Non-fluorinated polymer processing aid

Abstract

Polymer compositions comprising a polyolefin polymer and from 100 ppm to 10,000 ppm of a polyamide and methods of making and using the same are disclosed. The composition may be substantially free of polyolefin polymer / polyamide compatibilizers.

Description

Technical Field

[0001] This invention generally relates to polyolefin (e.g., polyethylene) compositions. These compositions may contain non-fluorinated polymer processing aids (PPAs) and may be substantially free of or contain no fluorinated PPAs. Compared to compositions containing fluorinated PPAs, these compositions may have improved melt fracture properties. Background Technology

[0002] Extruded polymers (such as blown polyethylene films) can exhibit surface defects resembling sharkskin, snakeskin, and / or orange peel. These surface defects are commonly referred to as "melt fracture." Melt fracture in extruded polymer compositions can cause degraded physical properties, obscured appearance, printing problems, and / or sealing issues in the resulting products. Melt fracture is believed to occur when the shear rate at the surface of the polymer composition is high enough that the surface of the polymer composition begins to fracture. That is, there is slippage of the surface of the extruded polymer composition relative to the bulk of the polymer composition. The surface often cannot flow fast enough to keep up with the bulk of the extrudate, thus fracture usually occurs in the melt, resulting in a loss of surface properties of the extrudate. Theoretically, melt fracture arises from a velocity gradient in the polymer composition within the extruder caused by friction on the extruder surface. This velocity gradient can cause a "slip-adhesion" phenomenon as the melt leaves the die, leading to surface irregularities or melt fracture.

[0003] Current solutions for preventing melt fracture involve using low levels (approximately 0.1 wt.%) of high molecular weight fluorinated compounds, such as fluoropolymers or fluoroelastomer copolymers of vinylidene fluoride and hexafluoropropylene. These additives coat the surfaces of the extruder and die to prevent sticking and allow for significantly increased processing rates to avoid melt fracture.

[0004] While attempts have been made to use PPAs other than those containing fluorine, these PPAs can be complex to use, expensive, and / or still cause melt fractionation problems. By way of example, U.S. Patent Application Publication No. 2023 / 0031000 by Ruocco et al. describes a PPA as a blend of polyethylene glycol, a surfactant containing sorbitan ester or polysorbate, and a metal salt of a fatty acid of at least two types. Such blends can be expensive, and introducing multiple components into a polymer resin can affect the resin's properties. As another example, U.S. Patent Application Publication No. 2023 / 0036922 by Leaf et al. discloses the use of a polyethylene glycol (PEG)-based polymer processing aid. Compared to fluorinated PPAs, the elimination of melt fractionation in PEG can be relatively slow. Invention Overview The following findings have been made: These findings provide solutions to at least one or more problems related to replacing fluorinated PPAs and reducing melt fracture in extruded polyolefin compositions. In one aspect, the solution may include the use of polyamides (e.g., polylactams, such as nylon-based polylactams) as the PPA. It has been found that the use of polyamides can have improved melt fracture properties (reduced melt fracture problems) compared to fluorinated PPAs (e.g., high molecular weight fluorinated polymers of vinylidene fluoride and hexafluoropropylene, or fluorinated elastomer copolymers). In one non-limiting example, it has been found that the use of polyamide 6 homopolymer (nylon 6) in linear low-density polyethylene (LLDPE)-based compositions performs better than known fluorinated PPAs in reducing melt fracture problems when extruding the composition into blown films. In another non-limiting example, it has been found that the use of polyamide 6 / 6,6 copolymer (nylon 6 / 6,6) in linear low-density polyethylene (LLDPE)-based compositions performs better than known fluorinated PPAs in reducing melt fracture problems when extruding the composition into blown films. This discovery can be environmentally beneficial, for example by providing an efficient alternative to fluorinated PPAs used in polyolefin compositions. The advantage of this discovery also lies in further reducing melt fracture problems in extruded polymer compositions. In one aspect of the invention, the polyolefin compositions of the invention can be substantially free of or free of fluorinated PPAs and / or compounds, minimizing or eliminating melt fracture problems during extrusion (e.g., into blown films).

[0006] It has also been found that the polymer compositions of the present invention can be substantially free of (e.g., 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, or 0.01 wt.% or less) or free of polyolefin polymer / polyamide (e.g., polylactam) compatibilizers (e.g., compounds containing maleic anhydride and / or polymers or copolymers of polyolefins linked to polar polymers) while still maintaining their improved melt fracture properties. An advantage of this discovery is, for example, that the polyamide (or combination of polyamides) can be used as the sole PPA and can be used to reduce melt fracture problems, which can reduce the cost and / or complexity of the resulting polymer compositions.

[0007] In one aspect of the invention, a polymer composition is described. The polymer composition may comprise a polyolefin polymer and 100 ppm to 10,000 ppm of a polyamide (e.g., a polylactam, such as a nylon-based polymer). The polymer composition may contain 100 ppm or substantially none (e.g., less than 50 ppm, preferably less than 40 ppm, 30 ppm, 20 ppm, 10 ppm, 5 ppm, 4 ppm, 3 ppm, 2 ppm, or 1 ppm) or none (0 wt.%) of fluorinated PPA (e.g., a high molecular weight fluorinated polymer or fluorinated elastomer copolymer of vinylidene fluoride and hexafluoropropylene). The polymer composition may be substantially free of (e.g., 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, or 0.01 wt.% or less) or free of (0 wt.%) polyolefin polymer / polyamide compatibilizers (e.g., maleic anhydride, polyethylene maleic anhydride, grafted polypropylene, maleic anhydride grafted polypropylene, maleic anhydride ethylene, copolymers of polyolefins linked to polar polymers, or combinations thereof). In some aspects, the polymer composition may contain 100 ppm to 1 wt.% polyethylene glycol and additives (e.g., antioxidants, UV stabilizers, or both). In certain aspects, the polymer composition may comprise: (1) 98 wt.%–99.9 wt.% of a polyolefin polymer; 200–2,000 ppm of polyamide; and 0–1 wt.% of additives; (2) 99 wt.%–99.9 wt.% of a polyolefin polymer, 500–1,000 ppm of polyamide, and 0–1 wt.% of additives; or (3) 99.5 wt.%–99.9 wt.% of a polyolefin polymer, 600–800 ppm of polyamide, and 0–1 wt.% of additives. The polymer composition may be substantially free of (e.g., 2 wt.% or less) or free of polyolefin polymer / polyamide compatibilizers. The weight-average molecular weight M of the polymer compositions of the present invention is... WThe concentration can range from greater than 2,500 g / mol (Da) to 250,000 g / mol (Da). In some aspects, as measured on a blown film production line, the time for the polymer composition to clear melt fracture can be less than 50 minutes. In one example, melt fracture can be measured using a Little Macro blown film production line as described in Example 2. The polymer compositions of the present invention can be in the form of granules, powders, molded parts, or films. In some aspects, the polymer compositions can be extruded articles, injection molded articles, compression molded articles, rotationally molded articles, blow molded articles, injection blow molded articles, 3-D printed articles, thermoformed articles, foamed articles, blown films, cast films, or writable films. In particular, the polymer compositions may be free of, substantially free of, or contain less than 100 ppm of fluorine-based compounds. Non-limiting examples of fluorine-based compounds may include fluoropolymers, fluorinated elastomers, or combinations thereof.

[0008] In some aspects, polyolefins may include polyethylene. Polyethylene may be a copolymer of ethylene and at least one α-olefin selected from the group consisting of 1-butene, 1-hexene, 4-methyl-1-pentene, or 1-octene. In some aspects, polyethylene may have a melt index (MI2) of 0.1-10 g / 10 min and a melt flow rate of 0.88-0.970 g / cm³. 3 Its density, melt index (MI2) of 0.1-10 g / 10 min, and density of 0.93-0.970 g / cm³ 3 Its density, or melt index (MI2) of 0.1-10 g / 10 min and 0.88-0.94 g / cm³ 3 The density. In one aspect of the invention, the polyolefin can be linear low-density polyethylene (LLDPE). LLDPE can have an MI2 of 0.85 g / 10 min and a density of 0.913 g / cm³. 3 The density of LLDPE can be as follows: MI2 of 0.85 g / 10 min and MI2 of 0.914 g / cm³. 3 The density. In one aspect of the invention, the polyamide may include a polylactam, such as a polycaprolactam homopolymer (e.g., polyamide 6 homopolymer (nylon 6)). In another aspect of the invention, the polyamide may include a polylactam, including polylactam copolymers, such as polycaprolactam copolymers (e.g., polyamide 6 / 6,6 copolymer (nylon 6 / 6,6)). Based on the total weight of the polyolefin composition, the polyolefin / polyamide compatibilizer may be present in the following amounts: 0 wt.% to less than 1 wt.%, preferably 0 wt.% to less than 0.1 wt.%, or more preferably 0 wt.% to less than 0.01 wt.%.

[0009] A method for producing a polymer composition is also described. The method may include melt-blending a polyolefin (e.g., polyethylene) and a polyamide (e.g., a polylactam, such as polycaprolactam) to produce a mixture. The mixture may be extruded to obtain a polymer composition. Extrusion may include a blown film extrusion process at a temperature of 180°C to 275°C.

[0010] In some embodiments, methods for reducing melt fracture in extruded polyolefin compositions are described. The methods may include adding 100 ppm to 10,000 ppm of polyamide to the polyolefin composition and then extruding the composition. The composition may be substantially free of or free of polyolefin / polyamide compatibilizers and / or fluorinated compounds.

[0011] In some embodiments, the polyolefin (e.g., polyethylene) composition of the present invention may be a masterbatch containing a concentrated amount of polyamide, additives, or both in the polyolefin. For example, based on the total weight of the polyolefin (e.g., polyethylene) composition of the present invention, the polymer composition may comprise: (1) 89 wt.%-99.5 wt.% (or any range or value thereof, e.g., 89 wt.%, 90 wt.%, 91 wt.%, 92 wt.%, 93 wt.%, 94 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 99 wt.%, 99.5 wt.%) of a polyolefin polymer (e.g., polyethylene, e.g., linear low-density polyethylene, low-density polyethylene, or high-density polyethylene, preferably linear low-density polyethylene); (2) 1 wt.%-10 wt.% of polyamide, preferably 5 wt.%-10 wt.% (or any range or value thereof, e.g., 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, or 10 wt.%). (3) 0 wt.% to 1 wt.% of additives (or any range or value thereof, such as 0 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.% or 1 wt.%). The polyolefin composition may be substantially free of (e.g. 2 wt.% or less) or free of (0 wt.%) polyolefin polymer / polyamide compatibilizers.

[0012] Other embodiments of the invention have been discussed throughout this application. Any embodiment discussed with respect to one aspect of the invention is equally applicable to other aspects of the invention, and vice versa. The embodiments described herein should be understood as embodiments of the invention applicable to other aspects of the invention. It is contemplated that any embodiment or aspect discussed herein may be combined with other embodiments or aspects implemented with respect to any method or composition of the invention discussed herein, and vice versa. Furthermore, the methods of the invention may be implemented using the compositions of the invention.

[0013] The following includes definitions of various terms and phrases used throughout this specification.

[0014] The term "masterbatch" refers to a concentrated mixture of polyamide, additives, or combinations thereof in a polyolefin carrier.

[0015] The term "about" or "approximately" is defined in a manner similar to that understood by those skilled in the art. In one non-limiting embodiment, the term is defined as within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0016] The terms “wt.%”, “vol.%”, or “mol.%” refer to the weight percentage, volume percentage, or mole percentage of a component, respectively, based on the total weight, volume, or moles of the material containing that component. In a non-limiting example, 10 grams of component in 100 grams of material is 10 wt.% of the component.

[0017] When used in the claims and / or description, the terms “suppress” or “reduce” or “prevent” or “avoid” or any variations thereof include any measurable reduction or complete suppression to achieve the desired result.

[0018] The term “effective”, when used in the specification and / or claims, means sufficient to achieve the desired, anticipated, or intended result.

[0019] When used in conjunction with any of the terms “comprising,” “including,” “containing,” or “having” in the claims or description, the use of the word “a” can mean “a”, but it is also consistent with the meaning of “a” or “more than”, “at least one”, and “a” or “more than one”.

[0020] The words “comprising” (and any form of “comprising”, such as “comprise” and “comprises”), “having” (and any form of “having”, such as “have” and “has”), “including” (and any form of “including”, such as “includes” and “include”), or “containing” (and any form of “containing”, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, undescribed elements or steps of the process.

[0021] The polymer compositions of the present invention may “comprising” the specific ingredients, components, compositions, etc. disclosed throughout the specification; “consistently made of” the specific ingredients, components, compositions, etc. disclosed throughout the specification; or “composed of” the specific ingredients, components, compositions, etc. disclosed throughout the specification. Regarding the transitional phrase “consistently made of”, in a non-limiting aspect, a fundamental and novel characteristic of the polymer compositions of the present invention is that they may contain polyamides (e.g., polylactams, such as polycaprolactam-based polymers, such as polyamide 6 homopolymers (nylon 6) or polyamide 6 / 6,6 copolymers (nylon 6 / 6,6)) as polymer processing aids, and may be substantially free of or contain no fluorinated polymer processing aids. Compared to polymer compositions containing fluorinated polymer processing aids, the compositions of the present invention may have improved melt fracture properties.

[0022] Other objects, features, and advantages of the invention will become apparent from the following drawings, detailed description, and embodiments. However, it should be understood that the drawings, detailed description, and embodiments (although indicating specific embodiments of the invention) are given by way of illustration only and are not intended to be limiting. Furthermore, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from a particular embodiment may be combined with features from other embodiments. For example, a feature from one embodiment may be combined with features from any other embodiment. In further embodiments, additional features may be added to the specific embodiments described herein. Brief description of the attached diagram The advantages of the present invention will become apparent to those skilled in the art from the following detailed description and with reference to the accompanying drawings.

[0024] Figure 1This shows melt fracture removal data on the Little Macro blown film production line. C1 is the resin without processing aids (gray diamond). C2 is the comparative fluoropolymer (black square). N1 is non-limiting formulation 1 (dashed line, black circle). N2 is non-limiting formulation 2 (dashed line, gray square). N3 is non-limiting formulation 3 (gray triangle). N4 is non-limiting formulation 4 (dashed line, black plus sign).

[0025] While the invention is susceptible to various modifications and alternatives, specific embodiments thereof are shown by way of example in the accompanying drawings. The drawings may not be drawn to scale.

[0026] Implementation Plan Description The following findings have been made, providing solutions to at least one or more problems that may be associated with the use of fluorine-based polyolefin processing aids in polyolefin compositions. In one aspect, it has been found that polyamides (e.g., nylon-based polymers such as nylon 6 or nylon 6 / 6,6) can be used as polymer processing aids and can exhibit better melt fracture properties compared to fluorine-based polyolefin processing aids. This allows the polymer compositions of the present invention to be substantially free (e.g., less than 100 ppm based on the weight of the polymer composition) or free (0 wt.%) of fluorine-based polymer processing aids.

[0027] These and other non-limiting aspects of the invention are discussed in further detail in the following sections.

[0028] A. Polymer composition The polymer compositions of the present invention may comprise polyolefin polymers and polyamide polymer processing aids. In some aspects, based on the total weight of the polymer compositions of the present invention, the polymer compositions may comprise 98 wt.%-99.9 wt.% of a polyolefin polymer, 100-10,000 ppm of polyamide, and 0-1 wt.% of additives. In another aspect, the polymer compositions of the present invention may comprise 98 wt.%-99.9 wt.% of a polyolefin polymer, 200-2,000 ppm of polyamide, and 0-1 wt.% of additives. In yet another aspect, the polymer compositions may comprise 99 wt.%-99.5 wt.% of a polyolefin polymer, 600-800 ppm of polyamide, and 0-1 wt.% of additives. In other embodiments, the polymer compositions of the present invention may comprise polydiols. Polymer compositions containing polydiols may contain 97 wt.%–99.9 wt.% of a polyolefin polymer, 100–10,000 ppm of polyamide, 100–10,000 ppm of polydiol, and 0–1 wt.% of additives. In other respects, polymer compositions may contain: (1) 98 wt.%–99.9 wt.% of a polyolefin polymer; 200–2,000 ppm of polyamide; and 0–1 wt.% of additives; (2) 99 wt.%–99.9 wt.% of a polyolefin polymer, 500–1,000 ppm of polyamide, and 0–1 wt.% of additives; or (3) 99.5 wt.%–99.9 wt.% of a polyolefin polymer, 600–800 ppm of polyamide, and 0–1 wt.% of additives.

[0029] In another aspect of the invention, based on the total weight of the polymer composition, the polymer composition may comprise 89 wt.% to 99.5 wt.% (or any range or value thereof, e.g., 89 wt.%, 90 wt.%, 91 wt.%, 92 wt.%, 93 wt.%, 94 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 99 wt.%, 99.5 wt.%) of a polyolefin polymer, 1 wt.% to 10 wt.% (or any range or value thereof, e.g., 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, or 10 wt.%) of a polyamide, and 0 wt.% to 1 wt.% (or any range or value thereof, e.g., 0 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%) of a polyamide. Additives in wt.%, 0.6wt.%, 0.7wt.%, 0.8wt.%, 0.9wt.% or 1wt.%).

[0030] The polymer compositions of the present invention may be substantially free of (e.g., 2 wt.% or less, 1.5 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, or 0.01 wt.% or less) or free of (0 wt.%) polyolefin / polyamide compatibilizers.

[0031] The polymer compositions of the present invention may contain 100 parts per million (ppm) or less or substantially none (e.g., 50 ppm or less, preferably less than 40 ppm, 30 ppm, 20 ppm, 10 ppm, 5 ppm, 4 ppm, 3 ppm, 2 ppm or 1 ppm) or none (0 wt.%) of fluorinated PPA (e.g., high molecular weight fluorinated polymers or fluorinated elastomer copolymers of vinylidene fluoride and hexafluoropropylene).

[0032] The polymer compositions of the present invention may have a melt index (MI2) of 0.1-10 g / 10 min (e.g., 0.1 g / 10 min, 0.5 g / 10 min, 1 g / 10 min, 1.5 g / 10 min, 2 g / 10 min, 2.5 g / 10 min, 3 g / 10 min, 3.5 g / 10 min, 4 g / 10 min, 4.5 g / 10 min, 5 g / 10 min, 5.5 g / 10 min, 6 g / 10 min, 6.5 g / 10 min, 7 g / 10 min, 7.5 g / 10 min, 8 g / 10 min, 8.5 g / 10 min, 9 g / 10 min, 9.5 g / 10 min, 10 g / 10 min, or any range or value therebetween) and a viscosity of 0.88-0.970 g / cm³. 3 (e.g., 0.88 g / cm) 3 0.89 g / cm 3 0.9 g / cm 3 0.91 g / cm 3 0.92 g / cm 3 0.93 g / cm 3 0.94 g / cm 3 0.95 g / cm 3 0.96 g / cm 3 0.97 g / cm 3 The density is 0.1–10 g / 10 min (or any value or range thereof). In some particular aspects, the polymer composition may have a melt index (MI2) of 0.1–10 g / 10 min and a density of 0.88–0.940 g / cm³. 3 The density.

[0033] The polymer compositions of the present invention can be molded into a wide variety of shapes and / or articles (e.g., granules, powders, molded parts, films, etc.). The thickness of the film can be 0.001 mm to 1 mm, or 0.001 mm, 0.01 mm, 0.05 mm, 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3 mm, 0.35 mm, 0.4 mm, 0.45 mm, 0.5 mm, 0.55 mm, 0.6 mm, 0.65 mm, 0.7 mm, 0.75 mm, 0.8 mm, 0.85 mm, 0.9 mm, 0.95 mm, or 1 mm, or any value or range therebetween.

[0034] 1. Polyolefin polymers The polyolefin polymer of the present invention can be a thermoplastic polymer. The polyolefin may include those substituted with aromatic groups (e.g., styrene) or unsubstituted polyolefins (e.g., polyethylene) or copolymers (e.g., ethylene-α-olefin copolymers). In some aspects, the olefin polymer (or "polyolefin") may include at least 85% by weight of one or more C2-3 α-olefins and at most 15% by weight of one or more C4-8 α-olefins. Preferably, the polyolefin may include at least 90% by weight of ethylene and at most 10% by weight of one or more C4-8 α-olefins. Suitable C2-3 α-olefins include ethylene and propylene. Suitable C4-8 α-olefins may include butene, 4-methylpentene, hexene, and octene. The amount of polyolefin in the polymer composition can range from 97 wt.% to 99.9 wt.%, or 97.1 wt.%, 97.2 wt.%, 97.3 wt.%, 97.4 wt.%, 97.5 wt.%, 97.6 wt.%, 97.7 wt.%, 97.8 wt.%, 97.9 wt.%, 98 wt.%, 98.1 wt.%, 98.2 wt.%, 98.3 wt.%, 98.4 wt.%, 98.5 wt.%, 98.6 wt.%, 98.7 wt.%, 98.8 wt.%, 98.9 wt.%, 99 wt.%, 99.1 wt.%, 99.2 wt.%, 99.3 wt.%, 99.4 wt.%, 99.5 wt.%, 99.6 wt.%, 99.7 wt.%, 99.8 wt.% wt.%, 99.9 wt.%, or any range or value between them.

[0035] Polyolefins can be prepared by conventional methods. In the case of olefins with substituted aromatic groups, such as styrene, the polymer can be polymerized in thermally initiated bulk or solution polymerization or in bulk or solution polymerization via free radical polymerization. In the case of unsubstituted olefin polymers, polymerization can be carried out in the gas phase to produce products such as high-density polyethylene (e.g., density greater than 0.935 g / cc, preferably greater than 0.940 g / cc) and low-density polyethylene (density of about 0.910-0.935 g / cc). Gas-phase polymerization can include contacting the monomer with a catalyst in a fluidized bed reactor under polymerization conditions. In some aspects, polymerization conditions include pressures below 3.4 MPa (preferably below about 1.74 MPa) and temperatures below 130°C. Polymerization can also be carried out in solution or as a slurry in the presence of a polymerization catalyst (e.g., a coordination catalyst or a metallocene catalyst). Solution polymerization conditions can include temperatures of 130-250°C at atmospheric pressure or low pressure. In solution methods, ethylene and other comonomers can be dissolved in solvents such as hexane in the presence of a coordination catalyst. Depending on the polymerization type and the olefin, the weight-average M of the olefin polymer... w It can be up to 250,000, typically around 2,500-250,000 g / mol (Da). Weight-average M can be determined using methods known in the art. w Non-limiting examples of standard methods for weight-average molecular weight may include ASTM D6474, ASTM D40001, ISO 16014, etc.

[0036] Generally, the present invention is applicable to thermoplastic polyolefins. In a preferred aspect, the present invention can improve the extrusion of linear polyethylene (particularly linear low-density polyethylene or LLDPE). LLDPE is a copolymer of ethylene with another copolymerizable α-olefin (e.g., butene, hexene, or octene). The density of LLDPE can be less than 0.955 g / cm³. Other polyethylenes (e.g., low-density polyethylene (LDPE) and high-density polyethylene (HDPE)) can be used in the context of the present invention.

[0037] Polyolefins can be characterized by density and melt index (MI2). The melt index can be determined using known methods. A non-limiting example of a standard method for determining the melt index is ASTM D1238, Condition E, at 190°C. In some aspects, the polyethylene used in this invention may have a melt index (MI2) of 0.1-10 g / 10 min (e.g., 0.1 g / 10 min, 0.5 g / 10 min, 1 g / 10 min, 1.5 g / 10 min, 2 g / 10 min, 2.5 g / 10 min, 3 g / 10 min, 3.5 g / 10 min, 4 g / 10 min, 4.5 g / 10 min, 5 g / 10 min, 5.5 g / 10 min, 6 g / 10 min, 6.5 g / 10 min, 7 g / 10 min, 7.5 g / 10 min, 8 g / 10 min, 8.5 g / 10 min, 9 g / 10 min, 9.5 g / 10 min, 10 g / 10 min, or any range or value between therewith) and a melt index of 0.88-0.970 g / cm³. 3 (e.g., 0.88 g / cm) 3 0.89 g / cm 3 0.9 g / cm 3 0.91 g / cm 3 0.92 g / cm 3 0.93 g / cm 3 0.94 g / cm 3 0.95 g / cm 3 0.96 g / cm 3 0.97 g / cm 3 The density (or any value or range thereof). For example, polyethylene can have a melt index (MI2) of 0.1-10 g / 10 min and a density of 0.93-0.970 g / cm³. 3 The density. In another example, polyethylene can have a melt index (MI2) of 0.1-10 g / 10 min and a density of 0.88-0.94 g / cm³. 3 The density. In some aspects, LLDPE is used. The LLDPE of the present invention can have a density of 0.900-0.950 g / cm³. 3 (e.g., 0.9 g / cm) 3 0.91 g / cm 3 0.92 g / cm 3 0.93 g / cm 3 0.94g / cm 3 0.95 g / cm 3The density (and any values ​​or ranges thereof) and MI2 of 0.3–5.0 g / 10 min (e.g., 0.3 g / 10 min, 0.5 g / 10 min, 1 g / 10 min, 1.5 g / 10 min, 2 g / 10 min, 2.5 g / 10 min, 3 g / 10 min, 3.5 g / 10 min, 4 g / 10 min, 4.5 g / 10 min, 5 g / 10 min, or any range or values ​​thereof). In certain respects, LLDPE has an MI2 of 0.80–0.9 g / 10 min and an MI2 of 0.910–0.915 g / cm³. 3 The density, or MI2 of 0.85 g / 10 min and 0.913 g / cm³ 3 The density, or MI2 of 0.85 g / 10 min and 0.914 g / cm³ 3 The density of polyolefins can be determined using ASTM D792-13 (November 1, 2013).

[0038] 2. Polyamide The polymer compositions of the present invention may contain polyamides. Polyamides are polymers containing repeating amide (-CO-NH-) bonds. Polyamides are typically condensation copolymers formed by the reaction of a dicarboxylic acid with a diamine or by ring-opening of a lactam. Various polyamides can be generated by adjusting the number of carbon atoms.

[0039] In a particular embodiment of the invention, the polyamide may include a polylactam (e.g., polycaprolactam), which is a family of synthetic aliphatic thermoplastic resins produced via ring-opening polymerization of cyclic amides (lactams). Non-limiting examples of polylactams include nylon as a homopolymer, a bicomponent homopolymer, or a copolymer thereof. Homopolymer polylactams may have the following general formula [NH-(CH2)]. x -CO] n , where x is 4-25, and n This refers to the number of repeating (units) in the polymer (e.g., 3-20). Two-component homopolymers can have the general formula [NH−(CH2)x−NH−CO−(CH2)]. y -CO] n Where x is 4-12, y is 4-12, and n It is the number of repeating (units) of the polymer (e.g., 3-20).

[0040] Non-limiting examples of nylon (or polyamide) that may be used in the context of this invention include poly(4-aminobutyric acid) (nylon 4), poly(6-aminohexanoic acid) (nylon 6, also known as polycaprolactam), poly(7-aminoheptanoic acid) (nylon 7), poly(8-aminooctanoic acid) (nylon 8), poly(9-aminononanoic acid) (nylon 9), poly(10-aminodecanoic acid) (nylon 10), poly(11-aminoundecanoic acid) (nylon 11), nylon 4, 6, poly(hexamethylene adipamide) (nylon 6, 6), poly(hexamethylene decanamide) (nylon 6, 6), and poly(hexamethylene decanamide) (nylon 6, 6). Poly(Nylon 6,10), poly(heptamethyleneheptadamide) (Nylon 7,7), poly(octamethyleneoctadiamide) (Nylon 8,8), poly(hexamethylenenonadiamide) (Nylon 6,9), poly(nonamethylenenonadiamide) (Nylon 9,9), poly(decamethylenenonadiamide) (Nylon 10,9), tetramethylenediamine-oxalic acid copolymer (Nylon 4,2), polyamide of n-dodecanoic acid and hexamethylenediamine (Nylon 6,12), polyamide of dodecyl diamine and n-dodecanoic acid (Nylon 12,12), etc. Non-limiting examples of polyamide copolymers that can be used in the context of this invention include caprolactam / hexamethylene adipamide copolymers (Nylon 6,6 / 6), hexamethylene adipamide / caprolactam copolymers (Nylon 6 / 6,6), trimethylene adipamide / hexamethylene nonadiamide copolymers (Nylon trimethyl 6,2 / 6,2), hexamethylene adipamide-hexamethylene-nonadiamide-caprolactam copolymers (Nylon 6,6 / 6,9 / 6), and so on. In some preferred aspects of the invention, nylon 6, nylon 6,6, nylon 6 / 6,6, and mixtures thereof can be used. In a particular embodiment, nylon 6 is preferred. In a particular embodiment, nylon 6 / 6,6 is preferred. In a particular embodiment, nylon 6,6 / 6 is preferred.

[0041] On the one hand, polyamide is a homopolymer of polyamide 6 (also known as polycaprolactam or nylon 6).

[0042] On the one hand, polyamide is a copolymer of polyamide 6 / 6,6 (also known as nylon 6 / 6,6).

[0043] In some applications, polyamides can have melting points of 215°C-225°C and concentrations of 1.0-1.5 g / cm³. 3 The density (preferably 1.1-1.2 g / cm³) 3 (density). In some respects, polyamides can have melting points of 185℃-215℃ and densities of 1.0-1.5 g / cm³. 3 The density (preferably 1.1-1.2 g / cm³) 3(Density). Nylon is available from commercial manufacturers. Non-limiting examples of nylon manufacturers include UBE Corporation, Europe, SAU (Spain), Lanxess (Germany), BASF SE (USA), Huntsman International LLC (USA), Domo Chemicals (Italy), and TORAY, Industries, Inc. (Japan).

[0044] The amount of polyamide (based on the total weight of the polymer composition) can range from 100 to 10,000 ppm, or be 100 ppm, 500 ppm, 1,000 ppm, 1,500 ppm, 2,000 ppm, 2,500 ppm, 3,000 ppm, 3,500 ppm, 4,000 ppm, 4,500 ppm, 5,000 ppm, 5,500 ppm, 6,000 ppm, 6,500 ppm, 7,000 ppm, 7,500 ppm, 8,000 ppm, 8,500 ppm, 9,000 ppm, 9,500 ppm, 10,000 ppm, or any range or value between these values. In a further aspect, the amount of polyamide (e.g., a polyamide containing a polylactam such as polycaprolactam) may be 700 ppm to 800 ppm, or about 750 ppm, based on the total weight of the polymer composition. Still in a further aspect, the amount of polyamide (e.g., a polyamide containing a polylactam such as polycaprolactam) may be 1,250 ppm to 1,750 ppm, or about 1,500 ppm, based on the total weight of the polymer composition. In another aspect, the amount of polyamide (e.g., a polyamide containing a polylactam such as polycaprolactam) may be 500 ppm to 2,000 ppm, or 500 ppm to 1,750 ppm, or 650 ppm to 1,750 ppm, based on the total weight of the polymer composition.

[0045] 3. Polydiol In some aspects of the invention, the polymer composition may comprise a polydiol as an additional processing aid additive. In various aspects, the polydiol has a weight-average molecular weight of 2,000 g / mol to 50,000 g / mol or 3,000 g / mol to 3,500 g / mol. Non-limiting examples of polydiols include polyethylene glycol, PEG ethers, polypropylene glycol, polytetrahydrofuran, and mixtures thereof. PEG ethers include lauryl ether, cetearyl ether, cetyl ether, stearyl ether, oleyl ether, or mixtures thereof. Suitable non-limiting examples of PEG are commercially available under the trademark Polyglykol from Clariant Ltd. The amount of polydiol (based on the total weight of the polymer composition) can range from 100 to 10,000 ppm, or from 100 ppm, 500 ppm, 1,000 ppm, 1,500 ppm, 2,000 ppm, 2,500 ppm, 3,000 ppm, 3,500 ppm, 4,000 ppm, 4,500 ppm, 5,000 ppm, 5,500 ppm, 6,000 ppm, 6,500 ppm, 7,000 ppm, 7,500 ppm, 8,000 ppm, 8,500 ppm, 9,000 ppm, 9,500 ppm, 10,000 ppm, or any range or value between these values. On the other hand, the amount of PEG, based on the total weight of the polymer composition, can be from 500 ppm to 2,500 ppm. On the one hand, the amount of PEG, based on the total weight of the polymer composition, can be 700 ppm-800 ppm or about 750 ppm. The optimal addition level for a given extrusion process can be readily determined by those skilled in the art.

[0046] 4. Polyolefin polymers / polyamide compatibilizers The polyolefin-containing compositions of the present invention may be substantially free of (e.g., less than 2 wt.%) or free of polyolefin polymer / polyamide compatibilizers. In some aspects, based on the total weight of the composition containing polyolefins, the composition may contain the following amounts of polyolefin polymer / polyamide compatibilizer: up to or less than 0.01 wt.%, 0.02 wt.%, 0.03 wt.%, 0.04 wt.%, 0.05 wt.%, 0.06 wt.%, 0.07 wt.%, 0.08 wt.%, 0.09 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt.%, 1.1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 1.7 wt.%, 1.8 wt.%, 1.9 wt.%, or 2 wt.%. On the other hand, compositions containing polyolefins include 0 wt.% of a polyolefin polymer / polyamide compatibilizer.

[0047] Polyolefin polymer / polyamide compatibilizers include compounds and / or compositions that can stabilize blends of immiscible polymers. Non-limiting examples of polyolefin polymer / polyamide compatibilizers include maleic anhydride, polyethylene maleic anhydride, grafted polypropylene, maleic anhydride-grafted polypropylene, maleic anhydride-ethylene, and copolymers of polyolefins linked to polar polymers. Non-limiting examples of compatibilizers are found in U.S. Patent 10,100,140. Non-limiting examples of commercial compatibilizers are marketed under the trade name BYNEL. ® and RETAIN ® (Dow Chemical, USA), NOVACOM-P™ (Polygroup, USA), and LICOCENE ® (Sold by Clariant Plastics & Coatings Ltd., USA)

[0048] 5. Additives The polyolefin-containing compositions of the present invention may contain one or more additives, fillers, pigments, etc. Non-limiting examples of additives include antioxidants, light stabilizers, ultraviolet (UV) stabilizers, polyamide stabilizers, co-stabilizers, nucleating agents, metal passivators, slip agents, or mixtures thereof. Based on the total weight of the polymer composition, the composition may contain the following amounts of additives: 0 and 1 wt.%, preferably 0.01 wt.% to 1 wt.%, or between 0.01 wt.% and 1 wt.%, or 0.01 wt.% to less than 1 wt.%, or between 0.5 wt.% and less than 1 wt.%, or 0 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, or 1 wt.%, or any range or value between these.

[0049] Non-limiting examples of antioxidants include alkylated monophenols (also described herein as “hindered phenolic primary antioxidants”). Non-limiting examples of hindered phenols include 2,6-di-tert-butyl-4-methylphenol; 2-tert-butyl-4,6-dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol; 2,6-di-tert-butyl-4-isobutylphenol; 2,6-dicyclopentyl-4-methylphenol; 2-(α-methylcyclohexyl)-4,6-dimethylphenol; 2,6-di(octadecyl)-4-methylphenol; 2,4,6-tricyclohexylphenol; and 2,6-di-tert-butyl-4-methoxymethylphenol. Suitable hindered phenolic antioxidants that may be used in embodiments of this disclosure are available from BASF Corporation under the trademark IRGANOX. ® 1010 (CAS Registry No. 6683-19-8) and IRGANOX 1076 (CAS Registry No. 2082-79-3) are available for sale.

[0050] In some embodiments, the antioxidant may include alkylated hydroquinone. Non-limiting examples of alkylated hydroquinone include 2,6-di-tert-butyl-4-methoxyphenol; 2,5-di-tert-butylhydroquinone; 2,5-di-tert-pentylhydroquinone; and 2,6-diphenyl-4-octadecyloxyphenol.

[0051] Other non-limiting examples of antioxidants include thiodiphenyl ethers. Non-limiting examples of thiodiphenyl ethers include: 2,2'-thiobis(6-tert-butyl-4-methylphenol); 2,2'-thiobis(4-octylphenol); 4,4'-thiobis(6-tert-butyl-3-methylphenol); and 4,4'-thiobis(6-tert-butyl-2-methylphenol).

[0052] In embodiments of the present invention, the antioxidant may include alkylene bisphenols. Non-limiting examples of alkylene bisphenols may include 2,2'-methylenebis(6-tert-butyl-4-methylphenol); 2,2'-methylenebis(6-tert-butyl-4-ethylphenol); 2,2'-methylenebis(4-methyl-6-(α-methylcyclohexyl)phenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,2'-methylenebis(6-nonyl-4-methylphenol); 2,2'-methylenebis(6-nonyl-4-methylphenol); 2,2'-Methylenebis(6-nonyl-4-methylphenol); 2,2'-methylenebis(6-(α-methylbenzyl)-4-nonylphenol); 2,2'-methylenebis(6-(α,α-dimethylbenzyl)-4-nonylphenol); 2,2'-methylenebis(4,6-di-tert-butylphenol); 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol); 4,4'-methylenebis(2,6-di-tert-butylphenol); 4, 4'-Methylenebis(6-tert-butyl-2-methylphenol); 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenol)butane; 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol; 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecyl-mercaptobutane; ethyl Diol-bis(3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)-butyrate)-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene; bis(2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl) terephthalate; and other phenols, such as monoacrylates of bisphenols, such as ethylene bis(2,4-di-tert-butylphenol) monoacrylate.

[0053] In some respects, antioxidants can include benzyl compounds. Non-limiting examples of benzyl compounds include: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene; bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfides; 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid isooctyl ester; bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate; 1,3,5-isocyanuric acid... - Tris(3,5-di-tert-butyl-4,10-hydroxybenzyl) ester; 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) ester of isocyanurate; di(octadecyl) ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonate; calcium salt of monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonate; and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) ester of isocyanurate.

[0054] Non-limiting examples of acylaminophenol antioxidants may include: 4-hydroxy-laurate aniline; 4-hydroxy-stearate aniline; 2,4-bis(octylmercapto)-6-(3,5-tert-butyl-4-hydroxyaniline)-s-triazine; and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

[0055] Other non-limiting examples of antioxidants may include esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols. Non-limiting examples of such compounds include: methanol; diethylene glycol; octadecyl alcohol; triethylene glycol; 1,6-hexanediol; pentaerythritol; neopentyl glycol; tri(hydroxyethyl) isocyanurate; tridiethylene glycol; and dihydroxyethyl oxalate diamide. In embodiments of this disclosure, the primary antioxidant is selected from amides of β-(3,5-di-tert-butyl-4-hydroxyphenol)propionic acid, such as, for example, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine; N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine; and N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

[0056] Other non-limiting examples of antioxidants may include phosphites and phosphonites (also described herein as "phosphorus-containing co-oxidants"), such as, for example, triphenyl phosphite; diphenylalkyl phosphite; phenyl dialkyl phosphite; tri(nonylphenyl) phosphite [WESTON] ® 399, available from SI Group]; Mixed 2,4-bis(1,1-dimethylpropyl)phenyltriester and 4-(1,1-dimethylpropyl)phenyltriester of phosphite [WESTON 705, CAS Registry No. 939402-02-5, available from SI Group]; Trilauryl phosphite; Tri(octadecyl) phosphite; Distearate pentaerythritol diphosphite; Tris(2,4-di-tert-butylphenyl)phosphite [IRGAFOS] ®168, available from BASF]; diisodecyl pentaerythritol diphosphite; 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite; bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite [IRGAFOS 38, available from BASF]; 2,2',2"-hypo-nitro[triethyltri(3,3',5,5'-tetra-tert-butyl-1,r-biphenyl-2,2'-diyl)phosphite [IRGAFOS 12, available from BASF]; bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite; tripearylsorbitol triphosphite; tetra(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonate; 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxophosphazene heptane [SUMILIZER] ® [GP]; bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphate; bis(2,4-dicumylphenyl)pentaerythritol diphosphate; distearate 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; bis(isodecoxy-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'-biphenyl diphosphite [IRGAFOS P-EPQ, available from BASF]; bis(2,4-dicumylphenyl) pentaerythritol diphosphite [DOVERPHOS ® S9228-T or DOVERPHOS S9228-CT] and P-EPQ ® (CAS Registry No. 119345-01-06) (commercially available bisphosphonates); or mixtures thereof. In embodiments of this disclosure, the auxiliary antioxidant is selected from DOVERPHOS LGP-11, DOVERPHOS LGP-12, and DOVERPHOS LGP-12LV. In some embodiments, alkylphenol-free polymeric polyphosphites may be used. Non-limiting examples thereof are disclosed in U.S. Patent No. 8,563,637.

[0057] Antioxidants may also include hydroxylamines and amine oxides. Non-limiting examples of hydroxylamines and amine oxides may include N,N-dibenzylhydroxylamine; N,N-diethylhydroxylamine; N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N-di(tetradecyl)hydroxylamine; N,N-di(hexadecyl)hydroxylamine; N,N-di(octadecyl)hydroxylamine; N-hexadecyl-1-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 hydroxylamine that can be used in embodiments of this disclosure is N,N-dialkylhydroxylamine, sold by BASF as IRGASAB® 042, and which is reportedly prepared by the direct oxidation of N,N-di(hydrogenated) tallow amine.

[0058] In embodiments, the antioxidant may include nitrones. Non-limiting examples of nitrones include N-benzyl-α-phenyl nitrone; N-ethyl-α-methyl nitrone; N-octyl-α-heptyl nitrone; N-lauryl-α-undecyl nitrone; N-tetradecyl-α-tetrazyl nitrone; N-hexadecyl-α-pentadecanyl nitrone; N-octadecyl-α-heptadecyl nitrone; N-hexadecyl-α-heptadecyl nitrone; N-octadecyl-α-pentadecanyl nitrone; N-octadecyl-α-heptadecyl nitrone; and nitrones derived from N,N-dialkylhydroxylamine, which is derived from hydrogenated tallow amine.

[0059] Non-limiting examples of UV absorbers and / or light stabilizers include 2-(2'-hydroxyphenyl)-benzotriazole, such as, for example, 5'-methyl derivatives; 3',5'-di-tert-butyl derivatives; 5'-tert-butyl derivatives; 5'(1,1,3,3-tetramethylbutyl) derivatives; 5-chloro-3',5'-di-tert-butyl derivatives; 5-chloro-3'-tert-butyl-5'-methyl derivatives; 3'-sec-butyl-5'-tert-butyl derivatives; 4'-octoxy-3',5'-di-tert-pentyl derivatives; and 3',5'-bis(α,α-dimethylbenzyl) derivatives.

[0060] Other UV absorbers or light stabilizers may include 2-hydroxybenzophenone. Non-limiting examples of benzophenone include: 4-hydroxy derivatives; 4-methoxy derivatives; 4-octoxy derivatives; 4-decoxy derivatives; 4-dodecyloxy derivatives; 4-benzyloxy derivatives; 4,2',4'-trihydroxy derivatives; and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0061] In some embodiments, the UV absorber or light stabilizer may be a hindered amine. Non-limiting examples of hindered amines include: bis(2,2,6,6-tetramethylpiperidinyl) sebacate; bis-5-(1,2,2,6,6-pentamethylpiperidinyl) sebacate; n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid bis(1,2,2,6,6-pentamethylpiperidinyl) ester; a condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid; N,N'-(2,2,6,6-tetramethylpiperidinyl)-hexamethylene Condensation products of diamines with 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine; tris(2,2,6,6-tetramethylpiperidyl)-nitrotriacetate; tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetra-arbonic acid; and 1,1'(1,2-ethylenediyl)-bis(3,3,5,5-tetramethylpiperazinone). These amines are commonly referred to as HALS (hindered amine photostable) and include 2,2,6,6-tetramethylpiperidinol butanetetracarboxylate. Such amines include hydroxylamines derived from hindered amines, such as bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 1-hydroxy-2,2,6,6-tetramethyl-4-phenoxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-piperidine; and N-(1-hydroxy-2,2,6,6-tetramethyl-piperidin-4-yl)-α-caprolactam. Suitable commercially available HALS that can be used in embodiments of this disclosure include those sold under the following trademarks: CHIMASSORB from BASF. ® 119. CHIMASSORB 944. CHIMASSORB 2020. TINUVIN ® 622 and TINUVIN 770; and CYASORB from Solvay. ® UV 3346, CYASORB UV 3529, CYASORB UV 4801, and CYASORB UV 4802. In other embodiments, mixtures of more than one HALS are also considered.

[0062] Other examples of UV absorbers or light stabilizers are substituted and unsubstituted benzoic acids. Non-limiting examples of benzoic acids may include: 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.

[0063] In some embodiments, the UV absorber or light stabilizer may be an acrylate. Non-limiting examples of acrylates may include: ethyl α-cyano-β,β-diphenylacrylate or isooctyl α-cyano-β,β-diphenylacrylate; methyl α-methyl cinnamate; methyl α-cyano-β-methyl-p-methoxy-cinnamate or butyl α-cyano-β-methyl-p-methoxy-cinnamate; methyl α-methyl ester-p-methoxy-cinnamate; and N-(β-methyl ester-β-cyano-vinyl)-2-methyl-indoline.

[0064] Non-limiting examples of co-stabilizers may include melamine; polyvinylpyrrolidone; dicyandiamide; triallyl cyanurate; urea derivatives; hydrazine derivatives; amines; polyurethanes; alkali metal and alkaline earth metal salts of higher fatty acids, such as calcium stearate, calcium stearoyl lactylate, calcium lactate, zinc stearate, magnesium stearate, sodium ricinoleate, and potassium palmitate; antimony pyrocatechol or zinc pyrocatechol, including neutralizing agents such as hydrotalcite and synthetic hydrotalcite; and lithium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, and aluminum hydroxide. Hydrotalcite that can be used in embodiments of the invention may include hydrotalcite under the common trade name DHT-4. ® (A, C, or V), ZHT-4V ® HYCITE ® 713 and AC-207™ are commercially available materials.

[0065] Non-limiting examples of nucleating agents may include sodium salts of 4-tert-butylbenzoic acid; adipic acid; diphenylacetic acid; methylene bis-2,4-dibutylphenyl; cyclic phosphates; sorbitol tri-benzaldehyde acetal; and sodium salts of bis(2,4-di-tert-butylphenyl) phosphate or ethylene bis(2,4-di-tert-butylphenyl) phosphate. Nucleating agents can improve the stiffness of rotationally molded parts.

[0066] In some implementations, a lubricant may be used. Non-limiting examples of lubricants may include oleamide, erucamide, stearamide, and betaine.

[0067] In some respects, metal passivators can be used. Non-limiting examples of metal passivators may include N,N'-diphenyloxalate diamide, N-salicylidene-N'-salicylate, N,N'-bissalicylate, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-2-hydrazine, salicylamino-1,2,4-triazole, and bisbenzylidene-oxalate dihydrazine.

[0068] Non-limiting examples of polyamide stabilizers include combinations of copper salts with iodides and / or phosphorus compounds, and divalent manganese salts.

[0069] Other additives may include plasticizers, epoxidized vegetable oils (such as epoxidized soybean oil), lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, foaming agents, and thiosynergists, such as dilauryl thiodipropionate or distearate thiodipropionate.

[0070] Non-limiting examples of fillers and reinforcing agents may include calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and metal hydroxides, carbon black, and graphite. If present, in some embodiments of the invention, the amount of filler incorporated into the thermoplastic polyolefin (e.g., linear polyethylene) may be up to about 50% by weight, or up to about 30% by weight, or up to about 20% by weight, or up to about 10% by weight (based on the weight of the thermoplastic polyolefin).

[0071] B. Methods for preparing polymer compositions The polymer compositions of the present invention can be prepared using known compounding methods. For example, all components can be dry-blended in a suitable apparatus (e.g., a roller mixer) at the desired weight ratio. The resulting dry blend can then be melt-blended in a suitable compounding apparatus (e.g., an extruder). In another example, a masterbatch can be prepared using some polyolefins and other components. The masterbatch can then be fed into an extruder and melt-blended. In yet another example, the dry components of the blend can be directly metered into the extruder.

[0072] Extruders for thermoplastic polyolefins and the extrusion processes employing these extruders are well known to those skilled in the art. A typical extruder contains one (or two) threaded screws rotating within a drum or “barrel.” The polyolefin can be sheared between the barrel and the screw by the stress generated by the rotation of the screw. Additionally, the barrel of the extruder can be heated. Shearing and / or heat cause the plastic to melt, and the action of the threaded screw conveys it along the length of the extruder. The molten polyolefin composition extrudate can then be forced through a die to form the desired plastic part. The extruder used for the final extrusion can also be a single-screw extruder or a twin-screw extruder. The die can be a slit die or an annular die that extrudes a film of the polymer blend around stable air bubbles. The film may collapse after passing over or around the bubbles.

[0073] In methods involving extruders, the extruder can be a twin-screw extruder or a single-screw extruder. If it is a twin-screw extruder, it can operate in a co-rotation mode (i.e., both screws rotate in the same direction) or a counter-rotation mode (i.e., the screws rotate in opposite directions). The specific operating conditions of any extruder will differ from those of any other extruder. Differences between machines can usually be resolved through non-creative testing. An extruder can extrude a polymer composition as a filament, then cool and cut it into pellets for subsequent use (typically for film extrusion).

[0074] Regarding polyolefin compounding, conditions may include temperature and pressure. Temperature may range from 180°C to 275°C, or be 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, or 275°C, or any value or range between them. Depending on the compounding method, pressure may range from 0.1 MPa to 10 MPa, or be 0.1 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, or 10 MPa, or any value or range between them.

[0075] For membrane applications, and in some respects, pigments or fillers can be extruded, which can produce transparent or relatively transparent films. In other applications such as wires and cables (electrical cables or optical fibers), polymer compositions may contain pigments / fillers (e.g., carbon black) and other auxiliaries.

[0076] C. Articles containing polymer compositions The polymer compositions of the present invention can be molded into a wide variety of articles and shapes using a variety of methods (e.g., injection molding, extrusion, rotational molding, foam molding, calendering, blow molding, blown film molding, thermoforming, compaction, melt spinning, etc.). Non-limiting examples of articles include consumer articles, packaging products, pharmaceutical containers, bottles, caps, shells, liners, garbage bags, food packaging films and / or materials, laminates, toys, tanks, wire sheaths, cable sheaths, pipes, hoses, or fittings. In some embodiments, the articles may include printed or written graphics, text, etc. In some preferred aspects, the polymer compositions may be molded into blown films.

[0077] Additional non-limiting examples of articles that can be prepared from the polymer compositions of the present invention include exterior and / or interior components (e.g., panels, rear fenders, door sills, trim pieces, fenders, doors, trunk lids, rear trunk lids, hoods, valve covers, roofs, bumpers, dashboards, grilles, rearview mirror housings, pillar decals, cladding, body side moldings, wheel covers, wheel hubcaps, door handles, spoilers, window frames, headlight bezels, headlights, taillights, taillights, taillight exteriors) for transport vehicles (e.g., aircraft, automobiles, trucks, military vehicles (including automobiles, aircraft, and water vehicles), scooters, and motorcycles). Shells, taillight bezels, license plate housings, roof racks and steps; housings, enclosures, panels and components for outdoor vehicles and equipment; housings for electrical and telecommunications equipment; outdoor furniture; aircraft components; marine and marine equipment, including trim pieces, shells and enclosures, outboard motor housings, depth sounder housings, personal watercraft; motorboats; swimming pools; spas; hot tubs; steps; step coverings; architectural and construction applications such as glass fittings, roofs, windows, floors, decorative window coverings or treatments; treated glass covers for pictures, paintings, posters and similar display items; wall panels and doors; Countertops; protected graphics; outdoor and indoor signage; housings, enclosures, panels, and components for ATMs; computers; desktop computers; portable computers; laptops; PDA housings; monitors; printers; keyboards; fax machines; copiers; telephones; telephone bezels; mobile phones; radio transmitters; radio receivers; housings, enclosures, panels, and components for lawn and garden tractors, mowers, and tools (including lawn and garden tools); window and door coverings; sports equipment and toys; housings, enclosures, panels, and components for snowmobiles; recreational vehicle panels and... Components; sports field equipment; shoelaces; container lids; articles made from plastic-wood assemblies; golf course markings; utility pit covers; lamps; lighting fixtures; network interface equipment housings; transformer housings; air conditioner housings; cladding or seats for public transportation; cladding or seats for trains, subways, or buses; instrument housings; antenna housings; cladding for satellite antennas; coated helmets and personal protective equipment; coated synthetic or natural textiles; coated painted articles; coated dyed articles; coated fluorescent articles; coated foam articles; and similar applications.

[0078] Additionally, polymer compositions (with or without additives) can be molded into films or sheets, as well as assemblies of stacked polymer materials (e.g., laminates). Sheets can be foam sheets, paper sheets, or fabric sheets. Articles include, for example, fibers, sheets, films, multilayer sheets, multilayer films, molded parts, extruded profiles, coated parts and foams, windows, luggage racks, wall panels, chair parts, lighting panels, diffusers, shading, partitions, lenses, skylights, lighting fixtures, reflectors, piping systems, cable trays, conduits, pipes, cable ties, wire coatings, electrical connectors, air handling units, fans, louvers, insulators, boxes, storage containers, doors, hinges, handles, sinks, mirror housings, mirrors, toilet seats, coat hangers, coat hooks, shelves, ladders, handrails, steps, trolleys, trays, cookware, catering equipment, communication equipment, and instrument panels.

[0079] D. Example The invention will be described in more detail by way of specific embodiments. The following embodiments are provided for illustrative purposes only and are not intended to limit the invention in any way. Those skilled in the art will readily recognize that various non-critical parameters can be varied or modified to obtain substantially the same results.

[0080] 1. Example 1 (Preparation of the polymer composition of the present invention and the comparative composition) Under the conditions listed in Table 2, the polymer compositions (N1, N2, N3, and N4) and comparative compositions (C1 and C2) of the present invention were prepared by melt-blending the components listed in Table 1 using a Listritz twin-screw granulator. The resin used was octene LLDPE VPsK914 (MI2 = 0.85 g / 10 min; density = 0.914 g / cm³). 3 ).

[0081] Table 1 Table 2 2. Example 2 (Melt fracture removal test of the composition of the present invention and the comparative composition) Melt breakage removal tests were conducted on a Little Macro blown film production line using the processing conditions listed in Table 3. The effectiveness of adding polyamide (e.g., nylon 6, nylon 6 / 6,6) as a polymer processing aid (PPA) in removing melt defects from the extrudate was determined using a single-layer blown film production line equipped with a 3-inch diameter die (manufactured by MacroEngineering & Technology Inc., headquartered in Ontario, CA). The 3-inch Macro blown film production line has a standard output greater than 60 psi and is equipped with a 15 hp motor. The feed screw has a diameter of 1.5 inches and a length / diameter (L / D) ratio of 24 / 1. The feed screw is a barrier design and has a mixing element at the screw end. The film bubble is air-cooled using cold air, and the production line is operated at a blow-up ratio (BUR) between 2 / 1 and 4 / 1. The blown film production line is equipped with a 3-inch diameter annular die and mandrel, resulting in a die clearance of 35 mils for the experiments. Two mandrels were used, resulting in a mandrel gap of 35 mils for the experiment.

[0082] Table 3 Before adding the target thermoplastic composition, the blown film production line was purged with a resin containing 30-40% diatomaceous earth (containing no polymer processing aids) to clean the die head through abrasion. After purging, PPA-free LLDPE with a melt index of 0.8 g / 10 min was introduced to produce an extruder with 100% hard melt fracture across the entire film width (e.g., producing a film with severe surface defects resembling sharkskin). Next, the target thermoplastic composition was introduced, and this point was recorded as time zero. The target thermoplastic composition was extruded under constant conditions, and extruded film samples were collected every ten minutes to measure melt fracture defects as a percentage of the sample width. The melt extrusion process for each experiment lasted 80 minutes, and the melt fracture percentage was recorded at ten-minute intervals. When the melt fracture percentage reached zero, the thermoplastic composition extruder was considered to have cleared melt fracture. Melt fracture clearance data were displayed on... Figure 1 Table 4 lists the... Figure 1 The percentage of melt fracture shown is for each sample. C1 does not contain PPA, C2 contains a fluoropolymer, N1 contains a mixture of PEG and polycaprolactam, N2 contains polycaprolactam, N3 contains a mixture of PEG and high-viscosity polyamide 6 / 6,6 copolymer, and N4 contains high-viscosity polyamide 6 / 6,6 copolymer as PPA. Figure 1 The data in Table 4 demonstrate that the invention examples (N1, N2, N3 and N4) remove blown film (melt fracture) faster than conventional fluorine-based PPA (C2).

[0083] Table 4 While the embodiments and advantages of this application have been described in detail, it should be understood that various changes, substitutions, and modifications can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Furthermore, the scope of this application is not intended to be limited to the specific embodiments of the processes, machines, manufactures, compositions of matter, tools, methods, or steps described in the specification. As will be readily apparent to those skilled in the art from the foregoing disclosure, existing or future-developed processes, machines, manufactures, compositions of matter, tools, methods, or steps that perform substantially the same function or achieve substantially the same results as the corresponding embodiments described herein can be implemented using the corresponding embodiments described herein. Therefore, the appended claims are intended to include such processes, machines, manufactures, compositions of matter, tools, methods, or steps within their scope.

[0084] Industrial applicability Polyamides are used as polymer processing aids to improve the melt extrusion of polyolefins.

Claims

1. A polymer composition comprising: a polyolefin polymer; and 100 ppm to 10,000 ppm of a polyamide; wherein the composition is substantially free of a polyolefin polymer / polyamide compatibilizer.

2. The polymer composition of claim 1, wherein the polyolefin polymer is polyethylene.

3. The polymer composition of claim 2, wherein the polyethylene polymer is a copolymer of ethylene and at least one alpha-olefin selected from 1-butene, 1-hexene, methyl-1- pentene, or 1-octene.

4. The polymer composition of any of claims 2-3, wherein the polyethylene polymer has a melt index (Ml2) of 0.1 to 10 g / 10 min and a density of 0.88 to 0.970 g / cm 3 3. The polymer composition of any of claims 2-3, wherein the polyethylene polymer has a melt index (Ml2) of 0.1 to 10 g / 10 min and a density of 0.93 to 0.970 g / cm 3 3. The polymer composition of any of claims 2-3, wherein the polyethylene polymer has a melt index (Ml2) of 0.1 to 10 g / 10 min and a density of 0.93 to 0.970 g / cm 3 3. The polymer composition of any of claims 2-3, wherein the polyethylene polymer has a melt index (Ml2) of 0.1 to 10 g / 10 min and a density of 0.93 to 0.970 g / cm 5. The polymer composition of any one of claims 1-4, wherein the polyolefin polymer is a linear low density polyethylene (LLDPE).

6. The polymer composition of claim 5, wherein the LLDPE has an Ml2 of 0.85 g / 10 min and a density of 0.914 g / cm3. 3 of 0.914 g / cm3.

7. The polymer composition of any one of claims 1-6, wherein the polyamide comprises polycaprolactam.

8. The polymer composition of claim 7, wherein the polyamide is a polyamide 6 homopolymer.

9. The polymer composition of claim 7, wherein the polyamide is a polyamide 6 / 6,6 copolymer.

10. The polymer composition of any one of claims 1-9, wherein the polymer composition is free, substantially free, or contains less than 100 ppm of one or more fluorine-based polymer processing aids.

11. The polymer composition of claim 10, wherein the one or more fluorine-based polymer processing aids is polyvinylidene fluoride, vinylidene-hexafluoropropylene copolymer, or a combination thereof.

12. The polymer composition of any one of claims 1-11, further comprising 100 ppm to 1 wt.% of a polyethylene glycol.

13. The polymer composition of any one of claims 1-12, further comprising an antioxidant, an ultraviolet stabilizer, or both.

14. The polymer composition of any one of claims 1-13, wherein the polymer composition comprises, based on the total weight of the polymer composition: 98 wt.% to 99.9 wt.% of the polyolefin polymer, 200 to 2,000 ppm of a polyamide, and 0 to 1 wt.% of an additive; 99 wt.% to 99.9 wt.% of the polyolefin polymer, 500 to 1,000 ppm of a polyamide, and 0 to 1 wt.% of an additive; or 99.5 wt.% to 99.9 wt.% of the polyolefin polymer, 600 to 800 ppm of a polyamide, and 0 to 1 wt.% of an additive.

15. The polymer composition of any one of claims 1-14, wherein the weight average molecular weight Mw of the polyolefin polymer is greater than 2,500 g / mol (Da) - 250,000 g / mol (Da). W 250,000 g / mol (Da).

16. The polymer composition of any one of claims 1-15, wherein the polymer composition has a time to clear a melt fracture of less than 50 minutes as measured on a blown film line.

17. The polymer composition of any one of claims 1-16, wherein the polymer composition is in the form of a pellet, a powder, a molded part, or a film.

18. The polymer composition of any one of claims 1-17, wherein the polymer composition is an extruded article, an injection molded article, a compression molded article, a rotational molded article, a blow molded article, an injection blow molded article, a 3-D printed article, a thermoformed article, a foamed article, a blown film, a cast film, or a writable film.

19. The polymer composition of any one of claims 1-18, wherein the polyolefin polymer / polyamide compatibilizer comprises a maleic anhydride, a polyethylene maleic anhydride, a grafted polypropylene, a maleic anhydride grafted polypropylene, a maleic anhydride ethylene, a copolymer of a polyolefin linked to a polar polymer, or a combination thereof.

20. The polymer composition of any one of claims 1-19, wherein the polymer composition comprises, based on the total weight of the polymer composition: 0-2 wt.% of the polyolefin polymer / polyamide compatibilizer; 0-1 wt.% of the polyolefin polymer / polyamide compatibilizer; or 0-0.1 wt.% of the polyolefin polymer / polyamide compatibilizer.

21. A method of making the polymer composition of any one of claims 1-20, the method comprising: (a) melt compounding the polyolefin polymer and the polyamide to produce a mixture; and (b) extruding the mixture to obtain the polymer composition.

22. The method of claim 21, wherein: the polyolefin polymer is a polyethylene; the polyamide comprises a polycaprolactam; and the extruding comprises a blown film extrusion process conducted at a temperature of 180 °C to 275 °C.

23. A method of reducing melt fracture in an extruded polymer composition, the method comprising adding 100 ppm to 10,000 ppm of a polyamide to a polyolefin polymer, and then extruding the resulting polymer composition, wherein the polymer composition is substantially free of a polyolefin / polyamide compatibilizer.

24. A polyethylene resin composition comprising: (a) 89 wt.% to 99 wt.% of a polyethylene; (b) 1.0 wt.% to 1.0 wt.% of a polyamide; and (c) 0 wt.% to 1.0 wt.% of an additive; wherein the polyethylene resin composition is substantially free of a polyolefin polymer / polyamide compatibilizer.

25. The polyethylene resin composition of claim 24, wherein the polyethylene resin composition is free, substantially free, or contains less than 100 ppm of one or more fluorine-based polymeric processing aids.

26. The polymer composition of claim 25, wherein the one or more fluorine-based polymeric processing aids is a polyvinylidene fluoride, a vinylidene-hexafluoropropylene copolymer, or a combination thereof.

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