol to about 6,000 g / mol and is derived from ε-caprolactone using a branched diol (e.g., neopentyl glycol or butyl ethyl propylene 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 M of about 500 g / mol to about 6,000 g / mol and is derived from ε-caprolactone using a branched diol (e.g., neopentyl glycol or butyl ethyl propylene glycol) as an initiator. n The initiator is about 750 g / mol to about 4,000 g / mol and is derived from ε-caprolactone using a branched diol such as neopentyl glycol or butyl ethyl propylene glycol as an initiator.

[0286] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight M n In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight M n In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight M of about 200 g / mol to about 6,000 g / mol and is derived from ε-caprolactone using a linear triol as an initiator. n In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight M of about 200 g / mol to about 4,000 g / mol and is derived from ε-caprolactone using a linear triol as an initiator. n It is about 200 g / mol to about 3,000 g / mol and is derived from ε-caprolactone using a linear triol as an initiator.

[0287] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight M n The polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight M of about 100 g / mol to about 8,000 g / mol and is derived from ε-caprolactone using a branched triol (e.g., trimethylolpropane) as an initiator. nThe polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight M of about 200 g / mol to about 6,000 g / mol and is derived from ε-caprolactone using a branched triol (e.g., trimethylolpropane) as an initiator. n The polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight M of about 200 g / mol to about 4,000 g / mol and is derived from ε-caprolactone using a branched triol (e.g., trimethylolpropane) as an initiator. n It is about 200 g / mol to about 3,000 g / mol and is derived from ε-caprolactone using a branched triol (such as trimethylolpropane) as an initiator.

[0288] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone tetraol polymer having a number average molecular weight M n The polycaprolactone polymer is a polycaprolactone tetraol polymer having a number average molecular weight M of about 100 g / mol to about 15,000 g / mol and is derived from ε-caprolactone using a tetraol (e.g., pentaerythritol) as an initiator. n The polycaprolactone polymer is a polycaprolactone tetraol polymer having a number average molecular weight M of about 200 g / mol to about 10,000 g / mol and is derived from ε-caprolactone using a tetraol (e.g., pentaerythritol) as an initiator. n It ranges from about 200 g / mol to about 8,000 g / mol and is derived from ε-caprolactone using a tetraol (eg, pentaerythritol) as an initiator.

[0289] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone copolymer derived from ε-caprolactone using a polyalkylene glycol (eg, poly(tetramethylene ether) glycol, also known as polytetrahydrofuran) as an initiator.

[0290] 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 within this range and any values ​​within this range. Those skilled in the art can easily determine further optimized PPA addition levels and ranges for a given extrusion process. 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, 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, or from 750 to 4,000 ppm by weight, or from 750 to 4,000 ppm by weight. 0 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 (based on the weight of the thermoplastic polyolefin).

[0291] In one embodiment of the present disclosure, a 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. Generally, the term "masterbatch" refers to the practice of first melt-mixing an additive (e.g., a polycaprolactone polymer) with a small amount of a given thermoplastic polyolefin (e.g., linear polyethylene) and then blending the resulting "masterbatch" with the remainder of the thermoplastic polyolefin (e.g., linear polymer) (e.g., by melt mixing or dry blending).

[0292] In embodiments of the present disclosure, about 0.1 to about 15.0 wt%, or about 0.5 to about 15.0 wt%, or about 0.5 to about 10.0 wt%, or about 0.1 to about 10.0 wt%, or about 0.1 to about 7.5 wt%, or about 0.5 to about 7.5 wt%, or about 0.5 to about 5.0 wt%, or about 0.1 to about 5.0 wt%, or about 1.0 to about 15.0 wt%, or about 1.0 to about 5.0 wt%, or about 1.0 to about 7.5 wt%, or about 1.0 to about 5.0 wt%, or about 0.1 to about 2.5 wt%, or about 0.5 to about 2.5 wt% of a masterbatch is used in a blend with a host polymer (wherein the weight percentages of the masterbatch are based on the total weight of the masterbatch and the host polymer).

[0293] In embodiments of the present disclosure, a masterbatch (e.g., a linear polyethylene masterbatch) may contain polycaprolactone polymer in an amount ranging from 500 to 50,000 ppm by weight (based on the weight of the masterbatch), including subranges therein and any value therein. For example, in further embodiments of the present disclosure, the masterbatch may contain from 500 to 40,000 ppm, or from 500 to 35,000 ppm, or from 500 to 40,000 ppm, or from 500 to 25,000 ppm, or from 1,000 to 40,000 ppm, or from 1,000 to 35,000 ppm, or from 1,000 to 30,000 ppm, or from 1,000 to 25,000 ppm. m (by weight) (based on the weight of the masterbatch), 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 ppm, or 4,000 to 20,000 ppm, or 5,000 to 20,000 ppm, or 5,000 to 17,500 ppm, or 5,000 to 15,000 ppm ppm, 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 The polycaprolactone polymer is present in an amount ranging from 0 to 35,000 ppm, or 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.

[0294] Polycaprolactone (PCL) polymers used as polymer processing aids (PPAs) can be used in the form of a semi-solid or viscous liquid, or as a powder, pellets or granules.

[0295] High-pressure low-density polyethylene (LDPE)

[0296] In one embodiment of the present disclosure, the polymer processing aid will comprise high pressure low density polyethylene (LDPE).

[0297] In the present disclosure, high pressure low density polyethylene (LDPE) is an ethylene homopolymer prepared by free radical homopolymerization of ethylene.

[0298] Without wishing to be bound by theory, LDPE has a high degree of so-called long-chain branching (which may be as long as the main polymer backbone), which imparts a nonlinear microstructure to LDPE. Thus, high-pressure low-density polyethylene (LDPE) differs from linear polyethylene produced using ethylene polymerization catalysts, as described further below, which has a linear polymer microstructure. For a further description of high-pressure low-density polyethylene (LDPE) used in the present disclosure, see Norma Maraschin's "Polyethylene, Low Density," first published on March 18, 2005, in Kirk-Othmer Encyclopedia of Chemical Technology, which is incorporated herein by reference in its entirety.

[0299] In an embodiment of the present disclosure, high pressure low density polyethylene (LDPE) is produced in a tubular reactor or an autoclave reactor.

[0300] Tubular reactors operate in continuous mode and operate at high pressure and temperature. Typical operating pressures for tubular reactors are 2,000 to 3,500 bar, and operating temperatures range from 140 to 340°C. Reactor designs have large aspect 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 for multi-zone systems are typically 22% to 30% per pass, but can be as high as 36% to 40%. Tubular reactors may have multiple injection points for adding monomer or initiator to different reaction zones at different temperatures.

[0301] Autoclave reactors may have aspect ratios ranging from 2 to 20 and may be single-stage or multi-stage. Typically, low-temperature ethylene is passed into the heated reaction zone, and conversion can be controlled by the temperature difference between the incoming ethylene gas and the autoclave reactor. Conversion rates in autoclave reactors are generally lower than those in tubular reactors, reaching a maximum of 23% per pass, as tubular reactors have a higher polymerization heat removal capacity. Typical operating pressures in autoclave reactors range from 1,100 to 2,000 bar, and average operating temperatures range from 220 to 300°C, although temperatures as high as 340°C can be achieved.

[0302] The reactor of every type can use multiple initiators to initiate the free radical polymerization of ethene.Initiator can comprise oxygen or one or more organic peroxides, such as but not limited to di-tert-butyl peroxide, cumyl peroxide, tert-butyl peroxypivalate, tert-butyl hydroperoxide, benzoyl peroxide, tert-amyl peroxypivalate, peroxidized-2-ethylhexanoic acid tert-butyl ester and decanoyl peroxide.Chain transfer reagent also can be used for the reactor of every type to control polymer melt index.Chain transfer reagent includes but not limited to propane, normal butane, normal hexane, hexamethylene, propylene, 1-butylene and isobutylene.

[0303] In an embodiment of the present disclosure, the density of LDPE is about 0.910 g / cm 3 to about 0.940 g / cm 3 , including subranges within that range or any value within that range. For example, in an embodiment of the present disclosure, the density of LDPE is about 0.914 g / cm 3 to about 0.930g / cm 3 , or about 0.916 g / cm 3 to about 0.930g / cm 3 , or about 0.920 g / cm 3 to about 0.940 g / cm 3 , or about 0.920 g / cm 3 to about 0.930g / cm 3 .

[0304] In an embodiment, the LDPE used in the present 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.

[0305] In embodiments, the LDPE used in the present 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.

[0306] In an embodiment, the LDPE used in the present disclosure has a melt index (I2) 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. 5g / 10min, or 2.5 to 8.0g / 10min, or 3.0 to 9.0g / 10min, or 3.0 to 8.5g / 10min, or 3.0 to 8.0g / 10min, or 3.5 to 9.0g / 10min, or 3.5 to 8.5g / 10min, or 3.5 to 8.0g / 10min, or 4.0 to 9.0g / 10min, or 4.0 to 8.5g / 10min, or 4.0 to 8.0g / 10min.

[0307] In an embodiment, the LDPE used in the present disclosure has a melt index (I2) of less than 1.0 g / 10 min. Such LDPE may be referred to as a "frac melt" LDPE material. In a further embodiment, the LDPE used in the present 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.

[0308] In an embodiment of the present disclosure, the high pressure low density polyethylene (LDPE) is a blend of LDPE materials of different densities and / or different melt indices (I2).

[0309] In one embodiment, the low density polyethylene (LDPE) is a blend of LDPE produced in a tubular reactor and LDPE produced in an autoclave reactor.

[0310] In one embodiment, the LDPE polymer blend is prepared by physically blending different high-pressure LDPEs (e.g., an LDPE produced in a tubular reactor with an LDPE produced in an autoclave reactor). Physical blending is intended to encompass those processes in which two or more separate ethylene homopolymers are mixed after they have been removed from the polymerization reaction zone. Physical blending of the separate LDPEs can be achieved by dry blending (e.g., tumble blending), extrusion blending (coextrusion), solution blending, melt blending, or any other similar blending technique known to those skilled in the art.

[0311] Polydispersity (M w / M n ), also known as molecular weight distribution (MWD), is defined as the weight average molecular weight (M w ) divided by the number average molecular weight (M nIn an embodiment of the present disclosure, the MWD of the LDPE is determined by gel permeation chromatography (GPC)-viscometry. The GPC-viscometry technique is based on the ASTM D6474-99 method and uses a birefringence / viscometer detector system to analyze polymer samples. This method allows for online determination of intrinsic viscosity and is well known to those skilled in the art.

[0312] In embodiments of the present disclosure, the LDPE has a MWD greater than about 5.0. In embodiments of the present disclosure, the LDPE has a MWD of from about 8.0 to about 30.0.

[0313] The molecular weight distribution of LDPE or its blends can be further described as unimodal, bimodal, or multimodal. The term "unimodal" means that the molecular weight distribution can be described as having only one maximum in the molecular weight distribution curve. The molecular weight distribution curve can be generated according to the ASTM D6474-99 method. The term "bimodal" means that the molecular weight distribution can be described as having two maxima in the molecular weight distribution curve. The term "multimodal" indicates that more than two maxima are present in such a curve.

[0314] In embodiments of the present disclosure, the LDPE used has a unimodal, bimodal or multimodal molecular weight distribution.

[0315] In one embodiment of the present disclosure, the LDPE used is produced in a tubular reactor and has a multimodal molecular weight distribution.

[0316] In an embodiment of the present disclosure, the LDPE used is produced in an autoclave reactor and has a bimodal or multimodal molecular weight distribution.

[0317] In one embodiment of the present disclosure, an LDPE blend is used, and the blend has a multimodal molecular weight distribution.

[0318] In embodiments of the present disclosure, the antioxidant package used to stabilize LDPE is well known in the art and may include phenolic compounds and phosphite compounds. Two non-limiting examples of phenolic and phosphite stabilizers that can be added to LDPE in embodiments of the present disclosure are listed under the trade names 1076 and 168 sales. Phenolic compounds are sometimes called "primary" antioxidants and phosphite compounds are sometimes called "secondary" antioxidants.

[0319] In an embodiment of the present disclosure, the antioxidant level present in the LDPE is from 0 to 2,000 ppm by weight (based on the weight of the LDPE). In further embodiments, the antioxidant is present in the LDPE in an amount 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).

[0320] In embodiments of the present disclosure, LDPE may be used in the form of powder, pellets, granules, or any other extrudable form.

[0321] In the present disclosure, the amount of LDPE used as a polymer processing aid is relatively low relative to the weight of the main thermoplastic polyolefin material (e.g., linear polyethylene). Therefore, in embodiments of the present disclosure, the amount of LDPE used is 1.0 to 25.0 weight percent based on the total weight of LDPE and the main thermoplastic polyolefin (e.g., linear polyolefin), including subranges therein and any value therein. For example, in embodiments of the present disclosure, the amount of LDPE is from 1.0 to 20.0 weight percent, or from 3.0 to 20.0 weight percent, or from 5.0 to 20.0 weight percent, or from 5.0 to 15.0 weight percent, or from 5.0 to 12.5 weight percent, or from 7.5 to 12.5 weight percent, or from 7.5 to 15.0 weight percent, or from 7.5 to 20.0 weight percent, or from 3.0 to 17.5 weight percent, or from 3.0 to 15.0 weight percent, or from 2.5 to 20.0 weight percent, or from 2.5 to 15.0 weight percent, or from 2.5 to 12.5 weight percent, or from greater than 0 to 20.0 weight percent, or from greater than 0 to 15.0 weight percent, or from greater than 0 to 12.5 weight percent.

[0322] Thermoplastic polyolefins (e.g. linear polyethylene)

[0323] The present disclosure is generally applicable to extrudable thermoplastic polyolefins, but in one embodiment, the present disclosure is particularly useful for improving the extrusion of linear polyethylene.

[0324] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") comprises: a linear polyethylene; and a monovalent metal carboxylate; but is substantially free of fluoroelastomers, fluoropolymers, and other perfluorinated alkane derivatives.

[0325] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") comprises: a linear polyethylene; and a monovalent metal aliphatic carboxylate; but is substantially free of fluoroelastomers, fluoropolymers, and other perfluorinated alkane derivatives.

[0326] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") comprises: a linear polyethylene; a monovalent metal carboxylate; and one or more of:

[0327] Polyoxyalkylene polymers, also known as polyalkylene glycols (PAGs);

[0328] A polyether block amide copolymer, wherein the polyether block amide copolymer comprises a polyamide block and a polyether block;

[0329] Polycaprolactone (PCL) polymers; and

[0330] High-pressure low-density polyethylene (LDPE);

[0331] It is virtually free of fluoroelastomers, fluoropolymers and other perfluorinated alkane derivatives.

[0332] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") comprises: a linear polyethylene; a monovalent metal aliphatic carboxylate; and one or more of:

[0333] Polyoxyalkylene polymers, also known as polyalkylene glycols (PAGs);

[0334] A polyether block amide copolymer, wherein the polyether block amide copolymer comprises a polyamide block and a polyether block;

[0335] Polycaprolactone (PCL) polymers; and

[0336] High-pressure low-density polyethylene (LDPE);

[0337] It is virtually free of fluoroelastomers, fluoropolymers and other perfluorinated alkane derivatives.

[0338] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") comprises: a linear polyethylene; a monovalent metal carboxylate; and a polyoxyalkylene polymer, also known as a polyalkylene glycol (PAG);

[0339] It is virtually free of fluoroelastomers, fluoropolymers and other perfluorinated alkane derivatives.

[0340] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") comprises: a linear polyethylene; a monovalent metal aliphatic carboxylate; and a polyoxyalkylene polymer, also known as a polyalkylene glycol (PAG);

[0341] It is virtually free of fluoroelastomers, fluoropolymers and other perfluorinated alkane derivatives.

[0342] "Substantially free" means that the amount of fluoroelastomers, fluoropolymers and other perfluorinated alkane derivatives present is less than an amount that can improve the melt defect (e.g., melt fracture) performance of the thermoplastic composition during melt extrusion. In embodiments of the present disclosure, the fluoroelastomers, fluoropolymers and other perfluorinated alkane derivatives will be 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.

[0343] In one embodiment of the present disclosure, the major or predominant component of an extrudable or extruded thermoplastic composition ("extrudate") is a linear polyethylene. In embodiments, such an "extrudate" will comprise linear polyethylene in an amount of at least about 70 weight percent, or at least about 75 weight percent, or at least about 80 weight percent, or at least about 85 weight percent of the extrudate composition.

[0344] The extrudable or extruded thermoplastic composition ("extrudate"), in embodiments of the present disclosure, may comprise a mixture of more than one different type of linear polyethylene.

[0345] Linear polyethylene is distinguished from high-pressure low-density polyethylene (LDPE), which has a branched polymer microstructure (due to the presence of extensive long-chain branching) and is produced via a high-pressure free-radical polymerization process. Linear polyethylene is produced using transition metal-based olefin polymerization catalysts and has a linear polymer microstructure.

[0346] Olefin polymerization catalysts used to prepare linear polyethylene are well known in the art. Linear polyethylene can be prepared using so-called single-site polymerization catalysts 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.

[0347] Linear polyethylenes include homogeneously branched linear ethylene polymers (as described in U.S. Pat. No. 3,645,992); heterogeneously branched linear ethylene polymers (as described in U.S. Pat. No. 4,076,698); and homogeneously branched linear ethylene polymers containing long chain branching (but 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.

[0348] The term "homogeneously branched" refers to linear ethylene copolymers in which the α-olefin comonomer is randomly distributed among the copolymer molecules, substantially all copolymer molecules have the same ethylene to α-olefin monomer ratio, and the ethylene copolymer is characterized by a relatively narrow distribution of short chain branches, as indicated, for example, by the composition distribution index (CDBI). 50 ) is 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. Homogeneously branched ethylene copolymers are typically prepared using single-site olefin polymerization catalysts.

[0349] As used herein, the term "heterogeneously branched" is used to refer to linear ethylene copolymers characterized by a relatively broad distribution of short chain branches, as indicated, for example, by the composition distribution index (CDBI) 50 ) is less than about 75 weight percent, or in some embodiments, less than about 50 weight percent. Heterogeneously branched ethylene copolymers are typically prepared using multi-site olefin polymerization catalysts.

[0350] In an embodiment of the present disclosure, the linear polyethylene is selected from ethylene homopolymers and copolymers, comprising a polyethylene having the general formula CH2═CHR 3 The polymer unit, where R 3 In the embodiment of the present disclosure, R 3 is a hydrocarbon group having up to 10 carbon atoms. In other embodiments 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 (ie, styrene as an α-olefin) or an n-hexyl group (ie, 1-octene as an α-olefin).

[0351] In an embodiment of the present disclosure, the linear polyethylene is an ethylene homopolymer or an ethylene copolymer.

[0352] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more polymerized α-olefins (selected from the group consisting of C3-C 12 α-olefins).

[0353] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more polymerized α-olefins (selected from the group consisting of C3-C 12 α-olefins), and the polymerized ethylene constitutes at least 85 weight percent of the ethylene copolymer.

[0354] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more polymerized α-olefins (selected from the group consisting of C3-C 12 α-olefins), and the polymerized ethylene constitutes at least 90 weight percent of the ethylene copolymer.

[0355] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more than one polymerized α-olefin selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and 1-octadecene.

[0356] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more than one polymerized α-olefin selected from the group comprising 1-butene, 1-hexene, and 1-octene.

[0357] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more α-olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene, and the polymerized ethylene comprises at least 85 weight percent of the ethylene copolymer.

[0358] In an embodiment of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more polymerized α-olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene, and the polymerized ethylene comprises at least 90 weight percent of the ethylene copolymer.

[0359] Linear polyethylene can be prepared by using one or more olefin polymerization catalysts in any conventionally known process, such as gas phase polymerization, slurry phase polymerization, or solution phase polymerization.

[0360] In the gas phase polymerization process, the transition metal polymerization catalyst can be fixed on a suitable support material, and the resulting particle catalyst can be used for a fluidized bed polymerization process. Typically, a fluidized bed gas phase polymerization reactor employs a "bed" of polymer and catalyst particles fluidized by a stream of monomers and other optional components (which are at least partially gaseous). The heat generated by the enthalpy of polymerization of the monomers (and optional one or more comonomers) flows through the bed. Unreacted monomers and other optional gaseous components leave the fluidized bed and contact the cooling system to remove heat. The cooled gas stream, including monomers and optional other components (such as condensable liquids), is then recycled through the polymerization zone together with the "supplementary" monomer to replace the monomer of the previous polymerization. Simultaneously, the polymer product is taken out from the reactor. As will be appreciated by those skilled in the art, the "fluidization" property of the polymerization bed contributes to uniform distribution / mixing of reaction heat, thereby minimizing the formation of local temperature gradients.

[0361] In embodiments, the reactor pressure in the gas phase process can vary from about atmospheric pressure to about 600 psig. In another embodiment, the pressure range can be from about 100 psig (690 kPa) to about 500 psig (3448 kPa). In yet another embodiment, the pressure range can be from about 200 psig (1379 kPa) to about 400 psig (2759 kPa). In another embodiment, the pressure range can be from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).

[0362] In the slurry phase polymerization process, the transition metal polymerization catalyst can be fixed on a suitable support material, and the resulting particulate catalyst can be used in the 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 hydrocarbon, or a cycloalkane. The diluent can also be an α-olefin comonomer used for copolymerization. Some non-limiting alkane diluents include propane, butane (i.e., n-butane and / or isobutane), pentane, hexane, heptane, and octane. The monomer can be soluble in the diluent (or miscible with the diluent), but the polymer (under polymerization conditions) is not. In an embodiment, 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 α-olefin homopolymer or copolymer is generated in the form of solid particles. The reaction pressure is affected by the choice of diluent and reaction temperature. For example, in embodiments, the pressure range can be from 15 to 45 atmospheres (about 220 to 660 psi or about 1500 to about 4600 kPa) when isobutane is used as the diluent, to about twice that (i.e., 30 to 90 atmospheres - about 440 to 1300 psi or about 3000 to 9100 kPa) when propane is used. The pressure in the slurry process must be kept high enough to keep at least a portion of the ethylene and / or α-olefins polymerized in the liquid phase. The reaction is typically carried out in a jacketed closed loop reactor with an internal agitator (e.g., an impeller) and at least one settling leg. The catalyst, monomer, and diluent are fed into the reactor in the form of a liquid or suspension. The slurry is circulated through the reactor, and the jacket is used to control the temperature of the reactor. The slurry enters the settling legs through a series of letdown valves, where the pressure is then reduced to flash the diluent and unreacted monomer, and the polymer is typically recovered in a cyclone separator. The diluent and unreacted monomer are recovered and recycled back to the reactor.

[0363] Solution polymerization processes for the polymerization or copolymerization of olefins (such as ethylene and α-olefins) are well known in the art. Solution processes are typically carried out in the presence of an inert hydrocarbon solvent in which the resulting polyolefin is soluble under the polymerization conditions employed. In embodiments of the present disclosure, the solvent used in the solution phase polymerization process is selected from C 5-12 Hydrocarbons, which may be unsubstituted or replaced by C 1-4Alkyl substituted, including hydrocarbon solvents such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha. Another commercially available solvent suitable for use in the presently disclosed embodiments is "Isopar E" (C 8-12 Aliphatic solvents, Exxon Chemical Company). The polymerization temperature in a conventional solution process can be from about 80° C. to about 300° C. In embodiments of the present disclosure, the polymerization temperature in a solution process is from about 120° C. to about 250° C. The polymerization pressure in the solution process can be 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 embodiments 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).

[0364] In solution polymerization, the monomers are dissolved / dispersed in a solvent before being fed to the reactor (or for gaseous monomers, the monomers can be fed into the reactor to dissolve in the reaction mixture). Prior to mixing, the solvent and monomers are typically purified to remove potential catalyst poisons, such as water, oxygen, or metallic impurities. Raw material purification follows standard practices in the art, such as using molecular sieves, alumina beds, and oxygen scavenging catalysts to purify the monomers. The solvent itself (e.g., methylpentane, cyclohexane, hexane, or toluene) can also be treated in a similar manner.

[0365] The feedstock may be heated or cooled before being fed to the reactor.

[0366] Typically, olefin polymerization catalyst components (e.g., olefin polymerization catalyst molecules, ionic activators, and optional alkylaluminoxanes) can be premixed in a reaction solvent or fed into a solution phase polymerization reactor as a separate stream. In some cases, premixing may be necessary to provide reaction time for the catalyst components before entering the reaction. This "online mixing" technique is described in U.S. Patent No. 5,589,555.

[0367] The solution phase polymerization process can be carried out in one or more stirred tank reactors (eg, continuous stirred tank reactors), loop reactors, or similar equipment, which can be arranged in series or in parallel with each other.

[0368] Examples of well-known linear polyethylene 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).

[0369] In the present disclosure, high-density polyethylene (HDPE) is an ethylene homopolymer or a copolymer of ethylene and another α-olefin (e.g., 1-butene, 1-hexene, and / or 1-octene) having a density of about 0.949 g / cm 3 In an embodiment, the HDPE is an ethylene homopolymer or a copolymer of ethylene and another α-olefin (e.g., 1-butene, 1-hexene, and / or 1-octene) having 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 embodiments, HDPE is a homopolymer of ethylene or a copolymer of ethylene and another α-olefin (e.g., 1-butene, 1-hexene, and / or 1-octene) having a density ranging from about 0.950 g / cm 3 To about 0.970g / cm 3 , or from about 0.950g / cm 3 To about 0.965g / cm 3 .

[0370] In the present disclosure, linear low density polyethylene (LLDPE) is a copolymer of ethylene and another α-olefin (e.g., 1-butene, 1-hexene, and / or 1-octene) having a density of about 0.910 g / cm 3 to about 0.940 g / cm 3 In an embodiment of the present disclosure, the density of LLDPE is from 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 .

[0371] In the present disclosure, medium density polyethylene (MDPE) is a copolymer of ethylene and another α-olefin (e.g., 1-butene, 1-hexene, and / or 1-octene) having a density of about 0.940 g / cm 3 to about 0.949 g / cm 3 , including subranges within that range or any value within that range.

[0372] In the present disclosure, very low density polyethylene is a copolymer of ethylene and another α-olefin (e.g., propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and / or 1-octene) having a density of less than about 0.910 g / cm 3, and may include so-called elastomers and plastomers. In an embodiment, VLDPE is a copolymer of ethylene and another α-olefin (e.g., propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and / or 1-octene) having a density of about 0.880 g / cm 3 to about 0.910 g / cm 3 , or about 0.880 g / cm 3 to about 0.905g / cm 3 , or about 0.880 g / cm 3 to about 0.902g / cm 3 .

[0373] In an embodiment of the present disclosure, the linear polyethylene has a density of 0.900 to 0.955 g / cm 3 , or 0.900 to 0.950 g / cm 3 .

[0374] 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.

[0375] Depending on the type of polymerization process and olefin polymerization catalyst used, in embodiments of the present disclosure, the weight average molecular weight M of the linear polyethylene may be w The weight average molecular weight M of the linear polyethylene may be at least about 10,000 g / mol and up to about 1,500,000 g / mol, including any subranges therein or any values ​​therein. For example, in a further embodiment, the weight average molecular weight M of the linear polyethylene may be at least about 10,000 g / mol and up to about 1,500,000 g / mol. w The range is 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 from about 75,000 to about 500,000 g / mol 00 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.

[0376] In an embodiment of the present disclosure, the molecular weight distribution M of the linear polyethylene is w / M n is from about 2.0 to about 12.0, including subranges therein or any value therein. For example, in an embodiment of the present disclosure, the M of the linear polyethylene w / M n The values ​​are from about 2.0 to about 10.0, or from about 2.0 to about 8.0, or from about 2.0 to about 5.0.

[0377] In embodiments of the present disclosure, the linear polyethylene is characterized by its melt index I2, measured at 190°C according to ASTM D1238 Condition E. 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 subranges within that range or any value within that 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.

[0378] In an embodiment of the present disclosure, the linear polyethylene selected from LLDPE, MDPE, HDPE, VLDPE, and mixtures thereof may be used in the form of powder, pellets, granules, or any other extrudable form.

[0379] In an embodiment of the present disclosure, the linear polyethylene is LLDPE.

[0380] 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.

[0381] In one embodiment of the present disclosure, the linear polyethylene is a polyethylene having a density of about 0.910 g / cm 3 to about 0.936 g / cm 3 and LLDPE having a melt index I2 of 0.1 to 10.0 g / 10 min.

[0382] In one embodiment of the present disclosure, the linear polyethylene is a polyethylene having a density of about 0.910 g / cm 3 to about 0.936 g / cm 3 and LLDPE having a melt index I2 of 0.1 to 5.0 g / 10 min.

[0383] In an embodiment of the present disclosure, the linear polyethylene has a molecular weight distribution M w / M n LLDPE having an M of from about 2.0 to about 12.0, including subranges therein or any value therein. For example, in embodiments of the present disclosure, the LLDPE has an M of w / M n The values ​​are from about 2.0 to about 10.0, or from about 2.0 to about 8.0, or from about 2.0 to about 5.0.

[0384] In some embodiments of the present disclosure, the linear polyethylene will contain a small amount (defined as <3.0 weight percent, wt%, based on the total weight of the linear polymer and the LDPE) of high pressure low density polyethylene, LDPE, having a melt index below about 1.0 g / 10 min. In some embodiments of the present disclosure, the homogeneously branched linear polyethylene will contain a small amount (defined as <3.0 weight percent, wt%, based on the total weight of the linear polymer and the LDPE) of high pressure low density polyethylene, LDPE, having a melt index below about 1.0 g / 10 min. While not wishing to be bound by theory, the presence of a small amount of LDPE having a melt index below about 1.0 g / 10 min may be useful in many end-use applications.

[0385] The present disclosure relates to the extrusion of thermoplastic compositions in various extrusion processes, such as profile extrusion (in which extruded parts, such as pipes or profile parts, are made by extruding molten plastic through a shaped die) and film extrusion (in which plastic films are made by extruding molten plastic through a slot or annular die).

[0386] In one embodiment of the present disclosure, a film extrusion process is employed, such as a "blown film" extrusion process. This blown film extrusion process is described in more detail in the Examples section below.

[0387] For film applications, in one embodiment of the present disclosure, it is preferred that no pigments or fillers are added to the polyolefin (e.g., linear polyethylene) to produce a transparent or relatively transparent extruded film. In other applications, such as cables (electrical or optical), in one embodiment of the present disclosure, the polyolefin (e.g., linear polyethylene) may contain pigments / fillers (e.g., carbon black) and other additives.

[0388] The thermoplastic polyolefin (e.g., linear polyethylene) used in the present disclosure may further include fillers, antioxidants (e.g., primary antioxidants and optional secondary antioxidants), pigments, opacifiers, static control agents (e.g., glycerol monostearate), lubricants (e.g., fatty acid esters), light stabilizers (e.g., hindered amine light stabilizers), zinc oxide, antiblocking agents, and other additives. Caution should be exercised when using antiblocking agents (e.g., silica or talc) and / or hindered amine light stabilizers, as these may adversely affect the surface appearance of the extruded composition containing the polyolefin, as is known to those skilled in the art.

[0389] In embodiments of the present disclosure, an antioxidant (primary antioxidant alone or, alternatively, a primary antioxidant in combination with a secondary antioxidant) is added to a polyolefin (such as linear polyethylene) in an amount of about 0.01 to about 2 weight percent, or about 0.01 to about 1 weight percent.

[0390] In one embodiment, the linear polyethylene comprises a primary antioxidant and a secondary antioxidant.

[0391] In one embodiment, the linear polyethylene comprises a hindered phenol primary antioxidant and a phosphorus-containing secondary antioxidant.

[0392] Additives that may be added to thermoplastic polyolefins (such as linear polyethylene) in embodiments are further described below and include: primary antioxidants; secondary antioxidants; UV absorbers and light stabilizers; polyamide stabilizers; base co-stabilizers; nucleating agents; slip agents; fillers, antiblocking agents and reinforcing agents, as well as various other miscellaneous additives.

[0393] In embodiments of the present disclosure, the amount of additive added to the thermoplastic polyolefin (such as linear polyethylene) can be 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).

[0394] Primary antioxidant

[0395] In an embodiment of the present disclosure, the primary antioxidant is selected from alkylated monophenols (also known 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-(α-methylcyclohexyl)-4,6-dimethylphenol; 2,6-di(octadecyl)-4-methylphenol; 2,4,6-tricyclohexylphenol; and 2,6-di-tert-butyl-4-methoxymethylphenol. In embodiments of the present disclosure, suitable hindered phenol antioxidants that may be used are sold under the trademarks IRGANOX 1010 (CAS Reg. No. 6683-19-8) and IRGANOX 1076 (CAS Reg. No. 2082-79-3) by BASF Corporation.

[0396] 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-amylhydroquinone; and 2,6-diphenyl-4-octadecyloxyphenol.

[0397] In an embodiment of the present disclosure, the primary antioxidant is selected from hydroxylated thiodiphenyl ethers, such as: 2,2'-thiobis-(6-tert-butyl-4-methylphenol); 2,2'-thiobis-(4-octylphenol); 4,4'-thiobis-(6-tert-butyl-3-methylphenol); and 4,4'-thiobis-(6-tert-butyl-2-methylphenol).

[0398] In an embodiment of the present disclosure, the primary antioxidant is selected from alkylene bisphenols, such as: 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-(α-methylcyclohexyl)phenol); 2,2′-methylene bis-(4-methyl-6-cyclohexylphenol); 2,2′-methylene bis-(6-nonyl-4-methylphenol); phenol); 2,2'-methylenebis-(6-nonyl-4-methylphenol); 2,2'-methylenebis-(6-(α-methylbenzyl)-4-nonylphenol); 2,2'-methylenebis-(6-(α,α-dimethylbenzyl)-4-nonylphenol); 2,2'-methylenebis-(4,6-di-tert-butylphenol); 2,2'-ethylenebis-(6-tert-butyl-4-isobutylphenol); 4,4'-methylenebis-(2,6- di-tert-butylphenol); 4,4′-methylenebis-(6-tert-butyl-2-methylphenol); 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenol)butane; 2,6-bis-(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-dodecanol Alkylmercaptobutane; ethylene glycol bis-(3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate)-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene; bis(2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl) terephthalate; and other phenols, such as monoacrylates of bisphenols, for example, ethylene bis-2,4-di-tert-butylphenol monoacrylate.

[0399] In an embodiment of the present disclosure, the primary antioxidant is selected from benzyl compounds, 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; 3,5-di-tert-butyl-4-hydroxybenzylthioglycolate isooctyl ester; 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; calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate; and 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

[0400] In an embodiment of the present disclosure, the primary antioxidant is selected from amidophenols, such as: 4-hydroxylauric acid aniline; 4-hydroxystearic acid aniline; 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine; and N-(3,5-di-tert-butyl-4-hydroxyphenyl)-octyl carbamate.

[0401] In an embodiment of the present disclosure, the primary antioxidant is selected from esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols, such as: methanol; diethylene glycol; octadecyl alcohol; triethylene glycol; 1,6-hexanediol; pentaerythritol; neopentyl glycol; trishydroxyethyl isocyanurate; thiodiethylene glycol; and dihydroxyethyl oxalic acid diamide.

[0402] In an embodiment of the present disclosure, the primary antioxidant is selected from amides of β-(3,5-di-tert-butyl-4-hydroxyphenol)-propionic acid, such as: N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine; N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine; and N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

[0403] 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).

[0404] Secondary antioxidants

[0405] In embodiments of the present disclosure, the secondary antioxidant is selected from phosphites and phosphonites (also referred to herein as "phosphorus-containing secondary antioxidants"), for example: triphenyl phosphite; diphenyl alkyl phosphites; phenyl dialkyl phosphites; tris(nonylphenyl) phosphite [ 399, available from SI GROUP]; phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters [WESTON 705, CAS Reg. No. 939402-02-5, available from SIGROUP]; trilauryl phosphite; trioctadecyl phosphite; distearyl pentaerythritol diphosphite; tris(2,4-di-tert-butylphenyl) phosphite

[0406] [IRGAFOS 168, available from BASF]; diisodecyl pentaerythritol 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]dioxaphosphopepane[ 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[ 626, available from SI GROUP]; bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite; diisodecyloxypentaerythritol 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′-biphenylene diphosphonite [IRGAFOS P-EPQ, available from BASF]; bis(2,4-dicumylphenyl)pentaerythritol diphosphite [ S9228-T or DOVERPHOS S9228-CT] and (CAS Reg. No. 119345-01-06, a commercially available bisphosphonate); 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.

[0407] In an embodiment of the present disclosure, the secondary antioxidant is selected from alkylphenol-free polymeric polyphosphites, examples of which are disclosed in US Pat. No. 8,563,637.

[0408] In an embodiment of the present disclosure, the secondary antioxidant is selected from a peroxide scavenger, such as β-thiodipropionate. β-thiodipropionate can be selected from lauryl, stearyl, myristyl, or tridecyl esters. In certain embodiments, other peroxide scavengers used as secondary antioxidants can be selected from mercaptobenzimidazole; or zinc salt of 2-mercaptobenzimidazole; zinc dibutyldithiocarbamate; dioctadecyl disulfide; and pentaerythritol tetrakis(β-dodecylmercapto)propionate.

[0409] In embodiments of the present disclosure, the secondary antioxidant is selected from hydroxylamines and amine oxides, such as: N,N-dibenzylhydroxylamine; N,N-diethylhydroxylamine; N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N-di-tetradecylhydroxylamine; N,N-di-hexadecylhydroxylamine; N,N-di-octadecylhydroxylamine; N-hexadecyl-N-stearylhydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; and N,N-dialkylhydroxylamines derived from hydrogenated tallow amine. Similar amine oxides are also suitable. Examples of commercially available hydroxylamines that can be used in embodiments of the present disclosure are N,N-di-alkylhydroxylamines, such as 042 (from BASF) which is reportedly prepared by direct oxidation of N,N-di(hydrogenated) tallowamine.

[0410] In an embodiment of the present disclosure, the secondary antioxidant is selected from nitrones such as: N-benzyl-α-phenylnitrone; N-ethyl-α-methylnitrone; N-octyl-α-heptylnitrone; N-lauryl-α-undecylnitrone; N-tetradecyl-α-tridecylnitrone; N-hexadecyl-α-pentadecylnitrone; N-octadecyl-α-heptadecylnitrone; N-hexadecyl-α-heptadecylnitrone; N-octadecyl-α-pentadecylnitrone; N-heptadecyl-α-heptadecylnitrone; N-octadecyl-α-hexadecylnitrone; and nitrones derived from N,N-dialkylhydroxylamines, which are derived from hydrogenated tallow amine.

[0411] In embodiments of the present disclosure, the secondary antioxidant 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).

[0412] UV absorbers and light stabilizers

[0413] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from 2-(2'-hydroxyphenyl)-benzotriazole, such as: 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'-octyloxy, 3',5'-di-tert-pentyl-; and 3',5'-bis(α,α-dimethylbenzyl) derivatives.

[0414] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from 2-hydroxybenzophenones, such as: 4-hydroxy-; 4-methoxy-; 4-octyloxy-; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4,2',4'-trihydroxy-; and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0415] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from sterically hindered amines, such as: bis(2,2,6,6-tetramethylpiperidinyl) sebacate; bis-5(1,2,2,6,6-pentamethylpiperidinyl) sebacate; bis(1,2,2,6,6-pentamethylpiperidinyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate; condensation products of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid. The following are some of the following: amines: condensation products of N,N'-(2,2,6,6-tetramethylpiperidinyl)-hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine; tris(2,2,6,6-tetramethylpiperidinyl)-nitrilotriacetate; tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylic acid; and 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone). These amines are commonly referred to as HALS (hindered amine light stabilizers) and include 2,2,6,6-tetramethylpiperidinol butanetetracarboxylate. Such amines include hydroxylamines derived from hindered amines such as bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; 1-hydroxy-2,2,6,6-tetramethyl-4-phenoxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-piperidine; and N-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)-ε-caprolactam. Suitable commercially available HALS that may be used in embodiments of the present disclosure include those sold under the trademark 119;CHIMASSORB 944;CHIMASSORB 2020; 622 and TINUVIN770 (from BASF) and Those sold by Solvay include CYASORB UV 3346, CYASORB UV 3529, CYASORB UV 4801, and CYASORB UV 4802. In other embodiments of the present disclosure, the use of mixtures of more than one HALS is also contemplated.

[0416] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from esters of substituted and unsubstituted benzoic acid, for example: phenyl salicylate; 4-tert-butylphenyl salicylate; octylphenyl salicylate; dibenzoylresorcinol; bis(4-tert-butylbenzoyl)resorcinol; benzoylresorcinol; 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate; and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0417] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from acrylates, such as: ethyl or isooctyl α-cyano-β,β-diphenylacrylate; methyl α-methoxycarbonylcinnamate; methyl or butyl α-cyano-β-methyl-p-methoxycinnamate; methyl α-methoxycarbonyl-p-methoxycinnamate; and N-(β-methoxycarbonyl-β-cyanovinyl)-2-methylindole.

[0418] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from nickel compounds, for example: nickel complexes of 2,2'-thiobis(4-(1,1,1,3-tetramethylbutyl)-phenol), such as 1:1 or 1:2 complexes, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine; nickel dibutyldithiocarbamate; nickel salts of monoalkyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate, such as the methyl, ethyl or butyl ester; nickel complexes of ketoximes, such as 2-hydroxy-4-methylphenylundecylketoxime; and nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.

[0419] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from oxalic acid diamides, such as: 4,4'-dioctyloxy oxalanilide; 2,2'-dioctyloxy-5',5'-di-tert-butyl oxalanilide; 2,2'-di(dodecyloxy)-5',5'-di-tert-butyl oxalanilide; 2-ethoxy-2'-ethyl oxalanilide; N,N'-bis(3-dimethylaminopropyl)-oxalamide; 2-ethoxy-5-tert-butyl-2'-ethyl oxalanilide and a mixture thereof with 2-ethoxy-2'-ethyl-5,4-di-tert-butyl oxalanilide; and a mixture of ortho- and para-methoxy and ortho- and para-ethoxy disubstituted oxalanilides.

[0420] In an embodiment of the present disclosure, the UV absorber or light stabilizer is selected from hydroxyphenyl-s-triazines, 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; 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis(2-hydroxy-4-(2-hydroxyethoxy)phenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis(2-hydroxy-4-(2-hydroxyethoxy)phenyl)-6-phenyl-s-triazine; 2,4-bis(2-hydroxy-4-(2-hydroxyethoxy)phenyl)-6-(2,4-dimethylphenyl)-s-triazine; 2,4-bis(2-hydroxy-4-(2-hydroxyethoxy)phenyl)-6-(4-bromophenyl)-s-triazine; 2,4-bis(2-hydroxy-4-(2-acetoxyethoxy)phenyl)-6-(4-chlorophenyl)-s-triazine; and 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-1-s-triazine.

[0421] Polyamide stabilizer

[0422] In an embodiment of the present disclosure, the polyamide stabilizer is selected from, for example, a combination of a copper salt with an iodide and / or a phosphorus compound, and a divalent manganese salt.

[0423] Basic co-stabilizer

[0424] In an embodiment of the present disclosure, the basic co-stabilizer is selected from, for example, melamine; polyvinyl pyrrolidone; dicyandiamide; triallyl isocyanurate; urea derivatives; hydrazine derivatives; amines; polyamides; polyurethanes; alkali metal salts and alkaline earth metal salts of higher fatty acids, such as calcium stearate, calcium stearoyl lactylate, calcium lactate, zinc stearate, magnesium stearate, sodium ricinoleate and potassium palmitate; antimony catecholate or zinc catecholate, including neutralizing agents such as zinc oxide, hydrotalcite and synthetic hydrotalcite; and hydroxycarbonates of lithium, sodium, magnesium, calcium and aluminum.

[0425] In an embodiment, the hydrotalcite has the formula: [M 2+ 1-x M 3+ x (OH)2] x+ [(A n- ) x / n mH2O] x- , where M 2+ For divalent Mg, Ni, Zn, Cu or M n ;M 3+ For trivalent Al, Fe or Cr; A n- Anions, such as CO32- , or SO4 2- 、NO3 2- 、Cl 1- or OH 1- ; x is 0.1 to 0.5. In one embodiment, the formula of the hydrotalcite is: Mg6Al2(OH) 16 CO3·nH2O. In one embodiment, the hydrotalcite is a mineral hydrotalcite (Mg6Al2(OH) 16 CO3·4H2O). Hydrotalcites that can be used in embodiments of the present disclosure include those sold under the general trade name (A, C or V), 713 and AC-207 TM Commercially available materials.

[0426] Nucleating agent

[0427] 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, ie, an additive that modifies the crystallization behavior of a polymer as the polymer melt cools.

[0428] Reviews of nucleating agents are provided in US Pat. Nos. 5,981,636, 6,465,551, and 6,599,971, the disclosures of which are incorporated herein by reference.

[0429] A nucleating agent that is commercially available and can be added to thermoplastic polyolefins, such as linear polyethylene, is dibenzylidene sorbitol ester. Other 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 their salts, such as bicyclo[2.2.1]heptenedicarboxylate disodium salt); saturated versions of the structures disclosed in U.S. Pat. No. 5,981,636 (as disclosed in U.S. Pat. No. 6,465,551 to Zhao et al., issued 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., issued to Milliken); and phosphates, such as those disclosed in U.S. Pat. No. 5,342,868 and those sold by Asahi Denka Kogyo under the trade names NA-11 and NA-21; cyclic dicarboxylic acid esters and their salts, such as the divalent metal or metalloid salts (particularly the 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 as substituents on adjacent atoms of the ring structure. As disclosed in U.S. Patent No. 6,599,971, the other four carbon atoms in the ring may be substituted. An example is 1,2-cyclohexanedicarboxylic acid calcium salt (CAS Reg. No. 491589-22-1). In addition, other examples of nucleating agents that can be added to thermoplastic polyolefins (e.g., linear polyethylene) include those disclosed in WO2015042561, WO2015042563, WO2015042562, and WO2011050042.

[0430] In one embodiment of the present disclosure, the amount of nucleating agent used is relatively small - 100 to 3,000 ppm by weight (based on the weight of the thermoplastic polyolefin), so those skilled in the art will understand that care should be taken to ensure that the nucleating agent is well dispersed. In one embodiment of the present disclosure, the nucleating agent is added to the thermoplastic polyolefin (e.g., linear polyethylene) in fine powder form (less than 50 microns, particularly less than 10 microns) to facilitate mixing. This "physical blending" (i.e., a mixture of the nucleating agent and the solid form of the resin) is preferably performed in some embodiments using a "masterbatch" of the nucleating agent (the term "masterbatch" refers to the practice of first melt mixing the additive - in this case, the nucleating agent - with a small amount of the thermoplastic polyolefin and then melt mixing the "masterbatch" with the remaining bulk of the thermoplastic polyolefin).

[0431] In one embodiment of the present disclosure, additives (e.g., nucleating agents) may be added to thermoplastic polyolefins via a "masterbatch," wherein the term "masterbatch" refers to the practice of first melt mixing the additive (e.g., nucleating agent) with a small amount of thermoplastic polyolefin and then melt mixing the "masterbatch" with the bulk of the remaining thermoplastic polyolefin.

[0432] 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).

[0433] Slip agents

[0434] In an embodiment of the present disclosure, the slip agent is selected from the group consisting of oleamide, erucamide, stearamide, and behenamide.

[0435] Fillers, antiblocking agents and reinforcing agents

[0436] In an embodiment of the present disclosure, the filler, antiblock or reinforcing agent is selected from the group consisting of 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.

[0437] If 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).

[0438] Miscellaneous additives

[0439] In an embodiment of the present disclosure, the miscellaneous additives are selected from plasticizers, epoxidized vegetable oils (such as epoxidized soybean oil), lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, antifogging agents, foaming agents, and thiosynergists (such as dilauryl thiodipropionate or distearyl thiodipropionate).

[0440] Melt extrusion

[0441] The extrudable thermoplastic compositions according to the present disclosure can be prepared by any one or more methods. In one embodiment, the polymer processing aid component 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 formulated with the polyolefin into a so-called "masterbatch." This masterbatch can be used to deliver a useful dilution amount of one or more polymer processing aid components. The masterbatch can be added to the main thermoplastic polyolefin for extrusion into an extruded article during the melt extrusion process.

[0442] 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, an internal mixer, or a mixing extruder, wherein the polymer processing aid component is uniformly distributed throughout the thermoplastic polyolefin. Such mixing can be carried out at a temperature above the melting point or softening point of the polyolefin, or such mixing can simply be a dry blend of the solid thermoplastic polyolefin and the polymer processing aid component.

[0443] In one embodiment, the extrudable thermoplastic composition of the present disclosure will be prepared by melt blending a thermoplastic polyolefin (eg, linear polyethylene) with a polymer processing aid prior to final extrusion in a melt extrusion process (eg, a blown film extrusion process).

[0444] Several methods are available for producing extrudable thermoplastic compositions of the present disclosure. In one embodiment, all components are dry blended in suitable equipment (such as a tumble blender) with required weight ratio. The gained dry blend is then melted in suitable equipment (such as an extruder). In an alternative embodiment, a masterbatch containing some thermoplastic polyolefins and other compositions (comprising polymer processing aids or other additives) can be prepared. In this embodiment, the thermoplastic polyolefin masterbatch is subsequently fed into the extruder and melt-blended with required other components (comprising, for example, main polyolefin, polymer processing aids or other additives). In another embodiment, every kind of component that is used to constitute an extrudable thermoplastic composition can be directly metered into the extruder for the melt extrusion process.

[0445] The melt extrusion process is well known to those skilled in the art, and non-limiting examples 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 the embodiments of the present disclosure can be a twin-screw or single-screw extruder. If a twin-screw extruder is used, it can be operated in a co-rotating mode (i.e., two screws rotate in the same direction) or a counter-rotating mode (i.e., screws rotate in opposite directions).

[0446] The specific operating conditions of any extruder during the melt extrusion process will be different from the conditions of any other extruder. These differences between extruder machines can generally be addressed by conventional optimization methods familiar to those skilled in the art. In one embodiment of the present disclosure, a laboratory-scale twin-screw extruder will be operated within the following condition package: the barrel is heated to a temperature of about 180 to 210°C, or about 190 to 200°C; the screw speed is operated at about 50 to 150 rpm, or about 100 to 130 rpm. The specific operating conditions of any particular extruder can be easily determined by those skilled in the art through non-inventive testing based on the above condition package. The extruder typically extrudes the thermoplastic composition into strips, which are then cooled and cut into pellets for subsequent use, such as for film extrusion. The extruder used for the final extrusion can also be a single-screw or twin-screw extruder. In blown film extrusion, the die can be a slit die or an annular ring die, which extrude a polyolefin film around a stable air bubble. In blown film extrusion, the film is flattened after passing over or around the bubble.

[0447] The specific details of extruder and its operation are well known to those skilled in the art. Typical extruders comprise one (or two) lead screws that rotate in a barrel or "barrel". The thermoplastic polyolefin is sheared between the barrel and the screw due to the stress generated by the screw rotation. In addition, the barrel of the extruder can be heated. Shearing and / or heat cause the thermoplastic polyolefin to melt, and the effect of the lead screw is transported along the extruder length. The molten thermoplastic polyolefin extrudate is subsequently forced through a die to form required plastic parts.

[0448] In one embodiment of the present disclosure, the melt extrusion process is a blown film melt extrusion process.

[0449] In the blown film melt extrusion process, an extruder heats, melts, mixes, and conveys a thermoplastic polyolefin composition. Once melted, the thermoplastic composition is forced through an annular die to produce a thermoplastic tube. In the case of coextrusion, multiple extruders are used to produce a multilayer thermoplastic tube. The temperature of the extrusion process is primarily determined by the thermoplastic polyolefin composition being processed, such as the melting temperature 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 pulled out through a pair of nip rollers. Due to the air inflation, the diameter of the tube increases, forming bubbles of the desired size. Due to the pulling action of the nip rollers, the bubbles are stretched in the machine direction. Therefore, the bubbles are stretched in two directions: the transverse direction (TD), where the blowing air increases the diameter of the bubbles; and the machine direction (MD), where the nip rollers stretch the bubbles. During the blown film process, air is also blown into the outer bubble circumference to cool the thermoplastic polyolefin exiting the annular die. The final width of the film is determined by controlling the blowing air or internal bubble pressure; in other words, increasing or decreasing the bubble diameter. Film thickness is primarily controlled by increasing or decreasing the speed of the nip rolls to control the draw-off rate. After exiting the nip rolls, the bubble or tube is flattened and can be slit in the machine direction to produce a sheet. Each sheet can be wound into a film roll. Each roll can be further slit to produce film of the desired width. Each roll of film can be further processed into a variety of consumer products.

[0450] The cast film process is similar in that single or multiple extruders can be used; however, various thermoplastic materials are metered into a flat die and extruded into a single or multi-layer sheet rather than a tube. In the cast film process, the extruded sheet solidifies on a chill roll.

[0451] In an embodiment of the present disclosure, a polymer processing aid is used during the melt extrusion of a thermoplastic polyolefin into a thermoplastic polyolefin extrudate.

[0452] In an embodiment of the present disclosure, a polymer processing aid is used during the melt extrusion of a thermoplastic polyolefin into a thermoplastic polyolefin extrudate to reduce melt defects during the extrusion of the thermoplastic polyolefin.

[0453] In one embodiment of the present disclosure, the use of a polymer processing aid during the 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 generating melt defects in the thermoplastic polyolefin extrudate, as compared to the shear rate at which melt defects occur in the thermoplastic polyolefin extrudate in the absence of the polymer processing aid.

[0454] In embodiments of the present disclosure, a polymer processing aid is used during the melt extrusion of a thermoplastic polyolefin into a thermoplastic polyolefin extrudate to increase the shear rate at which the melt extrusion process can be operated without generating melt defects in the thermoplastic polyolefin extrudate by at least 10%, or at least 25%, or at least 50%, or at least 75%, or at least 100%, or at least 200%, or at least 300%, or at least 400%, or at least 500% as compared to the shear rate at which melt defects occur in the thermoplastic polyolefin extrudate in the absence of the polymer processing aid.

[0455] One embodiment of the present disclosure is a method of reducing melt defects during extrusion of a thermoplastic composition comprising a linear polyethylene, the method comprising:

[0456] combining a linear polyethylene with a monovalent metal carboxylate; and

[0457] Extruded thermoplastic polyolefins.

[0458] One embodiment of the present disclosure is a method of reducing melt defects during extrusion of a thermoplastic composition comprising a linear polyethylene, the method comprising:

[0459] combining a linear polyethylene with a monovalent metal carboxylate and one or more of: a polyoxyalkylene polymer (also known as a polyalkylene glycol, PAG); a polyether block amide copolymer, wherein the polyether block amide copolymer comprises polyamide blocks and polyether blocks; a polycaprolactone (PCL) polymer; and a high pressure low density polyethylene (LDPE); and

[0460] Extruding the thermoplastic composition.

[0461] One embodiment of the present disclosure is a method of reducing melt defects during extrusion of a thermoplastic composition comprising a linear polyethylene, the method comprising:

[0462] combining a linear polyethylene with a monovalent metal carboxylate and one or more polyoxyalkylene polymers (also known as polyalkylene glycols, PAGs); and

[0463] Extruding the thermoplastic composition.

[0464] In some embodiments of the present disclosure, the use of a polymer processing aid comprising a monovalent metal carboxylate and one or more of: a polyoxyalkylene polymer (also known as a polyalkylene glycol, PAG); a polyether block amide copolymer, wherein the polyether block amide copolymer comprises a polyamide block and a polyether block; a polycaprolactone (PCL) polymer; and a high pressure low density polyethylene (LDPE); also helps to reduce die lip buildup (DLBU) during the melt extrusion of thermoplastic polyolefins (e.g., linear polyethylene) into thermoplastic polyolefin extrudates.

[0465] In some embodiments of the present disclosure, a polymer processing aid comprising a monovalent metal carboxylate and a polyoxyalkylene polymer (also known as a polyalkylene glycol, PAG) is used; it also helps to reduce die lip buildup (DLBU) during the melt extrusion of thermoplastic polyolefins (e.g., linear polyethylene) into thermoplastic polyolefin extrudates.

[0466] One embodiment of the present disclosure is a method of reducing melt defects during extrusion of a thermoplastic composition comprising a linear polyethylene, the method comprising:

[0467] combining a linear polyethylene with a monovalent metal aliphatic carboxylate; and

[0468] Extruded thermoplastic polyolefins.

[0469] One embodiment of the present disclosure is a method of reducing melt defects during extrusion of a thermoplastic composition comprising a linear polyethylene, the method comprising:

[0470] combining a linear polyethylene with a monovalent metal aliphatic carboxylate and one or more of: a polyoxyalkylene polymer (also known as a polyalkylene glycol, PAG); a polyether block amide copolymer, wherein the polyether block amide copolymer comprises polyamide blocks and polyether blocks; a polycaprolactone (PCL) polymer; and a high pressure low density polyethylene (LDPE); and

[0471] Extruding the thermoplastic composition.

[0472] One embodiment of the present disclosure is a method of reducing melt defects during extrusion of a thermoplastic composition comprising a linear polyethylene, the method comprising:

[0473] combining a linear polyethylene with a monovalent metal aliphatic carboxylate and one or more polyoxyalkylene polymers (also known as polyalkylene glycols, PAGs); and

[0474] Extruding the thermoplastic composition.

[0475] In some embodiments of the present disclosure, the use of a polymer processing aid comprising a monovalent metal aliphatic carboxylate and one or more of: a polyoxyalkylene polymer (also known as a polyalkylene glycol, PAG); a polyether block amide copolymer, wherein the polyether block amide copolymer comprises a polyamide block and a polyether block; a polycaprolactone (PCL) polymer; and a high pressure low density polyethylene (LDPE); also helps to reduce die lip buildup (DLBU) during the melt extrusion of thermoplastic polyolefins (e.g., linear polyethylene) into thermoplastic polyolefin extrudates.

[0476] In some embodiments of the present disclosure, a polymer processing aid comprising a monovalent metal aliphatic carboxylate and a polyoxyalkylene polymer (also known as a polyalkylene glycol, PAG) is used; it also helps to reduce die lip buildup (DLBU) during the melt extrusion of thermoplastic polyolefins (e.g., linear polyethylene) into thermoplastic polyolefin extrudates.

[0477] The following examples are presented for the purpose of illustrating selected embodiments of the present disclosure; it is understood that the presented examples do not limit the presented claims.

[0478] Example

[0479] Polymer Characterization and Test Methods

[0480] Each polymer sample was conditioned at 23±2°C and 50±10% relative humidity for at least 24 hours prior to testing. Subsequent testing was 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; the test samples were conditioned in this laboratory for at least 24 hours prior to testing. ASTM stands for the American Society for Testing and Materials.

[0481] density

[0482] The density of polymers, such as linear polyethylene polymers, is determined using ASTM D792-13 (November 1, 2013).

[0483] Melt index

[0484] The polyethylene melt index is measured using ASTM D1238 (August 1, 2013). Melt index I2, I6, I 10 and I 21 The measurements were made at 190° C. using weights of 2.16 kg, 6.48 kg, 10 kg, and 21.6 kg, respectively.

[0485] Gel Permeation Chromatography (GPC)

[0486] Polyethylene sample (polymer) solutions (1 to 3 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel in an oven at 150°C for 4 hours. An antioxidant (2,6-di-tert-butyl-4-methylphenol, BHT) was added to the mixture to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. The polymer solution was heated at 140°C in a PL 220 high temperature chromatography unit (equipped with four Chromatographic analyses were performed on columns (HT803, HT804, HT805, and HT806) using TCB as the mobile phase at a flow rate of 1.0 mL / min and a differential refractive index (DRI) as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect the GPC column from oxidative degradation. The sample injection volume was 200 μL. The GPC column was calibrated using 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). GPC raw data were obtained using GPC software was used to generate the molar mass average (M n 、M w 、M z ) and molar mass distribution (e.g. polydispersity, M w / M n ). In the polyethylene field, a common term equivalent to GPC is SEC, which stands for size exclusion chromatography.

[0487] Melt extrusion

[0488] 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 widely accepted formula for estimating the shear rate at the die is shown in Equation 1:

[0489] (1)γ=2Q(S+2) / ρπd 2 D

[0490] Where γ = shear rate (inverse of seconds, s -1 ); ρ = density of polymer melt; S = 1 / power law exponent; d = die gap width; D = die diameter; Q = mass flow rate of polymer.

[0491] The widely accepted estimate of the density of molten polyethylene is 0.76 g / cm3 (g / cm 3 ), which is used in all calculations. A widely accepted value for the power law exponent is 0.5, which is used in all calculations.

[0492] Example 1

[0493] An extrudable thermoplastic polyolefin composition for blown film extrusion was prepared by melt compounding a linear polyethylene with a polymer processing aid and other additives on a Leistritz twin-screw pelletizer under mild conditions with nitrogen purge, the conditions being shown in Table 1.

[0494] Table 1. Melt compounding conditions

[0495] Amperage (amps) 21.5 Nitrogen purge Open Output (lbs / hour) 18.5 Pressure (psi) 1410–1440 Melt temperature (℃) 200

[0496] The monovalent metal aliphatic carboxylate used as PPA is potassium stearate, which is commercially available as Potassium Stearate PSV-10 from PMC Crystal. The divalent metal aliphatic carboxylate used in comparative examples to explore whether it is effective as PPA is calcium stearate, which is commercially available as CEASIT from Baerlocher. TM AV FI VEG commercially available.

[0497] The linear polyethylene used in these experiments was linear low-density polyethylene (LLDPE) with a density of 0.920 g / cm 3 , with a melt index I2 of approximately 1.0 g / 10 minutes, and is sold by NOVA Chemicals under the trade name FP120. FP120 is also available in various formulations, such as FP120-A, FP120-AS, and FP120-C. FP120, FP120-A, FP120-AS, and FP120-C are copolymers of ethylene and 1-octene, produced in a solution phase polymerization process using a Ziegler-Natta catalyst. FP120, a linear polyethylene, contains a conventional primary antioxidant (hindered phenol = 500 ppm IRGANOX 1076); a conventional secondary antioxidant (phosphite = 500 ppm IRGAFOS 168); and hydrotalcite (800 ppm), where ppm (or parts per million) is based on the weight of the linear polyethylene. Linear polyethylene FP120-C contains 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 of VITON Z110 (a PPA containing an elastomeric fluoropolymer and polyethylene glycol, where the ppm (or parts per million) is based on the weight of the linear polyethylene). Linear polyethylene FP120-AS contains two conventional primary antioxidants (hindered phenol = 500 ppm IRGANOX 1076 and hindered phenol = 250 ppm IRGANOX 1010); a conventional secondary antioxidant (phosphite = 1,000 ppm IRGAFOS 168); hydrotalcite (800 ppm); and calcium stearate (lubricant = 1,250 ppm CEASIT AV FI VEG).

[0498] Blown films were produced on a 3-inch Macro blown film line with a standard output of greater than 60 lb / hr and a 15 hp motor. The feed screw had a 1.5-inch diameter and a length / diameter (L / D) ratio of 24 / 1. The feed screw was a barrier design with a mixing element at the end of the screw. The bubbles were cooled with cold 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 used so that the die gap for the experiments was either 35 or 85 mils.

[0499] In Example 1A, a linear polyethylene FP120-C containing an elastomeric fluoropolymer (VITON Z110) as the PPA was melt extruded on a blown film line.

[0500] In Example 1B, linear polyethylene FP120 was preformulated (eg, melt compounded in an extruder / pelletizer) with 1,500 ppm by weight (based on the weight of the linear polyethylene) of potassium stearate (PSV-10) and then melt extruded on a blown film line.

[0501] In Example 1C, linear polyethylene FP120-AS was blended with 0.125 wt.% of a masterbatch containing 20 wt.% calcium stearate (CEASIT AV FIVEG), 4 wt.% IRGANOX 1076, and 4 wt.% IRGANOX 1010, and then melt extruded on a blown film line.

[0502] In melt fracture removal experiments on a blown film line, the extruder was operated at a mass flow rate "target point" of approximately 65 lb / hr (corresponding to a shear rate of approximately 460 s -1 The term "melt fracture" is well known to those skilled in the art and generally refers to visible signs of film surface defects, which appear as die marks, foggy bands, or small bands of soft melt fracture (orange peel) or hard melt fracture (sharkskin). The phrase "clear of melt fracture" refers to a film surface that is clean and free of defects.

[0503] Details of the components and melt extrusion process used for the extrudable thermoplastic composition are given in Table 2.

[0504] Table 2. Melt Fracture Clearance in Extrudable Thermoplastic Polyolefin Compositions 1

[0505]

[0506]

[0507] Note 1: Some die lip buildup (DLBU) was observed in Examples 1B and 1C.

[0508] Before adding the target thermoplastic composition, the blown film line was cleaned with LLDPE or LDPE containing 30-40% diatomaceous earth and without any polymer processing aids, and the die was cleaned by abrasion. After cleaning, the introduced density was about 0.92 g / cm 3 , a PPA-free LLDPE with a melt index of 0.8 g / 10 min to produce an extrudate with 100% hard melt fracture across the entire width of the film (e.g., to produce a film with severe surface defects similar to the appearance of shark skin). Next, the target thermoplastic composition is introduced and this is recorded as time zero. The target thermoplastic composition is extruded under constant conditions and extrudate film samples are collected every ten minutes and the percentage of melt fracture defects as a percentage of the sample width is measured. The melt extrusion process for each experiment lasted 60 to 90 minutes and the percentage of melt fracture was recorded at 10 minute intervals. When the percentage of melt fracture reached zero, the extrudate was considered to be clear of melt fracture. As a general non-limiting guide, if the melt fracture is cleared in about 60 minutes or less of extruder operation, the polymer processing aid (PPA) is considered to provide good performance. Melt fracture clearance experimental results are shown in Figure 1 .

[0509] Those skilled in the art will Figure 1 From the data provided in, it can be observed that thermoplastic compositions containing only potassium stearate as the PPA (e.g., 1500 ppm PSV-10) and linear polyethylene are able to completely eliminate melt fracture in about 30 minutes (see Example 1B), which is similar to thermoplastic compositions containing linear polyethylene and elastomeric fluoropolymer and polyethylene glycol (e.g., Viton Z110; see Example 1A).

[0510] Figure 1 The data also show that thermoplastic compositions containing only divalent stearate (calcium stearate) as the PPA (e.g., 1500 ppm CEASIT AV FI VEG) and linear polyethylene were unable to eliminate melt fracture after 90 minutes of extrusion (see Example 1C). Furthermore, during extrusion of thermoplastic compositions containing linear polyethylene and calcium stearate, the thermoplastic composition extrudate became unstable at approximately 30 minutes, resulting in bubble collapse, which is an undesirable result in commercial operations.

[0511] Figure 1 The data presented in

[15] indicate that monovalent metal aliphatic carboxylates can be used alone as effective polymer processing aids in linear polyethylene, even in the absence of fluoropolymers and polyethylene glycol.

[0512] Example Set 2

[0513] The extrudable thermoplastic polyolefin composition for blown film extrusion was prepared by melt compounding the linear polyethylene with the polymer processing aid and other additives on a Leistritz twin-screw pelletizer under mild conditions with nitrogen purge, the conditions shown in Table 3.

[0514] Table 3. Melt compounding conditions

[0515] Amperage (amps) 21.5 Nitrogen purge Open Output (lbs / hour) 18.5 Pressure (psi) 1410–1440 Melt temperature (℃) 200

[0516] The monovalent metal aliphatic carboxylates used as PPAs were potassium stearate (available as Potassium Stearate PSV-10 from PMC Crystal), sodium stearate (available as Sodium stearate from Thermo Fisher Scientific), sodium hexanoate (available as Sodium hexanoate from MilliporeSigma), potassium benzoate, and potassium acetate (all available from Sigma-Aldrich). Sodium hexanoate, potassium benzoate, and potassium acetate were dried in a vacuum oven at 70° C. before melt compounding.

[0517] The polyamide / polyether block copolymer used in admixture with the linear polyethylene was commercially available as PEBAX MV1074 from Arkema.

[0518] The PEG used in combination with the linear polyethylene was PEG 3350, which has a weight average molecular weight (M w ) is about 3,350 g / mol, or PEG 3350 (weight average molecular weight M w About 3,350g / mol) and PEG 35000 (weight average molecular weight M w PEG 3350 and PEG 35000 are commercially available from Clariant under the trade names POLYGLYKOL 3350 and POLYGLYKOL 35000, respectively.

[0519] In the comparative examples, the PPA used in combination with the linear polyethylene is a blend of elastomeric fluoropolymer and polyethylene glycol, commercially available as VITON Z110 from The Chemours Company.

[0520] The linear polyethylene used in the experiment is linear low-density polyethylene (LLDPE) with a density of 0.914 g / cm 3VPsK914 is a copolymer of ethylene and 1-octene, with a melt index (I2) of approximately 0.85 g / 10 min. It is sold under the trade name VPsK914. VPsK914 is available in various formulations, including VPsK914-A, VPsK914-A04, and VPsK914-C. VPsK914 is a copolymer of ethylene and 1-octene, produced in a solution-phase polymerization process using dual-reactor single-site catalysts and Ziegler-Natta catalyst technology.

[0521] The linear polyethylene VPsK914-A used in the experiment contained a conventional primary antioxidant (hindered phenol = 350 ppm IRGANOX 1076); a conventional secondary antioxidant (phosphite = 750 ppm IRGAFOS168); a special antioxidant (500 ppm SUMILIZER GP) and hydrotalcite (800 ppm), where ppm (or parts per million) is based on the weight of the linear polyethylene.

[0522] Blown films were produced on a 3-inch Macro blown film line with a standard output of greater than 60 lb / hr and a 15 hp motor. The feed screw had a 1.5-inch diameter and a length / diameter (L / D) ratio of 24 / 1. The feed screw was a barrier design with a mixing element at the end of the screw. The bubbles were cooled with cold 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 used, resulting in a die gap of 35 or 85 mils for the experiments.

[0523] In Example 2A, linear polyethylene VPsK914-A was blended with 1,000 ppm by weight (based on the weight of the linear polyethylene) of an elastomeric fluoropolymer and polyethylene glycol ( Z110) is pre-formulated (e.g. melt compounded in an extruder / pelletizer) and then melt extruded on a blown film line.

[0524] In Example 2B, linear polyethylene VPsK914-A was preformulated (eg, melt compounded in an extruder / pelletizer) with 500 ppm by weight (based on the weight of the linear polyethylene) of potassium stearate (PSV-10) and then melt extruded on a blown film line.

[0525] In Example 2C, linear polyethylene VPsK914-A is preformulated (e.g., melt compounded in an extruder / pelletizer) with 500 ppm by weight (based on the weight of the linear polyethylene) of potassium stearate (PSV-10) and 1,000 ppm by weight (based on the weight of the linear polyethylene) of polyethylene glycol (PEG 3350) and then melt extruded on a blown film line.

[0526] In Example 2D, linear polyethylene VPsK914-A was preformulated (e.g., melt compounded in an extruder / pelletizer) with 500 ppm by weight (based on the weight of the linear polyethylene) of potassium stearate (PSV-10), 500 ppm by weight (based on the weight of the linear polyethylene) of PEG 3350, and 500 ppm by weight (based on the weight of the linear polyethylene) of PEG 35000, and then melt extruded on a blown film line.

[0527] In Example 2E, linear polyethylene VPsK914-A is preformulated (e.g., melt compounded in an extruder / pelletizer) with 500 ppm by weight (based on the weight of the linear polyethylene) of potassium stearate (PSV-10) and 1,000 ppm by weight (based on the weight of the linear polyethylene) of a polyamide / polyether block copolymer (PEBAX MV 1074) and then melt extruded on a blown film line.

[0528] In Example 2F, linear polyethylene VPsK914-A was preformulated (eg, melt compounded in an extruder / pelletizer) with 1,500 ppm by weight (based on the weight of the linear polyethylene) of sodium stearate and then melt extruded on a blown film line.

[0529] In Example 2G, linear polyethylene VPsK914-A is preformulated (e.g., melt compounded in an extruder / pelletizer) with 500 ppm by weight (based on the weight of the linear polyethylene) of sodium stearate and 1,000 ppm by weight (based on the weight of the linear polyethylene) of polyethylene glycol (PEG 3350) and then melt extruded on a blown film line.

[0530] In Example 2H, linear polyethylene VPsK914-A was preformulated (eg, 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.

[0531] In Example 2I, linear polyethylene VPsK914-A is preformulated (e.g., melt compounded in an extruder / pelletizer) with 500 ppm by weight (based on the weight of the linear polyethylene) of sodium hexanoate and 1,000 ppm by weight (based on the weight of the linear polyethylene) of polyethylene glycol (PEG 3350) and then melt extruded on a blown film line.

[0532] In Example 2J, linear polyethylene VPsK914-A was preformulated (e.g., melt compounded in an extruder / pelletizer) with 500 ppm by weight (based on the weight of the linear polyethylene) of potassium benzoate and 1,000 ppm by weight (based on the weight of the linear polyethylene) of polyethylene glycol (PEG 3350) and then melt extruded on a blown film line.

[0533] In Example 2K, linear polyethylene VPsK914-A is preformulated (e.g., melt compounded in an extruder / pelletizer) with 500 ppm by weight (based on the weight of the linear polyethylene) of potassium acetate and 1,000 ppm by weight (based on the weight of the linear polyethylene) of polyethylene glycol (PEG 3350) and then melt extruded on a blown film line.

[0534] In melt fracture removal experiments on a blown film line, the extruder was operated at a mass flow rate "target point" of approximately 65 lb / hr (corresponding to a shear rate of approximately 460 s -1 The term "melt fracture" is well known to those skilled in the art and generally refers to visible signs of film surface defects, which appear as die marks, foggy bands, or small bands of soft melt fracture (orange peel) or hard melt fracture (sharkskin). The phrase "clear of melt fracture" refers to a film surface that is clean and free of defects.

[0535] Details of the components and melt extrusion process used for the extrudable thermoplastic composition are given in Table 4.

[0536] Table 4. Melt Fracture Clearance in Extrudable Thermoplastic Polyolefin Compositions 1,2

[0537]

[0538] Table 4 - Continued. Melt Fracture Clearance in Extrudable Thermoplastic Polyolefin Compositions 1,2

[0539]

[0540]

[0541] Table 4 - Continued. Melt Fracture Clearance in Extrudable Thermoplastic Polyolefin Compositions 1,2

[0542]

[0543] Note 1: PEG 3350 = polyethylene glycol, M w ~3350g / mol; PEG 35000 = polyethylene glycol, M w ~35,000g / mol.

[0544] Note 2: Some die lip buildup (DLBU) was observed in Examples 2F and 2H, while there was no evidence of die lip buildup in Examples 2B or 2G.

[0545] Before adding the target thermoplastic composition, the film line was cleaned with LLDPE or LDPE containing 30-40% diatomaceous earth and without any polymer processing aids, and the die was cleaned by abrasion. After cleaning, the introduced density was about 0.92 g / cm 3 , a PPA-free LLDPE with a melt index of about 0.8 g / 10 min is used to produce an extrudate with 100% hard melt fracture across the entire width of the film (e.g., to produce a film with severe surface defects similar to the appearance of shark skin). Next, the target thermoplastic composition is introduced and this is recorded as time zero. The target thermoplastic composition is extruded under constant conditions and extrudate film samples are collected every ten minutes and the percentage of melt fracture defects as a percentage of the sample width is measured. The melt extrusion process lasts for a maximum of 90 minutes and the percentage of melt fracture is recorded at 10 minute intervals. When the percentage of melt fracture reaches zero, the extrudate is considered to be clear of melt fracture. As a general non-limiting guide, if the melt fracture is cleared in about 60 minutes or less of extruder operation, the polymer processing aid (PPA) is considered to provide good performance. Melt clearing test results are shown in Figure 2 、 Figure 3 and Figure 4 .

[0546] Those skilled in the art will Figure 2 and Figure 3 As can be seen from the data provided in the accompanying drawings, thermoplastic compositions containing only monovalent metal stearates (potassium stearate in Example 2B; or sodium stearate in Example 2F) as the PPA and linear polyethylene are able to significantly reduce melt fracture (to about 20%) within about 20 to 40 minutes. Surprisingly, the melt fracture clearing onset time for the linear polyethylene containing potassium or sodium stearate as the PPA (see Examples 2B and 2F) is significantly shorter than that for the linear polyethylene containing an elastomeric fluoropolymer (Viton Z110) as the PPA (see Figure 2 and 3 Example 2A) earlier. Figure 2 and Figure 3 It was further shown that when 500 ppm of potassium stearate or 500 ppm of sodium stearate was added to a linear polyethylene and used in combination with polyethylene glycol (e.g., PEG 3350, or PEG 3350 and PEG 35000) as the PPA, the thermoplastic composition was able to completely eliminate melt fracture in about 60 to 70 minutes or even less (see Examples 2C, 2D, and 2G). Figure 2 The data also showed that when 500 ppm of potassium stearate was added to a linear polyethylene and used as a PPA in combination with a polyamide / polyether block copolymer (e.g., PEBAX MV 1074), the thermoplastic composition was able to clear melt fracture in about 40 to 50 minutes. Figure 3The data in Figure 2 demonstrate that monovalent metal salts of hexanoic acid (e.g., sodium hexanoate) work very well as PPAs when added to linear polyethylene, either alone (see Example 2H) or in combination with polyethylene glycol (e.g., PEG 3350; see Example 2I). In fact, in both cases, melt fracture was completely eliminated within 60 minutes.

[0547] Figure 4 The data presented in show that when a combination of a monovalent metal salt (e.g., potassium benzoate or potassium acetate) and a polyethylene glycol (e.g., PEG 3350) is used as the PPA in linear polyethylene, melt fracture clearance is significantly improved compared to the baseline examples without added PPA (compare Examples 2J and 2K with Example 2L).

[0548] The data demonstrate that monovalent metal aliphatic carboxylates can be used alone, or optionally with polyethylene glycol or polyamide / polyether block copolymers, as effective polymer processing aids in linear polyethylene, even in the absence of fluoropolymers.

[0549] Non-limiting embodiments of the present disclosure include the following:

[0550] Embodiment 1: A method of preparing an extrudate of a thermoplastic composition, the method comprising extruding a thermoplastic composition in a melt extrusion process; the thermoplastic composition comprising: i) a linear polyethylene; and ii) (based on the weight of the linear polyethylene) 200 to 4000 ppm of a monovalent metal carboxylate;

[0551] wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE and mixtures thereof;

[0552] wherein the thermoplastic composition is substantially free of fluoropolymer; and

[0553] The melt extrusion process is carried out in the absence of a fluoropolymer.

[0554] Embodiment 2: The method according to embodiment 1, wherein the monovalent metal carboxylate is a monovalent metal aliphatic carboxylate.

[0555] Embodiment 3: The method of Embodiment 2, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 2 to 30 carbon atoms.

[0556] Embodiment 4: The method of Embodiment 2, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 30 carbon atoms.

[0557] Embodiment 5: The method of Embodiment 2, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 26 carbon atoms.

[0558] Embodiment 6: The method of Embodiment 2, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 22 carbon atoms.

[0559] Embodiment 7: The method of embodiment 2, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof.

[0560] Embodiment 8: The method of embodiment 2, wherein the monovalent metal aliphatic carboxylate 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.

[0561] Embodiment 9: The method of embodiment 2, wherein the monovalent metal aliphatic carboxylate is potassium stearate.

[0562] Embodiment 10: The method of embodiment 2, wherein the monovalent metal aliphatic carboxylate is sodium stearate.

[0563] Embodiment 11: The method of Embodiment 2, wherein the monovalent metal aliphatic carboxylate is sodium hexanoate or potassium hexanoate.

[0564] Embodiment 12: The method of Embodiment 1, wherein the monovalent metal carboxylate is a monovalent metal aromatic carboxylate.

[0565] Embodiment 13: The method of Embodiment 12, wherein the monovalent metal aromatic carboxylate is derived from an aromatic carboxylic acid having 7 to 30 carbon atoms.

[0566] Embodiment 14: The method of Embodiment 12, wherein the monovalent metal aromatic carboxylate is derived from an aromatic carboxylic acid having 7 to 20 carbon atoms.

[0567] Embodiment 15: The method of Embodiment 12, wherein the monovalent metal aromatic carboxylate is potassium benzoate or sodium benzoate.

[0568] Embodiment 16: The method of any one of Embodiments 1-15, wherein the thermoplastic composition further comprises one or more of the following:

[0569] iii) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of polyethylene glycol; and

[0570] iv) (based on the weight of the linear polyethylene) 200 to 4,000 ppm of a polyether block amide copolymer, wherein the polyether block amide copolymer comprises polyamide blocks and polyether blocks.

[0571] Embodiment 17: The method of any of Embodiments 1-16, wherein the linear polyethylene is LLDPE.

[0572] Embodiment 18: The method of Embodiment 17, wherein the LLDPE has a melt index I2 of 0.1 to 5.0 g / 10 minutes.

[0573] Embodiment 19: The method of embodiment 17 or 18, wherein the density of LLDPE is 0.910 to 0.936 g / cm 3 .

[0574] Embodiment 20: The method of any of Embodiments 17-19, wherein the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more α-olefins selected from 1-butene, 1-hexene, and 1-octene.

[0575] Embodiment 21: The method of any 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, would produce a thermoplastic composition extrudate having melt fracture defects.

[0576] Embodiment 22: The method of any of Embodiments 1-21, wherein the thermoplastic composition comprises (based on the weight of the linear polyethylene) 200 to 2,000 ppm of a monovalent metal carboxylate.

[0577] Embodiment 23: An extrudable thermoplastic composition comprising: i) a linear polyethylene; and ii) from 200 to 4,000 ppm (based on the weight of the linear polyethylene) of a monovalent metal carboxylate;

[0578] wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; and

[0579] wherein the extrudable thermoplastic composition is substantially free of fluoropolymer.

[0580] Embodiment 24: The extrudable thermoplastic composition of Embodiment 23, wherein the monovalent metal carboxylate is a monovalent metal aliphatic carboxylate.

[0581] Embodiment 25: The extrudable thermoplastic composition of Embodiment 24, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 2 to 30 carbon atoms.

[0582] Embodiment 26: The extrudable thermoplastic composition of Embodiment 24, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 30 carbon atoms.

[0583] Embodiment 27: The extrudable thermoplastic composition of Embodiment 24, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 26 carbon atoms.

[0584] Embodiment 28: The extrudable thermoplastic composition of Embodiment 24, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 22 carbon atoms.

[0585] Embodiment 29: The extrudable thermoplastic composition of Embodiment 24, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof.

[0586] Embodiment 30: The extrudable thermoplastic composition of Embodiment 24, wherein the monovalent metal aliphatic carboxylate 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.

[0587] Embodiment 31: The extrudable thermoplastic composition of Embodiment 24, wherein the monovalent metal aliphatic carboxylate is potassium stearate.

[0588] Embodiment 32: The extrudable thermoplastic composition of Embodiment 24, wherein the monovalent metal aliphatic carboxylate is sodium stearate.

[0589] Embodiment 33: The extrudable thermoplastic composition of Embodiment 24, wherein the monovalent metal aliphatic carboxylate is sodium hexanoate or potassium hexanoate.

[0590] Embodiment 34: The extrudable thermoplastic composition of Embodiment 23, wherein the monovalent metal carboxylate is a monovalent metal aromatic carboxylate.

[0591] Embodiment 35: The extrudable thermoplastic composition of Embodiment 34, wherein the monovalent metal aromatic carboxylate is derived from an aromatic carboxylic acid having 7 to 30 carbon atoms.

[0592] Embodiment 36: The extrudable thermoplastic composition of Embodiment 34, wherein the monovalent metal aromatic carboxylate is derived from an aromatic carboxylic acid having 7 to 20 carbon atoms.

[0593] Embodiment 37: The extrudable thermoplastic composition of Embodiment 34, wherein the monovalent metal aromatic carboxylate is potassium benzoate or sodium benzoate.

[0594] Embodiment 38: The extrudable thermoplastic composition of any of Embodiments 23-37, wherein the thermoplastic composition further comprises one or more of the following:

[0595] iii) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of polyethylene glycol; and

[0596] iv) (based on the weight of the linear polyethylene) 200 to 4,000 ppm of a polyether block amide copolymer, wherein the polyether block amide copolymer comprises polyamide blocks and polyether blocks.

[0597] Embodiment 39: The extrudable thermoplastic composition of any of Embodiments 23-38, wherein the linear polyethylene is LLDPE.

[0598] Embodiment 40: The extrudable thermoplastic composition of Embodiment 39, wherein the LLDPE has a melt index I2 of 0.1 to 5.0 g / 10 minutes.

[0599] Embodiment 41: The extrudable thermoplastic composition of Embodiment 39 or 40, wherein the LLDPE has a density of 0.910 to 0.936 g / cm 3 .

[0600] Embodiment 42: The extrudable thermoplastic composition of any of Embodiments 39-41, wherein the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more α-olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

[0601] Embodiment 43: The extrudable thermoplastic composition of any of Embodiments 23-42, wherein the thermoplastic composition comprises (based on the weight of the linear polyethylene) 200 to 2,000 ppm of a monovalent metal carboxylate.

[0602] Embodiment 44: A method of reducing melt extrusion defects during extrusion of a thermoplastic composition comprising a linear polyethylene, the method comprising:

[0603] adding at least one monovalent metal carboxylate to the linear polyethylene; and

[0604] extruding the thermoplastic composition in a melt extrusion process;

[0605] The linear polyethylene is selected from LLDPE, MDPE, VLDPE, HDPE and mixtures thereof.

[0606] Embodiment 45: The method of Embodiment 44, wherein the thermoplastic composition further comprises one or more of the following:

[0607] iii) 200 to 4,000 ppm (based on the weight of the linear polyethylene) of polyethylene glycol; and

[0608] iv) (based on the weight of the linear polyethylene) 200 to 4,000 ppm of a polyether block amide copolymer, wherein the polyether block amide copolymer comprises polyamide blocks and polyether blocks.

[0609] Embodiment 46: The method of Embodiment 44 or 45, wherein the thermoplastic composition is substantially free of fluoropolymer.

[0610] Embodiment 47: The method of any of Embodiments 44-46, wherein the melt extrusion process is performed in the absence of a fluoropolymer.

[0611] Embodiment 48: The method of any one of Embodiments 44-47, wherein the at least one monovalent metal carboxylate comprises a monovalent metal aliphatic carboxylate.

[0612] Embodiment 49: The method of Embodiment 48, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 2 to 30 carbon atoms.

[0613] Embodiment 50: The method of Embodiment 48, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 30 carbon atoms.

[0614] Embodiment 51: The method of Embodiment 48, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 26 carbon atoms.

[0615] Embodiment 52: The method of Embodiment 48, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 22 carbon atoms.

[0616] Embodiment 53: The method of embodiment 48, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof.

[0617] Embodiment 54: The method of embodiment 48, wherein the monovalent metal aliphatic carboxylate 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.

[0618] Embodiment 55: The method of Embodiment 48, wherein the monovalent metal aliphatic carboxylate is potassium stearate.

[0619] Embodiment 56: The method of Embodiment 48, wherein the monovalent metal aliphatic carboxylate is sodium stearate.

[0620] Embodiment 57: The method of Embodiment 48, wherein the monovalent metal aliphatic carboxylate is sodium hexanoate or potassium hexanoate.

[0621] Embodiment 58: The method of any one of Embodiments 44-47, wherein the at least one monovalent metal carboxylate comprises a monovalent metal aromatic carboxylate.

[0622] Embodiment 59: The method of Embodiment 58, wherein the monovalent metal aromatic carboxylate is derived from an aromatic carboxylic acid having 7 to 30 carbon atoms.

[0623] Embodiment 60: The method of Embodiment 58, wherein the monovalent metal aromatic carboxylate is derived from an aromatic carboxylic acid having 7 to 20 carbon atoms.

[0624] Embodiment 61: The method of Embodiment 58, wherein the monovalent metal aromatic carboxylate is potassium benzoate or sodium benzoate.

[0625] Embodiment 62: The method of any of Embodiments 44-61, wherein the linear polyethylene is LLDPE.

[0626] Embodiment 63: The method of Embodiment 62, wherein the LLDPE has a melt index I2 of 0.1 to 5.0 g / 10 minutes.

[0627] Embodiment 64: The method of embodiment 62 or 63, wherein the LLDPE has a density of 0.910 to 0.936 g / cm 3 .

[0628] Embodiment 65: The method of any of Embodiments 62-64, wherein the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more α-olefins selected from 1-butene, 1-hexene, and 1-octene.

[0629] Embodiment 66: The method of any of Embodiments 44-65, wherein the thermoplastic composition comprises (based on the weight of the linear polyethylene) 200 to 2,000 ppm of a monovalent metal carboxylate.

[0630] Industrial Applicability

[0631] Polymer processing aids (PPAs) are provided that reduce melt fracture defects in extruded polyolefins in the absence of fluoropolymers.

Claims

1. A method for preparing an extrudate of a thermoplastic composition, the method comprising extruding a thermoplastic composition during a melt extrusion process; the thermoplastic composition comprising: i) linear polyethylene; and ii) a monovalent metal carboxylate in an amount of 200 to 4,000 ppm (based on the weight of the linear polyethylene); wherein the linear polyethylene is selected from LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; wherein the thermoplastic composition is substantially free of fluoropolymers; and wherein the melt extrusion process is carried out in the absence of fluoropolymers.

2. The method according to claim 1, wherein the monovalent metal carboxylate is a monovalent metal aliphatic carboxylate.

3. The method according to claim 2, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 2 to 30 carbon atoms.

4. The method according to claim 2, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 30 carbon atoms.

5. The method according to claim 2, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 26 carbon atoms.

6. The method according to claim 2, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid having 6 to 22 carbon atoms.

7. The method according to claim 2, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid selected from the following: hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof.

8. The method according to claim 2, wherein the monovalent metal aliphatic carboxylate is selected from: lithium acetate, sodium acetate, potassium acetate, lithium stearate, sodium stearate, potassium stearate, lithium hexanoate, sodium hexanoate, potassium hexanoate, and mixtures thereof.

9. The method according to claim 2, wherein the monovalent metal aliphatic carboxylate is potassium stearate.

10. The method according to claim 2, wherein the monovalent metal aliphatic carboxylate is sodium stearate.

11. The method according to claim 2, wherein the monovalent metal aliphatic carboxylate is sodium hexanoate or potassium hexanoate.

12. The method according to claim 1, wherein the monovalent metal carboxylate is a monovalent metal aromatic carboxylate.

13. The method according to claim 12, wherein the monovalent metal aromatic carboxylate is derived from an aromatic carboxylic acid having 7 to 30 carbon atoms.

14. The method according to claim 12, wherein the monovalent metal aromatic carboxylate is derived from an aromatic carboxylic acid having 7 to 20 carbon atoms.

15. The method according to claim 12, wherein the monovalent metal aromatic carboxylate is potassium benzoate or sodium benzoate.

16. The method according to any one of claims 1 to 15, wherein the thermoplastic composition further comprises one or more of the following: iii) polyethylene glycol in an amount of 200 to 4,000 ppm (based on the weight of the linear polyethylene); and iv) 200 to 4,000 ppm of a polyether block amide copolymer (based on the weight of the linear polyethylene), wherein the polyether block amide copolymer comprises a polyamide block and a polyether block.

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

18. The method according to claim 17, wherein the melt index I of the LLDPE 2 is from 0.1 to 5.0 g / 10 min.

19. The method according to claim 17 or 18, wherein the density of the LLDPE is 0.910 to 0.936 g / cm3.

20. The method according to any one of claims 17 to 19, wherein the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more α-olefins selected from: 1-butene, 1-hexene, and 1-octene.

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

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

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

24. The extrudable thermoplastic composition according to claim 23, wherein the monovalent metal carboxylate is a monovalent metal aliphatic carboxylate.

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

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

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

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

29. The extrudable thermoplastic composition according to claim 24, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid selected from: caproic 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. The extrudable thermoplastic composition according to claim 24, wherein the monovalent metal aliphatic carboxylate is selected from: lithium acetate, sodium acetate, potassium acetate, lithium stearate, sodium stearate, potassium stearate, lithium caproate, sodium caproate, potassium caproate, and mixtures thereof.

31. The extrudable thermoplastic composition according to claim 24, wherein the monovalent metal aliphatic carboxylate is potassium stearate.

32. The extrudable thermoplastic composition according to claim 24, wherein the monovalent metal aliphatic carboxylate is sodium stearate.

33. The extrudable thermoplastic composition according to claim 24, wherein the monovalent metal aliphatic carboxylate is sodium hexanoate or potassium hexanoate.

34. The extrudable thermoplastic composition according to claim 23, wherein the monovalent metal carboxylate is a monovalent metal aromatic carboxylate.

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

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

37. The extrudable thermoplastic composition according to claim 34, wherein the monovalent metal aromatic carboxylate is potassium benzoate or sodium benzoate.

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

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

40. The extrudable thermoplastic composition according to claim 39, wherein the melt index I of the LLDPE 2 is from 0.1 to 5.0 g / 10 min.

41. The extrudable thermoplastic composition according to claim 39 or 40, wherein the density of the LLDPE is 0.910 to 0.936 g / cm3.

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

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

44. A method for reducing melt extrusion defects during the extrusion of a thermoplastic composition comprising linear polyethylene, the method comprising: adding at least one monovalent metal carboxylate to the linear polyethylene; and extruding the thermoplastic composition during the melt extrusion process; wherein the linear polyethylene is selected from LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof.

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

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

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

48. The method according to any one of claims 44 to 47, wherein the at least one monovalent metal carboxylate comprises a monovalent metal aliphatic carboxylate.

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

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

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

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

53. The method according to claim 48, wherein the monovalent metal aliphatic carboxylate is derived from an aliphatic carboxylic acid selected from the following: caproic 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. The method according to claim 48, wherein the monovalent metal aliphatic carboxylate is selected from: lithium acetate, sodium acetate, potassium acetate, lithium stearate, sodium stearate, potassium stearate, lithium caproate, sodium caproate, potassium caproate, and mixtures thereof.

55. The method according to claim 48, wherein the monovalent metal aliphatic carboxylate is potassium stearate.

56. The method according to claim 48, wherein the monovalent metal aliphatic carboxylate is sodium stearate.

57. The method according to claim 48, wherein the monovalent metal aliphatic carboxylate is sodium caproate or potassium caproate.

58. The method according to any one of claims 44 to 47, wherein the at least one monovalent metal carboxylate comprises a monovalent metal aromatic carboxylate.

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

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

61. The method according to claim 58, wherein the monovalent metal aromatic carboxylate is potassium benzoate or sodium benzoate.

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

63. The method according to claim 62, wherein the melt index I of the LLDPE 2 is from 0.1 to 5.0 g / 10 min.

64. The method according to claim 62 or 63, wherein the density of the LLDPE is 0.910 to 0.936 g / cm3.

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

66. The method according to any one of claims 44 to 65, wherein the thermoplastic composition comprises from 200 to 2,000 ppm, based on the weight of the linear polyethylene, of a monovalent metal carboxylate.

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