Fluorine-free polymer processing aid

Abstract

Polymer processing aids (PPAs) reduce melt defects in extruded polyolefins in the absence of fluoropolymers. Polymer processing aids comprising block copolymers having polyamide blocks and polyether blocks effectively reduce melt defects in thermoplastic polyolefins such as linear low density polyethylene (LLDPE). By incorporating an auxiliary PPA containing polycaprolactone or a polycaprolactone diol polymer, the melt fracture behavior in thermoplastic resins is further improved in the absence of fluoropolymers.

Description

Technical Field

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

Background Art

[0002] During the extrusion of polyolefin polymers, surface defects including those referred to as sharkskin, snake skin, and orange peel may occur, and each type of surface defect is generally related to the rheology of the polymer melt. A particularly serious surface defect that may occur is "melt fracture". This is thought to occur when the shear rate at the surface of the polyolefin polymer becomes high enough that the surface of the polymer begins to fracture. That is, the surface of the extruded polymer slides relative to the body of the polymer melt. This surface generally cannot flow fast enough to catch up with the body of the extrudate, resulting in melt fracture, and as a result, the surface properties of the extruded polymer are significantly impaired.

[0003] U.S. Patent No. 3,125,547 discloses a blend of polyethylene and a small amount of fluoropolymer that provides a smooth surface on polyethylene extrudates at high extrusion speeds.

[0004] U.S. Patent No. 3,222,314 discloses a blend of polyethylene and low molecular weight polyethylene glycol that provides a heat-sealable film suitable for printing.

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

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

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

[0008] U.S. 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. 6,894,118 discloses a polymer processing aid which is a combination of a fluoropolymer and a polycaprolactone having a number average molecular weight Mn of 2,000 to 10,000.

[0010] U.S. Patent No. 7,449,520 discloses using polycaprolactone, which is a polyester polymer, as a surfactant in combination with a fluoropolymer processing aid. The extrusion of a melt-processable polymer containing a fluoropolymer processing aid having a weight average particle size exceeding 2 microns is disclosed.

[0011] Since fluoroelastomers and fluoropolymers are expensive materials, there is an economic incentive to avoid their use. Furthermore, it has increasingly been recognized that perfluorinated alkanes and perfluorinated surfactant compounds such as perfluorooctanesulfonic acid and perfluorooctanoic acid used during the production of fluoropolymers can have an adverse impact on the environment.

[0012] In U.S. Patent Application Publication No. 2005 / 0070644, the inventors disclosed that high molecular weight polyethylene glycol, particularly PEG with a molecular weight exceeding 20,000 g / mol, reduces melt fracture during the extrusion of polyolefins in the absence of a fluoropolymer.

[0013] U.S. Patent No. 10,982,079 also details the performance of polymer processing aids in the absence of added fluoropolymers. The polymer processing aids include high molecular weight polyethylene glycol with improved thermal stability by incorporating metal salts of carboxylic acid, sulfonic acid, or alkyl sulfuric acid. SUMMARY OF THE INVENTION

[0014] The inventors report that a block copolymer having a polyamide block and a polyether block, when used in combination with polycaprolactone, functions well as a polymer processing aid during the extrusion of thermoplastic polyolefins even in the absence of a fluoropolymer.

[0015] This disclosure provides a useful alternative to fluorinated alkene-based polymer processing aids.

[0016] One embodiment is a process for preparing a thermoplastic composition extrudate, the process comprising the step of extruding the thermoplastic composition in a melt extrusion process, wherein the thermoplastic composition comprises: i) linear polyethylene; ii) 200 to 4,000 ppm of a poly(ether-block-amide) copolymer (based on the weight of the linear polyethylene); and iii) 200 to 4,000 ppm of a polycaprolactone polymer (based on the weight of the linear polyethylene), wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof, the poly(ether-block-amide) copolymer comprises a polyamide block and a polyether block, the thermoplastic composition is substantially free of fluoropolymer, and the melt extrusion process is carried out in the absence of fluoropolymer.

[0017] One embodiment is a process for preparing a thermoplastic composition extrudate, the process comprising the step of extruding the thermoplastic composition in a melt extrusion process, wherein the thermoplastic composition comprises: i) linear polyethylene; ii) 200 to 4,000 ppm of a poly(ether-block-amide) copolymer (based on the weight of the linear polyethylene); iii) 200 to 4,000 ppm of a polycaprolactone polymer (based on the weight of the linear polyethylene); and iv) 200 to 4,000 ppm of a polyethylene glycol (based on the weight of the linear polyethylene), wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof, the poly(ether-block-amide) copolymer comprises a polyamide block and a polyether block, the thermoplastic composition is substantially free of fluoropolymer, and the melt extrusion process is carried out in the absence of fluoropolymer.

[0018] One embodiment is an extrudable thermoplastic composition comprising: i) linear polyethylene; ii) 200 to 4,000 ppm of a poly(ether-block-amide) copolymer (based on the weight of the linear polyethylene); and iii) 200 to 4,000 ppm of a polycaprolactone polymer (based on the weight of the linear polyethylene), wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof, the poly(ether-block-amide) copolymer comprises a polyamide block and a polyether block, and the extrudable thermoplastic composition is substantially free of fluoropolymers.

[0019] In one embodiment, the extrudable thermoplastic composition further comprises iv) 200 to 4,000 ppm of polyethylene glycol (based on the weight of the linear polyethylene).

[0020] One embodiment is a process for preparing a thermoplastic composition extrudate, comprising: a) preparing a thermoplastic composition by combining linear polyethylene with at least one poly(ether-block-amide) copolymer at 200 to 4,000 ppm (based on the weight of the linear polyethylene) and at least one polycaprolactone polymer at 200 to 4,000 ppm (based on the weight of the linear polyethylene); and b) extruding the thermoplastic composition in a melt extrusion process, wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof, the at least one poly(ether-block-amide) copolymer comprises a polyamide block and a polyether block, the thermoplastic composition is substantially free of fluoropolymers, and the melt extrusion process is carried out in the absence of fluoropolymers.

[0021] One embodiment is a process for preparing a thermoplastic composition extrudate, comprising: a) preparing a thermoplastic composition by combining linear polyethylene with at least one poly(ether-block-amide) copolymer (200 to 4000 ppm, based on the weight of the linear polyethylene), at least one polycaprolactone polymer (200 to 4,000 ppm, based on the weight of the linear polyethylene), and at least one polyethylene glycol (200 to 4,000 ppm, based on the weight of the linear polyethylene); and b) extruding the thermoplastic composition in a melt extrusion process, wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof, at least one poly(ether-block-amide) copolymer comprises a polyamide block and a polyether block, the thermoplastic composition is substantially free of fluoropolymer, and the melt extrusion process is carried out in the absence of fluoropolymer.

[0022] In one embodiment, the melt extrusion process is carried out at a shear rate that produces a thermoplastic composition extrudate having a melt fracture defect when carried out using a thermoplastic composition consisting essentially of linear polyethylene.

[0023] In one embodiment, the linear polyethylene comprises zinc oxide (ZnO).

[0024] In an embodiment, the linear polyethylene has the formula: [M 2+ 1-x M 3+ x (OH) 2 x+ [(A n- ) x / n ·mH 2 O] x- and comprises hydrotalcite, wherein M 2+ is divalent Mg, Ni, Zn, Cu, or Mn, M 3+ is trivalent Al, Fe, or Cr, and A n- is, for example, CO 3 2- ​、 or SO 4 2- 、 NO 3 2- 、 Cl 1- 、 or OH 1- and are anions such as, and x is from 0.1 to 0.5.

[0025] In one embodiment, the linear polyethylene is of the formula: Mg 6 Al 2 (OH) 16 CO 3 ·nH 2 O and contains hydrotalcite.

[0026] In one embodiment, the linear polyethylene is a mineral hydrotalcite (Mg 6 Al 2 (OH) 16 CO 3 ·4H 2 O).

[0027] In one embodiment, the linear polyethylene contains a hindered phenol primary antioxidant and a phosphorus-containing secondary antioxidant.

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

[0029] In one embodiment, the LLDPE has a melt index I of 0.1 to 5.0 grams per 10 minutes 2 .

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

[0031] In one embodiment, the LLDPE is an ethylene copolymer containing polymerized ethylene and one or more alpha-olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

Brief Description of the Drawings

[0032]

Figure 1

DETAILED DESCRIPTION OF THE INVENTION

[0033] As used herein, the term "monomer" refers to a small molecule that can chemically react and chemically bond to itself or other monomers to form a polymer.

[0034] As used herein, the term "α-olefin" or "alpha-olefin" is used to describe a monomer having a linear hydrocarbon chain containing 3 to 20 carbon atoms with a double bond at one end of the chain, and the equivalent term is "linear α-olefin". Alpha-olefins are also referred to as comonomers.

[0035] As used herein, the terms "polyethylene" or "ethylene polymer" refer to a polymer produced from ethylene monomers and optionally one or more additional monomers, regardless of the specific catalyst or process used to make the ethylene polymer. In the field of polyethylene, one or more additional monomers are often referred to as "comonomers" and typically include alpha-olefins. The term "homopolymer" generally 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 types of polyethylene include high-pressure low-density polyethylene (LDPE), high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE) or ultra-low-density polyethylene (ULDPE), and are also known as plastomers and elastomers. The term polyethylene also includes polyethylene terpolymers that can contain two or more comonomers in addition to ethylene. The term polyethylene also includes combinations or blends of the above types of polyethylene.

[0036] As used herein, the term "fluoropolymer" refers to homopolymers and copolymers of fluorinated olefins. The fluorinated olefins can have a fluorine atom to carbon ratio of at least 1:2, or in some embodiments, at least 1:1. Homopolymers include, for example, those derived from vinylidene fluoride and vinyl fluoride. Copolymers include, for example, those derived from vinylidene fluoride and one or more additional olefins, where the one or more additional olefins may be fluorinated, such as hexafluoropropylene, or may not be fluorinated, such as propylene. Non-limiting examples of the term "fluoropolymer" as used in this disclosure include, for example, those described in 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 U.S. Patent Application Publication No. 2010 / 0311906. Examples of commercially available fluoropolymers include, for example, copolymers of hexafluoropropylene and vinylidene fluoride available under the trade names "DYNAMAR® FX 9613" and "DYNAMAR FX 9614"; and copolymers of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene available under the trade names "DYNAMAR FX 5911" and "DYNAMAR FX 5912". Other commercially available fluoropolymers include "VITON® A", "VITON FREEFLOW", "DAI-EL®", and "KYNAR®", all of which are available in various grades.

[0037] In this disclosure, the terms polyalkylene oxide, poly(oxyalkylene), and polyalkylene glycol are used interchangeably. Thus, the terms polyethylene oxide, poly(oxyethylene), and polyethylene glycol are also used interchangeably; and the same is true for the terms polypropylene oxide, poly(oxypropylene), and polypropylene glycol.

[0038] The term "film" is used herein to mean a film having one or more layers formed by extrusion of a polymer through one or more die openings. The term "film structure" is used to mean a film structure in which the film can have multiple layers (e.g., at least two layers, at least three layers, at least four layers, at least five layers, etc.).

[0039] The terms "alkyl group" and the prefix "alk-" include both straight-chain and branched-chain groups, as well as cyclic groups having up to 30 carbon atoms, unless otherwise specified. The cyclic group can be monocyclic or polycyclic and, in some embodiments, has 3 to 10 ring carbon atoms.

[0040] For example, with respect to alkyl, alkylene, or arylalkylene, the phrase "interrupted by one or more ether linkages" means having alkyl, alkylene, or arylalkylene moieties on both sides of the functional group. An example of alkylene interrupted by -O- is -CH 2 -CH 2 -O-CH 2 -CH 2 -.

[0041] 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, one or more alkyl groups having up to 4 carbon atoms (e.g., methyl or ethyl), alkoxy having up to 4 carbon atoms, halo (i.e., fluoro, chloro, bromo or iodo), hydroxy, or a carbocyclic aromatic ring or ring system optionally substituted with up to 5 substituents including nitro groups. Examples of aryl groups include phenyl, naphthyl, biphenyl, fluorenyl as well as furyl, thienyl, oxazolyl, and thiazolyl. "Arylalkylene" refers to the "alkylene" moiety to which an aryl group is attached. "Alkylarylene" refers to the "arylene" moiety to which an alkyl group is attached.

[0042] In embodiments of the present disclosure, the extrusion of thermoplastic polyolefins is improved ( "assisted") by using a polymer processing aid (PPA).

[0043] In embodiments of the present disclosure, one or more components of the polymer processing aid can be mixed (e.g., premixed) with the thermoplastic polyolefin or pre-blended (e.g., dry blended or melt blended), followed by extrusion of the polyolefin.

[0044] In embodiments of the present disclosure, one or more components of the polymer processing aid can be fed into an extruder together with the thermoplastic polyolefin.

[0045] In embodiments of the present disclosure, one or more components of a polymer processing aid can be added to a thermoplastic polyolefin to prepare a masterbatch of the polyolefin containing one or more components of the polymer processing aid. The resulting polyolefin masterbatch can then be used to introduce one or more components of the polymer processing aid into the thermoplastic polyolefin in a conventional manner (e.g., dry blending or melt blending) before extrusion of the polyolefin or during extrusion of the polyolefin (e.g., feeding into an extruder together with the polyolefin).

[0046] <Polymer processing aid> In one embodiment of the present disclosure, a polymer processing aid (PPA) used to assist in the extrusion of a thermoplastic polyolefin includes i) a poly(ether-block-amide) copolymer having a polyamide block and a polyether block, and ii) a polycaprolactone (PCL) polymer.

[0047] In one embodiment of the present disclosure, a polymer processing aid (PPA) used to assist in the extrusion of a thermoplastic polyolefin includes i) at least one poly(ether-block-amide) copolymer having a polyamide block and a polyether block, and ii) at least one polycaprolactone (PCL) polymer.

[0048] In one embodiment of the present disclosure, the polymer processing aid (PPA) used to assist in the extrusion of a thermoplastic polyolefin further includes one or more poly(oxyalkylene) polymers.

[0049] In one embodiment of the present disclosure, the polymer processing aid (PPA) used to assist in the extrusion of a thermoplastic polyolefin further includes one or more poly(oxyethylene) polymers.

[0050] In one embodiment of the present disclosure, the polymer processing aid (PPA) used to assist in the extrusion of a thermoplastic polyolefin further includes high-pressure low-density polyethylene (LDPE).

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

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

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

[0054] In 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, all of which are well known to those skilled in the art.

[0055] <Polyamide / polyether block copolymer (i.e., poly(ether-block-amide), PEBA)> In one embodiment of the present disclosure, the polymer processing aid (PPA) used to assist in the extrusion of thermoplastic polyolefins includes a poly(ether-block-amide) copolymer having a polyamide block and a polyether block. In the present disclosure, such a block copolymer having a polyamide block and a polyether block is also referred to as a "polyamide / polyether block copolymer". In the present disclosure, the term "poly(ether-block-amide) copolymer" can be abbreviated as "PEBA copolymer", and similarly, the term "poly(ether-block-amide)" can be abbreviated as "PEBA".

[0056] In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula:

Chemical formula

[0057] In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula:

Chemical formula

[0058] In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula: [Chemical formula] In the formula, n represents the length of the polyamide block, x represents the length of the amide component in the polyamide block, m represents the length of the poly(ether) block, y represents the length of the ether component in the poly(ether) block, p represents the length of the PEBA copolymer, and represents the total number of polyamide blocks and polyether blocks.

[0059] In an embodiment of the present disclosure, a poly(ether-block-amide) copolymer ("PEBA copolymer") includes a polyamide block and a polyether block.

[0060] Suitable poly(ether-block-amide) copolymers for use in embodiments of the present disclosure are described in U.S. Patent No. 5,986,005, which is hereby incorporated by reference in its entirety. Suitable PEBA copolymers for use in embodiments of the present disclosure, including methods for their preparation, are further described in Chapter 9, "Thermoplastic Poly(Ether-b-Amide) Elastomers: Synthesis," of The Handbook of Condensation Thermoplastic Elastomers, by Malet, F.L.G., 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, pages 243-262, and Chapter 10, "Poly(Ether-b-Amide) Thermoplastic Elastomers: Structure, Properties, and Applications," of The Handbook of Condensation Thermoplastic Elastomers, by Eustache, R.P., 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, pages 263-281, both of which are hereby incorporated by reference in their entirety.

[0061] In one embodiment, the poly(ether-block-amide) copolymer is the result of a co-condensation reaction between one or more polyamides having reactive end groups and one or more poly(oxyalkylene)s, such as poly(oxyethylene), having reactive end groups. The reactive end groups of the polyamide include, for example, diamine chain ends and dicarboxyl chain ends. The reactive end groups of the poly(oxyalkylene) include, for example, dicarboxyl chain ends, diol chain ends, and diamine chain ends.

[0062] In an embodiment, a poly(oxyalkylene) having a diamine chain end is obtained by cyanoethylation and hydrogenation of an alpha-omega-dihydroxy aliphatic poly(oxyalkylene), which is also known in the art as a polyether diol.

[0063] In an embodiment, a polyamide having a dicarboxylic acid chain end is obtained by condensation of an alpha-omega-aminocarboxylic acid of a lactam (e.g., laurolactam), which is a bifunctional monomer, or by condensation of a dicarboxylic acid and a diamine. The condensation polymerization may be carried out in the presence of a chain-limiting dicarboxylic acid.

[0064] In an embodiment, the polyamide block in the PEBA copolymer is derived from polyamide-12 (PA-12), or polyamide-11 (PA-11), or polyamide-6 (PA-6), or polyamide-66 (PA-66).

[0065] In an embodiment, the polyamide block in the PEBA copolymer is derived from polyamide-12 (PA-12).

[0066] In an embodiment, the polyamide block in the PEBA copolymer is derived from polyamide-11 (PA-11).

[0067] In an embodiment, the polyamide block in the PEBA copolymer is derived from polyamide-6 (PA-6).

[0068] The weight average molecular weight of the PEBA copolymer (e.g., M w and M n ) can be measured by techniques known in the art using polymer standards with a narrow molecular weight distribution, for example, by gel permeation chromatography (i.e., size exclusion chromatography).

[0069] In embodiments, the number average molecular weight M n of the polyamide block in the PEBA copolymer is 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.

[0070] In embodiments, the number average molecular weight M n of the polyether block in the PEBA copolymer is 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 3000 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.

[0071] In embodiments, the number average molecular weight M n of the PEBA copolymer is from 10,000 to 500,000 g / mol, including sub - ranges within this range and any numbers within this range. For example, in embodiments of the present disclosure, the number average molecular weight M nis 10,000 to 400,000 g / mol, or 10,000 to 300,000 g / mol, or 10,000 to 250,000 g / mol, or 15,000 to 300,000 g / mol, or 20,000 to 300,000 g / mol, or 15,000 to 200,000 g / mol, or 20,000 to 200,000 g / mol, or 30,000 to 250,000 g / mol, or about 25,000 to about 75,000 g / mol, or about 50,000 to about 75,000 g / mol, or about 100,000 to about 150,000 g / mol.

[0072] In an embodiment, the number average molecular weight M of the PEBA copolymer n is at least 10,000 g / mol, or at least 20,000 g / mol, or at least 25,000 g / mol, or greater than 25,000 g / mol, or at least 30,000 g / mol, or greater than 30,000 g / mol, or at least 35,000 g / mol, or greater than 35,000 g / mol, or at least 50,000 g / mol, or greater than 50,000 g / mol.

[0073] In an embodiment, the weight average molecular weight M of the PEBA copolymer w is 25,000 to 500,000 g / mol, including sub - ranges within this range and any values within this range. For example, in embodiments of the present disclosure, the weight average molecular weight M of the PEBA copolymer w is about 100,000 to about 250,000 g / mol, or about 100,000 to about 150,000 g / mol, or about 125,000 to about 150,000 g / mol.

[0074] In an embodiment, the polyamide and polyether blocks within the PEBA copolymer may be randomly distributed.

[0075] In an embodiment, the PEBA copolymer includes a polyamide block and a polyether block, and the polyamide block accounts for at least 50% by weight of the copolymer. In an embodiment, the PEBA copolymer includes a polyamide block and a polyether block, and the polyether block accounts for at least 50% by weight of the copolymer. In a further embodiment, the PEBA copolymer includes a polyamide block and a polyether block, and the molar ratio of the polyamide block to the polyether block is in the range of 1:3 to 3:1, or 1:2 to 2:1, or 3:2 to 1:3, or 2:3 to 3:1, or about 1:1.

[0076] In an embodiment, a PEBA copolymer having a polyamide block and a polyether block can be prepared by the reaction of a polyamide and a polyether block precursor. For example, a lactam, a polyether diol, and a chain-limiting diacid are reacted in the presence of a small amount of water to obtain a PEBA copolymer having polyamide blocks and polyether blocks of variable length that are statistically randomly distributed within the block copolymer chains.

[0077] In an embodiment, the polyether block may be derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, each in its natural state and co-polycondensed with a polyamide block containing carboxyl chain ends. A chain-limiting agent may be present during the polycondensation reaction to obtain a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed within the block copolymer.

[0078] In an embodiment, the polyether block may be derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, which are first converted to polyether diamine by amination and then co-polycondensed with a polyamide block containing a carboxyl chain end. A chain limiter may be present during the co-polycondensation reaction, and a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed within the block copolymer can be obtained.

[0079] PEBA copolymers suitable for use in embodiments of the present disclosure are described in U.S. Pat. Nos. 4,331,786, 4,115,475, 4,195,015, 4,839,441, 4,864,014, 4,230,838, 4,332,920, and 5,986,005, each of which is hereby incorporated by reference in its entirety. Additional PEBA copolymers that can be used in some embodiments of the present disclosure are described in U.S. Pat. No. 8,231,950.

[0080] In an embodiment of the present disclosure, the polyether block may be derived from poly(oxyethylene), also known as polyethylene glycol (PEG).

[0081] In an embodiment of the present disclosure, the polyether block may be derived from poly(oxypropylene), also known as polypropylene glycol (PPG).

[0082] In an embodiment of the present disclosure, the polyether block may be derived from poly(tetramethylene ether) glycol (PTMG), also known as polytetramethylene oxide (PTMEO) or polytetrahydrofuran (PTHF).

[0083] In embodiments 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), polytetrahydrofuran (PTHF), or a mixture thereof.

[0084] In embodiments of the present disclosure, the PEBA copolymer comprises: i) a polyamide block selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or a mixture thereof; and ii) a polyether block that is polyethylene glycol (PEG).

[0085] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polyethylene glycol (PEG).

[0086] In some embodiments of the present disclosure, the PEBA copolymer comprises 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

[0087] In some embodiments of the present disclosure, the PEBA copolymer comprises only one type of polyamide block and only one type of polyether block.

[0088] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 30 to 70 weight percent of the copolymer, and the polyethylene glycol block accounts for about 70 to 30 weight percent of the copolymer.

[0089] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 40 to 50 weight percent of the copolymer, and the polyethylene glycol block accounts for about 60 to 40 weight percent of the copolymer.

[0090] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 45 weight percent of the copolymer, and the polyethylene glycol block accounts for about 55 weight percent of the copolymer.

[0091] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) 10 to 20 polyamide blocks that are polyamide-12 (PA-12); and ii) 10 to 20 polyether blocks that are polyethylene glycol (PEG).

[0092] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polyethylene glycol (PEG), and the number average molecular weight Mn is from about 25,000 to about 75,000 g / mol.

[0093] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polyethylene glycol (PEG), and the number average molecular weight Mn is from about 50,000 to about 75,000 g / mol.

[0094] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polyethylene glycol (PEG), and the number average molecular weight Mn is about 66,100 g / mol.

[0095] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polyethylene glycol (PEG), and has a weight average molecular weight Mw of from about 100,000 to about 150,000 g / mol.

[0096] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polyethylene glycol (PEG), and has a weight average molecular weight Mw of from about 125,000 to about 150,000 g / mol.

[0097] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 134,000 g / mol.

[0098] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-6 (PA-6); and ii) a polyether block that is polyethylene glycol (PEG).

[0099] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-6 (PA-6); and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-6 block accounts for about 30 to 60 weight percent of the copolymer, and the polyethylene glycol block accounts for about 70 to 40 weight percent of the copolymer.

[0100] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-6 (PA-6), and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-6 block accounts for about 50 to 35 weight percent of the copolymer, and the polyethylene glycol block accounts for about 50 to 65 weight percent of the copolymer.

[0101] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) 10 to 20 polyamide blocks that are polyamide-6 (PA-6), and ii) 10 to 20 polyether blocks that are polyethylene glycol (PEG).

[0102] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-11 (PA-11), and ii) a polyether block that is polyethylene glycol (PEG).

[0103] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0104] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF), wherein the polyamide-12 block accounts for about 75 to 10 weight percent of the copolymer, and the polytetrahydrofuran block accounts for about 25 to 90 weight percent of the copolymer.

[0105] In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF), wherein the polyamide-12 block accounts for about 80 to 60 weight percent of the copolymer, and the polytetrahydrofuran block accounts for about 20 to 40 weight percent of the copolymer.

[0106] In one embodiment of the present disclosure, the PEBA copolymer includes: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polytetrahydrofuran (PTHF), wherein the polyamide-12 block accounts for about 40 to 60 weight percent of the copolymer, and the polytetrahydrofuran block accounts for about 60 to 40 weight percent of the copolymer.

[0107] In one embodiment of the present disclosure, the PEBA copolymer includes: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polytetrahydrofuran (PTHF), wherein the polyamide-12 block accounts for about 30 to 10 weight percent of the copolymer, and the polytetrahydrofuran block accounts for about 70 to 90 weight percent of the copolymer.

[0108] In one embodiment of the present disclosure, the PEBA copolymer includes: i) 10 to 20 polyamide blocks that are polyamide-12 (PA-12); and ii) 10 to 20 polyether blocks that are polytetrahydrofuran (PTHF).

[0109] In one embodiment of the present disclosure, the PEBA copolymer includes: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polytetrahydrofuran (PTHF), and the number average molecular weight Mn is from about 25,000 to about 75,000 g / mol.

[0110] In one embodiment of the present disclosure, the PEBA copolymer includes: i) a polyamide block that is polyamide-12 (PA-12); and ii) a polyether block that is polytetrahydrofuran (PTHF), and the number average molecular weight Mn is from about 40,000 to about 60,000 g / mol.

[0111] In one embodiment of the present disclosure, the PEBA copolymer includes i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 50,000 g / mol.

[0112] In one embodiment of the present disclosure, the PEBA copolymer includes i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0113] In one embodiment of the present disclosure, the PEBA copolymer includes i) a polyamide block that is polyamide-11 (PA-11) and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0114] In one embodiment of the present disclosure, the PEBA copolymer is a commercially available elastomer and is sold under the trade name PEBAX®.

[0115] In a further specific 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 3533 SA 01 MED, PEBAX 3533 SP 01, PEBAX 4011, PEBAX 4033 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP 01, PEBAX 4533 SA 01, PEBAX 4533 SA 01 MED, PEBAX 4533 SP 01, PEBAX 5513 SA 01, PEBAX 5513 SP 01, PEBAX 5533 SA 01, PEBAX 5533 SA 01 MED, PEBAX 5533 SN 70 BLACK, PEBAX 5533 SP 01, PEBAX 6333 SA 01, PEBAX 6333 SA 01 MED, PEBAX 6333 SP01, PEBAX 7033 SA 01, PEBAX 7033 SA 01 MED, PEBAX 7033 SP 01, PEBAX 7233 SA 01, PEBAX 7233 SA 01 MED, PEBAX 7233 SP 01, PEBAX 7433 SA 01 MED, PEBAX Clear 1200, PEBAX ES 9002 UV, PEBAX MH 1657, PEBAX MH2030, PEBAX MV 1074 SA 01, PEBAX MV 1074 SA 01 MED, PEBAX MV 1074 SP 01, PEBAX MV 2080, PEBAX MV 3000 SP 01, PEBAX RNEW (registered trademark) 30R51 SA 01, PEBAX RNEW 35R53 SP 01, PEBAX RNEW 40 R53 SP 01, PEBAX RNEW 55R53 SP 01, PEBAX RNEW 63R53 SP 01, PEBAX RNEW 70R53 SP 01, PEBAX RNEW 72R53 SP 01, PEBAX RNEW 80R53 SP 02, and mixtures thereof.

[0116] In one embodiment of the present disclosure, the PEBA copolymer is a commercially available elastomer and is sold under the trade names VESTAMID® or VESTAMID E.

[0117] In a further specific 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.

[0118] In one embodiment of the present disclosure, the polymer processing aid comprises two poly(ether - block - amide) copolymers with different number average molecular weights M n n.

[0119] In one embodiment of the present disclosure, the polymer processing aid comprises two poly(ether - block - amide) copolymers with different number average molecular weights M n n, and the two poly(ether - block - amide) copolymers having different M n n are present in a molar ratio of 1:99 to 99:1, including any sub - range within the range and any value within the range. For example, in an embodiment of the present disclosure, the polymer processing aid comprises two poly(ether - block - amide) copolymers with different number average molecular weights M n n in a molar ratio of 5:95 to 95:5, or 10:90 to 90:10, or 20:80 to 80:20, or 25:75 to 75:25, or 35:65 to 65:35, or 40:60 to 60:40, or about 50:50.

[0120] In one embodiment of the present disclosure, the amount of the PEBA copolymer used as a polymer processing aid (PPA) is from 100 to 5,000 ppm by weight, including any sub-range within the range and any value within the range (based on the weight of the thermoplastic polyolefin). The more optimized PPA addition levels and ranges for a given extrusion process can be readily determined by those skilled in the art. For example, in certain embodiments, the amount of the PEBA copolymer used as a polymer processing aid (PPA) is from 100 to 4,000 ppm by weight (based on the weight of the thermoplastic polyolefin), or from 200 to 4,000 ppm by weight, or from 100 to 3,000 ppm by weight, or from 200 to 3,000 ppm by weight, or from 100 to 2,000 ppm by weight, or from 200 to 2,500 ppm by weight, or from 300 to 2,500 ppm by weight, or from 300 to 2,500 ppm by weight, or from 400 to 2,500 ppm by weight, or from 500 to 2,500 ppm by weight, or from 750 to 4,000 ppm by weight, or from 750 to 3,000 ppm by weight, or from 750 to 2,500 ppm by weight, or from 1,000 to 4,000 ppm by weight, or from 1,000 to 3,000 ppm by weight, or from 1,000 to 2,500 ppm by weight, or from 1,000 to 2,250 ppm by weight, or from 1,000 to 2,000 ppm by weight, or from 1,250 to 1,750 ppm by weight, or from 500 to 2,250 ppm by weight, or from 500 to 2,000 ppm by weight, or from 300 to 2,000 ppm by weight, or from 200 to 2,000 ppm by weight.

[0121] In embodiments of the present disclosure, the amount of the PEBA copolymer used as a polymer processing aid (PPA) is 200 to 1,500 ppm by weight, or 300 to 1,500 ppm by weight, or 400 to 1,500 ppm by weight, or 500 to 1,500 ppm by weight, or 750 to 1,500 ppm by weight, or 300 to 1,250 ppm by weight, or 400 to 1,250 ppm by weight, or 500 to 1,250 ppm by weight, or 750 to 1,250 ppm by weight, or 200 to 1,000 ppm by weight, or 300 to 1,000 ppm by weight, or 500 to 1,000 ppm by weight, or 750 to 1,000 ppm by weight (based on the weight of the thermoplastic polyolefin).

[0122] In one embodiment of the present disclosure, the PEBA copolymer is added to the thermoplastic polyolefin (e.g., linear polyethylene) using a masterbatch formulation containing the PEBA copolymer. The term masterbatch is well known to those skilled in the art. Generally, the term "masterbatch" refers to the initial melt mixing of an additive, such as a PEBA copolymer, with a small amount of a given thermoplastic polyolefin (e.g., linear polyethylene), followed by the implementation of a blend (e.g., melt mixing or dry blending) of the resulting "masterbatch" with the remaining bulk of the thermoplastic polyolefin (e.g., linear polymer).

[0123] In embodiments of the present disclosure, a masterbatch of from about 0.1 to about 15.0 weight percent, or from about 0.5 to about 15.0 weight percent, or from about 0.5 to about 10.0 weight percent, or from about 0.1 to about 10.0 weight percent, or from about 0.1 to about 7.5 weight percent, or from about 0.5 to about 7.5 weight percent or from about 0.5 to about 5.0 weight percent, or from about 0.1 to about 5.0 weight percent, or from about 1.0 to about 15.0 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 1.0 to about 7.5 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 0.1 to about 2.5 weight percent, or from about 0.5 to about 2.5 weight percent is used in a blend with a bulk polymer (the weight percent of the masterbatch is based on the total weight of the masterbatch and the bulk polymer).

[0124] In an embodiment of the present disclosure, the masterbatch (e.g., linear polyethylene) may contain an amount of a PEBA copolymer in the range of 500 to 50,000 ppm by weight, including sub-ranges within the range and any number within the range (based on the weight of the masterbatch). For example, in a further embodiment of the present disclosure, the masterbatch is 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, or 5,000 to 25,000 ppm, or 1,000 to 20,000 ppm, or 2,000 to 20,000 ppm, or 3,000 to 20,000, or 4,000 to 20,000 ppm, or 5,000 to 20,000 ppm, or 5,000 to 17,500, or 5,000 to 15,000 or 5,000 to 12,500 ppm, or 2,500 to 15,000 ppm, or 5,000 to 15,000 ppm, or 7,500 to 15,000 ppm, or 7,500 ppm to 12,500 ppm, or 5,000 to 50,000 ppm, or 7,500 to 50,000 ppm, or 10,000 to 50,000 ppm, or 10,000 to 35,000 ppm, or 10,000 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 a PEBA copolymer by weight (based on the weight of the masterbatch).

[0125] The PEBA copolymer used as a polymer processing aid (PPA) may be used in the form of a semi-solid or viscous liquid, or as a powder, pellet, or granule.

[0126] <Polycaprolactone (PCL) polymer> In one embodiment of the present disclosure, the polymer processing aid includes a polycaprolactone polymer.

[0127] In the present disclosure, the term "polycaprolactone" or its abbreviation "PCL" is used to mean a polycaprolactone polymer that is a polymer containing, as repeating units, i) an ester derived from the polycondensation of a hydroxycarboxylic acid, 6-hydroxyhexanoic acid, or ii) an ester derived from the ring-opening polymerization of epsilon-caprolactone (a cyclic ester containing a 7-membered ring) or a substituted derivative thereof (see, for example, Labet M, Thielemans W., "Synthesis of Polycaprolactone: A Review", Chemical Society Reviews, December 2009, 38(12):3484-3504).

[0128] Accordingly, in the present disclosure, the term "polycaprolactone" refers to a polymer having, as a repeating unit, the following general formula:

Chemical formula

[0129] Catalysts such as tin octanoate (i.e., tin(II) 2-ethylhexanoate) can be used to catalyze the ring-opening polymerization reaction.

[0130] It is also well known to those skilled in the art that polycaprolactone polymers can be prepared by the ring-opening polymerization of epsilon-caprolactone using a suitable hydroxyl group-functionalized organic compound as an initiator. For example, monools such as methanol, ethanol, and isopropanol, or diols such as diethylene glycol and 1,4-butanediol can be used as initiators for the polymerization of epsilon-caprolactone.

[0131] In embodiments of the present disclosure, the polycaprolactone polymer may be a polycaprolactone monool, polycaprolactone diol, polycaprolactone triol, polycaprolactone tetrol, or a mixture thereof. For example, in embodiments of the present disclosure, the polycaprolactone polymer has the general formula: [Chemical formula] It is a polycaprolactone monoalcohol having or a general formula: [Chemical formula] It is a polycaprolactone diol having or a general formula: [Chemical formula] It is a polycaprolactone triol having or a general formula: [Chemical formula] It is a polycaprolactone tetrol having and In the formula, each of m, n, p, and q represents a plurality of caprolactone units, and R is an organic group corresponding to the organic alcohol compound used to initiate the ring-opening polymerization of epsilon-caprolactone.

[0132] As described above, the above R group is a specific monoalcohol, diol, triol, tetrol, or polyol compound R-(OH) used as an initiator for the ring-opening polymerization of caprolactone r reflects the properties of. For example, ethanol has an R group of -CH 2 CH 2 where r is 1, and diethylene glycol has an R group of -CH 2 CH 2 -O-CH 2 CH 2 - where r is 2, and 1,4-butanediol has an R group of -CH 2 CH 2 CH 2 CH 2 - where r is 2.

[0133] In this disclosure, it is also contemplated to use either or both of unsubstituted polycaprolactone polymers and substituted polycaprolactone polymers as polymer processing aids. Such unsubstituted or substituted polycaprolactone polymers have the general formula: [Chemical formula] and can be represented by wherein R is defined as above, R' is hydrogen, alkyl, alkoxy, aryl, cycloalkyl, alkylaryl, or arylalkyl moiety, each moiety having up to 20 carbon atoms; m is an integer representing the average number of repeating ester units, and r represents the number of hydroxy groups. In one embodiment, r is 1. In one embodiment, r is from 2 to 8. In one embodiment, at least six of the R' moieties are hydrogen. In one embodiment, each R' is hydrogen. In one embodiment, r is from 2 to 4.

[0134] Further specific examples of polycaprolactone polymers derived from polyols and polyalkylene glycols that can be used in embodiments of the present disclosure, as well as methods for their preparation, are described in U.S. Patent No. 3,169,945 and U.S. Patent No. 4,751,112.

[0135] 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 that constitute a polyoxyalkylene polymer.

[0136] In one embodiment of the present disclosure, the polycaprolactone polymer is a commercially available polyester sold under the trade name CAPA®.

[0137] In one embodiment of the present disclosure, the polycaprolactone polymer is a commercially available polyester sold under the trade names TONE®, CAPROMER®, and PLACCEL®.

[0138] In embodiments of the present disclosure, the polycaprolactone polymer is made from the 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 butylethylpropanediol.

[0139] The weight average molecular weight of the polycaprolactone polymer (e.g., M w and M n ) can be measured by techniques known in the art using polymer standards of narrow molecular weight distribution, for example, by gel permeation chromatography (i.e., size exclusion chromatography).

[0140] In embodiments, the number average molecular weight M n of the polycaprolactone polymer is 100 to 32,000 g / mol, or 100 to 25,000 g / mol, or 100 to 20,000 g / mol, or 100 to 15,000 g / mol, or 100 to 12,500 g / mol, or 100 to 10,000 g / mol, or 200 to 15,000 g / mol, or 200 to 12,500 g / mol, or 200 to 10,000 g / mol, or 200 to 9,000 g / mol, or 200 to 8,000 g / mol, or 200 to 7,000 g / mol, or 200 to 6,000 g / mol, or 200 to 5,000 g / mol, or 200 to about 4,500 g / mol, or 200 to 4,000 g / mol, or 200 to 3,000 g / mol, or 200 to 2,000 g / mol, or 1,000 to 10,000 g / mol, or 1,500 to 10,000 g / mol, or 2000 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.

[0141] In embodiments, the number average molecular weight M nis 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 n is 30,000 to 100,000 g / mol, or 30,000 to 90,000 g / mol, or 35,000 to 90,000 g / mol, or 35,000 to 85,000 g / mol.

[0142] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 400 g / mol and is derived from epsilon-caprolactone using a diol (e.g., 1,4-butane) as an initiator.

[0143] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 1,000 g / mol and is derived from epsilon-caprolactone using a diol (e.g., 1,4-butane) as an initiator.

[0144] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 2,000 g / mol and is derived from epsilon-caprolactone using a diol (e.g., 1,4-butane) as an initiator.

[0145] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 4,000 g / mol and is derived from epsilon-caprolactone using a diol (e.g., 1,4-butanediol) as an initiator.

[0146] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 32,000 g / mol and is derived from epsilon-caprolactone using a diol (e.g., 1,4-butanediol) as an initiator.

[0147] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 32,000 g / mol and is derived from epsilon-caprolactone using a diol (e.g., 1,4-butanediol) as an initiator.

[0148] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 200 g / mol to about 10,000 g / mol and is derived from epsilon-caprolactone using a linear monoalcohol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 400 g / mol to about 8,000 g / mol and is derived from epsilon-caprolactone using a linear monoalcohol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 500 g / mol to about 6,000 g / mol and is derived from epsilon-caprolactone using a linear monoalcohol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 750 g / mol to about 4,000 g / mol and is derived from epsilon-caprolactone using a linear monoalcohol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 750 g / mol to about 2,000 g / mol and is derived from epsilon-caprolactone using a linear monoalcohol (e.g., cetyl alcohol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 500 g / mol to about 1,500 g / mol and is derived from epsilon-caprolactone using a linear monoalcohol (e.g., cetyl alcohol) as an initiator.

[0149] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 200 g / mol to about 10,000 g / mol and is derived from epsilon-caprolactone using a branched monoalcohol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 400 g / mol to about 8,000 g / mol and is derived from epsilon-caprolactone using a branched monoalcohol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 500 g / mol to about 6,000 g / mol and is derived from epsilon-caprolactone using a branched monoalcohol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 750 g / mol to about 4,000 g / mol and is derived from epsilon-caprolactone using a branched monoalcohol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 750 g / mol to about 2,000 g / mol and is derived from epsilon-caprolactone using a branched monoalcohol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone monoalcohol polymer having a number average molecular weight Mn of about 500 g / mol to about 1,500 g / mol and is derived from epsilon-caprolactone using a branched monoalcohol as an initiator.

[0150] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 200 g / mol to about 10,000 g / mol and is derived from epsilon-caprolactone using a linear diol (e.g., 1,4-butanediol, hexanediol, diethylene glycol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 400 g / mol to about 8,000 g / mol and is derived from epsilon-caprolactone using a linear diol (e.g., 1,4-butanediol, hexanediol, diethylene glycol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 500 g / mol to about 6,000 g / mol and is derived from epsilon-caprolactone using a linear diol (e.g., 1,4-butanediol, hexanediol, diethylene glycol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 750 g / mol to about 4,000 g / mol and is derived from epsilon-caprolactone using a linear diol (e.g., 1,4-butanediol, hexanediol, diethylene glycol) as an initiator.

[0151] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 200 g / mol to about 10,000 g / mol and is derived from epsilon-caprolactone using a branched diol (e.g., neopentyl diol, or butylethylpropanediol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 400 g / mol to about 8,000 g / mol and is derived from epsilon-caprolactone using a branched diol (e.g., neopentyl diol, or butylethylpropanediol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 500 g / mol to about 6,000 g / mol and is derived from epsilon-caprolactone using a branched diol (e.g., neopentyl diol, or butylethylpropanediol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 750 g / mol to about 4,000 g / mol and is derived from epsilon-caprolactone using a branched diol (e.g., neopentyl diol, or butylethylpropanediol) as an initiator.

[0152] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 100 g / mol to about 8,000 g / mol and is derived from epsilon-caprolactone using a linear triol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 6,000 g / mol and is derived from epsilon-caprolactone using a linear triol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 4,000 g / mol and is derived from epsilon-caprolactone using a linear triol as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 3,000 g / mol and is derived from epsilon-caprolactone using a linear triol as an initiator.

[0153] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 100 g / mol to about 8,000 g / mol and is derived from epsilon-caprolactone using a branched triol (e.g., trimethylolpropane) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 6,000 g / mol and is derived from epsilon-caprolactone using a branched triol (e.g., trimethylolpropane) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 4,000 g / mol and is derived from epsilon-caprolactone using a branched triol (e.g., trimethylolpropane) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone triol polymer having a number average molecular weight Mn of about 200 g / mol to about 3,000 g / mol and is derived from epsilon-caprolactone using a branched triol (e.g., trimethylolpropane) as an initiator.

[0154] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone tetrol polymer having a number average molecular weight Mn of about 100 g / mol to about 15,000 g / mol and is derived from epsilon-caprolactone using a tetrol (e.g., pentaerythritol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone tetrol polymer having a number average molecular weight Mn of about 200 g / mol to about 10,000 g / mol and is derived from epsilon-caprolactone using a tetrol (e.g., pentaerythritol) as an initiator. In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone tetrol polymer having a number average molecular weight Mn of about 200 g / mol to about 8,000 g / mol and is derived from epsilon-caprolactone using a tetrol (e.g., pentaerythritol) as an initiator.

[0155] In one embodiment of the present disclosure, the polycaprolactone polymer is a polycaprolactone copolymer derived from epsilon-caprolactone using a polyalkylene glycol (e.g., polytetramethylene ether glycol, also known as polytetrahydrofuran) as an initiator.

[0156] In one embodiment of the present disclosure, the amount of the polycaprolactone polymer used as a polymer processing aid (PPA) is from 100 to 5,000 ppm by weight, including any sub-range within the range and any value within the range (based on the weight of the thermoplastic polyolefin). The further optimized PPA addition levels and ranges for a given extrusion process can be readily determined by those skilled in the art. For example, in certain embodiments, the amount of the 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 3,000 ppm by weight, or from 750 to 2,500 ppm by weight, or from 1,000 to 4,000 ppm by weight, or from 1,000 to 3,000 ppm by weight, or from 1,000 to 2,500 ppm by weight, or from 1,000 to 2,250 ppm by weight, or from 1,000 to 2,000 ppm by weight, or from 1,250 to 1,750 ppm by weight, or from 500 to 2,250 ppm by weight, or from 500 to 2,000 ppm by weight, or from 300 to 2,000 ppm by weight, or from 200 to 2,000 ppm by weight (based on the weight of the thermoplastic polyolefin).

[0157] In one embodiment of the present disclosure, the polycaprolactone polymer is added to a thermoplastic polyolefin (such as 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 initial melt mixing of an additive, such as a polycaprolactone polymer, with a small amount of a given thermoplastic polyolefin (such as linear polyethylene), followed by the blending (such as melt blending or dry blending) of the resulting "masterbatch" with the remaining bulk of the thermoplastic polyolefin (such as a linear polymer).

[0158] In embodiments of the present disclosure, a masterbatch of from about 0.1 to about 15.0 weight percent, or from about 0.5 to about 15.0 weight percent, or from about 0.5 to about 10.0 weight percent, or from about 0.1 to about 10.0 weight percent, or from about 0.1 to about 7.5 weight percent, or from about 0.5 to about 7.5 weight percent or from about 0.5 to about 5.0 weight percent, or from about 0.1 to about 5.0 weight percent, or from about 1.0 to about 15.0 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 1.0 to about 7.5 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 0.1 to about 2.5 weight percent, or from about 0.5 to about 2.5 weight percent is used in a blend with a bulk polymer (the weight percent of the masterbatch is based on the total weight of the masterbatch and the bulk polymer).

[0159] In embodiments of the present disclosure, the masterbatch (e.g., linear polyethylene) may contain an amount of polycaprolactone polymer in the range of 500 to 50,000 ppm by weight, including sub-ranges within the range and any number within the range (based on the weight of the masterbatch). For example, in further embodiments of the present disclosure, the masterbatch is in the range of 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, or 5,000 to 25,000 ppm, or 1,000 to 20,000 ppm, or 2,000 to 20,000 ppm, or 3,000 to 20,000, or 4,000 to 20,000 ppm, or 5,000 to 20,000 ppm, or 5,000 to 17,500, or 5,000 to 15,000 or 5,000 to 12,500 ppm, or 2,500 to 15,000 ppm, or 5,000 to 15,000 ppm, or 7,500 to 15,000 ppm, or 7,500 ppm to 12,500 ppm, or 5,000 to 50,000 ppm, or 7,500 to 50,000 ppm, or 10,000 to 50,000 ppm, or 10,000 to 35,000 ppm, or 10,000 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 by weight of polycaprolactone polymer.

[0160] The polycaprolactone (PCL) polymer used as a polymer processing aid (PPA) may be used in the form of a semi-solid or viscous liquid, or as a powder, pellet, or granule.

[0161] <Poly(oxyalkylene) polymer> In one embodiment of the present disclosure, the polymer processing aid includes a poly(oxyalkylene) polymer (also known as polyalkylene glycol (PAG) or polyalkylene oxide).

[0162] In one embodiment of the present disclosure, the polymer processing aid includes a poly(oxyethylene) polymer (also known as polyethylene glycol or polyethylene oxide).

[0163] In one embodiment of the present disclosure, the polymer processing aid includes poly(oxypropylene) glycol (also known as polypropylene glycol or polypropylene oxide).

[0164] The poly(oxyalkylene) polymer, in embodiments of the present disclosure, can be represented by the formula A[(OR 1 ) x OR 2 y wherein A is typically alkylene interrupted by one or more ether linkages, y is 2 or 3, (OR 1 ) x is a poly(oxyalkylene) chain having a plurality (x) of oxyalkylene groups OR 1 , wherein each R 1 is independently C 2 -C 5 alkylene, and in some embodiments C 2 -C 3 alkylene, R 2 is hydrogen, alkyl, aryl, arylalkenyl, alkylarylenyl, -C(O)-alkyl, -C(O)-aryl, -C(O)-arylalkenyl, or -C(O)-alkylarylenyl, wherein -C(O)- is bonded to the O of OR 2 .

[0165] In one embodiment of the present disclosure, for the poly(oxyalkylene) polymer, each R 1 is -CH 2 CH 2 ​- a homopolymer such as a poly(oxyethylene) polymer (also referred to as polyethylene glycol in the present disclosure), or each R 1 is -C 3 H 6 - and can be a homopolymer such as a poly(oxypropylene) polymer.

[0166] In another embodiment of the present disclosure, the poly(oxyalkylene) polymer comprises chains of randomly distributed oxyalkylene groups (e.g., -OC 2 H 4 - and -OC 3 H 6 - units-containing copolymer), or has alternating blocks of repeating oxyalkylene groups (e.g., (-OC 2 H 4 -) a and (-OC 3 H 6 -) b blocks, and a + b is x), and is a poly(oxyalkylene) polymer.

[0167] A poly(oxyalkylene) copolymer comprising randomly distributed or alternately arranged (-OC 2 H 4 -) and (-OC 3 H 6 -) units, or (-OC 2 H 4 -) a and (-OC 3 H 6 -) b blocks is sometimes referred to as a "poloxamer" and is commercially available under the trade names PLURONIC®, KOLLIPHOR®, and SYNPERONIC®.

[0168] In some embodiments of the present disclosure, A is ethylene, -CH 2 -CH(-)-CH 2 - (derived from glycerol), CH 3 CH 2 C(CH 2-) 3 (Derived from 1,1,1-trimethylolpropane), poly(oxypropylene), -CH 2 CH 2 -O-CH 2 CH 2 -, or -CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -.

[0169] In some embodiments of the present disclosure, R 2 is hydrogen, methyl, butyl, phenyl, benzyl, acetyl, benzoyl, or stearyl.

[0170] In other embodiments of the present disclosure, the poly(oxyalkylene) polymer is, for example, a polyester prepared from a dicarboxylic acid and a poly(oxyalkylene) polymer represented by the formula A[(OR 1 ) x OR 2 y [wherein A, R 1 , and x are as defined above, R 2 is hydrogen, and y is 2].[[]END]]

[0171] In one embodiment of the present disclosure, the major portion by weight of the poly(oxyalkylene) polymer is the repeating oxyalkylene group (OR 1 ).

[0172] In one embodiment of the present disclosure, the poly(oxyalkylene) polymer is polyethylene glycol (PEG). Polyethylene glycol (PEG) can be represented by the formula H(O-CH 2 CH 2 -) x OH. Many polyethylene glycols, as well as their ethers, and their esters are commercially available, and all of them are contemplated for use in embodiments of the present disclosure.

[0173] ​The weight-average molecular weight (e.g., M n and M w ) of a polyalkylene glycol such as polyethylene glycol (PEG) can be measured by techniques known in the art using, for example, a poly(oxyalkylene) polymer (e.g., polyethylene glycol) with a narrow molecular weight distribution as a standard by gel permeation chromatography (i.e., size exclusion chromatography).

[0174] In embodiments of the present disclosure, the polyalkylene glycol (PAG) has a value of x such that the weight-average molecular weight M w of the polyalkylene glycol polymer is at least about 20,000 g / mol, or at least about 30,000 g / mol, or at least about 40,000 g / mol, or at least about 50,000 g / mol, or at least about 60,000 g / mol.

[0175] In embodiments of the present disclosure, the polyalkylene glycol (PAG) has a value of x such that the weight-average molecular weight M w of the polyalkylene glycol polymer has an upper limit of about 500,000 g / mol, or about 450,000 g / mol, or about 400,000 g / mol, or about 350,000 g / mol, or about 300,000 g / mol.

[0176] In embodiments of the present disclosure, the polyalkylene glycol (PAG) has a value of x such that the weight-average molecular weight M whas a value of x such that it is 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 400,000 g / mol, or from about 60,000 g / mol to about 350,000 g / mol, or from about 70,000 g / mol to about 400,000 g / mol, or from about 70,000 g / mol to about 350,000 g / mol, or from about 100,000 g / mol to about 350,000 g / mol, or from about 150,000 g / mol to about 350,000 g / mol, or from about 200,000 g / mol to about 350,000 g / mol, or from about 250,000 g / mol to about 350,000 g / mol.

[0177] In an embodiment of the present disclosure, the polyalkylene glycol (PAG) has a weight average molecular weight M of the polyalkylene glycol polymer w has a value of x such that it is less than 20,000 g / mol, or less than 15,000 g / mol, or less than 10,000 g / mol, or less than 5,000 g / mol.

[0178] In an embodiment of the present disclosure, the polyalkylene glycol (PAG) has a weight average molecular weight M of the polyalkylene glycol polymer w has a value of x such that it is from about 200 g / mol to about 20,000 g / mol, or from about 400 g / mol to about 15,000 g / mol, or from about 400 g / mol to about 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.

[0179] In an embodiment of the present disclosure, the polyalkylene glycol (PAG) has a weight average molecular weight M of the polyalkylene glycol polymer whas an x value such that it is from about 1000 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.

[0180] In embodiments of the present disclosure, the polyalkylene glycol (PAG) has a weight average molecular weight M of the polyalkylene glycol polymer w has an x value such that it is 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.

[0181] In embodiments of the present disclosure, the polyethylene glycol (PEG) has a weight average molecular weight M of the polyethylene glycol polymer w has an x value such that it is at least about 20,000 g / mol, or at least about 30,000 g / mol, or at least about 40,000 g / mol, or at least about 50,000 g / mol, or at least about 60,000 g / mol.

[0182] In embodiments of the present disclosure, the polyethylene glycol (PEG) has a weight average molecular weight M of the polyethylene glycol polymer w has an x value such that it has an upper limit of about 500,000 g / mol, or about 450,000 g / mol, or about 400,000 g / mol, or about 350,000 g / mol, or about 300,000 g / mol.

[0183] In embodiments of the present disclosure, polyethylene glycol (PEG) has a value of x such that the weight average molecular weight M of the polyethylene glycol polymer w is 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 400,000 g / mol, or from about 60,000 g / mol to about 350,000 g / mol, or from about 70,000 g / mol to about 400,000 g / mol, or from about 70,000 g / mol to about 350,000 g / mol, or from about 100,000 g / mol to about 350,000 g / mol, or from about 150,000 g / mol to about 350,000 g / mol, or from about 200,000 g / mol to about 350,000 g / mol, or from about 250,000 g / mol to about 350,000 g / mol.

[0184] In embodiments of the present disclosure, polyethylene glycol (PEG) has a value of x such that the weight average molecular weight M of the polyethylene glycol polymer w is less than 20,000 g / mol, or less than 15,000 g / mol, or less than 10,000 g / mol, or less than 5,000 g / mol.

[0185] In embodiments of the present disclosure, polyethylene glycol (PEG) has a value of x such that the weight average molecular weight M of the polyethylene glycol polymer w is from about 200 g / mol to about 20,000 g / mol, or from about 400 g / mol to about 15,000 g / mol, or from about 400 g / mol to about 15,000 g / mol, or from about 400 g / mol to about 10,000 g / mol, or from about 400 g / mol to about 7,500 g / mol, or from about 400 g / mol to about 5,000 g / mol.

[0186] In an embodiment of the present disclosure, polyethylene glycol (PEG) has a weight average molecular weight M of a polyethylene glycol polymer w such that x has a value of 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.

[0187] In an embodiment of the present disclosure, polyethylene glycol (PEG) has a weight average molecular weight M of a polyethylene glycol polymer w such that x has a value of 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.

[0188] In one embodiment of the present disclosure, polyethylene glycol (PEG) has a weight average molecular weight M of at least 20,000 g / mol, or at least 25,000 g / mol w thereof.

[0189] In one embodiment of the present disclosure, polyethylene glycol (PEG) has a weight average molecular weight M of from about 20,000 g / mol to about 50,000 g / mol w thereof.

[0190] In an embodiment of the present disclosure, polyethylene glycol (PEG) has a weight average molecular weight M of 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. w has.

[0191] In one embodiment of the present disclosure, polyethylene glycol (PEG) commercially available under the trademark POLYGLYKOL is used as a polymer processing aid.

[0192] In one embodiment of the present disclosure, polyethylene glycol (PEG) commercially available under the trademark CARBOWAX® or PLURIOL® is used as a polymer processing aid.

[0193] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyalkylene glycols having different weight average molecular weights M. w of.

[0194] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols having different weight average molecular weights M. w of.

[0195] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols having different weight average molecular weights M. w wherein the first polyethylene glycol has a weight average molecular weight M of less than 10,000 g / mol. w and the second polyethylene glycol has a weight average molecular weight M greater than 25,000 g / mol. w has.

[0196] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols having different weight average molecular weights M. w wherein the first polyethylene glycol has a weight average molecular weight M of less than 25,000 g / mol. whaving, and the second polyethylene glycol has a weight average molecular weight M of at least 25,000 g / mol w having.

[0197] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols with different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of less than 25,000 g / mol w and the second polyethylene glycol has a weight average molecular weight M of at least 250,000 g / mol w having.

[0198] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols with different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of less than 10,000 g / mol w and the second polyethylene glycol has a weight average molecular weight M of at least 250,000 g / mol w having.

[0199] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols with different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of about 2,000 to about 10,000 g / mol w and the second polyethylene glycol has a weight average molecular weight M of about 25,000 to about 350,000 g / mol w having.

[0200] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols with different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of about 2,000 to about 10,000 g / mol w and the second polyethylene glycol has a weight average molecular weight M of about 15,000 to about 50,000 g / mol w having.

[0201] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols with different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of about 2,000 to about 10,000 g / mol w and the second polyethylene glycol has a weight average molecular weight M of about 15,000 to about 25,000 g / mol w .

[0202] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols with different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of about 2,000 to about 10,000 g / mol w and the second polyethylene glycol has a weight average molecular weight M of about 25,000 to about 50,000 g / mol w .

[0203] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols with different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of about 2,000 to about 10,000 g / mol w and the second polyethylene glycol has a weight average molecular weight M of about 250,000 to about 350,000 g / mol w .

[0204] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols with different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of less than 10,000 g / mol w and the second polyethylene glycol has a weight average molecular weight M greater than 10,000 g / mol w .

[0205] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols with different weight average molecular weights M wcomprising at least two polyethylene glycols, wherein the first polyethylene glycol has a weight average molecular weight M of less than about 10,000 g / mol w and the second polyethylene glycol has a weight average molecular weight M of at least about 50,000 g / mol w .

[0206] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols having different weight average molecular weights M w wherein the first polyethylene glycol has a weight average molecular weight M of from about 2,000 to about 8,000 g / mol w or the first polyethylene glycol has a weight average molecular weight M of from about 2,000 to about 8,000 g / mol w and the second polyethylene glycol has a weight average molecular weight M of from about 25,000 to about 350,000 g / mol w or the second polyethylene glycol has a weight average molecular weight M of from about 25,000 to about 350,000 g / mol w .

[0207] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols having different weight average molecular weights M w wherein the difference in weight average molecular weight M between the at least two polyethylene glycols is in the range of 2:1 to 100,000:1, including any sub-range and any value within the range. For example, in an embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols having different weight average molecular weights M w wherein the difference in weight average molecular weight M between the at least two polyethylene glycols 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 w . w

[0208] In one embodiment of the present disclosure, the polymer processing aid comprises at least two polyethylene glycols having different weight average molecular weights M​w contains at least two polyethylene glycols with different M w The at least two polyethylene glycols are present in a molar ratio of 1:99 to 99:1, including any sub-range within the range and any value within the range. For example, in an embodiment of the present disclosure, the polymer processing aid has different weight-average molecular weights M w The at least two polyethylene glycols are included in a molar ratio of 5:95 to 95:5, or 10:90 to 90:10, or 20:80 to 80:20, or 25:75 to 75:25, or 35:65 to 65:35, or 40:60 to 60:40, or about 50:50.

[0209] In one embodiment of the present disclosure, the amount of polyalkylene glycol (PAG) or the amount of polyethylene glycol (PEG) used as a polymer processing aid (PPA) is within any sub-range within the range and any value within the range (based on the weight of the thermoplastic polyolefin such as linear polyethylene), and is 100 to 5,000 ppm by weight. The further optimized PPA addition levels and ranges for a given extrusion process can be readily determined by those skilled in the art. For example, in certain embodiments, the amount of polyalkylene glycol (PAG) or the amount of polyethylene glycol (PEG) used as a polymer processing aid (PPA) is 100 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 2,000 ppm by weight, or 300 to 2,000 ppm by weight, or 400 to 2,000 ppm by weight, or 200 to 1,500 ppm by weight, or 300 to 1,500 ppm by weight, or 400 to 1,500 ppm by weight, or 200 to 1,200 ppm by weight, or 300 to 1,200 ppm by weight, or 400 to 1,200 ppm by weight (based on the weight of the thermoplastic polyolefin such as linear polyethylene).

[0210] 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 PAG or PEG. The term masterbatch is well known to those skilled in the art. Generally, the term "masterbatch" refers to the initial melt mixing of an additive, such as PEG, with a small amount of a given thermoplastic polyolefin (e.g., linear polyethylene), followed by the blending (e.g., melt blending or dry blending) of the resulting "masterbatch" with the remainder of the bulk of the thermoplastic polyolefin (e.g., linear polymer).

[0211] In embodiments of the present disclosure, a masterbatch of from about 0.1 to about 15.0 weight percent, or from about 0.5 to about 15.0 weight percent, or from about 0.5 to about 10.0 weight percent, or from about 0.1 to about 10.0 weight percent, or from about 0.1 to about 7.5 weight percent, or from about 0.5 to about 7.5 weight percent or from about 0.5 to about 5.0 weight percent, or from about 0.1 to about 5.0 weight percent, or from about 1.0 to about 15.0 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 1.0 to about 7.5 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 0.1 to about 2.5 weight percent, or from about 0.5 to about 2.5 weight percent is used in the blend with the bulk polymer (the weight percent of the masterbatch is based on the total weight of the masterbatch and the bulk polymer).

[0212] In an embodiment of the present disclosure, a masterbatch (e.g., linear polyethylene) may contain PAG or PEG in an amount in the range of 500 to 50,000 ppm by weight, including sub-ranges within the range and any number within the range (based on the weight of the masterbatch). For example, in a further embodiment of the present disclosure, the masterbatch is 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, or 5,000 to 25,000 ppm, or 1,000 to 20,000 ppm, or 2,000 to 20,000 ppm, or 3,000 to 20,000, or 4,000 to 20,000 ppm, or 5,000 to 20,000 ppm, or 5,000 to 17,500, or 5,000 to 15,000 or 5,000 to 12,500 ppm, or 2,500 to 15,000 ppm, or 5,000 to 15,000 ppm, or 7,500 to 15,000 ppm, or 7,500 ppm to 12,500 ppm, or 5,000 to 50,000 ppm, or 7,500 to 50,000 ppm, or 10,000 to 50,000 ppm, or 10,000 to 35,000 ppm, or 10,000 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 by weight of PAG or PEG (based on the weight of the masterbatch).

[0213] The polyalkylene glycol or polyethylene glycol used as a polymer processing aid (PPA) may be used in the form of a semi-solid or viscous liquid, or as a powder, pellet, or granule.

[0214] <High-pressure low-density polyethylene (LDPE)> In one embodiment of the present disclosure, the polymer processing aid includes high-pressure low-density polyethylene LDPE.

[0215] In the present disclosure, high-pressure low-density polyethylene (LDPE) is an ethylene homopolymer and is prepared by free radical homopolymerization of ethylene.

[0216] Although not 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 non-linear microstructure to LDPE. Thus, high-pressure low-density polyethylene (LDPE) is prepared using an ethylene polymerization catalyst and is distinguished from linear polyethylene having a linear polymer microstructure, as further described below. Further description of the high-pressure low-density polyethylene LDPE used in the present disclosure is provided in the chapter entitled "Polyethylene, Low Density" by Norma Maraschin in the Kirk-Othmer Encyclopedia of Chemical Technology, first edition, March 18, 2005, the disclosure of which is hereby incorporated by reference in its entirety.

[0217] In embodiments of the present disclosure, high-pressure low-density polyethylene (LDPE) is prepared in either a tubular reactor or an autoclave reactor.

[0218] The tubular reactor operates at high pressure and high temperature in a continuous mode. A typical operating pressure of the tubular reactor is 2,000 to 3,500 bar. The operating temperature can range from 140 to 340 °C. The reactor is designed to have a large length-to-diameter ratio (e.g., 400 to 40,000) and may have a plurality of reaction zones in the shape of an elongated coil. A high gas velocity (at least 10 m / s) is used to provide optimal heat transfer. The conversion rate of the multi-zone system is typically 22 to 30% per pass, but may reach 36 to 40%. The tubular reactor may have a plurality of injection points for adding monomers or initiators to different reaction zones at different temperatures.

[0219] The autoclave reactor may have a length-to-diameter ratio of 2 to 20 and may be single-stage or multi-stage. Typically, low-temperature ethylene is passed through a high-temperature reaction zone, and the conversion rate can be controlled by the temperature difference between the incoming ethylene gas and the temperature of the autoclave reactor. The conversion rate in an autoclave reactor is usually lower than that in a tubular reactor with a higher ability to remove the heat of polymerization and is up to 23% per pass. The typical operating pressure for an autoclave reactor is 1,100 to 2,000 bar. The average operating temperature is 220 to 300 °C, but the temperature may reach 340 °C.

[0220] To initiate the free-radical polymerization of ethylene, various initiators may be used in each type of reactor. Examples of initiators include oxygen or one or more organic peroxides such as di-tert-butyl peroxide, cumyl peroxide, tert-butyl-peroxypivalate, tert-butyl hydroperoxide, benzoyl peroxide, tert-amyl peroxypivalate, tert-butyl-peroxy-2-ethylhexanoate, and decanoyl peroxide, but are not limited thereto. Chain transfer reagents can also be used to control the polymer melt index in each type of reactor. Examples of chain transfer reagents include propane, n-butane, n-hexane, cyclohexane, propylene, 1-butene, and isobutylene, but are not limited thereto.

[0221] In embodiments of the present disclosure, LDPE has a density of from about 0.910 g / cm 3 to about 0.940 g / cm 3 . For example, in embodiments of the present disclosure, LDPE has a density of from about 0.914 g / cm 3 to about 0.930 g / cm 3 , or from about 0.916 g / cm 3 to about 0.930 g / cm 3 , or from about 0.920 g / cm 3 to about 0.940 g / cm 3 , or from about 0.920 g / cm 3~about 0.930 g / cm 3 has a density of.

[0222] In an embodiment, the LDPE used in the present disclosure has a melt index I 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 2 has.

[0223] In an embodiment, the LDPE used in the present disclosure has a melt index I 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 2 has.

[0224] In an embodiment, the LDPE used in the present disclosure has a melt index I of 1.0 to 10.0 g / 10 min, or 1.5 to 10.0 g / 10 min, or 2.0 to 10 g / 10 min, or 2.5 to 10.0 g / 10 min, or 3.0 to 10.0 g / 10 min, or 3.5 to 10.0 g / 10 min, or 4.0 to 10.0 g / 10 min, or 2.5 to 9.0 g / 10 min, or 2.5 to 8.5 g / 10 min, or 2.5 to 8.0 g / 10 min, or 3.0 to 9.0 g / 10 min, or 3.0 to 8.5 g / 10 min, or 3.0 to 8.0 g / 10 min, or 3.5 to 9.0 g / 10 min, or 3.5 to 8.5 g / 10 min, or 3.5 to 8.0 g / 10 min, or 4.0 to 9.0 g / 10 min, or 4.0 to 8.5 g / 10 min or 4.0 to 8.0 g / 10 min 2 has.

[0225] In an embodiment, the LDPE used in the present disclosure has a melt index I of less than 1.0 g / 10 min 2 has. Such LDPE may sometimes be referred to as "frac melt" LDPE material. In a further embodiment, the LDPE used in the present disclosure has a melt index I of 0.01 to 1.0 g / 10 min, or less than 0.01 to 1.0 g / 10 min 2 has.

[0226] In embodiments of the present disclosure, high-pressure low-density polyethylene (LDPE) is a blend of LDPE materials having different densities and / or different melt indices I 2 and is a blend of LDPE materials having different densities and / or different melt indices I.

[0227] In one embodiment, the low-density polyethylene LDPE is a blend of LDPE made in a tubular reactor and LDPE made in an autoclave reactor.

[0228] In one embodiment, the LDPE polymer blend is prepared by physically blending different high-pressure LDPEs (e.g., LDPE produced in a tubular reactor and LDPE produced in an autoclave reactor). Physically blending is intended to include the process in which two or more individual ethylene homopolymers are mixed after being taken out of the polymerization reaction zone. The physical blend of the individual LDPEs can be achieved by dry blending (e.g., tumble blending), extrusion blending (coextrusion), solution blending, melt blending, or other similar blending techniques known to those skilled in the art.

[0229] The polydispersity M w / M n is also called the molecular weight distribution (MWD) and is defined as the value obtained by dividing the weight-average molecular weight M w by the number-average molecular weight M n . The MWD of LDPE can be determined by gel permeation chromatography (GPC)-viscosity measurement in embodiments of the present disclosure. The GPC-viscosity measurement technique is based on the method of ASTM D6474-99 and analyzes the polymer sample using a dual refractometer / viscometer detector system. By this approach, the intrinsic viscosity can be measured online and is well known to those skilled in the art.

[0230] In embodiments of the present disclosure, the LDPE has an MWD greater than about 5.0. In embodiments of the present disclosure, the LDPE has an MWD of from about 8.0 to about 30.0.

[0231] The molecular weight of LDPE or its blend can be further described as unimodal, bimodal or multimodal. By using the term "unimodal", it means that the molecular weight distribution can be said to have only one maximum value in the molecular weight distribution curve. The molecular weight distribution curve can be generated according to the method of ASTM D6474-99. By using the term "bimodal", it means that the molecular weight distribution can be said to have two maximum values in the molecular weight distribution curve. The term "multimodal" means that there are more than two maximum values in such a curve.

[0232] In an embodiment of the present disclosure, the LDPE used has a unimodal, bimodal or multimodal molecular weight distribution.

[0233] In one embodiment of the present disclosure, the LDPE used is produced in a tubular reactor and has a multimodal molecular weight distribution.

[0234] 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.

[0235] In one embodiment of the present disclosure, a blend of LDPE is used, and the blend has a multimodal molecular weight distribution.

[0236] The antioxidant package for stabilizing LDPE in the embodiments of the present disclosure is well-known in the art and may include phenolic and phosphite compounds. Two non-limiting examples of phenolic and phosphite stabilizers that can be added to LDPE in the embodiments of the present disclosure are sold under the trade names IRGANOX® 1076 and IRGAFOS® 168, respectively. Phenolic compounds are sometimes called "primary" antioxidants. Phosphite compounds are sometimes called "secondary" antioxidants.

[0237] In embodiments of the present disclosure, the level of antioxidant present in LDPE is from 0 to 2,000 ppm by weight (based on the weight of LDPE). In further embodiments, the amount of antioxidant present in LDPE is from 0 to 1000 ppm, or 0 to 500 ppm, or 0 to 300 ppm by weight (based on the weight of LDPE).

[0238] In embodiments of the present disclosure, LDPE can be used in the form of powder, pellets, granules, or other extrudable forms.

[0239] In the present disclosure, the amount of LDPE used as a polymer processing aid is relatively low compared to the weight of the bulk thermoplastic polyolefin material (e.g., linear polyethylene). Thus, in embodiments of the present disclosure, LDPE is used in an amount that is 1.0 to 25.0 weight percent of the total weight of LDPE and the bulk thermoplastic polyolefin (e.g., linear polyolefin), including sub-ranges within the range and any value within the range. For example, in embodiments of the present disclosure, the amount of LDPE is 1.0 to 20.0 weight percent, or 3.0 to 20.0 weight percent, or 5.0 to 20.0 weight percent, or 5.0 to 15.0 weight percent, or 5.0 to 12.5 weight percent, or 7.5 to 12.5 weight percent, or 7.5 to 15.0 weight percent, or 7.5 to 20.0 weight percent, or 3.0 to 17.5 weight percent, or 3.0 to 15.0 weight percent, or 2.5 to 20.0 weight percent, or 2.5 to 15.0 weight percent, or 2.5 to 12.5 weight percent, or 3.0 to 12.5 weight percent, or greater than 0 to 20.0 weight percent, or greater than 0 to 15.0 weight percent, or greater than 0 to 12.5 weight percent of the total weight of LDPE and the thermoplastic polyolefin (e.g., linear polyethylene).

[0240] <Thermoplastic polyolefin (e.g., linear polyethylene)> The present disclosure is generally useful for extrudable thermoplastic polyolefins, and in one embodiment, the present disclosure is particularly suitable for improving the extrusion of linear polyethylene.

[0241] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") comprises: i) linear polyethylene; ii) a poly(ether-block-amide) copolymer comprising blocks of polyamide and polyether; iii) a polycaprolactone polymer, but substantially free of fluoroelastomers, fluoropolymers, and other fully fluorinated alkane derivatives.

[0242] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") comprises: i) linear polyethylene; ii) a poly(ether-block-amide) copolymer comprising blocks of polyamide and polyether; iii) a polycaprolactone polymer; iv) a poly(oxyalkylene) polymer, but substantially free of fluoroelastomers, fluoropolymers, and other fully fluorinated alkane derivatives.

[0243] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") comprises: i) linear polyethylene; ii) a poly(ether-block-amide) copolymer comprising blocks of polyamide and polyether; iii) a polycaprolactone polymer; iv) polyethylene glycol, but substantially free of fluoroelastomers, fluoropolymers, and other fully fluorinated alkane derivatives.

[0244] In one embodiment of the present disclosure, an extrudable or extruded thermoplastic composition ("extrudate") further comprises a high-pressure low-density polymer (LDPE) in an amount of 1.0 to 25.0 weight percent, based on the weight of the linear polyethylene.

[0245] "Substantially free" means that fluoroelastomers, fluoropolymers, and other fully fluorinated alkane derivatives are present in an amount less than an amount capable of improving the melt defect (e.g., melt fracture) performance of the thermoplastic composition during the melt extrusion process. In embodiments of the present disclosure, fluoroelastomers, fluoropolymers, and other fully fluorinated alkane derivatives are less than about 1 weight percent, or less than about 0.5 weight percent, or less than 0.1 weight percent, or less than 500 ppm, or less than 100 ppm, or less than 90 ppm, or less than 75 ppm, or less than 50 ppm, or less than 25 ppm, or less than 10 ppm, or about 0 weight percent, or about 0 ppm of the extrudable or extruded thermoplastic composition.

[0246] In one embodiment of the present disclosure, the major or dominant component in the extrudable or extruded thermoplastic composition ("extrudate") is linear polyethylene. In embodiments, such an "extrudate" comprises 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.

[0247] The extrudable or extruded thermoplastic composition ("extrudate") may, in embodiments of the present disclosure, comprise a mixture of more than one different type of linear polyethylene.

[0248] Linear polyethylene is made by a transition metal-based olefin polymerization catalyst and has a linear polymer microstructure, unlike high-pressure low-density polyethylene LDPE which has a branched polymer microstructure (due to the presence of a large number of long-chain branches) and is made by a high-pressure free radical polymerization process.

[0249] Olefin polymerization catalysts used in the preparation of 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, geometrically constrained catalysts, phosphine imine catalysts, and catalysts having a four-site ligand are also well known to those skilled in the art.

[0250] Linear polyethylene includes uniformly branched linear ethylene polymers as described in U.S. Patent No. 3,645,992; non-uniformly branched linear ethylene polymers as described in U.S. Patent No. 4,076,698; and those described in U.S. Patent Nos. 5,272,236, 5,278,272, 5,582,923, and 5,733,155, which contain long-chain branches (less long-chain branches than LDPE) and are sometimes called "substantially linear ethylene polymers" and are uniformly branched linear ethylene polymers; and / or blends thereof.

[0251] The term "uniformly branched" means a linear ethylene copolymer in which the α-olefin comonomer is randomly distributed within the copolymer molecule and substantially all copolymer molecules have the same ethylene-to-α-olefin monomer ratio, and the ethylene copolymer has, for example, a composition distribution index CDBI greater than about 50 weight percent, or in some embodiments greater than about 75 weight percent, or greater than about 80 weight percent, or greater than about 90 weight percent 50 as shown, and is characterized by a relatively narrow short-chain branch distribution. Uniformly branched ethylene copolymers are generally prepared using single-site olefin polymerization catalysts.

[0252] The term "non-uniformly branched" as used herein means, for example, a composition distribution index CDBI of less than about 75 weight percent, or in some embodiments less than about 50 weight percent 50As shown by, it is used to refer to a linear ethylene copolymer characterized by a relatively broad short-chain branching distribution. Heterogeneously branched ethylene copolymers are generally prepared using a multi-site olefin polymerization catalyst.

[0253] In embodiments of the present disclosure, the linear polyethylene is selected from ethylene homopolymers and copolymers comprising polymerized units having the general formula CH 2 =CHR 3 [wherein R 3 is hydrogen or an alkyl group]. In embodiments 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 (i.e., styrene as an alpha olefin) or an n-hexyl group (i.e., 1-octene as an alpha olefin).

[0254] In embodiments of the present disclosure, the linear polyethylene is an ethylene homopolymer or an ethylene copolymer.

[0255] In embodiments of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more polymerized alpha olefins selected from the group comprising C 3 ~C 12 alpha olefins.

[0256] In embodiments of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more polymerized alpha olefins selected from the group comprising C 3 ~C 12 alpha olefins, and the polymerized ethylene comprises at least 85 weight percent of the ethylene copolymer.

[0257] In embodiments of the present disclosure, the ethylene copolymer comprises polymerized ethylene and one or more polymerized alpha olefins selected from the group comprising C 3 ~C 12It includes one or more polymerized alpha-olefins selected from the group including alpha-olefins, and the polymerized ethylene includes at least 90 weight percent of the ethylene copolymer.

[0258] In an embodiment of the present disclosure, the ethylene copolymer includes polymerized ethylene and one or more polymerized alpha-olefins selected from the group including propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and 1-octadecene.

[0259] In an embodiment of the present disclosure, the ethylene copolymer includes polymerized ethylene and one or more polymerized alpha-olefins selected from the group including 1-butene, 1-hexene, and 1-octene.

[0260] In an embodiment of the present disclosure, the ethylene copolymer includes polymerized ethylene and one or more alpha-olefins selected from the group including 1-butene, 1-hexene, and 1-octene, and the polymerized ethylene accounts for at least 85 weight percent of the ethylene copolymer.

[0261] In an embodiment of the present disclosure, the ethylene copolymer includes polymerized ethylene and one or more polymerized alpha-olefins selected from the group including 1-butene, 1-hexene, and 1-octene, and the polymerized ethylene accounts for at least 90 weight percent of the ethylene copolymer.

[0262] Linear polyethylene can be prepared by any conventionally known process such as gas phase polymerization, slurry phase polymerization, or solution phase polymerization by using one or more olefin polymerization catalysts.

[0263] In a gas phase polymerization process, a transition metal polymerization catalyst can be immobilized on a suitable support material, and the resulting particulate catalyst can be used in a fluidized bed polymerization process. Generally, a fluidized bed gas phase polymerization reactor uses a "bed" of polymer and catalyst particles fluidized by a flow of monomers and other optional components that are at least partially gaseous. Heat is generated by the enthalpy of polymerization of the monomers (and optional comonomer(s)) flowing through the bed. Unreacted monomers and other optional gaseous components exit the fluidized bed and contact a cooling system to remove this heat. The cooled gas stream containing the monomers and any other optional components (such as condensable liquids) is then recycled through the polymerization zone together with "make-up" monomers to replace what was polymerized in the previous pass. At the same time, the polymer product is withdrawn from the reactor. As will be understood by those skilled in the art, the "fluidized" nature of the polymerization bed helps to minimize the formation of local temperature gradients by evenly distributing / mixing the heat of the reaction.

[0264] In embodiments, the reactor pressure of the gas phase process can vary from approximately atmospheric pressure to about 600 psig. In another embodiment, the pressure can be in the range of about 100 psig (690 kPa) to about 500 psig (3448 kPa). In yet another embodiment, the pressure can be in the range of about 200 psig (1379 kPa) to about 400 psig (2759 kPa). In yet another embodiment, the pressure can be in the range of about 250 psig (1724 kPa) to about 350 psig (2414 kPa).

[0265] In a slurry phase polymerization process, a transition metal polymerization catalyst can be immobilized 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, isoalkanes), an aromatic, or a cycloalkane. The diluent may be an alpha olefin comonomer used in the copolymerization. Some non-limiting alkane diluents include propane, butane (i.e., normal butane and / or isobutane), pentane, hexane, heptane, and octane. The monomer can be soluble (or miscible) in the diluent, but the polymer is not (under the polymerization conditions). In embodiments, the polymerization temperature is about 5 °C to about 200 °C, or less than about 120 °C, or about 10 °C to about 100 °C. The reaction temperature is selected such that a homopolymer or copolymer of ethylene or an alpha olefin is produced 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 can range from 15 to 45 atmospheres (about 220 to 660 psi or about 1,500 to about 4,600 kPa) when using isobutane as the diluent to about twice that (i.e., 30 to 90 atmospheres - about 440 to 1,300 psi or about 3,000 - 9,100 kPa) when using propane. The pressure in the slurry process must be maintained high enough such that at least a portion of the ethylene and / or alpha olefin polymerizes in the liquid phase. The reaction is typically carried out in a jacketed closed-loop reactor equipped with an internal agitator (e.g., an impeller) and at least one settling leg. The catalyst, monomer, and diluent are fed to the reactor as a liquid or suspension. The slurry circulates through the reactor, and the jacket is used to control the temperature of the reactor. The slurry enters the settling leg through a series of pressure relief valves, and then the pressure is reduced to flash off the diluent and unreacted monomer, and the polymer is typically recovered with a cyclone. The diluent and unreacted monomer are recovered and recycled back to the reactor.

[0266] Solution polymerization processes for the polymerization or copolymerization of olefins such as ethylene and alpha - olefins are well - known in the art. Solution processes are generally carried out in the presence of an inert hydrocarbon solvent in which the resulting polyolefin is soluble under the polymerization conditions used. In one embodiment of the present disclosure, the solvent used in the solution - phase polymerization process is either unsubstituted or C 1-4 optionally substituted by C 5-12 hydrocarbons selected from the group consisting of hydrocarbons such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, and hydrogenated naphtha are included. Another example of a commercially available solvent suitable for use in embodiments of the present disclosure is "ISOPAR® E" (C 8-12 aliphatic solvent, Exxon Chemical Co.). The polymerization temperature in conventional solution processes can be from about 80 °C to about 300 °C. In one embodiment of the present disclosure, the polymerization temperature in the solution process is from about 120 °C to about 250 °C. The polymerization pressure in the solution process is a "medium - pressure process", meaning that the pressure in the reactor is less than about 6,000 psi (about 42,000 kilopascals or kPa). In one embodiment of the present disclosure, the polymerization pressure in the 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., about 2,000 psi to about 3,000 psi).

[0267] In solution polymerization, the monomers are dissolved / dispersed in the solvent before being fed to the reactor (or in the case of gaseous monomers, the monomers can be fed to the reactor so as to dissolve in the reaction mixture). Before mixing, the solvent and monomers are generally purified to remove potential catalyst poisons such as water, oxygen, or metal impurities. The purification of the feedstock is carried out according to standard practices in the art. For example, molecular sieves, alumina beds, and oxygen - removal catalysts are used for the purification of the monomers. The solvent itself (e.g., methylpentane, cyclohexane, hexane, or toluene) can be treated similarly.

[0268] The feedstock may be heated or cooled before being fed to the reactor.

[0269] Generally, olefin polymerization catalyst components (e.g., olefin polymerization catalyst molecules, ionic activators, and optionally alkylaluminoxanes) may be premixed in a solvent for the reaction or supplied as separate streams to a solution phase polymerization reactor. In some cases, premixing may be desirable as it provides a reaction time for the catalyst components prior to entering the reaction. Such "in-line mixing" techniques are described in U.S. Patent No. 5,589,555.

[0270] The solution phase polymerization process can be carried out in one or more stirred tank reactors (e.g., continuous stirred tank reactors), loop reactors, etc., and these reactors can be configured in series or parallel with each other.

[0271] 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).

[0272] In the present disclosure, high density polyethylene (HDPE) is an ethylene homopolymer or an ethylene copolymer with another alpha-olefin (e.g., 1-butene, 1-hexene, and / or 1-octene, etc.) and has a density of about 0.949 g / cm 3 or greater. In embodiments, HDPE is an ethylene homopolymer or an ethylene copolymer with another alpha-olefin (e.g., 1-butene, 1-hexene, and / or 1-octene, etc.) 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 an ethylene homopolymer or an ethylene copolymer with another alpha-olefin (e.g., 1-butene, 1-hexene, and / or 1-octene, etc.) having a density of about 0.950 g / cm 3 to about 0.970 g / cm 3 , or about 0.950 g / cm 3 to about 0.965 g / cm 3It is an ethylene homopolymer or an ethylene copolymer with another alpha-olefin (such as 1-butene, 1-hexene, and / or 1-octene, etc.) having a density of

[0273] In the present disclosure, linear low-density polyethylene (LLDPE) is an ethylene homopolymer or an ethylene copolymer with another alpha-olefin (such as 1-butene, 1-hexene, and / or 1-octene, etc.), and includes, including sub-ranges or any values within the range, about 0.910 g / cm 3 ~ about 0.940 g / cm 3 having a density of. In an embodiment of the present disclosure, the LLDPE has a density of 0.910 to 0.936 g / cm 3 or 0.912 to 0.936 g / cm 3 or 0.910 to 0.932 g / cm 3 or 0.912 to 0.932 g / cm 3 having a density of.

[0274] In the present disclosure, medium-density polyethylene (MDPE) is an ethylene copolymer with another alpha-olefin (such as 1-butene, 1-hexene, and / or 1-octene, etc.), and includes, including sub-ranges or any values within the range, about 0.940 g / cm 3 ~ about 0.949 g / cm 3 having a density of.

[0275] In the present disclosure, very-low-density polyethylene is an ethylene copolymer with another alpha-olefin (such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and / or 1-octene, etc.), having a density of less than about 0.910 g / cm and may include so-called elastomers and plastomers. In an embodiment, VLDPE is an ethylene copolymer with another alpha-olefin (such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and / or 1-octene, etc.), about 0.880 g / cm 3 ~ about 0.910 g / cm 3 or about 0.880 g / cm 3 3 ​~about 0.905 g / cm 3 、 or about 0.880 g / cm 3 ~about 0.902 g / cm 3 and has a density of

[0276] 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 and has a density of

[0277] 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.

[0278] Depending on the polymerization process used and the type of olefin polymerization catalyst, in an embodiment of the present disclosure, the linear polyethylene has a weight average molecular weight M of at least about 10,000 g / mol and up to about 1,500,000 g / mol, including any sub-range within the range or any value within the range. w For example, in a further embodiment, the linear polyethylene has a weight average molecular weight M of about 50,000 to about 1,000,000 g / mol, or about 100,000 to about 1,000,000 g / mol, or about 75,000 to about 750,000 g / mol, or about 100,000 to about 750,000 g / mol, or about 75,000 to about 500,000 g / mol, or about 100,000 to about 500,000 g / mol, or about 50,000 to about 350,000 g / mol, or about 75,000 to about 350,000 g / mol, or about 100,000 to about 350,000 g / mol, or about 50,000 to about 300,000 g / mol, or about 75,000 to about 300,000 g / mol, or about 100,000 to about 300,000 g / mol, or about 50,000 to about 250,000 g / mol, or about 75,000 to about 250,000 g / mol, or about 100,000 to about 250,000 g / mol. w and has a density of

[0279] In embodiments of the present disclosure, the linear polyethylene has a molecular weight distribution M of from about 2.0 to about 12.0, including sub-ranges within the range or any value within the range. w / M n For example, in embodiments of the present disclosure, the linear polyethylene has an M w / M n value of 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.

[0280] In embodiments of the present disclosure, the linear polyethylene is characterized by a melt index I determined at 190 °C under ASTM D1238, Condition E. 2 In embodiments of the present disclosure, the linear polyethylene has a melt index I of from 0.1 to 20.0 g / 10 min, including any sub-range within the range or any value within the range. 2 For example, in embodiments of the present disclosure, the linear polyethylene has a melt index I of from 0.1 to 15.0 g / 10 min, or from 0.1 to 10.0 g / 10 min, or from 0.3 to 15.0 g / 10 min, or from 0.3 to 10.0 g / 10 min, or from 0.1 to 5.0 g / 10 min or from 0.3 to 5.0 g / 10 min, or from 0.5 to 15.0 g / 10 min, or from 0.5 to 10.0 g / 10 min, or from 0.5 to 5.0 g / 10 min. 2

[0281] In embodiments of the present disclosure, the linear polyethylene selected from the group consisting of LLDPE, MDPE, HDPE, VLPDE, and mixtures thereof can be used in the form of powder, pellets, granules, or other extrudable forms.

[0282] In embodiments of the present disclosure, the linear polyethylene is LLDPE.

[0283] In embodiments of the present disclosure, the linear polyethylene is LLDPE having a melt index I of from 0.1 to 10.0 g / 10 min, or from 0.5 to 5.0 g / 10 min. 2

[0284] ​​In one embodiment of the present disclosure, the linear polyethylene has a density of about 0.910 g / cm 3 to about 0.936 g / cm 3 and a melt index I of 0.1 to 10.0 g / 10 min 2 and is LLDPE.

[0285] In one embodiment of the present disclosure, the linear polyethylene has a density of about 0.910 g / cm 3 to about 0.936 g / cm 3 and a melt index I of 0.1 to 5.0 g / 10 min 2 and is LLDPE.

[0286] In embodiments of the present disclosure, the linear polyethylene is LLDPE having a molecular weight distribution M w / M n in the range of about 2.0 to about 12.0, including sub-ranges or any value within the range. For example, in embodiments of the present disclosure, the LLDPE has an M w / M n value in the range of about 2.0 to about 10.0, or about 2.0 to about 8.0, or about 2.0 to about 5.0.

[0287] In some embodiments of the present disclosure, the linear polyethylene includes a small amount of high-pressure low-density polyethylene LDPE having a melt index of less than about 1.0 g / 10 min, defined as less than 3.0 weight percent (wt%, based on the total weight of the linear polymer and LDPE). In some embodiments of the present disclosure, the uniformly branched linear polyethylene includes a small amount of high-pressure low-density polyethylene LDPE having a melt index of less than about 1.0 g / 10 min, defined as less than 3.0 weight percent (wt%, based on the total weight of the linear polymer and LDPE). Without wishing to be bound by theory, the presence of a small amount of LDPE having a melt index of less than about 1.0 g / 10 min can be useful in various end uses.

[0288] The present disclosure relates to the extrusion of thermoplastic compositions in a wide range of extrusion processes, such as profile extrusion prepared by extruding molten plastic through a forming die for extruded parts such as pipes or profile parts, and film extrusion prepared by extruding molten plastic through a slit or annular die for plastic films.

[0289] In one embodiment of the present disclosure, for example, a film extrusion process such as an "inflation film" extrusion process is used. Such an inflation film extrusion process will be described in more detail in the examples section below.

[0290] In the case of film applications, in one embodiment of the present disclosure, it is preferable not to add pigments or fillers to polyolefins (e.g., linear polyethylene) in order to produce transparent or relatively transparent extruded films. In the case of other applications such as wires and cables (electrical or optical), in one embodiment of the present disclosure, polyolefins (e.g., linear polyethylene) may contain pigments / fillers such as carbon black and other auxiliary agents.

[0291] Thermoplastic polyolefins such as linear polyethylene used in the present disclosure may further contain fillers, antioxidants (primary antioxidants, and optionally secondary antioxidants, etc.), pigments, opacifying agents, antistatic agents such as glycerol monostearate, lubricants such as fatty acid esters, light stabilizers (hindered amine light stabilizers, etc.), zinc oxide, antiblocking agents, and other auxiliary agents. When using antiblocking agents (such as silica or talc) and / or hindered amine light stabilizers, care is required as these may adversely affect the surface appearance of the extrusion composition containing the polyolefin, as is known to those skilled in the art.

[0292] In embodiments of the present disclosure, an antioxidant (either a primary antioxidant alone or, optionally, a combination of a primary antioxidant and a secondary antioxidant) is added to a polyolefin (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.

[0293] In one embodiment, the linear polyethylene comprises a primary antioxidant and a secondary antioxidant.

[0294] In one embodiment, the linear polyethylene comprises a hindered phenol primary antioxidant and a phosphorus-containing secondary antioxidant.

[0295] In embodiments, further description of additives that can be added to thermoplastic polyolefins such as linear polyethylene is provided below, and this includes primary antioxidants; secondary antioxidants; UV absorbers and light stabilizers; polyamide stabilizers; basic co-stabilizers; nucleating agents; slip agents; fillers, antiblocking agents, and reinforcing materials, as well as various further additives.

[0296] In embodiments of the present disclosure, the additives added to a thermoplastic polyolefin (such as linear polyethylene) can 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).

[0297] <Primary antioxidant> In embodiments of the present disclosure, the primary antioxidant is an alkylated mono-phenol (also described herein as a "hindered phenolic primary antioxidant"), for example, 2,6-di-tert-butyl-4-methylphenol; 2-tert-butyl-4,6-dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol; 2,6-di-tert-butyl-4-isobutylphenol; 2,6-dicyclopentyl-4-methylphenol; 2-(alpha-methylcyclohexyl)-4,6-dimethylphenol; 2,6-di-octadecyl-4-methylphenol; 2,4,6,-tricyclohexylphenol; and 2,6-di-tert-butyl-4-methoxymethylphenol, etc., and is selected from these. Suitable hindered phenolic antioxidants that can be used in embodiments of the present disclosure are sold under the trademarks IRGANOX® 1010 (CAS registration number 6683-19-8) and IRGANOX 1076 (CAS registration number 2082-79-3) by BASF Corporation.

[0298] In embodiments of the present disclosure, the primary antioxidant is an alkylated hydroquinone, for example, 2,6-di-tert-butyl-4-methoxyphenol; 2,5-di-tert-butylhydroquinone; 2,5-di-tert-amyl-hydroquinone; and 2,6-diphenyl-4-octadecyloxyphenol, etc., and is selected from these.

[0299] In embodiments of the present disclosure, the primary antioxidant is a hydroxylated thiodiphenyl ether, for example, 2,2'-thio-bis-(6-tert-butyl-4-methylphenol); 2,2'-thio-bis-(4-octylphenol); 4,4'-thio-bis-(6-tert-butyl-3-methylphenol); and 4,4'-thio-bis-(6-tert-butyl-2-methylphenol), etc., and is selected from these.

[0300] In an embodiment of the present disclosure, the primary antioxidant is selected from, for example, alkylidene bisphenols such as the following: 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol); 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol); 2,2'-methylene-bis-(4-methyl-6-(alpha-methylcyclohexyl)phenol); 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol); 2,2'-methylene-bis-(6-nonyl-4-methylphenol); 2,2'-methylene-bis-(6-nonyl-4methylphenol); 2,2'-methylene-bis-(6-(alpha-methylbenzyl)-4-nonylphenol); 2,2'-methylene-bis-(6-(alpha,alpha-dimethylbenzyl)-4-nonyl-phenol); 2,2'-methylene-bis-(4,6-di-tert-butylphenol); 2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol); 4,4'-methylene-bis-(2,6-di-tert-butylphenol); 4,4'-methylene-bis-(6-tert-butyl-2-methylphenol); 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)butane 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol; 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecyl-mercaptobutane; ethylene glycol-bis-(3,3,-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate)-di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene; di-(2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl) terephthalate; and other phenols such as monoacrylate esters of bisphenols such as ethylidene bis-2,4-di-t-butylphenol monoacrylate ester.

[0301] In embodiments 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; isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate; bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol-terephthalate; 1,3,5-tris-(3,5-di-tert-butyl-4,10 hydroxybenzyl)isocyanurate; 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate; dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate; calcium salt of monoethyl 3,5-di-tertbutyl-4-hydroxybenzylphosphonate; and 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, etc.

[0302] In embodiments of the present disclosure, the primary antioxidant is selected from acylaminophenols such as 4-hydroxy-lauric acid anilide; 4-hydroxy-stearic acid anilide; 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine; and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate, etc.

[0303] In embodiments of the present disclosure, the primary antioxidant is selected from esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols such as methanol; diethylene glycol; octadecanol; triethylene glycol; 1,6-hexanediol; pentaerythritol; neopentyl glycol; tris-hydroxyethyl isocyanurate; thidiethylene glycol; and dihydroxyethyl oxalic acid diamide, etc.

[0304] In embodiments of the present disclosure, the primary antioxidant is an amide of beta-(3,5-di-tert-butyl-4-hydroxyphenol)-propionic acid, such as N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine; N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine; and N,N'-di(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, etc., and is selected from these.

[0305] In embodiments of the present disclosure, the primary antioxidant can 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).

[0306] <Secondary antioxidant> In embodiments of the present disclosure, the secondary antioxidant is a phosphite and a phosphonite (also described herein as a "phosphorus-containing secondary antioxidant"), for example, triphenyl phosphite; diphenyl alkyl phosphite; phenyl dialkyl phosphite; tris(nonyl-phenyl) phosphite [available from WESTON® 399, SI Group]; phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester [WESTON 705, CAS Reg. No. 939402-02-5, available from SI Group]; trilauryl phosphite; trioctadecyl phosphite; distearyl pentaerythritol diphosphite; tris(2,4-di-tert-butylphenyl) phosphite [available from IRGAFOS 168, 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 [available from IRGAFOS 38, BASF]; 2,2’,2”-nitrilo[triethyl tris(3,3’5,5’-tetra-tert-butyl-1,1’-biphenyl-2,2’-diyl) phosphite [available from IRGAFOS® 12, 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-butyl dibenzo[d,f][1,3,2] dioxaphospepin [SUMILIZER® GP]; bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphate; bis(2,4-dicumylphenyl) pentaerythritol diphosphate; distearyl pentaerythritol diphosphate; diisodecyl pentaerythritol diphosphate;Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite [ULTRANOX® 626, available from SI Group]; bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite; bisisodecyloxy-pentaerythritol diphosphite; bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite; bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite; tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene-diphosphonite [IRGAFOS P-EPQ, available from BASF]; bis(2,4-dicumylphenyl)pentaerythritol diphosphite [DOVERPHOS® S9228-T or DOVERPHOS S9228-CT] and P-EPQ® (CAS Reg. No. 119345-01-06) commercially available diphosphonates; or mixtures thereof, etc., are selected. In embodiments of the present disclosure, the secondary antioxidant is selected from DOVERPHOS LGP-11, DOVERPHOS LGP-12 and DOVERPHOS LGP-12LV.;

[0307] In embodiments of the present disclosure, the secondary antioxidant is selected from polymer polyphosphites that do not contain alkylphenols, examples of which are disclosed in U.S. Patent No. 8,563,637.

[0308] In embodiments of the present disclosure, the secondary antioxidant is selected from peroxide scavengers such as esters of beta-thiodipropionic acid. The beta-thiodipropionic acid ester can be selected from the group consisting of lauryl, stearyl, myristyl or tridecyl esters. In certain embodiments, other peroxide scavengers used as secondary antioxidants are mercaptobenzimidazole; or zinc salt of 2-mercaptobenzimidazole; zinc-dibutyldithiocarbamate; dioctadecyl disulfide; and pentaerythritol tetrakis-(beta-dodecylmercapto)-propionate.

[0309] 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-ditetradecylhydroxylamine; N,N-dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine; N-hexadecyl-N-octadecylhydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; and N,N-dialkylhydroxylamine derived from hydrogenated tallow amine. Similar amine oxides are also suitable. A commercially available example of a hydroxylamine that can be used in embodiments of the present disclosure is N,N-di(alkyl)hydroxylamine sold as IRGASTAB® 042 (BASF), which has been reported to be prepared by direct oxidation of N,N-di(hydrogenated)tallow amine.

[0310] In embodiments of the present disclosure, the secondary antioxidant is selected from nitrones such as, for example, N-benzyl-alpha-phenylnitrone; N-ethyl-alpha-methylnitrone; N-octyl-alpha-heptylnitrone; N-lauryl-alpha-undecylnitrone; N-tetradecyl-alpha-tridecylnitrone; N-hexadecyl-alpha-pentadecylnitrone; N-octadecyl-alpha-heptadecylnitrone; N-hexadecyl-alpha-heptadecylnitrone; N-octadecyl-alpha-pentadecylnitrone; N-heptadecyl-alpha-heptadecylnitrone; N-octadecyl-alpha-hexadecylnitrone; and nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

[0311] In embodiments of the present disclosure, the secondary antioxidant can also 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).

[0312] <UV Absorbers and Light Stabilizers> In embodiments of the present disclosure, the UV absorber or light stabilizer is selected from, for example, 2-(2'-hydroxyphenyl)-benzotriazoles 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'-octoxy, 3',5'-di-tert-amyl-; and 3',5'-bis-(alpha,alpha-dimethylbenzyl)-derivatives.

[0313] In embodiments of the present disclosure, the ultraviolet absorber or the light stabilizer is selected from, for example, 2-hydroxy-benzophenones such as the following: 4-hydroxy-; 4-methoxy-; 4-octyloxy-; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4,2’,4’-trihydroxy-; and 2’-hydroxy-4,4’-dimethoxy derivatives.

[0314] In embodiments of the present disclosure, the ultraviolet absorber or light stabilizer is selected from, for example, the following hindered amines: bis(2,2,6,6-tetramethylpiperidyl)-sebacate; bis-5(1,2,2,6,6-pentamethylpiperidyl)-sebacate; n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid bis(1,2,2,6,6,-pentamethylpiperidyl) ester; the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid; the condensation product of N,N’-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine; tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetra-carbonate; and 1,1’(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone). These amines are typically called HALS (Hindered Amines Light Stabilizing) and include 2,2,6,6-tetramethylpiperidinol ester of butanetetracarboxylic acid. Such amines include hydroxylamines derived from hindered amines. For example, di(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 1-hydroxy 2,2,6,6-tetramethyl-4-benzyloxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-piperidine; and N-(1-hydroxy-2,2,6,6-tetramethyl-piperidin-4-yl)-ε-caprolactam.Commercially available HALS suitable for use in embodiments of the present disclosure include those sold under the trademarks CHIMASSORB® 119; CHIMASSORB 944; CHIMASSORB 2020; TINUVIN® 622 and TINUVIN 770 from BASF, and HALS sold under the trademarks CYASORB® UV3346, CYASORB UV3529, CYASORB UV4801, and CYASORB UV4802 from Solvay. In other embodiments of the present disclosure, the use of mixtures of two or more HALS is also contemplated.

[0315] In embodiments of the present disclosure, the UV absorber or light stabilizer is selected from esters of substituted and unsubstituted benzoic acids such as phenyl salicylate; 4-tert-butylphenyl salicylate; octylphenyl salicylate; dibenzoylresorcinol; bis-(4-tert-butylbenzoyl)-resorcinol; benzoylresorcinol; 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoate; and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.

[0316] In embodiments 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-carbomethoxycinnamate; methyl or butyl α-cyano-β-methyl-p-methoxycinnamate; methyl α-carbomethoxy-p-methoxycinnamate; and N-(β-carbomethoxy-β-cyano-vinyl)-2-methylindoline.

[0317] In embodiments of the present disclosure, the UV absorber or light stabilizer is selected from nickel compounds such as nickel complexes of 2,2'-thio-bis(4-(1,1,1,3-tetramethylbutyl)-phenol) (e.g., 1:1 or 1:2 complexes, optionally containing additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine); nickel dibutyldithiocarbamate; nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, such as methyl, ethyl, or butyl esters; nickel complexes of ketoximes such as 2-hydroxy-4-methyl-phenylundecyl ketoxime; and nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole (optionally containing additional ligands), etc.

[0318] In embodiments of the present disclosure, the UV absorber or light stabilizer is selected from oxalic acid diamides such as 4,4'-di-octyloxy-oxanilide; 2,2'-di-octyloxy-5',5'-di-tert-butyloxanilide; 2,2'-di-dodecyloxy-5',5'-di-tert-butyl-oxanilide; 2-ethoxy-2'-ethyl-oxanilide; N,N'-bis(3-dimethylaminopropyl)-oxalamide; 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4-di-tert-butyloxanilide; and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides, etc.

[0319] In embodiments 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; 5,2,4-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-bromo-phenyl)-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 and the like.

[0320] <Polyamide stabilizer> In embodiments of the present disclosure, the polyamide stabilizer is selected from, for example, combinations of copper salts with iodides and / or phosphorus compounds, and salts of divalent manganese.

[0321] <Basic co-stabilizer> In embodiments of the present disclosure, it includes a basic co-stabilizer, for example, melamine; polyvinylpyrrolidone; dicyandiamide; triallyl cyanurate; urea derivatives; hydrazine derivatives; amines; polyamides; polyurethanes; alkali metal salts and alkaline earth metal salts of higher fatty acids, such as Ca stearate, calcium stearoyl lactate, calcium lactate, Zn stearate, Mg stearate, Na ricinoleate, and K palmitate; antimony pyrocatecholate or zinc pyrocatecholate, a neutralizing agent, for example, zinc oxide, hydrotalcite, and synthetic hydrotalcite; and Li, Na, Mg, Ca, Al hydroxycarbonates.

[0322] In an embodiment, the hydrotalcite has the formula: [M 2+ 1-x M 3+ x (OH) 2 x+ [(A n- ) x / n ·mH 2 O] x- [wherein, M 2+ is divalent Mg, Ni, Zn, Cu, or Mn, M 3+ is trivalent Al, Fe, or Cr, A n- is an anion such as CO 3 2- , or SO 4 2- , NO 3 2- , Cl 1- , or OH 1- etc., and x is 0.1 to 0.5]. In one embodiment, the hydrotalcite has the formula: Mg 6 Al 2 (OH) 16 CO 3 ·nH 2 O. In one embodiment, the hydrotalcite is mineral hydrotalcite (Mg 6 Al 2 (OH) 16 CO 3 ·4H 2 ​(O). Examples of hydrotalcite that can be used in the embodiments of the present disclosure include substances commercially available under the general trade names DHT-4 (A, C, or V) (trademark), ZHT-4V (trademark), HYCITE (registered trademark) 713, and AC-207 (trademark).

[0323] <Nucleating agent> As used herein, the term "nucleating agent" is intended to convey to those skilled in the art of preparing nucleated polyolefin compositions its conventional meaning, namely, an additive that changes the crystallization behavior of a polymer when the polymer melt is cooled.

[0324] A review of nucleating agents is described in U.S. Pat. Nos. 5,981,636, 6,465,551, and 6,599,971, the disclosures of which are incorporated herein by reference.

[0325] Commercially available nucleating agents that can be added to thermoplastic polyolefins (e.g., linear polyethylene) are dibenzylidene sorbitol esters. Further examples of nucleating agents that can be added to thermoplastic polyolefins (e.g., linear polyethylene) include the cyclic organic structures (and their salts, e.g., disodium bicyclo[2.2.1]heptene dicarboxylate) disclosed in U.S. Patent No. 5,981,636; the saturated version of the structure disclosed in U.S. Patent No. 5,981,636 (disclosed in U.S. Patent No. 6,465,551; from Zhao et al. to Milliken); the salts of certain cyclic dicarboxylic acids having a hexahydrophthalic acid structure (or "HHPA" structure) disclosed in U.S. Patent No. 6,599,971 (Dotson et al. to Milliken); and phosphate esters such as those disclosed in U.S. Patent No. 5,342,868 and sold under the trade names NA-11 and NA-21 by Asahi Kasei Chemicals, cyclic dicarboxylic acid salts such as the divalent metal salts or metalloid salts (especially calcium salts) of the HHPA structure disclosed in U.S. Patent No. 6,599,971, and their salts. For clarity, the HHPA structure includes a ring structure having 6 carbon atoms in the ring and 2 carboxylic acid groups that are substituents on adjacent atoms of the ring structure. As disclosed in U.S. Patent No. 6,599,971, the other 4 carbon atoms in the ring may be substituted. One example is calcium 1,2-cyclohexanedicarboxylate (CAS registration number 491589-22-1). Further examples of nucleating agents that can be added to thermoplastic polyolefins (e.g., linear polyethylene) include those disclosed in International Publication Nos. 2015 / 042561, 2015 / 042563, 2015 / 042562, and 2011 / 050042.

[0326] In one embodiment of the present disclosure, the amount of the nucleating agent used is relatively small, being 100 to 3,000 weight ppm (based on the weight of the thermoplastic polyolefin), and thus it will be understood by those skilled in the art that care must 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 a finely divided form (less than 50 microns, especially less than 10 microns) to facilitate mixing. This type of "physical blend" (i.e., a mixture of the solid-state nucleating agent and the resin) is, in some embodiments, preferred over using a "masterbatch" of the nucleating agent (where the term "masterbatch" refers to an embodiment in which the additive (in this case, the nucleating agent) is first melt-mixed with a small amount of the thermoplastic polyolefin and then the "masterbatch" is melt-mixed with the remaining bulk of the thermoplastic polyolefin).

[0327] In one embodiment of the present disclosure, additives such as nucleating agents may be added to the thermoplastic polyolefin by the "masterbatch" method, where the term "masterbatch" refers to an embodiment in which the additive (e.g., the nucleating agent) is first melt-mixed with a small amount of the thermoplastic polyolefin and subsequently the "masterbatch" is melt-mixed with the remaining bulk of the thermoplastic polyolefin.

[0328] In embodiments, the nucleating agent, or a 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.

[0329] <Slip agent> In embodiments of the present disclosure, the slip agent is selected from oleic acid amide, erucic acid amide, stearic acid amide, and behenic acid amide.

[0330] <Filler, antiblocking agent, and reinforcing agent> In embodiments of the present disclosure, the filler, antiblocking agent, or reinforcing agent is selected from calcium carbonate, diatomaceous earth, natural silica and synthetic silica, silicate, glass fiber, asbestos, talc, kaolin, mica, barium sulfate, metal oxide and metal hydroxide, carbon black, and graphite.

[0331] When present, in some embodiments of the present disclosure, the filler can be incorporated 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, into the thermoplastic polyolefin (e.g., linear polyethylene).

[0332] <Other additives> In embodiments of the present disclosure, the other additives are selected from plasticizers, epoxidized vegetable oils such as epoxidized soybean oil, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, anti-fogging agents, foaming agents, and thio synergists such as dilauryl thiodipropionate or distearyl thiodipropionate.

[0333] <Melt extrusion> The extrudable thermoplastic composition according to the present disclosure can be prepared by any one or various processes. In one embodiment, during the melt extrusion process, the polymer processing aid component can be mixed with the thermoplastic polyolefin. In an alternative embodiment, one or more polymer processing aid components can be compounded with the polyolefin in a so-called "masterbatch". Such masterbatches can be used to provide useful dilutions of one or more polymer processing aid components. The masterbatch can be added to the bulk thermoplastic polyolefin for extrusion in the melt extrusion process into the extrudate.

[0334] The extruded thermoplastic polyolefin and the polymer processing aid component can be combined using any blending means well known to those skilled in the art, such as a compounding mill, a Banbury mixer, or a co - rotating extruder that uniformly distributes the polymer processing aid component within the thermoplastic polyolefin. Such mixing may be carried out at a temperature above the melting point or softening point of the polyolefin, or alternatively, such mixing may simply be a dry - blend mixing of the solid thermoplastic polyolefin with the polymer processing aid component.

[0335] In one embodiment, the extrudable thermoplastic composition of the present disclosure is prepared by melt - blending a thermoplastic polyolefin (such as linear polyethylene) with a polymer processing aid prior to final extrusion in a melt - extrusion process (such as an inflation - film extrusion process).

[0336] There are several methods that can be used to make the extrudable thermoplastic composition of the present disclosure. In one embodiment, all components are dry - blended in the desired weight ratio using a suitable device such as a tumble blender. The resulting dry - blend is then melted using a suitable device such as an extruder. In an alternative embodiment, a masterbatch can be prepared using a portion of the thermoplastic polyolefin and other components including the polymer processing aid or other additives. In such an embodiment, the thermoplastic polyolefin masterbatch is then fed to an extruder and melt - blended with other components including, for example, bulk polyolefin, the polymer processing aid, or other additives as needed. In yet another embodiment, each component used to make the extrudable thermoplastic composition may be directly metered and fed into the extruder used in the melt - extrusion process.

[0337] The melt extrusion process is well known to those skilled in the art, and non-limiting examples thereof 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 may be a twin-screw or single-screw extruder. When using a twin-screw extruder, it can operate in a co-rotating mode (i.e., both screws rotate in the same direction) or a counter-rotating mode (i.e., the screws rotate in opposite directions).

[0338] The specific conditions for operating the extruder in the melt extrusion process are different from those for operating other extruders. Variations between extruders can usually be eliminated by routine optimization methods well known to those skilled in the art. In one embodiment of the present disclosure, a laboratory-scale twin-screw extruder operates within the following range of conditions: the barrel is heated to a temperature of about 180 - 210 °C, or about 190 - 200 °C; the screw speed operates at about 50 - about 150 rpm, or about 100 - about 130 rpm. The specific operating conditions for a particular extruder can be readily determined by those skilled in the art by routine testing, taking into account the aforementioned conditions. The extruder typically extrudes the thermoplastic composition as strands, which are then cooled and cut into pellets for subsequent use such as film extrusion. The extruder used for the final extrusion may also be a single-screw or twin-screw extruder. In blown film extrusion, the die may be a slot die or an annular ring die that extrudes a polyolefin film around a stable air bubble. In blown film extrusion, the film is collapsed after passing over or around the bubble.

[0339] The specific details of the extruder and its operation are known to those skilled in the art. A typical extruder includes one (or two) screw(s) with blades that rotate within a cylinder or "barrel". The thermoplastic polyolefin is sheared between the barrel and the screw by the stress generated by the rotation of the screw. Additionally, the barrel of the extruder may be heated. Due to the shear and / or heat, the thermoplastic polyolefin melts and is conveyed along the length of the extruder by the action of the screw with blades. The molten thermoplastic polyolefin extrudate is then extruded through a die to form the desired plastic part.

[0340] In an embodiment of the present disclosure, the melt extrusion process is an inflation film melt extrusion process.

[0341] In the inflation film melt extrusion process, an extruder heats, melts, mixes, and conveys a thermoplastic polyolefin composition. The molten thermoplastic composition is pushed into an annular die, and a thermoplastic tube is produced. In the case of coextrusion, multiple extruders are used to produce a multi-layer thermoplastic tube. The temperature of the extrusion process is mainly determined by the thermoplastic polyolefin composition being processed, for example, the melting point or glass transition temperature of the thermoplastic polyolefin composition, and the desired viscosity of the melt. In the case of thermoplastic polyolefins, typical extrusion temperatures are 330°F to 550°F (166°C to 288°C). When the thermoplastic tube exits the annular die, it is inflated with air, cooled, solidified, and pulled through a pair of nip rollers. The inflation with air increases the diameter of the tube and forms bubbles of the desired size. The pulling action of the nip rollers stretches the bubbles in the machine direction. Thus, the bubbles are stretched in two directions: in the transverse direction (TD), the diameter of the bubbles is enlarged by the inflating air, and in the machine direction (MD), the nip rollers stretch the bubbles. In the inflation film process, when the thermoplastic polyolefin exits the annular die, air is also blown onto the outer circumference of the bubble for cooling. The final width of the film is determined by controlling the inflating air or the internal bubble pressure, in other words, by increasing or decreasing the diameter of the bubble. The thickness of the film is mainly controlled by increasing or decreasing the speed of the nip rollers to control the drawdown ratio. After exiting the nip rollers, the bubble or tube is collapsed, slit in the machine direction, and a sheet is produced. Each sheet is wound onto a film roll. Each roll is further slit to produce a film of the desired width. Each film roll is further processed into various consumer products.

[0342] The cast film process is similar in that single or multiple extruders can be used, but various thermoplastic materials are metered into a flat die and extruded into a single-layer or multi-layer sheet instead of a tube. In the cast film process, the extruded sheet is solidified on a chill roll.

[0343] In embodiments of the present disclosure, a polymer processing aid is used when melt extruding a thermoplastic polyolefin into a thermoplastic polyolefin extrudate.

[0344] In embodiments of the present disclosure, by using a polymer processing aid when melt extruding a thermoplastic polyolefin into a thermoplastic polyolefin extrudate, melt defects during extrusion of the thermoplastic polyolefin are reduced.

[0345] In one embodiment of the present disclosure, by using a polymer processing aid when melt extruding a thermoplastic polyolefin into a thermoplastic polyolefin extrudate, the shear rate at which melt defects occur in the thermoplastic polyolefin extrudate in the absence of the polymer processing aid is compared, and the shear rate at which the melt extrusion process can be operated without melt defects occurring in the thermoplastic polyolefin extrudate increases.

[0346] In embodiments of the present disclosure, by using a polymer processing aid when melt extruding a thermoplastic polyolefin into a thermoplastic polyolefin extrudate, the shear rate at which melt defects occur in the thermoplastic polyolefin extrudate in the absence of the polymer processing aid is compared, and the shear rate at which the melt extrusion process can be operated without melt defects occurring in the thermoplastic polyolefin extrudate is increased by at least 10 percent, or at least 25 percent, or at least 50 percent, or at least 75 percent, or at least 100 percent, or at least 200 percent, or at least 300 percent, or at least 400 percent, or at least 500 percent.

[0347] One embodiment of the present disclosure is a method for reducing melt defects during extrusion of linear polyethylene, the method comprising combining linear polyethylene with at least one poly(ether-block-amide) and at least one polycaprolactone polymer to obtain an extrudable thermoplastic composition, and extruding the thermoplastic composition.

[0348] One embodiment of the present disclosure is a method for reducing melt defects during extrusion of a thermoplastic composition, the method comprising combining linear polyethylene with at least one poly(ether-block-amide) copolymer, at least one polycaprolactone polymer, and at least one polyalkylene glycol to obtain a thermoplastic composition, and melt-extruding the thermoplastic composition.

[0349] One embodiment of the present disclosure is a method for reducing melt defects during extrusion of a thermoplastic composition, the method comprising combining linear polyethylene with at least one poly(ether-block-amide) copolymer, at least one polycaprolactone polymer, at least one polyalkylene glycol, and high-pressure low-density polyethylene (LDPE) to obtain a thermoplastic composition, and melt-extruding the thermoplastic composition.

[0350] The following examples are presented for the purpose of illustrating selected embodiments of the present disclosure, and it is understood that the presented examples do not limit the presented claims.

Examples

[0351] <Polymer Property Evaluation and Test Methods> Prior to testing, each polymer specimen was conditioned at 23 ± 2 °C and 50 ± 10% relative humidity for at least 24 hours, and subsequent tests were conducted at 23 ± 2 °C and 50 ± 10% relative humidity. As used herein, the term "ASTM conditions" refers to a laboratory maintained at 23 ± 2 °C and 50 ± 10% relative humidity, and the test specimens were conditioned in this laboratory for at least 24 hours prior to testing. ASTM refers to the American Society for Testing and Materials.

[0352] <Density> The density of the polymer (e.g., linear polyethylene or LDPE) was determined using ASTM D792-13 (November 1, 2013).

[0353] <Melt Index> The melt index of polyethylene was determined using ASTM D1238 (August 1, 2013). The melt index, I 2 , I 6 , I 10 , and I 21 were measured at 190 °C using weights of 2.16 kg, 6.48 kg, 10 kg, and 21.6 kg, respectively.

[0354] <Gel Permeation Chromatography (GPC)> A polyethylene sample (polymer) solution (1 - 3 mg / mL) was prepared by heating the polymer in 1,2,4 - trichlorobenzene (TCB) and rotating it on a wheel at 150 °C for 4 hours in an oven. To stabilize the polymer against oxidative degradation, an antioxidant (2,6 - di - tert - butyl - 4 - methylphenol (BHT)) was added to the mixture. The BHT concentration was 250 ppm. The polymer solution was chromatographed using a PL220 high - temperature chromatography unit equipped with four SHODEX® columns (HT803, HT804, HT805, and HT806), with TCB as the mobile phase, a flow rate of 1.0 mL / min, at 140 °C, and a differential refractive index (DRI) as the concentration detector. To protect the GPC columns from oxidative degradation, BHT was added to the mobile phase at a concentration of 250 ppm. The sample injection volume was 200 μL. The GPC columns were calibrated with narrow - distribution polystyrene standards. Using the Mark - Houwink equation, as described in ASTM standard test method D6474 - 12 (December 2012), the polystyrene molecular weight was converted to polyethylene molecular weight. The raw GPC data was processed with CIRRUS® GPC software to generate the molar mass average (M n , M w , M z ) and the molar mass distribution (e.g., polydispersity M w / M n ). In the technical field of polyethylene, the commonly used term corresponding to GPC is SEC, i.e., size - exclusion chromatography.

[0355] <Melt Extrusion> The performance of polymer processing aids ("PPA") in reducing melt defects in polyolefin extrudates has been observed to be affected by the shear rate at the extruder die. The generally accepted equation for estimating the shear rate at the die is Equation 1: (1) γ = 2Q(S + 2) / ρπd 2 D [where γ = shear rate (reciprocal of seconds, s -1 ); ρ = density of the polymer melt; S = 1 / power exponent; d = die gap width; D = die diameter; Q = mass flow rate of the polymer] as shown.

[0356] The generally accepted estimate of the density of molten polyethylene is 0.76 grams per cubic centimeter (g / cm 3 ), and this value was used in all calculations. The generally accepted value of the power exponent is 0.5, and this value was used in all calculations.

[0357] <Melt Fracture Removal> An extrudable thermoplastic polyolefin composition for inflation film extrusion was prepared by melt compounding linear polyethylene with a polymer processing aid and other additives in a Leistritz twin-screw pelletizer under mild conditions with a nitrogen purge. See Table 1 for the conditions.

[0358]

Table 1

[0359] The polyamide / polyether block copolymer used in the mixture with linear polyethylene was PEBAX MV 1074, commercially available from Arkema.

[0360] The polycaprolactone polymer used in the mixture with linear polyethylene was CAPA 2403D, commercially available from Ingevity. CAPA 2403D is a polycaprolactone polyol diol initiated with 1,4-butanediol and has a molecular weight (Mn) of 4000 g / mol.

[0361] The linear polyethylene used in the experiment had a density of 0.920 g / cm 3 and a melt index I of about 1.0 g / 10 min. 2 It was linear low density polyethylene LLDPE. This is sold under the trade name FP120 by NOVA Chemicals and is available in various formulations as FP120-A and FP120-C. FP120, FP120-A, and FP120-C are copolymers of ethylene and 1-octene and are produced by a solution phase polymerization process using a Ziegler-Natta catalyst. Linear polyethylene FP120 contained a conventional primary antioxidant (hindered phenol = 500 ppm IRGANOX 1076); a conventional secondary antioxidant (phosphite = 500 ppm IRGAFOS 168); and hydrotalcite (800 ppm). Here, ppm is based on the weight of the linear polyethylene. Linear polyethylene FP120-C contained a conventional primary antioxidant (hindered phenol = 500 ppm IRGANOX 1076); a conventional secondary antioxidant (phosphite = 500 ppm IRGAFOS 168); hydrotalcite (800 ppm); and 650 ppm of VITON® Z110 (a PPA containing an elastomeric fluoropolymer and polyethylene glycol, where ppm is based on the weight of the linear polyethylene).

[0362] Using a single - layer inflation film line with a 3 - inch diameter die (manufactured by Macro Engineering & Technology Inc., based in Ontario, California), the effectiveness of adding a polyimide / polyether block copolymer and a polycaprolactone polymer as polymer processing aids (PPAs) in removing melt defects from extrudates was determined.

[0363] The 3 - inch Macro inflation film line had a standard output greater than 60 pounds per hour and was equipped with a 15 - horsepower motor. The feed screw had a 1.5 - inch diameter and a length - to - diameter (L / D) ratio of 24 / 1. The feed screw was of barrier design, with mixing elements attached at the end of the screw. The film bubble was cooled air using cold air, and the line operated at a blow - up ratio (BUR) of 2 / 1 to 4 / 1. The inflation film line was fitted with a 3 - inch diameter annular die. Two die pins were used to set a die gap of 35 or 85 mils for the experiment.

[0364] In Example 1A, linear polyethylene FP120 was pre - compounded (e.g., melt - compounded in an extruder / pelletizer) with 1,500 ppm (by weight based on the weight of linear polyethylene) of a polyamide / polyether block copolymer (PEBAX MV 1074), and then melt - extruded on the inflation film line.

[0365] In Example 1B, a commercially available FP120 - C containing an elastomeric fluoropolymer and a polyethylene glycol material (Viton Z110) as a PPA was melt - extruded on the inflation film line.

[0366] In Example 1C, linear polyethylene FP120 was premixed with 750 ppm (by weight based on the weight of the linear polyethylene) of a polyamide / polyether block copolymer (PEBAX MV 1074) and 750 ppm (by weight based on the weight of the linear polyethylene) of a polycaprolactone polymer (CAPA 2403D) (e.g., melt compounded using an extruder / pelletizer), and then melt extruded on an inflation film line.

[0367] During the melt fracture removal experiment on the inflation film line, the extruder was operated at a mass flow rate “target point” of about 65 pounds per hour (equivalent to a shear rate of about 460 s -1 ). The term “melt fracture” is well known to those skilled in the art and generally refers to a film that has obvious signs of surface imperfections that appear as die lines, haze bands, or small bands of soft melt fracture (orange peel) or hard melt fracture (sharkskin). The expression “removal of melt fracture” means that the film has a transparent and defect-free surface.

[0368] The components used in the extrudable thermoplastic composition and the details of the melt extrusion process are shown in Table 2.

[0369]

Table 2

[0370] Before adding the target thermoplastic composition, the inflation film line was purged using LLDPE or LDPE containing 30 - 40% diatomaceous earth without a polymer processing aid to clean the die by abrasion. Following the purge, a polymer having a density of about 0.92 g / cm 3, an LLDPE without PPA having a melt index of 0.8 g / 10 min was introduced to produce an extrudate having 100% hard melt fracture across the entire width of the film (for example, a film having a rough surface defect with an appearance similar to sharkskin was produced). Next, the target thermoplastic composition was introduced and recorded as time zero. The target thermoplastic composition was extruded under certain conditions, and samples of the extruded film were collected every 10 minutes, and the melt fracture defects were measured as a percentage of the width of the sample. The melt extrusion process was continued for 60 minutes in each experiment, and the melt fracture percentage was recorded at 10-minute intervals. When the melt fracture percentage reached zero, the extrudate was considered to have the melt fracture removed. As a general non-limiting guideline, if the melt fracture is removed within about 60 minutes from the start of the operation of the extruder, the polymer processing aid (PPA) can be considered to exhibit good performance. The results of the melt fracture removal experiment are shown in Figure 1.

[0371] One skilled in the art will notice from the data shown in Figure 1 that a thermoplastic composition containing linear polyethylene and only a polyamide / polyether block copolymer as PPA (for example, PEBAX MV 1074 in Example 1A) was able to completely remove the melt fracture within about 30 minutes. When an elastomeric fluoropolymer and polyethylene glycol (for example, VITON Z110) were used as the polymer processing aid (Example 1B), the start of the removal of the melt fracture was earlier, starting at about 10 minutes, but it took about 40 minutes to completely remove the melt fracture. As further shown in Figure 1, when both a polyamide / polyether block copolymer and a polycaprolactone polymer were used (Example 1C), the removal performance of the melt fracture was further improved, the removal of the melt fracture started at about 10 minutes, and was completed by about 30 minutes.

[0372] This data shows that the combination of a poly(ether-block-amide) copolymer (PEBA copolymer) and a polycaprolactone polymer can be used as an effective polymer processing aid even in the absence of a fluoropolymer.

[0373] Non-limiting embodiments of the present disclosure include the following:

[0374] Embodiment A. A process for preparing a thermoplastic composition extrudate, comprising extruding the thermoplastic composition in a melt extrusion process, wherein the thermoplastic composition comprises i) linear polyethylene; ii) 200 to 4,000 ppm of a poly(ether-block-amide) copolymer (based on the weight of the linear polyethylene); and iii) 200 to 4,000 ppm of a polycaprolactone polymer (based on the weight of the linear polyethylene), the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof, the poly(ether-block-amide) copolymer comprises a polyamide block and a polyether block, the thermoplastic composition is substantially free of fluoropolymer, the melt extrusion process is carried out in the absence of fluoropolymer, the above process.

[0375] Embodiment B. The process according to Embodiment A, wherein the thermoplastic composition further comprises iii) 200 to 4,000 ppm of polyethylene glycol (based on the weight of the linear polyethylene).

[0376] Embodiment C. The process according to Embodiment A or B, wherein the linear polyethylene comprises zinc oxide.

[0377] Embodiment D. The process according to Embodiment A, B, or C, wherein the linear polyethylene comprises hydrotalcite.

[0378] Embodiment E. The process according to Embodiment A, B, C, or D, wherein the linear polyethylene is LLDPE.

[0379] Embodiment F. The melt index I of LLDPE is 0.1 to 5.0 grams per 10 minutes2 The process according to embodiment E, having

[0380] Embodiment G. The LLDPE has a density of 0.910 - 0.936 g / cm 3 The process according to embodiment E or F, having

[0381] Embodiment H. The LLDPE is an ethylene copolymer containing ethylene and one or more alpha-olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene. The process according to embodiment E, F, or G.

[0382] Embodiment I. The poly(ether-block-amide) copolymer contains a polyamide block that is a polyamide-12 (PA-12) block and a polyether block that is a polyethylene glycol (PEG) block. The process according to embodiment A, B, C, D, E, F, G, or H.

[0383] Embodiment J. The polyamide-12 (PA-12) block accounts for about 40 - 50 weight percent of the poly(ether-block-amide) copolymer, and the polyethylene glycol (PEG) block accounts for about 60 - 50 weight percent of the poly(ether-block-amide) copolymer. The process according to embodiment I.

[0384] Embodiment K. The poly(ether-block-amide) copolymer contains 10 - 20 polyamide blocks and 10 - 20 polyether blocks. The process according to embodiment A, B, C, D, E, F, G, or H.

[0385] Embodiment L. The poly(ether-block-amide) copolymer contains 10 - 20 polyamide blocks that are polyamide-12 (PA-12) blocks and 10 - 20 polyether blocks that are polyethylene glycol (PEG) blocks. The process according to embodiment A, B, C, D, E, F, G, or H.

[0386] Embodiment M. The process according to embodiment A, B, C, D, E, F, G, H, or I, wherein the number average molecular weight Mn of the poly(ether-block-amide) copolymer is from about 50,000 to about 75,000 g / mol.

[0387] Embodiment N. The process according to embodiment A, B, C, D, E, F, G, H, I, J, K, L, or M, wherein the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of from about 500 g / mol to about 6,000 g / mol and is derived from epsilon-caprolactone using 1,4-butanediol as an initiator.

[0388] Embodiment O. The process according to embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, or N, wherein the thermoplastic composition comprises 200 to 2,000 ppm of a poly(ether-block-amide) copolymer (based on the weight of the linear polyethylene).

[0389] Embodiment P. The process according to embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, or O, wherein the thermoplastic composition comprises 200 to 2,000 ppm of a polycaprolactone polymer (based on the weight of the linear polyethylene).

[0390] Embodiment Q. The process according to embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, wherein the melt extrusion process is carried out at a shear rate that produces a thermoplastic composition extrudate having melt defects when carried out using a thermoplastic composition consisting essentially of linear polyethylene.

[0391] Embodiment R. An extrudable thermoplastic composition comprising: i) linear polyethylene; ii) 200 to 4,000 ppm of a poly(ether-block-amide) copolymer (based on the weight of the linear polyethylene); and iii) 200 to 4,000 ppm of a polycaprolactone polymer (based on the weight of the linear polyethylene). The linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof, The poly(ether-block-amide) copolymer contains a polyamide block and a polyether block, The extrudable thermoplastic composition substantially does not contain a fluoropolymer, The above-mentioned extrudable thermoplastic composition.

[0392] Embodiment S. iii) The extrudable thermoplastic composition according to Embodiment R, further comprising 200 to 4,000 ppm of polyethylene glycol (based on the weight of the linear polyethylene).

[0393] Embodiment T. The extrudable thermoplastic composition according to Embodiment R or S, wherein the linear polyethylene contains zinc oxide.

[0394] Embodiment U. The extrudable thermoplastic composition according to Embodiment R, S, or T, wherein the linear polyethylene contains hydrotalcite.

[0395] Embodiment V. The extrudable thermoplastic composition according to Embodiment R, S, T, or U, wherein the linear polyethylene is LLDPE.

[0396] Embodiment W. The extrudable thermoplastic composition according to Embodiment V, wherein the LLDPE has a melt index I of 0.1 to 5.0 grams per 10 minutes 2 and.

[0397] Embodiment X. The extrudable thermoplastic composition according to Embodiment V or W, wherein the LLDPE has a density of 0.910 to 0.936 g / cm 3 3.

[0398] Embodiment Y. The extrudable thermoplastic composition according to Embodiment V, W, or X, wherein the LLDPE is an ethylene copolymer containing polymerized ethylene and one or more alpha-olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

[0399] Embodiment Z. An extrudable thermoplastic composition according to Embodiment R, S, T, U, V, W, X, or Y, wherein the poly(ether-block-amide) copolymer comprises a polyamide block that is a polyamide-12 (PA-12) block and a polyether block that is a polyethylene glycol (PEG) block.

[0400] Embodiment AA. An extrudable thermoplastic composition according to Embodiment Z, wherein the polyamide-12 (PA-12) block accounts for about 40 to 50 weight percent of the poly(ether-block-amide) copolymer, and the polyethylene glycol (PEG) block accounts for about 60 to 50 weight percent of the poly(ether-block-amide) copolymer.

[0401] Embodiment BB. An extrudable thermoplastic composition according to Embodiment R, S, T, U, V, W, X, or Y, wherein the poly(ether-block-amide) copolymer comprises 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

[0402] Embodiment CC. An extrudable thermoplastic composition according to Embodiment R, S, T, U, V, W, X, or Y, wherein the poly(ether-block-amide) copolymer comprises 10 to 20 polyamide blocks that are polyamide-12 (PA-12) blocks and 10 to 20 polyether blocks that are polyethylene glycol (PEG) blocks.

[0403] Embodiment DD. An extrudable thermoplastic composition according to Embodiment R, S, T, U, V, W, X, Y, or Z, wherein the number average molecular weight Mn of the poly(ether-block-amide) copolymer is from about 50,000 to about 75,000 g / mol.

[0404] Embodiment EE. An extrudable thermoplastic composition according to Embodiment R, S, T, U, V, W, X, Y, Z, AA, BB, CC, or DD, wherein the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 500 g / mol to about 6,000 g / mol and is derived from epsilon-caprolactone using 1,4-butanediol as an initiator.

[0405] Embodiment FF. An extrudable thermoplastic composition according to Embodiment R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, or EE, wherein the thermoplastic composition contains 200 to 2,000 ppm of a poly(ether-block-amide) copolymer (based on the weight of the linear polyethylene).

[0406] Embodiment GG. An extrudable thermoplastic composition according to Embodiment R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE, or FF, wherein the thermoplastic composition contains 200 to 2,000 ppm of a polycaprolactone polymer (based on the weight of the linear polyethylene).

[0407] Embodiment HH. A process for preparing a thermoplastic composition extrudate, a) preparing a thermoplastic composition by combining linear polyethylene with at least one poly(ether-block-amide) copolymer at 200 to 4,000 ppm (based on the weight of the linear polyethylene) and at least one polycaprolactone polymer at 200 to 4,000 ppm (based on the weight of the linear polyethylene); b) extruding the thermoplastic composition in a melt extrusion process and comprising, wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof, wherein the at least one poly(ether-block-amide) copolymer contains a polyamide block and a polyether block, wherein the thermoplastic composition is substantially free of fluoropolymers, The melt extrusion process is carried out in the absence of a fluoropolymer, The above process.

[0408] Embodiment II. The process according to Embodiment HH, wherein the linear polyethylene contains zinc oxide.

[0409] Embodiment JJ. The process according to Embodiment HH or II, wherein the linear polyethylene contains hydrotalcite.

[0410] Embodiment KK. A process for preparing a thermoplastic composition extrudate, a) preparing a thermoplastic composition by combining linear polyethylene with at least one poly(ether-block-amide) copolymer (200 to 4,000 ppm based on the weight of the linear polyethylene), at least one polycaprolactone polymer (200 to 4,000 ppm based on the weight of the linear polyethylene), and at least one polyethylene glycol (200 to 4,000 ppm based on the weight of the linear polyethylene); b) extruding the thermoplastic composition in a melt extrusion process; comprising, the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof, at least one poly(ether-block-amide) copolymer contains a polyamide block and a polyether block, the thermoplastic composition is substantially free of fluoropolymers, the melt extrusion process is carried out in the absence of a fluoropolymer, The above process.

[0411] Embodiment LL. The process according to Embodiment KK, wherein the linear polyethylene contains zinc oxide.

[0412] Embodiment MM. The process according to Embodiment KK or LL, wherein the linear polyethylene contains hydrotalcite.

Industrial Applicability

[0413] A polymer processing aid (PPA) is provided that reduces melt fracture defects in extruded polyolefins in the absence of fluoropolymers.

Claims

1. A process for preparing a thermoplastic composition extrudate, comprising the step of extruding the thermoplastic composition in a melt extrusion process, wherein the thermoplastic composition comprises: i) linear polyethylene; ii) 200 to 4000 ppm of a poly(ether block amide) copolymer (based on the weight of the linear polyethylene); and iii) 200 to 4000 ppm of a polycaprolactone polymer (based on the weight of the linear polyethylene). The linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof. The poly(ether block amide) copolymer comprises a polyamide block and a polyether block. The thermoplastic composition is substantially free of fluoropolymer. The melt extrusion process is carried out in the absence of fluoropolymer. The above process.

2. The process according to claim 1, wherein the thermoplastic composition further comprises iii) 200 to 4000 ppm of polyethylene glycol (based on the weight of the linear polyethylene).

3. The process according to claim 1, wherein the linear polyethylene comprises zinc oxide.

4. The process according to claim 1, wherein the linear polyethylene comprises hydrotalcite.

5. The process according to claim 1, wherein the linear polyethylene is LLDPE.

6. The process according to claim 5, wherein the LLDPE has a melt index I of from 0.1 to 5.0 grams per 10 minutes ２ ​

7. The process according to claim 5, wherein the LLDPE has a density of 0.910 to 0.936 g / cm ３ .

8. The process according to claim 5, wherein the LLDPE is an ethylene copolymer comprising polymerized ethylene and one or more alpha-olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

9. The process according to claim 1, wherein the melt extrusion process is carried out at a shear rate that produces a thermoplastic composition extrudate having a melt fracture defect when carried out using a thermoplastic composition comprising linear polyethylene.

10. The process according to claim 1, wherein the poly(ether block amide) copolymer comprises a polyamide block that is a polyamide-12 (PA-12) block and a polyether block that is a polyethylene glycol (PEG) block.

11. The process according to claim 10, wherein the polyamide-12 (PA-12) block occupies about 40 to 50 weight percent of the poly(ether block amide) copolymer, and the polyethylene glycol (PEG) block occupies about 60 to 50 weight percent of the poly(ether block amide) copolymer.

12. The process according to claim 1, wherein the poly(ether block amide) copolymer comprises 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

13. The process according to claim 1, wherein the poly(ether block amide) copolymer comprises 10 to 20 polyamide blocks which are polyamide-12 (PA-12) blocks and 10 to 20 polyether blocks which are polyethylene glycol (PEG) blocks.

14. The process according to claim 1, wherein the number average molecular weight Mn of the poly(ether block amide) copolymer is from about 50,000 to about 75,000 g / mol.

15. The process according to claim 1, wherein the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of from about 500 g / mol to about 6,000 g / mol and is derived from epsilon-caprolactone using 1,4-butanediol as an initiator.

16. The process according to claim 1, wherein the thermoplastic composition comprises 200 to 2,000 ppm of the poly(ether block amide) copolymer (based on the weight of the linear polyethylene).

17. The process according to claim 1, wherein the thermoplastic composition comprises 200 to 2,000 ppm of the polycaprolactone polymer (based on the weight of the linear polyethylene).

18. An extrudable thermoplastic composition comprising: i) linear polyethylene; ii) 200 to 4,000 ppm of the poly(ether block amide) copolymer (based on the weight of the linear polyethylene); and iii) 200 to 4,000 ppm of the polycaprolactone polymer (based on the weight of the linear polyethylene), wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof, and the poly(ether block amide) copolymer comprises a polyamide block and a polyether block. The extrudable thermoplastic composition substantially does not contain a fluoropolymer. The above extrudable thermoplastic composition.

19. iii) (Based on the weight of linear polyethylene) further containing 200 to 4,000 ppm of polyethylene glycol, the extrudable thermoplastic composition according to claim 18.

20. The extrudable thermoplastic composition according to claim 18, wherein the linear polyethylene contains zinc oxide.

21. The extrudable thermoplastic composition according to claim 18, wherein the linear polyethylene contains hydrotalcite.

22. The extrudable thermoplastic composition according to claim 18, wherein the linear polyethylene is LLDPE.

23. The LLDPE has a melt index I of 0.1 to 5.0 grams per 10 minutes ２ The extrudable thermoplastic composition according to claim 22

24. The extrudable thermoplastic composition according to claim 22, wherein the LLDPE has a density of 0.910 to 0.936 g / cm ３ .

25. The extrudable thermoplastic composition according to claim 22, wherein the LLDPE is an ethylene copolymer containing polymerized ethylene and one or more alpha-olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

26. The extrudable thermoplastic composition according to claim 18, wherein the poly(ether block amide) copolymer contains a polyamide block which is a polyamide-12 (PA-12) block and a polyether block which is a polyethylene glycol (PEG) block.

27. The extrudable thermoplastic composition according to claim 26, wherein the polyamide-12 (PA-12) block occupies about 40 to 50 weight percent of the poly(ether block amide) copolymer, and the polyethylene glycol (PEG) block occupies about 60 to 50 weight percent of the poly(ether block amide) copolymer.

28. The extrudable thermoplastic composition according to claim 18, wherein the poly(ether block amide) copolymer contains 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

29. The extrudable thermoplastic composition according to claim 18, wherein the poly(ether block amide) copolymer contains 10 to 20 polyamide blocks which are polyamide-12 (PA-12) blocks and 10 to 20 polyether blocks which are polyethylene glycol (PEG) blocks.

30. The extrudable thermoplastic composition according to claim 18, wherein the number average molecular weight Mn of the poly(ether block amide) copolymer is about 50,000 to about 75,000 g / mol.

31. The extrudable thermoplastic composition according to claim 18, wherein the polycaprolactone polymer is a polycaprolactone diol polymer having a number average molecular weight Mn of about 500 g / mol to about 6,000 g / mol and is derived from epsilon-caprolactone using 1,4-butanediol as an initiator.

32. The extrudable thermoplastic composition according to claim 18, wherein the thermoplastic composition comprises 200 to 2,000 ppm of a poly(ether block amide) copolymer (based on the weight of the linear polyethylene).

33. The extrudable thermoplastic composition according to claim 18, wherein the thermoplastic composition comprises 200 to 2,000 ppm of a polycaprolactone polymer (based on the weight of the linear polyethylene).

34. A process for preparing an extrudate of a thermoplastic composition, comprising: a) preparing a thermoplastic composition by combining linear polyethylene with at least one poly(ether block amide) copolymer in an amount of 200 to 4,000 ppm (based on the weight of the linear polyethylene) and at least one polycaprolactone polymer in an amount of 200 to 4,000 ppm (based on the weight of the linear polyethylene); b) extruding the thermoplastic composition in a melt extrusion process; wherein the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; the at least one poly(ether block amide) copolymer comprises a polyamide block and a polyether block; the thermoplastic composition is substantially free of fluoropolymers; the melt extrusion process is carried out in the absence of fluoropolymers. The above process.

35. The process according to claim 34, wherein the linear polyethylene contains zinc oxide.

36. The process according to claim 34, wherein the linear polyethylene contains hydrotalcite.

37. A process for preparing an extrudate of a thermoplastic composition, comprising: a) preparing a thermoplastic composition by combining linear polyethylene with at least one poly(ether block amide) copolymer (200 to 4,000 ppm based on the weight of the linear polyethylene), at least one polycaprolactone polymer (200 to 4,000 ppm based on the weight of the linear polyethylene), and at least one polyethylene glycol (200 to 4,000 ppm based on the weight of the linear polyethylene); b) extruding the thermoplastic composition in a melt extrusion process; comprising: the linear polyethylene is selected from the group consisting of LLDPE, MDPE, VLDPE, HDPE, and mixtures thereof; the at least one poly(ether block amide) copolymer comprises a polyamide block and a polyether block; the thermoplastic composition is substantially free of fluoropolymer; the melt extrusion process is carried out in the absence of fluoropolymer; the above process.

38. The process according to claim 37, wherein the linear polyethylene contains zinc oxide.

39. The process according to claim 37, wherein the linear polyethylene contains hydrotalcite.

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