Non-fluorinated polymer processing aid

Abstract

A polymer composition comprising a polyolefin polymer and 100 ppm to 10,000 ppm of polyamide, as well as a method for producing the same and a method for using the same, are disclosed. This composition may be substantially free of polyolefin polymer / polyamide compatibilizers.

Description

[Technical Field]

[0001] The present 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 free of fluorinated PPAs. These compositions may have improved melt-fracture properties compared to compositions containing fluorinated PPAs. [Background technology]

[0002] Extruded polymers (e.g., blown polyethylene films) may exhibit surface defects that resemble sharkskin, snakeskin, and / or orange peel. These surface defects are typically referred to as "melt fractures." Melt fractures in extruded polymer compositions can cause reduced physical properties, a dull appearance, printing problems, and / or sealing problems in the resulting articles. Melt fractures are thought to occur when the shear rate on the surface of the polymer composition becomes high enough that the surface of the polymer composition begins to fracture. In other words, the surface of the extruded polymer composition is slippery relative to the body of the polymer composition. This surface generally cannot flow fast enough to keep up with the body of the extruder, causing the molten material to fracture, and consequently impairing the surface properties of the extruded polymer. Melt fractures are thought to occur due to friction on the extruder surface, which creates a velocity gradient in the polymer composition within the extruder. This velocity gradient leads to a "slip-stick" phenomenon as the molten material exits the die, causing surface inhomogeneity and melt fracture.

[0003] The current solution to prevent melt fracture is to use low concentrations (about 0.1 wt%) of high molecular weight fluorine-containing compounds (e.g., fluoropolymer copolymers or fluoroelastomer copolymers of vinylidene difluoride and hexafluoropropylene). These additives coat the surfaces of the extruder and die to prevent adhesion and allow for a significant increase in processing speed to avoid melt fracture.

[0004] Attempts have been made to use PPAs other than fluorine-containing additives, but the use of these PPAs is complex, costly, and / or may still cause melt-fraction problems. For example, U.S. Patent Application Publication 2023 / 0031000 by Ruocco et al. describes a PPA blended with polyethylene glycol, a surfactant containing sorbitan ester or polysorbate, and at least two of a fatty acid metal salt. Such blends can be costly, and introducing numerous components into a polymer resin can affect the resin's properties. Another example is U.S. Patent Application Publication 2023 / 0036922 by Leaf et al., which discloses the use of a polyethylene glycol (PEG)-based polymer processing aid. Compared to fluorine-containing PPAs, PEG may result in relatively slower removal of melt fractions. [Overview of the project]

[0005] Discoveries have been made that provide solutions to at least one problem related to the replacement of fluorine-containing PPA and the reduction of melt-fracture problems in extruded polyolefin compositions. In one embodiment, the solution may include using polyamide (e.g., polylactams such as nylon-based polylactams) as PPA. It has been found that the use of polyamide can improve melt-fracture properties (reduce melt-fracture problems) compared to fluorine-containing PPA (e.g., high molecular weight fluoropolymer copolymers or fluoroelastomer copolymers of vinylidene difluoride and hexafluoropropylene). In a non-limiting example, it has been found that the use of polyamide 6 homopolymer (nylon 6) in linear low-density polyethylene (LLDPE) based compositions exhibits superior performance compared to known fluorine-containing PPAs in reducing melt-fracture problems when the composition is extruded into an inflation film. In another non-limiting example, it has been discovered that when polyamide 6 / 6,6 copolymer (nylon 6 / 6,6) is used in linear low-density polyethylene (LLDPE)-based compositions, it exhibits superior performance compared to known fluorine-containing PPAs in reducing melt-fraction problems when the composition is extruded into an inflation film. This discovery could be environmentally beneficial, for example, by providing an effective alternative to using fluorine-containing PPAs in polyolefin compositions. It is also advantageous in further reducing melt-fracture problems in extruded polymer compositions. In one aspect of the present invention, the polyolefin composition of the present invention is substantially free of or may be free of fluorine-containing PPAs and / or compounds, and exhibits minimal or no melt-fracture problems when extruded (e.g., into an inflation film).

[0006] It has also been discovered that the polymer compositions of the present invention can maintain improved melt-fracture properties even if they are substantially free of (e.g., 2% by weight or less, 1% by weight or less, 0.5% by weight or less, 0.1% by weight or less, or 0.01% by weight or less) or free of polyolefin polymer / polyamide (e.g., polylactam) compatibilizers (e.g., maleic anhydride-containing compounds and / or polymers or copolymers of polyolefins bonded to polar polymers). This discovery is advantageous in that, for example, polyamide (or a combination of polyamides) can be used as a single PPA, thereby reducing the melt-fracture problem. This can reduce the cost and / or complexity of the resulting polymer composition.

[0007] One aspect of the present invention describes a polymer composition. The polymer composition may include a polyolefin polymer and 100 ppm to 10,000 ppm of polyamide (e.g., a polylactam such as a nylon-based polymer). The polymer composition may contain fluorine-containing PPA (e.g., a high molecular weight fluoropolymer or fluoroelastomer copolymer of vinylidene difluoride and hexafluoropropylene) at a concentration of parts per million (ppm), or substantially none (e.g., less than 50 ppm, preferably less than 40, 30, 20, 10, 5, 4, 3, 2, or 1 ppm), or may not contain fluorine-containing PPA (e.g., a high molecular weight fluoropolymer or fluoroelastomer copolymer of vinylidene difluoride and hexafluoropropylene), or may not contain fluorine-containing PPA (0% by weight). The polymer composition may be substantially free (e.g., 2% by weight or less, 1% by weight or less, 0.5% by weight or less, 0.1% by weight or less, or 0.01% by weight or less) or free (0% by weight) of polyolefin polymer / polyamide compatibilizers (e.g., maleic anhydride, polyethylene maleic anhydride, grafted polypropylene, maleic anhydride grafted polypropylene, ethylene maleic anhydride, copolymers of polyolefins bonded to polar polymers, or combinations thereof). In some embodiments, the polymer composition may contain 100 ppm to 1% by weight of polyethylene glycol and additives (e.g., antioxidants, UV stabilizers, or both). In some specific embodiments, the polymer composition may include (1) 98% to 99.9% by weight of a polyolefin polymer, 200 to 2,000 ppm of polyamide, and 0 to 1% by weight of additives; (2) 99% to 99.9% by weight of a polyolefin polymer, 500 to 1,000 ppm of polyamide, and 0 to 1% by weight of additives; or (3) 99.5% to 99.9% by weight of a polyolefin polymer, 600 to 800 ppm of polyamide, and 0 to 1% by weight of additives. The polymer composition may be substantially free of (e.g., 2% by weight or less) or free of polyolefin polymer / polyamide compatibilizers. The polymer composition of the present invention has a weight-average molecular weight M greater than 2,500 g / mol(Da) and between 250,000 g / mol(Da). wIt may have the following characteristics. In some embodiments, the polymer composition may have a time of less than 50 minutes for removing melt fractures when measured on an inflation film line. In one example, melt fractures can be measured using a Little Macro inflation film line, as described in Example 2. The polymer composition of the present invention may take the form of pellets, powders, molded parts, or films. In some embodiments, the polymer composition may be 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 3D printed article, a thermoformed article, a foamed article, an inflation film, a cast film, or a writable film. In particular, the polymer composition may be free of, substantially free of, or contain less than 100 ppm of fluorine-based compounds. Non-limiting examples of fluorine-based compounds include fluoropolymers, fluoroelastomers, or combinations thereof.

[0008] In some embodiments, polyolefins may include polyethylene. Polyethylene can be a copolymer of ethylene and at least one alpha-olefin selected from 1-butene, 1-hexene, 4-methyl-1-pentene, or 1-octene. In some embodiments, polyethylene has a melt index (MI2) of 0.1 to 10 g / 10 min and a density of 0.88 to 0.970 g / cm³. 3 Alternatively, the melt index (MI2) is 0.1-10 grams / 10 minutes, and the density is 0.93-0.970 g / cm³. 3 Either the melt index (MI2) is 0.1 to 10 grams / 10 minutes and the density is 0.88 to 0.94 g / cm³. 3 It can be. In one aspect of the present invention, the polyolefin can be linear low-density polyethylene (LLDPE). LLDPE has a MI2 of 0.85 g / 10 and 0.913 g / cm³ 3 It can have a density of 0.85 g / 10 min MI2 and 0.914 g / cm³. LLDPE has a density of 0.85 g / 10 min MI2 and 0.914 g / cm³. 3It can have a density of . In one aspect of the present invention, the polyamide may include a polylactam such as a polycaprolactam homopolymer (e.g., polyamide 6 homopolymer (nylon 6)). In one aspect of the present invention, the polyamide may include a polylactam comprising a polylactam copolymer such as a polycaprolactam copolymer (e.g., polyamide 6 / 6,6 copolymer (nylon 6 / 6,6)). The polyolefin / polyamide compatibilizer may be present in an amount of 0% to less than 1% by weight, preferably 0% to less than 0.1% by weight, and more preferably 0% to less than 0.01% by weight, based on the total weight of the polyolefin composition.

[0009] Methods for producing polymer compositions are also described. These methods may include melt-compounding polyolefins (e.g., polyethylene) and polyamides (e.g., polylactams such as polycaprolactam) to produce a mixture. This mixture can then be extruded to obtain the polymer composition. Examples of extrusion include an inflation film extrusion process at temperatures between 180°C and 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 before extruding the composition. The composition may be substantially free of polyolefin / polyamide compatibilizers and / or fluorine-containing compounds.

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

[0012] Other embodiments of the present invention will be described throughout this application. Any embodiment described in relation to one aspect of the present invention is applicable to other aspects of the present invention, and vice versa. Each embodiment described herein is understood to be an embodiment of the present invention that is applicable to other aspects of the present invention. Any embodiment or aspect described herein can be combined with any other embodiment or aspect described herein and / or can be implemented with respect to any method or composition of the present invention, and vice versa. Furthermore, the compositions of the present invention can be used to achieve the methods of the present invention.

[0013] The definitions of various terms and phrases used throughout this specification are given below.

[0014] The term "masterbatch" refers to a mixture in which a polyamide, an additive, or a combination thereof is concentrated in a polyolefin carrier.

[0015] The terms "about" or "approximately" are defined as being close to what a person skilled in the art would understand. In a non-limiting embodiment, these terms are defined as being 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 molar percentage of a component based on the total weight, total volume, or total number of moles of the material containing the component, respectively. In a non-limiting example, 10 grams of a component in 100 grams of material is 10 wt% of the component.

[0017] The terms "inhibit", "reduce", "prevent", "avoid", or any variations of these terms, when used in the claims and / or the specification, include any measurable decrease or complete inhibition to achieve the desired result.

[0018] The term "effective", when used in this specification and / or the claims, means being sufficient to achieve the desired, expected, or intended result.

[0019] The use of the word "a" or "an", when combined with any of the terms "comprising", "including", "containing", "having" in the claims or this specification, may mean "one", but is also consistent with the meanings of "one or more", "at least one", "a plurality".

[0020] The terms "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, unrecited elements or method steps (operations).

[0021] The polymer compositions of the present invention can "comprise", "consist essentially of", or "consist of" the specific components, constituents, compositions, etc. disclosed throughout this specification. With respect to the transitional phrase "consist essentially of", in one non-limiting aspect, the basic and novel features of the polymer compositions of the present invention can include, as a polymer processing aid, a polyamide (e.g., a polyamide such as a polycaprolactam-based polymer such as a polyamide 6 homopolymer (nylon 6) or a polyamide 6 / 6,6 copolymer (nylon 6 / 6,6)), and can be substantially free of, or free of, a fluorinated polymer processing aid. The compositions of the present invention can have improved melt fracture properties compared to polymer compositions containing a fluorinated polymer processing aid.

[0022] Other objects, features, and advantages of the present invention will become apparent from the following figures, detailed description, and examples. However, it should be understood that the figures, detailed description, and examples, while illustrating specific embodiments of the present invention, are for illustrative purposes only and are not intended to limit it. Furthermore, changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features of a particular embodiment can be combined with features of other embodiments. For example, features of one embodiment can be combined with any of the features of other embodiments. In further embodiments, additional features can be added to the particular embodiments described herein.

[0023] The advantages of the present invention will become apparent to those skilled in the art by referring to the following detailed description and accompanying drawings. [Brief explanation of the drawing]

[0024] [Figure 1] Figure 1 shows melt fracture removal data in the Little Macro inflation film line. C1 is a resin without processing aids (gray diamond). C2 is a comparative fluoropolymer (black square). N1 is non-limiting formulation 1 of the present invention (dashed line, black circle). N2 is non-limiting formulation 2 of the present invention (dashed line, gray square). N3 is non-limiting formulation 3 of the present invention (gray triangle). N4 is non-limiting formulation 4 of the present invention (dashed line, black plus sign). The present invention is subject to various modifications and alternative forms, but specific embodiments are shown as examples in the drawings. The drawings may not be to scale. [Modes for carrying out the invention]

[0025] Discoveries have been made that can provide solutions to at least one or more problems that may be associated with using fluorine-based polyolefin processing aids in polyolefin compositions. In one aspect, as a polymer processing aid, polyamide (e.g., nylon-based polymers (e.g., nylon 6, or nylon 6 / 6,6)) can be used, and it has been discovered that it can have better melt fracture properties compared to fluorine-based polyolefin processing aids. Thereby, the polymer compositions of the present invention can be substantially free of (e.g., less than 100 ppm based on the weight of the polymer composition) or free (0 wt%) of fluorine-based polymer processing aids.

[0026] These and other non-limiting aspects of the present invention will be described in more detail in the following sections.

[0027] <A. Polymer Composition> The polymer composition of the present invention may include a polyolefin polymer and a polyamide polymer processing aid. In some embodiments, the polymer composition of the present invention may include 98% to 99.9% by weight of polyolefin polymer, 100 to 10,000 ppm of polyamide, and 0 to 1% by weight of additives, based on the total weight of the polymer composition. In another embodiment, the polymer composition of the present invention may include 98% to 99.9% by weight of polyolefin polymer, 200 to 2,000 ppm of polyamide, and 0 to 1% by weight of additives. In yet another embodiment, the polymer composition may include 99% to 99.5% by weight of polyolefin polymer, 600 to 800 ppm of polyamide, and 0 to 1% by weight of additives. In other embodiments, the polymer composition of the present invention may include polyglycol. A polymer composition containing polyglycol may include 97% to 99.9% by weight of polyolefin polymer, 100 to 10,000 ppm of polyamide, 100 to 10,000 ppm of polyglycol, and 0 to 1% by weight of additives. In other embodiments, the polymer composition may include (1) 98% to 99.9% by weight of polyolefin polymer, 200 to 2,000 ppm of polyamide, and 0 to 1% by weight of additives; (2) 99% to 99.9% by weight of polyolefin polymer, 500 to 1,000 ppm of polyamide, and 0 to 1% by weight of additives; or (3) 99.5% to 99.9% by weight of polyolefin polymer, 600 to 800 ppm of polyamide, and 0 to 1% by weight of additives.

[0028] In another aspect of the present invention, the polymer composition comprises, based on the total weight of the polymer composition, 89% to 99.5% by weight (or any range or number therein, e.g., 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5% by weight) of polyolefin polymer, 1% to 10% by weight of polyamide, preferably 5% to 10% by weight (or any range or number therein, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10%), and 0% to 1% by weight of additives (or any range or number therein, e.g., 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1%).

[0029] The polymer composition of the present invention may be substantially free of polyolefin / polyamide compatibilizers (for example, 2% by weight or less, 1.5% by weight or less, 1% by weight or less, 0.5% by weight or less, 0.1% by weight or less, or 0.01% by weight or less) or may not contain any polyolefin / polyamide compatibilizers (0% by weight).

[0030] The polymer composition of the present invention may contain fluorine-containing PPA (e.g., a high molecular weight fluoropolymer or fluoroelastomer copolymer of vinylidene difluoride and hexafluoropropylene) in an amount of 1 part per million (ppm) or less, or substantially not contain it (e.g., 50 ppm or less, preferably 40, 30, 20, 10, 5, 4, 3, 2, or less than 1 ppm), or may not contain it at all (0% by weight).

[0031] The polymer composition of the present invention has a melt index (MI2) of 0.1 to 10 grams / 10 min (for example, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 grams / 10 min, or any range or value in between) and a density of 0.88 to 0.970 g / cm³. 3 (For example, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97 g / cm³) 3), or any value or range therebetween). In some specific embodiments, the polymer composition has a melt index (MI2) of 0.1 to 10 grams / 10 minutes and a density of 0.88 to 0.940 g / cm 3 .

[0032] The polymer composition of the present invention can be formed into various shapes and / or articles (e.g., pellets, powders, molded parts, films, etc.). The thickness of the film can be 0.001 mm to 1 mm, or 0.001, 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1 mm, or any value or range therebetween).

[0033] <1. Polyolefin Polymer> The polyolefin polymer of the present invention may be a thermoplastic polymer. Examples of polyolefins include those substituted with aromatic groups (e.g., styrene), unsubstituted polyolefins such as polyethylene, or copolymers such as ethylene alphaolefin copolymers. In some embodiments, the olefin polymer (or "polyolefin") may consist of at least 85% by weight of one or more C2-3 alphaolefins and up to 15% by weight of one or more C4-8 alphaolefins. Preferably, the polyolefin may contain at least 90% by weight of ethylene and up to 10% by weight of one or more C4-8 alphaolefins. Suitable C2-3 alpha olefins include ethylene and propylene. Suitable C4-8 alpha olefins include butene, 4-methylpentene, hexene, and octene. The amount of polyolefin in the polymer composition may be 97% to 99.9% by weight, or 97.1% by weight, 97.2% by weight, 97.3% by weight, 97.4% by weight, 97.5% by weight, 97.6% by weight, 97.7% by weight, 97.8% by weight, 97.9% by weight, 98% by weight, 98.1% by weight, 98.2% by weight, 98.3% by weight, 98.4% by weight, 98.5% by weight, 98.6% by weight, 98.7% by weight, 98.8% by weight, 98.9% by weight, 99% by weight, 99.1% by weight, 99.2% by weight, 99.3% by weight, 99.4% by weight, 99.5% by weight, 99.6% by weight, 99.7% by weight, 99.8% by weight, 99.9% by weight, or any range or value in between.

[0034] Polyolefins can be prepared by conventional processes. In the case of olefins substituted with aromatic groups such as styrene, the polymer can be polymerized by bulk polymerization initiated by thermal or free radical polymerization or by solution polymerization. In the case of unsubstituted olefin polymers, polymerization can be carried out in the gas phase, and 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 about 0.910 to 0.935 g / cc) can be produced. Polymerization in the gas phase involves contacting monomers and catalysts in a fluidized bed reactor under polymerization conditions. In some embodiments, polymerization conditions include pressures less than 3.4 MPa, preferably less than about 1.74 MPa, and temperatures less than 130°C. Polymerization can also be carried out in solution or as a slurry in the presence of a polymerization catalyst (e.g., coordination catalyst or metallocene catalyst). Solution polymerization conditions include atmospheric pressure or low pressure and temperatures of 130 to 250°C. In solution processes, ethylene and other comonomers can be dissolved in a solvent such as hexane in the presence of a coordination catalyst. Depending on the type of polymerization and the olefin, the weight-average molecular weight (Mw) of the olefin polymer may be up to 250,000, typically around 2,500 to 250,000 g / mol(Da). w This can be determined using methods known in the art. Non-limiting examples of standard methods for weight-average molecular weight include ASTM D6474, ASTM D40001, and ISO 16014.

[0035] The present invention is useful for thermoplastic polyolefins in general. In a preferred embodiment, the present invention can improve the extrudeability of linear polyethylene, particularly linear low-density polyethylene (LLDPE). LLDPE is a copolymer of ethylene and other copolymerizable alpha-olefins (e.g., butene, hexene, or octene). LLDPE can have a density of less than 0.955 grams / cubic centimeter. Other polyethylenes can also be used in the present invention (e.g., low-density polyethylene (LDPE) and high-density polyethylene (HDPE)).

[0036] Polyolefins can be characterized by their 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, 190°C. In some embodiments, the polyethylene used in the present invention has a melt index (MI2) of 0.1 to 10 grams / 10 min (e.g., 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 grams / 10 min, or any range or value between them) and a density of 0.88 to 0.970 g / cm³. 3 (For example, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97 g / cm³) 3 It can be any value or range between them. For example, polyethylene has a melt index (MI2) of 0.1 to 10 grams / 10 min and 0.93 to 0.970 g / cm³. 3 It can have a density of 0.1 to 10 grams / 10 min melt index (MI2) and 0.88 to 0.94 g / cm³. 3 It can have a density of 0.900 to 0.950 g / cm³. In some embodiments, LLDPE is used. The LLDPE of the present invention has a density of 0.900 to 0.950 g / cm³. 3 (For example, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95 g / cm³) 3 The MI2 can be 0.3 to 5.0 grams / 10 min (e.g., 0.3, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 grams / 10 min, or any range or value in between). In specific embodiments, LLDPE may have an MI2 of 0.80 to 0.9 g / 10 min and a density of 0.910 to 0.915 g / cm³. 3 Alternatively, the MI2 content is 0.85 g / 10 min, and the density is 0.913 g / cm³. 3Either MI2 is 0.85 g / 10 min and the density is 0.914 g / cm³. 3 The density of the polyolefin may be determined using ASTM D792-13 (November 1, 2013).

[0037] <2. Polyamide> The polymer composition of the present invention may include polyamides. Polyamides are polymers containing repeating amide (-CO-NH-) bonds. Polyamides are typically condensation copolymers formed by the reaction of dicarboxylic acids with diamines, or by ring-opening of lactams. Various polyamides can be produced by adjusting the number of carbon atoms.

[0038] In certain embodiments of the present invention, the polyamide may include polylactams such as polycaprolactams, which are a family of synthetic aliphatic thermoplastic resins produced by ring-opening polymerization of cyclic amides (lactams). Non-limiting examples of polylactams include nylon, which is a homopolymer, a binary homopolymer, or a copolymer thereof. Homopolymer polylactams have the following general formula [NH-(CH2) x -CO] n It can be expressed as follows, where x is 4 to 25 and n is the number of polymer repeats (e.g., 3 to 20). A binary homopolymer is represented by the general formula [NH-(CH2) x -NH-CO-(CH2) y -CO] n It can be expressed as follows, where x is between 4 and 12, y is between 4 and 12, and n is the number of polymer repeats (for example, 3 to 20).

[0039] Non-limiting examples of nylon (or polyamide) that can be used in the present invention include poly(4-aminobutyric acid) (nylon 4), poly(6-aminohexanoic acid) (nylon 6, also known as poly(caprolactam)), 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), and poly(hexamethylene sevacamide). Examples include poly(nylon 6,10), poly(heptamethylenepimeramide) (nylon 7,7), poly(octamethylenesveramide) (nylon 8,8), poly(hexamethyleneazeramide) (nylon 6,9), poly(nonamethyleneazeramide) (nylon 9,9), poly(decamethyleneazeramide) (nylon 10,9), poly(tetramethylenediamine-co-oxalic acid) (nylon 4,2), polyamide of n-dodecanediamine and hexamethylenediamine (nylon 6,12), and polyamide of dodecamethylenediamine and n-dodecanediamine (nylon 12,12). Non-limiting examples of polyamide copolymers that can be used in the present invention include caprolactam / hexamethylene adipamide copolymer (nylon 6,6 / 6), hexamethylene adipamide / caprolactam copolymer (nylon 6 / 6,6), trimethylene adipamide / hexamethylene azeraamide copolymer (nylon trimethyl 6,2 / 6,2), and hexamethylene adipamide-hexamethylene-azelaamide-caprolactam copolymer (nylon 6,6 / 6,9 / 6). In some preferred embodiments of the present invention, nylon 6, nylon 6,6, nylon 6 / 6,6, and mixtures thereof can be used. In certain embodiments, nylon 6 is preferred. In certain embodiments, nylon 6 / 6,6 is preferred. In certain embodiments, nylon 6,6 / 6 is preferred.

[0040] In one embodiment, the polyamide is a polyamide 6 homopolymer, also known as polycaprolactam or nylon 6.

[0041] In one embodiment, the polyamide is a polyamide 6 / 6,6 copolymer, also known as nylon 6 / 6,6.

[0042] In some embodiments, the polyamide has a melting point of 215°C to 225°C and a concentration of 1.0 to 1.5 g / cm³. 3 The density is preferably 1.1 to 1.2 g / cm³. 3 It can have a density of 1.0 to 1.5 g / cm³. In some embodiments, the polyamide has a melting point of 185°C to 215°C and a density of 1.0 to 1.5 g / cm³. 3 The density is preferably 1.1 to 1.2 g / cm³. 3 It can have a density of . Nylon is available from commercially available manufacturers. Non-exclusive 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).

[0043] The amount of polyamide (based on the total weight of the polymer composition) may be in the range of 100 to 10,000 ppm, or 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 in between. In a further embodiment, the amount of polyamide (e.g., polyamide containing a polylactam such as polycaprolactam) can be 700 ppm to 800 ppm, or about 750 ppm, based on the total weight of the polymer composition. In yet another embodiment, the amount of polyamide (e.g., polyamide containing a polylactam such as polycaprolactam) can be 1,250 ppm to 1,750 ppm, or about 1,500 ppm, based on the total weight of the polymer composition. In one embodiment, the amount of polyamide (e.g., polyamide containing a polylactam such as polycaprolactam) can 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.

[0044] In some embodiments of the present invention, the polymer composition may contain polyglycol as an additive that serves as an additional processing aid. In some embodiments, the weight-average molecular weight of the polyglycol is 2,000 g / mol to 50,000 g / mol, or 3,000 g / mol to 3,500 g / mol. Non-limiting examples of polyglycol include polyethylene glycol, PEG ethers, polypropylene glycol, polytetrahydrofuran, and mixtures thereof. Examples of PEG ethers include lauryl ether, cetearyl ether, cetyl ether, stearyl ether, oleyl ether, or mixtures thereof. A non-limiting example of suitable PEG is one commercially available from Clariant Ltd. under the trademark Polyglykol. The amount of polyglycol (based on the total weight of the polymer composition) can be in the range of 100 to 10,000 ppm, or 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 in between. In one embodiment, the amount of PEG can be 500 ppm to 2,500 ppm based on the total weight of the polymer composition. In one embodiment, the amount of PEG can be 700 ppm to 800 ppm, or about 750 ppm, based on the total weight of the polymer composition. The optimal addition level in a particular extrusion process can be easily determined by those skilled in the art.

[0045] <4. Polyolefin polymer / polyamide compatibilizer> The polyolefin-containing compositions of the present invention may contain, or be substantially free of, polyolefin polymer / polyamide compatibilizers (e.g., less than 2% by weight). In certain embodiments, the polyolefin-containing composition may contain, based on the total weight of the composition, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or less than or equal to 2% by weight of the polyolefin polymer / polyamide compatibilizer. In another embodiment, the polyolefin-containing composition contains 0% by weight of the polyolefin polymer / polyamide compatibilizer.

[0046] Examples of 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, ethylene maleic anhydride, and copolymers of polyolefins bonded to polar polymers. Non-limiting examples of compatibilizers are described in U.S. Patents 10, 100, and 140. Non-limiting examples of commercially available compatibilizers include those sold under the trademarks BYNEL® and RETAIN® (Dow Chemical, USA), NOVACOM-P® (Polygroup, USA), and LICOCENE® (Clariant Plastics & Coatings Ltd., USA).

[0047] <5. Additives> The polyolefin-containing composition 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, auxiliary stabilizers, nucleating agents, metal deactivators, slip agents, or mixtures thereof. The polymer composition may contain additives in amounts of 0 to 1% by weight, preferably 0.01% to 1% by weight, or between 0.01% and 1% by weight, or between 0.01% and less than 1% by weight, or between 0.5% and less than 1% by weight, or 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% by weight, or any range or value in between, based on the total weight of the composition.

[0048] Non-limiting examples of antioxidants include alkylated monophenols (also referred to herein as "hindered phenol 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-(alpha-methylcyclohexyl)-4,6-dimethylphenol; 2,6-di-octadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol; and 2,6-di-tert-butyl-4-methoxymethylphenol. Suitable hindered phenol antioxidants that can be used in embodiments of this disclosure are sold by BASF Corporation under the trademarks IRGANOX® 1010 (CAS Registry No. 6683-19-8) and IRGANOX 1076 (CAS Registry No. 2082-79-3).

[0049] In some embodiments, alkylated hydroquinones are used as antioxidants. Non-limiting examples of alkylated hydroquinones include 2,6-di-tert-butyl-4-methoxyphenol; 2,5-di-tert-butylhydroquinone; 2,5-di-tert-amyl-hydroquinone; and 2,6-diphenyl-4-octadecyloxyphenol.

[0050] Other non-limiting examples of antioxidants include thiodiphenyl ethers. Non-limiting examples of thiodiphenyl ethers include 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).

[0051] In embodiments of the present invention, alkylidenebisphenols are used as antioxidants. Non-limiting examples of alkylidenebisphenols include 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol); 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol); 2,2'-methylene-bis-(4-methyl-6-(alpha-methylcyclohexyl)phenol); 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol); 2,2'-methylene-bis-(6-nonyl-4-methylphenol); 2,2'-methylene-bis-(6- Nonyl-4-methylphenol); 2,2'-methylene-bis-(6-(alpha-methylbenzyl)-4-nonylphenol); 2,2'-methylene-bis-(6-(alpha,alpha-dimethylbenzyl)-4-nonylphenol); 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 Su-(6-tert-butyl-2-methylphenol); 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenol)butane, 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol; 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecylmercaptobutane; ethylene glycol-bis-(3, Examples include 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 monoacrylates of bisphenols, including ethylidenebis-2,4-di-t-butylphenol monoacrylate.

[0052] In certain embodiments, benzyl compounds can be used as antioxidants. 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) sulfide; isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate; bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol-terephthalate; 1,3,5-tris-(3,5-di-tert-butyl-4,10-hydroxybenzyl) isocyanurate; 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate; dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate; monoethyl Examples include the calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0053] Non-limiting examples of acylaminophenol antioxidants include 4-hydroxy-laurate anilide; 4-hydroxy-stearate 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.

[0054] Non-limiting examples of other antioxidants include esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols. Non-limiting examples of such compounds include methanol; diethylene glycol; octadecanol; triethylene glycol; 1,6-hexanediol; pentaerythritol; neopentyl glycol; tris-hydroxyethyl isocyanurate; tridiethylene glycol; and dihydroxyethyl oxalic acid diamide. In embodiments of the present disclosure, the primary antioxidant is selected from amides of beta-(3,5-di-tert-butyl-4-hydroxyphenol)-propionic acid, such as N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine; N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine; and N,N'-di(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

[0055] Other non-limiting examples of antioxidants include phosphates and phosphonites (also referred to herein as "phosphorus-containing secondary antioxidants"), e.g., triphenyl phosphite; diphenylalkyl phosphite; phenyl dialkyl phosphite; tris(nonylphenyl) phosphite [WESTON® 399, available from SI Group]; phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters [WESTON 705, CAS Registry No. 939402-02-5, SI Group]. Available from Group]; Trilauryl phosphite; Trioctadecyl phosphite; Distearyl 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"-nitrilo[triethyltris(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 tristearyl sorbitol triphosphite; Tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphonate; 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepine [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 Examples include S9228-CT] and the commercially available diphosphonate P-EPQ® (CAS Registry No. 119345-01-06); or mixtures thereof. In embodiments of this disclosure, the secondary antioxidant is selected from DOVERPHOS LGP-11, DOVERPHOS LGP-12, and DOVERPHOS LGP-12LV. In some embodiments, alkylphenol-free polymer polyphosphites can be used. Non-limiting examples are disclosed in U.S. Patent No. 8,563,637.

[0056] Antioxidants also include hydroxylamines and amine oxides. Non-limiting examples of hydroxylamines and amine oxides include N,N-dibenzylhydroxylamine; N,N-diethylhydroxylamine; N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N-ditetradecylhydroxylamine; N,N-dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine; N-hexadecyl-N-octadecylhydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; and N,N-dialkylhydroxylamines derived from hydrogenated tallowamines. Similar amine oxides are also suitable. A commercially available hydroxylamine usable in embodiments of this disclosure is N,N-di(alkyl)hydroxylamine, sold as IRGASTAB® 042 (manufactured by BASF), which has been reported to be prepared by direct oxidation of N,N-di(hydrogenated) tallowamine.

[0057] In embodiments, examples of antioxidants include nitrones. Non-limiting examples of nitrones include 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; and nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallowamines.

[0058] Non-limiting examples of UV absorbers and / or light stabilizers include 2-(2'-hydroxyphenyl)-benzotriazole, e.g., 5'-methyl-;3'5'-di-tert-butyl-;5'-tert-butyl-;5'(1,1,3,3-tetramethylbutyl)-;5-chloro-3',5'-di-tert-butyl-;5-chloro-3'-tert-butyl-5'-methyl-;3'-sec-butyl-5'-tert-butyl-;4'-octoxy,3',5'-ditert-amyl-; and 3',5'-bis-(alpha,alpha-dimethylbenzyl)-derivatives.

[0059] Other UV absorbers or light stabilizers include 2-hydroxybenzophenone. Non-limiting examples of benzophenones include 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy-, and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0060] In some embodiments, sterically hindered amines can be used as UV absorbers or light stabilizers. Non-limiting examples of sterically hindered amines include bis(2,2,6,6-tetramethylpiperidyl)-sebacate; bis-5(1,2,2,6,6-pentamethylpiperidyl)-sebacate; n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate bis(1,2,2,6,6-pentamethylpiperidyl) ester; condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid; N,N'-(2,2 Examples include the condensation product of 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-butanetetracarboxylic acid; and 1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinon). These amines are typically called HALS (Hindered Amines Light Stabilizing) and include 2,2,6,6-tetramethylpiperidinol ester of butanetetracarboxylic acid. Such amines also include hydroxylamines derived from hindered amines. For example, these include di(1-hydroxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate; 1-hydroxy-2,2,6,6-tetramethyl-4-benzoxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-piperidine; and N-(1-hydroxy-2,2,6,6-tetramethyl-piperidine-4-yl)-ε-caprolactam.Suitable commercially available HALS for use in the embodiments of this disclosure include those sold by BASF under the trademarks CHIMASSORB® 119; CHIMASSORB 944; CHIMASSORB 2020; TINUVIN® 622 and TINUVIN 770, and those sold by Solvay under the trademarks CYASORB® UV3346, CYASORB UV3529, CYASORB UV4801 and CYASORB UV4802. In other embodiments, the use of mixtures of two or more HALS may also be considered.

[0061] Other examples of UV absorbers or light stabilizers include substituted and unsubstituted benzoic acid. Non-limiting examples of benzoic acid include phenyl salicylate; 4-tert-butylphenyl salicylate; octylphenyl salicylate; dibenzoyl resorcinol; bis-(4-tert-butylbenzoyl)-resorcinol; benzoyl resorcinol; 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.

[0062] In some embodiments, acrylates can be used as UV absorbers or light stabilizers. Non-limiting examples of acrylates include alpha-cyano-beta,beta-diphenylacrylate ethyl ester or isooctyl ester; alpha-carbomethoxycinnamate methyl ester; alpha-cyano-beta-methyl-p-methoxycinnamate methyl ester or butyl ester; alpha-carbomethoxy-p-methoxycinnamate methyl ester; and N-(beta-carbomethoxy-beta-cyano-vinyl)-2-methyl-indoline.

[0063] Non-limiting examples of auxiliary stabilizers include melamine; polyvinylpyrrolidone; dicyandiamide; triallyl cyanurate; urea derivatives; hydrazine derivatives; amines; polyurethanes; alkali metal salts and alkaline earth metal salts of higher fatty acids (e.g., calcium stearate, calcium stearoyl lactate, calcium lactate, zinc stearate, magnesium stearate, sodium ricinoleate, and potassium palmitate); antimony pyrocatecholate or zinc pyrocatecholate (including neutralizing agents such as hydrotalcite and synthetic hydrotalcite); and Li, Na, Mg, Ca, Al hydroxycarbonates. Hydrotalcite usable in embodiments of the present invention includes materials commercially available under the general trademark names DHT-4(registered trademark) (A, C, or V), ZHT-4V(registered trademark), HYCITE(registered trademark) 713, and AC-207(trademark).

[0064] Non-limiting examples of nucleating agents include 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium salt of methylenebis-2,4-dibutylphenyl, cyclic phosphate esters, sorbitol trisbenzaldehyde acetal, and sodium salt of bis(2,4-di-t-butylphenyl)phosphate or sodium salt of ethylidenebis(2,4-di-t-butylphenyl)phosphate. Nucleating agents may improve the rigidity of rotationally molded parts.

[0065] In some embodiments, a slip agent can be used. Non-limiting examples of slip agents include oleamide, erukaamide, stearamide, and behenamide.

[0066] In some embodiments, a metal deactivator can be used. Non-limiting examples include N,N'-diphenyl oxalic diamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis-salicylal hydrazine, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenyl propionyl)-2-hydrazine, salicyloyl amino-1,2,4-triazole, and bis-benzylidene-oxalic dihydrazide.

[0067] Non-limiting examples of polyamide stabilizers include copper salts in combination with iodides and / or phosphorus compounds, and salts of divalent manganese.

[0068] Other additives include plasticizers, epoxidized vegetable oils (such as epoxidized soybean oil), lubricants, emulsifiers, pigments, fluorescent whitening agents, flame retardants, antistatic agents, foaming agents, and thio synergists (such as dilauryl thiodipropionate or distearyl thiodipropionate).

[0069] Non-limiting examples of fillers and reinforcing agents include calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, and graphite. When present, in some embodiments of the present invention, the filler can be incorporated into the thermoplastic polyolefin (such as linear polyethylene) in an amount of up to about 50 weight percent, or up to about 30 weight percent, or up to about 20 weight percent, or up to about 10 weight percent (based on the weight of the thermoplastic polyolefin).

[0070] <B. Method for Producing Polymer Composition> The polymer composition of the present invention can be manufactured using known compounding methods. For example, all components may be dry-blended in the required weight ratio using a suitable device such as a tumble blender. The resulting dry blend can then be melted using a suitable compounding apparatus (e.g., an extruder). In another example, a masterbatch can be prepared using a portion of the polyolefin 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 may be directly metered and fed into an extruder.

[0071] Extruders for thermoplastic polyolefins and extrusion processes using these extruders are well known to those skilled in the art. A typical extruder comprises one (or two) vane-screws rotating in a cylinder or "barrel." The polyolefin may be sheared between the barrel and the screw due to the stress generated by the rotation of the screw. In addition, the barrel of the extruder may be heated. Due to the shearing and / or heat, the plastic melts and is carried along the length of the extruder by the action of the vane-screw. The extruded molten polyolefin composition can then be extruded through a die to form the desired plastic part. The extruder used for the final extrusion may be a single or twin-screw extruder. The die may be a slot die or an annular ring die that extrudes a film of polymer blend around a stable bubble of air. The film may collapse after passing over or around the bubble.

[0072] In the method using an extruder, a twin or single screw extruder can be used for the extruder. In the case of a twin screw extruder, it can be operated in a co-rotating mode (i.e., both screws rotate in the same direction) or a counter-rotating mode (i.e., the screws rotate in opposite directions). Specific conditions regarding the operation of the extruder vary depending on the type of the extruder. Variations between machines can usually be resolved by non-inventive tests. The extruder can extrude the polymer composition as strands, then cool and cut them into pellets for subsequent use (typically film extrusion).

[0073] In the case of a polyolefin formulation, the conditions include temperature and pressure. The temperature can be 180°C to 275°C, or 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 275°C, or any value or range between them. The pressure can be 0.1 MPa to 10 MPa, or 0.1 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, or any value or range between them depending on the formulation method.

[0074] In the case of film applications, in one aspect, pigments or fillers can be excluded, and as a result, a transparent or relatively transparent film may be obtained. For other applications such as (electrical or optical) wires and cables, the polymer composition can contain pigments / fillers such as carbon black and other auxiliaries.

[0075] <Article Containing Polymer Composition> The polymer compositions of the present invention can be molded into various articles and shapes using various methods (e.g., injection molding, extrusion molding, rotational molding, foam molding, calendering, blow molding, blow film molding, thermoforming, compression molding, melt spinning, etc.). Non-limiting examples of articles include consumer goods, packaging products, pharmaceutical containers, bottles, caps, closures, liners, garbage bags, food packaging films and / or materials, laminates, toys, tanks, wire sheathing, cable sheathing, pipes, hoses, or fittings. In some embodiments, the manufactured articles may include printed or written graphics, lettering, etc. In some preferred embodiments, the polymer composition can be molded into blow-molded films.

[0076] Additional non-limiting examples of articles that can be manufactured using the polymer compositions of the present invention include exterior and / or interior components for transport vehicles (e.g., aircraft, automobiles, trucks, military vehicles (including automobiles, aircraft, and water vehicles), scooters, and motorcycles) (e.g., panels, quarter panels, rocker panels, trim, fenders, doors, deck lids, trunk lids, hoods, bonnets, roofs, bumpers, fascias, grilles, mirror housings, pillar appliqués, cladding, body side moldings, wheel covers, wheel caps, door handles, spoilers, window frames, headlamp bezels, headlamps, taillamps, taillamp housings, taillamp bezels, license plate enclosures, roof racks, and running boards); enclosures, housings, panels, and components for outdoor vehicles and devices; enclosures for electrical and communication devices; outdoor furniture; aircraft components; boats and marine equipment (including trim, enclosures, and housings); outboard motor housings; depth gauge housings; personal watercraft; jet skis; swimming pools; spas; hot tubs; steps; Step covers; building and construction applications (glazing, roofs, windows, floors, decorative window fittings or treatments, etc.); treated glass covers for display items such as photographs, paintings, and posters; wall panels and doors; countertops; protected graphics; outdoor and indoor signage; enclosures, housings, panels, and components for ATMs; computers; desktop computers; portable computers; laptop computers; palm-held computer enclosures; monitors; printers; keyboards; fax machines; photocopiers; telephones; telephone bezels; mobile phones; radio transmitters; radio receivers; enclosures, housings, panels, and components for lawnmowers and garden tractors, lawnmowers, and tools (including lawnmowers and garden tools); window and door trims; sports equipment and toys; enclosures, housings, panels, and components for snowmobiles; panels and components for recreational vehicles; playground equipment; shoelaces; container lids; products made from plastic and wood composites; golf course markers; utility pit covers; lighting fixtures; lighting equipment; housings for network interface devices;Transformer housing; air conditioner housing; exterior materials or seats for public transportation; exterior materials or seats for trains, subways, or buses; meter housing; antenna housing; exterior materials for satellite broadcast receivers; covered helmets and personal protective equipment; covered synthetic fibers or natural fibers; covered painted products; covered dyed products; covered fluorescent products; covered foamed products; and similar applications, are included.

[0077] Furthermore, the polymer composition (with or without additives) can also be formed into components of films or sheets, as well as laminated polymer materials (e.g., laminates). The sheet can be a foamed sheet, paper sheet, or fabric sheet. Manufactured 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, shades, partitions, lenses, skylights, lighting devices, reflectors, ducts, cable trays, conduits, pipes, cable ties, wire coatings, electrical connectors, air conditioning devices, ventilation devices, louvers, heat insulators, bins, storage containers, doors, hinges, handles, sinks, mirror housings, mirrors, toilet seats, hangers, coat hooks, shelves, ladders, handrails, steps, carts, trays, cooking utensils, food service equipment, communication equipment, instrument panels, and the like.

Examples

[0078] <D. Example> The present invention will be described in more detail with specific examples. The following examples are for illustrative purposes only and do not limit the present invention in any way. Those skilled in the art will easily understand various non-critical parameters that can be changed or modified to obtain essentially the same results.

[0079] <1. Example 1> (Preparation of the Polymer Composition and Comparative Composition of the Present Invention) 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 under the conditions described in Table 2 using a Listritz twin-screw pelletizer. The resin used was Octene LLDPE VPsK914 (MI2 = 0.85 g / 10 min, density = 0.914 g / cm³). 3 ) was.

[0080] [Table 1]

[0081] [Table 2]

[0082] <2. Example 2> (Melt fracture removal test of the present invention and comparative compositions) Melt fracture removal tests were conducted on a Little Macro inflation film line using the processing conditions shown in Table 3. A single-layer inflation film line with a 3-inch diameter die (manufactured by Macro Engineering & Technology Inc., headquartered in Ontario, California) was used, and the effect of adding polyamide (e.g., nylon 6, nylon 6 / 6,6) as a polymer processing aid (PPA) to remove melt fractures from extruded materials was investigated. This 3-inch Macro inflation film line had a standard output of more than 60 pounds per hour and was equipped with a 15 horsepower motor. The feed screw had a diameter of 1.5 inches and a length / diameter (L / D) ratio of 24 / 1. The feed screw was a barrier design with a mixing element attached to the end of the screw. Film bubbles were 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 and die pins, and a die gap of 35 mils was obtained for the experiment. Two die pins were used to achieve a 35 mil die gap for the experiment.

[0083] [Table 3]

[0084] Before adding the target thermoplastic composition, the inflation film line was purged with a resin containing 30-40% diatomaceous earth and no polymer processing aids to clean the die by abrasion. Following purging, PPA-free LLDPE with a melt index of 0.8 g / 10 min was introduced to produce an extruded film with 100% hard melt fractures across the entire width of the film (e.g., producing a film with rough surface defects similar to sharkskin). Next, the target thermoplastic composition was introduced and recorded as time zero. The target thermoplastic composition was extruded under constant conditions, and samples of the extruded film were collected every 10 minutes, measuring the melt fracture defects as a percentage of the sample width. In each experiment, the melt extrusion process was continued for 80 minutes, and the melt fracture percentage was recorded at 10-minute intervals. When the melt fracture percentage reached zero, the extruded thermoplastic composition was considered to have had its melt fractures removed. The melt fracture removal data is shown in Figure 1. Table 4 shows the melt fracture percentages for the samples shown in Figure 1. 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. From the data in Figure 1 and Table 4, it is clear that the inventive examples (N1, N2, N3, and N4) remove melt fractures in the inflation film faster than conventional fluorine-based PPA (C2).

[0085] [Table 4]

[0086] While embodiments and their advantages have been described in detail in this application, it should be understood that various modifications, substitutions, and alterations are possible without departing from the spirit and scope of the embodiments defined by the appended claims. Furthermore, the scope of this application is not intended to be limited to specific embodiments of the processes, machines, articles, compositions, means, methods, and steps described herein. As will be readily apparent to those skilled in the art from the above disclosure, existing or future-developed processes, machines, articles, compositions, means, methods, or steps are available that perform substantially the same functions or achieve substantially the same results as the corresponding embodiments described herein. Accordingly, the appended claims are intended to include such processes, machines, articles, compositions, means, methods, or steps within their scope. [Industrial applicability]

[0087] Polyamides are used as polymer processing aids to improve the melt extrusion of polyolefins.

Claims

1. Polyolefin polymers, Polyamide in concentrations of 100 ppm to 10,000 ppm and A polymer composition comprising, The composition is substantially free of polyolefin polymer / polyamide compatibilizers. Polymer composition.

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

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

4. Polyethylene polymer has a melt index (MI) of 0.1 to 10 grams / 10 minutes. ２ ) and 0.88 to 0.970 g / cm³ ３ Density, melt index (MI) of 0.1 to 10 grams / 10 minutes ２ ) and 0.93-0.970 g / cm³ ３ The density, or the melt index (MI) of 0.1 to 10 grams / 10 minutes. ２ ) and 0.88-0.94 g / cm³ ３ A polymer composition according to claim 2 or 3, having a density of the above.

5. The polymer composition according to any one of claims 1 to 4, wherein the polyolefin polymer is linear low-density polyethylene (LLDPE).

6. LLDPE is 0.85 g / 10 min MI ２ and 0.914 g / cm³ ３ The polymer composition according to claim 5, having the density of .

7. A polymer composition according to any one of claims 1 to 6, wherein the polyamide comprises polycaprolactam.

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

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

10. The polymer composition according to any one of claims 1 to 9, wherein the polymer composition does not contain, substantially does not contain, or contains less than 100 ppm of one or more fluorine-based polymer processing aids.

11. The polymer composition according to claim 10, wherein the fluorine-based polymer processing aid (one or more) is polyvinylidene difluoride, polyvinylidene fluoride-co-hexafluoropropylene, or a combination thereof.

12. The polymer composition according to any one of claims 1 to 11, further comprising 100 ppm to 1% by weight of polyethylene glycol.

13. A polymer composition according to any one of claims 1 to 12, further comprising an antioxidant, an ultraviolet stabilizer, or both.

14. The polymer composition, based on the total weight of the polymer composition, 98% to 99.9% by weight of polyolefin polymer, 200 to 2,000 ppm of polyamide, and 0 to 1% by weight of additives. 99% to 99.9% by weight of polyolefin polymer, 500 to 1,000 ppm of polyamide, and 0 to 1% by weight of additives, or 99.5% to 99.9% by weight of polyolefin polymer, 600 to 800 ppm of polyamide, and 0 to 1% by weight of additives. A polymer composition according to any one of claims 1 to 13, comprising:

15. The polyolefin polymer has a weight average molecular weight M of more than 2,500 g / mol (Da) to 250,000 g / mol (Da). ｗ The polymer composition according to any one of claims 1 to 14, having the same.

16. The polymer composition according to any one of claims 1 to 15, wherein the time required to remove melt fractures, when measured on an inflation film line, is less than 50 minutes.

17. The polymer composition according to any one of claims 1 to 16, wherein the polymer composition is in the form of pellets, powder, molded parts, or film.

18. The polymer composition according to any one of claims 1 to 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 3D printed article, a thermoformed article, a foamed article, an inflation film, a cast film, or a writable film.

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

20. The polymer composition, based on the total weight of the polymer composition, 0-2% by weight of polyolefin polymer / polyamide compatibilizer, 0 to 1% by weight of a polyolefin polymer / polyamide compatibilizer, or 0-0.1% by weight of polyolefin polymer / polyamide compatibilizer A polymer composition according to any one of claims 1 to 19, comprising:

21. A method for producing a polymer composition according to any one of claims 1 to 20, (a) A melt compounding step in which a polyolefin polymer and a polyamide are melt-blended to produce a mixture, (b) Extrusion step to obtain a polymer composition by extruding the mixture Methods that include...

22. The method according to claim 21, Polyolefin polymer is polyethylene. The polyamide contains polycaprolactam, A method comprising an inflation film extrusion process in which the extrusion step is carried out at a temperature of 180°C to 275°C.

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

24. A polyethylene resin composition, (a) 89% to 99% by weight polyethylene, (b) 1.0% by weight to 1.0% by weight of polyamide, (c) Additives in an amount of 0% to 1.0% by weight and Includes, The polyethylene resin composition is substantially free of polyolefin polymer / polyamide compatibilizers. Polyethylene resin composition.

25. The polyethylene resin composition according to claim 24, wherein the polyethylene resin composition does not contain, substantially does not contain, or contains less than 100 ppm of a fluorine-based polymer processing aid (one or more).

26. The polyethylene composition according to claim 25, wherein the fluorine-based polymer processing aid (one or more) is polyvinylidene difluoride, polyvinylidene fluoride-co-hexafluoropropylene, or a combination thereof.

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