Polyalcohol as a polymer processing aid

Abstract

The present invention relates to a composition containing a polyalcohol used to reduce or eliminate surface defects caused by melt extrusion of thermoplastic polymers.

Description

Technical Field

[0001] This application claims the priority of U.S. Provisional Application No. 63 / 461,101, filed on April 21, 2023, the entire content of which is incorporated herein by reference.

[0002] Field of Invention The present invention relates to a polymer processing aid ("PAA") containing polyalcohol.

Background Art

[0003] In the melt extrusion process, solid polymers in the form of pellets or powder are usually supplied to an extruder and heated to a temperature higher than the melting point of the solid polymer to produce a polymer melt. Thereafter, the polymer melt is conveyed through an extrusion die at the tip of the extruder and formed into a desired shape such as a tube, sheet, rod, film or other shape.

[0004] In the extrusion process, the polymer melt is subjected to shear stress, which may cause surface defects, the most common of which is melt fracture. Melt fracture often appears as a cloudiness on the surface, often described as a "matte" finish, and when it expands, it appears visually as a rough sawtooth pattern. Melt fracture is considered an unacceptable quality problem that can have an adverse effect on optical and visual properties and may also have an adverse effect on physical and mechanical properties. Polymer processing aids are known to reduce and in most cases eliminate melt fracture. In most cases, polymer processing aids (PPAs) contain fluoropolymers, which are the active ingredients responsible for eliminating melt fracture. For polymer processing aids containing a fluoropolymer and a synergist, both the fluoropolymer and the synergist are considered to be active ingredients for eliminating melt fracture.

[0005] When conducting melt fracture elimination tests, in many cases, lower levels of active ingredients are used to make it easier to observe the elimination of melt fracture over a longer period. By slowing down the elimination of melt fracture, a better performance difference between tests can be obtained.

[0006] Additives such as mineral fillers (found in many polymer compounds) can further promote melt fracture. It is understood that the presence of such fillers reduces the ability of fluoropolymer-containing PPAs to eliminate melt fracture. When this occurs, PPA levels typically increase.

[0007] The relative performance of polymer processing aids is usually related to their ability to eliminate melt fracture of PPA. One way to evaluate the performance of PPA is to consider the time it takes for PPA to eliminate melt fracture. A typical test begins by setting extrusion conditions favorable to the formation of melt fracture. Once melt fracture is formed and the process is stable, PPA is added and the time until melt fracture is eliminated is recorded. In this test, a PPA with better performance is one that eliminates melt fracture in a shorter time. For example, in such a test, if the first PPA can eliminate melt fracture in 30 minutes and the second PPA can eliminate melt fracture in 60 minutes, and both are using the same addition level and process conditions, then the PPA that can eliminate melt fracture in 30 minutes can be said to be the better performing PPA.

[0008] Furthermore, the relative performance of polymer processing aids can also be evaluated by changing the amount of PPA required to achieve similar melt fracture elimination performance. For example, in such a study, if it is found that the first PPA is effective at 300 ppm and the second PPA is similarly effective at 500 ppm, then the PPA that was found to be effective at 300 ppm can be said to have superior performance.

[0009] There is a direct correlation between the ability to rapidly eliminate melt fracture and the ability to eliminate melt fracture at lower PPA addition levels. Generally, PPA that has been shown to rapidly eliminate melt fracture performs better at lower addition levels. Lower PPA addition levels offer several advantages, including reduced manufacturing costs and mitigated adverse effects on the properties of the final product.

[0010] Many commercially available polymer processing aids containing fluoropolymers also contain synergistic agents to improve melt fracture prevention performance. In such polymer processing aids, both the fluoropolymer and the synergistic agent are active ingredients and work to prevent melt fracture more effectively than when either component is used alone. Common PPA synergistic agents combined with fluoropolymers are described in several patents. One example is described in European Patent No. 1976927.

[0011] Polymer processing aids containing fluorinated polymers are known to be highly effective and have historically been used almost exclusively in the extrusion of polyolefin polymers. It is generally understood by those skilled in the art that polymer processing aids containing fluorinated polymers are superior to those without fluorinated polymers.

[0012] Currently, there is a global effort to reduce or completely eliminate the use of fluorinated chemicals, including fluorinated polymers, in many applications. More specifically, the present invention relates to the ongoing industrial effort to replace fluorinated polymers in polymer processing aids with other non-fluorinated chemicals. For these reasons, there is a need for effective polymer processing aids that do not contain fluorinated polymers. More specifically, there is a need for PPAs that do not contain fluorinated polymers but can eliminate melt fracture as efficiently as PPAs that contain fluorinated polymers. Prior to the present invention, no effective polymer processing aids that did not contain fluorinated polymers and had performance equivalent to those containing fluorinated polymers were known.

[0013] PPA manufactured without the use of fluoropolymers can be called Fluoropolymer-Free Polymer Processing Aid (FFPA). As mentioned above, FFPA, which is highly effective in eliminating melt fracture, was unknown prior to this discovery. For Fluoropolymer-Free Polymer Processing Aid (FFPA) to be useful, it must satisfy several performance characteristics. Particularly important is that FFPA must provide an acceptable level of melt fracture elimination at conventional addition levels. Preferably, FFPA is a drop-in substitute for fluoropolymer-containing PPA that provides similar performance characteristics at similar addition levels. Furthermore, in many applications, it is preferable that FFPA meets the requirements applicable to contact with food and water. The active ingredient of the present invention, identified as a polyalcohol, is commonly used as a food additive.

[0014] Prior to this discovery, PPAs containing fluoropolymers were the primary means of rapidly eliminating melt fracture, especially when low levels of additive were deemed necessary. It was unexpected to find that process additive compositions without fluoropolymers exhibited equivalent, and often superior, melt fracture elimination performance compared to polymer processing additives containing fluoropolymers. [Prior art documents] [Patent Documents]

[0015] [Patent Document 1] European Patent No. 1976927 [Overview of the project] [Problems that the invention aims to solve]

[0016] The invention described herein provides a polymer processing aid comprising one or more polyalcohols as an active ingredient. For the present invention to function effectively as a PPA, the addition of fluorinated polymers or synergistic agents is not necessary. Polymer processing aids comprising one or more polyalcohols have been found to effectively eliminate melt fracture during melt extrusion. The main active ingredient of the present invention is not a fluorinated polymer, but rather a polyalcohol, more specifically a "polyhydric" alcohol or "sugar" alcohol. The polyalcohols of the present invention differ from currently used polymer processing aids in that they are not fluorine-free and are not composed of polymers. The inventors have found that the polyalcohol (B) of the present invention can be used as a polymer processing aid to eliminate melt fracture in polymer melt extrusion processes. In addition to reducing quality defects such as melt fracture, the polyalcohol (B) of the present invention can also provide the advantages of other polymer processing aids known in the art, including, but not limited to, reduced die roll and reduced melt process pressure. The present invention also includes combinations of polyalcohol with other active ingredients for producing polymer processing aid compositions. [Means for solving the problem]

[0017] The present invention relates to a composition particularly useful for polyolefins, comprising a polyalcohol used to reduce or eliminate surface defects arising from the melt extrusion of thermoplastic polymers. The composition of the present invention comprising a polyalcohol may optionally contain other commercially available polymer processing aids and other components known in the art to reduce quality defects such as melt fracture.

[0018] The polymer processing aid (C) of the present invention comprises at least one polyalcohol (B). The polymer processing aid (C) may include one or more of the following: ii) processing aid additives, iii) alternative polymer processing aids. The polyalcohol (B), processing aid additives, and alternative polymer processing aids are all active ingredients.

[0019] Polyol (B) can provide better performance in combination with an alternative polymer processing aid than when the alternative polymer processing aid is used alone.

[0020] When the polymer processing aid contains two or more components, the polymer processing aid (C) can be produced by any process known in the art of producing a polymer processing aid by extrusion compounding, compression compounding, or blending the components. The polymer processing aid (C) can be in various forms, including pellets, powders, liquids, or any form known in the art for producing a polymer processing aid.

[0021] Polyol (B) can be added directly during the polymer melt extrusion process, or as a component in an extrudable compound (E), or as a component in a masterbatch (D), or as a component in the polymer processing aid (C), or in an article (F) produced therefrom.

[0022] For the purpose of reducing quality defects of the melt-processed thermoplastic resin, the process of producing an extrudable compound (E), or a masterbatch (D), or a polymer processing aid (C), or an article (F) containing polyol (B) is included as part of the present invention.

[0023] The masterbatch (D) of the present invention contains polyol (B) and a diluent (A). Polyol (B) may account for 50% by weight or less, preferably 10% by weight or less, and more than 0.1% by weight or more than 0.5% by weight of the total composition of the masterbatch (D). When polyol (B) is the only active ingredient of the masterbatch (D), it accounts for more than 1% of the whole masterbatch (D). In some embodiments, the diluent A is preferably a thermoplastic polymer (also called a carrier polymer) and can be partially used to contain and deliver the active ingredient.

[0024] The masterbatch (D) can be produced by extrusion compounding, compression compounding, or any process known in the art for blending the components to produce the masterbatch (D). The masterbatch (D) can be in various forms, including pellets, powders, liquids, or any form known in the art for producing polymer processing aids.

[0025] The present invention includes a polymer processing aid (C), a masterbatch (D), an extrudable compound (E), and an article (F) that contain a polyalcohol (B) and can include one or more of i) processing aid additives, ii) alternative polymer processing aids, and can also include other components such as additives, fillers, colorants, anti-blocking agents, antioxidants, lubricants, stabilizers, and other components (not limited to these).

[0026] A preferred embodiment of the present invention is specified as "fluoropolymer-free" and does not contain a fluorinated polymer or a fluorinated compound in its composition. This embodiment can be referred to as a fluoropolymer-free polymer processing aid (FFPA) and can include other active components, including other polymer processing aids, synergists, lubricants, and other additives, provided that they do not contain fluorine.

[0027] A preferred embodiment of the present invention contains a polyalcohol (B) derived from bio-renewable resources and can also contain one or more additional active components derived from natural and renewable resources. In this embodiment, ideally, the totality of all active components is derived from natural and renewable resources.

[0028] In some embodiments of the present invention, the polymer processing aid (C), or the masterbatch (D), or the extrudable compound (E), or the article (F) contains a fluoropolymer.

[0029] In some embodiments of the present invention, the polymer processing aid (C), or masterbatch (D), or extrudeable compound (E), or article (F) comprises polyethylene glycol (PEG).

[0030] In some embodiments of the present invention, the polymer processing aid (C), or masterbatch (D), or extrudeable compound (E), or article (F) comprises polyethylene glycol, fluoropolymers, and combinations thereof.

[0031] In some embodiments of the present invention, the polymer processing aid (C), or masterbatch (D), or extrudeable compound (E), or article (F) comprises a polyamide.

[0032] In some embodiments of the present invention, the polymer processing aid (C), or masterbatch (D), or extrudeable compound (E), or article (F) comprises another component that reduces melt fracture when added to polyethylene resin.

[0033] The present invention is useful for the melt processing of thermoplastic polymers, more preferably polyolefin polymers. Melting processes in which the present invention can be used include film extrusion, injection molding, extrusion blow molding, pipe and tube extrusion, wire and cable extrusion, and fiber and filament extrusion.

[0034] The present invention provides a method for melt processing a thermoplastic polymer, comprising: a) a step of combining a polymer processing aid (C) with a thermoplastic polymer, preferably a polyolefin polymer, wherein the amount of polyalcohol (B) is 1 ppm to less than 1% by weight, preferably less than 5000 ppm, based on the total weight of the thermoplastic polymer; b) a step of heating above the melting point of polyalcohol (B); and c) a step of melt processing the thermoplastic polymer composition by extrusion or molding. The polymer processing aid (C) may be any of the various embodiments of polymer processing aid (C) described herein. Polyalcohol B can be introduced into the thermoplastic polymer in either the form of polymer processing aid (C) or masterbatch (D) described herein.

[0035] The present invention provides many embodiments. Some preferred features of the present invention include the following:

[0036] The first part of the present invention comprises one or more polyalcohols (B), optionally one or more of the following: a. Processing aid additives selected from the group consisting of aliphatic polyesters such as polybutylene adipate, polylactic acid, and polycaprolactone (PCL) such as polycaprolactone diol; aromatic polyesters such as diisobutyl phthalate; polyethers such as polyether polyols; amine oxides such as octyldimethylamine oxide; carboxylic acids such as hydroxybutanediic acid; and fatty acid esters such as sorbitan monolaurate; and / or b. A polymer processing aid (C) is provided, comprising an alternative polymer processing aid selected from the group consisting of silicones; silicone-polyether copolymers; fluoropolymers; polyamides; polyether block amides (PEBA); polyethylene glycol; and silicone polyalkylene oxides such as polyethylene glycol (PEG). Here, polyalcohol (B) is not polymerizable and has a melting point below 240°C.

[0037] The second paragraph provides the processing aid of the first paragraph, wherein the polyalcohol (B) contains a polyhydric alcohol and has two or more hydroxyl groups, with a single hydroxyl group on each carbon.

[0038] The third paragraph provides the processing aid of the first paragraph, wherein the polyalcohol (B) is selected from the group consisting of ethylene glycol, glycerin (glycerol), erythritol, slaytol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fusitol, iditol, inositol, boremitol, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, polyglycitol, and combinations thereof.

[0039] The fourth paragraph provides the processing aid of the first paragraph, wherein the polyalcohol (B) contains D-mannitol.

[0040] Paragraph 5 provides the processing aid of paragraph 1, wherein the polyalcohol (B) contains sorbitol.

[0041] Item 6 provides the processing aid of Item 1, wherein the polyalcohol (B) has a melting point of 230°C or less, preferably 220°C or less. The melting point may be greater than 30°C, preferably greater than 40°C, or greater than 50°C, or greater than 60°C.

[0042] The seventh paragraph provides one or more processing aids according to any one of the first to sixth paragraphs, wherein polyalcohol (B) comprises at least two different polyalcohols.

[0043] The eighth item provides the processing aid of the seventh item, wherein the polyalcohol forms a eutectic blend.

[0044] Item 9 provides one or more processing aids from any one of items 1 to 8, further comprising additives selected from the group consisting of fillers, colorants, antiblocking agents, antioxidants, lubricants, stabilizers, synergists, and combinations thereof.

[0045] The 10th item provides one or more processing aids according to any one of the 1st to 9th items, wherein the amount of polyalcohol (B) in the polymer processing aid is in the range of more than 0.1% by weight to 99.9% by weight, preferably 1.0 to 99% by weight, more preferably 5 to 99% by weight, and even more preferably 50 to 98.5% by weight, based on the total weight of the polymer processing aid (C).

[0046] The 11th item provides a processing aid according to one or more of the 1st to 9th items, wherein the total amount of active ingredients in the polymer processing aid (C) is more than 50% by weight, preferably 95% by weight or more, preferably 99% by weight or more, and most preferably 100% by weight of the total polymer processing aid (C), and the polyalcohol (B) is 0.1% by weight to 100% by weight of the total amount of active ingredients in the polymer processing aid (C).

[0047] The 12th paragraph provides one or more polymer processing aids according to any one of the paragraphs 1 to 9, further comprising a diluent (A) to form a masterbatch (D).

[0048] Item 13 provides the polymer processing aid of item 12, wherein the total amount of active ingredients in the polymer processing aid is 50% by weight or less, preferably less than 30% by weight, more preferably less than 20% by weight, even more preferably 10% by weight or less, preferably more than 0.1% by weight, and more preferably more than 0.5% by weight. Polyalcohol (B) accounts for 0.01% to 100% by weight of the active ingredients contained in the polymer processing aid.

[0049] Paragraph 14 provides the processing aid of paragraph 13, wherein the diluent (A) comprises one or more polyolefins.

[0050] Paragraph 15 provides the processing aid of paragraph 13, wherein the diluent (A) comprises a polyethylene polymer.

[0051] Claim 16 provides the processing aid of Claim 13, wherein the diluent (A) comprises at least one polypropylene homopolymer or polypropylene copolymer.

[0052] Item 17 provides the processing aid of Item 13, wherein the diluent (A) is selected from the group consisting of LDPE, HDPE, LLDPE, and functionalized polyolefins. Alternatively, the diluent (A) may be any combination of medium-density polyethylene (MDPE) and polypropylene (PP). It may also be any mixture of LDPE, MDPE, HDPE, LLDPE, PP, and functionalized polyolefins.

[0053] Claim 18 provides the processing aid of Claim 13, wherein the diluent (A) comprises an ethylene copolymer selected from the group consisting of ethylene vinyl acetate, ethylene methacrylic acid, ethylene methacrylate, ethylene-propylene, ethylene-α-olefin and combinations thereof.

[0054] Item 19 provides the processing aid of item 13, wherein the diluent (A) comprises a solvent, preferably water.

[0055] Paragraph 20 provides an extrudeable compound (E) comprising a polyalcohol (B) and a thermoplastic polymer, preferably a polyolefin.

[0056] Paragraph 21 provides an extrudeable compound (E) comprising one or more polymer processing aids specified in paragraphs 1 to 19.

[0057] Item 22 provides an extrudeable compound (E) of item 21, comprising a polyalcohol (B) in an amount of 10 ppm to 2000 ppm, preferably up to 1000 ppm, and most preferably up to 750 ppm, based on the weight of the thermoplastic polymer.

[0058] The 23rd item provides the extrudeable compound (E) of the 21st item, wherein the active ingredients in the extrudeable compound (E) constitute 1 ppm or more, preferably 5 ppm or more, most preferably 10 ppm or more, and 0.5% by weight or less, preferably 0.25% by weight or less, most preferably 0.1% or less of the total weight of the active ingredients in the extrudeable compound (E), and the polyalcohol (B) constitutes 0.01% by weight to 100% by weight of the active ingredients contained in the extrudeable compound (E).

[0059] Paragraph 24 provides an article (F) containing one or more polymer processing aids specified in paragraphs 1 through 19.

[0060] Paragraph 25 provides an article (F) comprising one or more extrudeable compounds (E) from any of paragraphs 20 to 23.

[0061] Paragraph 26 provides the article (F) of paragraph 24 or 25, wherein the thermoplastic polymer is a polyolefin.

[0062] Paragraph 27 is a method for melt processing a thermoplastic polymer, a) A step of combining one or more polymer processing aids specified in items 1 to 19 with a thermoplastic polymer, preferably a polyolefin polymer, wherein the amount of polyalcohol (B) is 1 ppm to less than 1% by weight, preferably 5000 ppm or less, based on the total weight of the thermoplastic polymer. b) A step of heating the polyalcohol (B) to a temperature higher than its melting point, c) A step of melting the thermoplastic polymer composition by extrusion or molding, This provides a method that includes this.

[0063] Paragraph 28 provides the method of Paragraph 27, wherein the amount of polyalcohol (B) is 10 ppm to 0.25% by weight.

[0064] Item 29 is the following process: a) A step of producing a thermoplastic polymer composition by combining a polyalcohol (B) with a thermoplastic polymer, preferably a polyolefin polymer, wherein the amount of polyalcohol (B) is 1 ppm to 5000 ppm based on the total weight of the thermoplastic polymer, and then, b) A step of heating the thermoplastic polymer composition in an extruder, molding machine, or other melting apparatus at a temperature higher than the melting point of the thermoplastic polymer. c) A process of manufacturing an article (F) by extrusion, molding, or melt processing, The present invention provides a method for manufacturing an article (F) by melting, including the following:

[0065] The 30th paragraph provides a method for producing an article (F) by melt processing, comprising: a) providing an extrudeable compound (E) according to one or more of the items of paragraphs 20 to 23, wherein the extrudeable compound (E) contains an amount of polyalcohol (B) from 1 ppm to 5000 ppm based on the total weight of the thermoplastic polymer; and b) heating the extrudeable compound (E) composition at a temperature higher than the melting point of the thermoplastic polymer to melt process it and produce an article (F).

[0066] Paragraph 31 provides the method of paragraph 27 or 29, wherein the amount of polyalcohol (B) is at least 10 ppm and up to 5000 ppm, more preferably up to 2000 ppm, even more preferably up to 1000 ppm, and most preferably up to 750 ppm, based on the weight of the thermoplastic polymer.

[0067] Paragraph 32 provides the method of paragraph 27 or 29, wherein the amount of the active ingredient is 1 ppm or more, preferably 5 ppm or more, most preferably 10 ppm or more and 0.5% by weight or less, preferably 0.25% by weight or less, most preferably 0.1% or less of the total weight of the active ingredients in article (F), and the polyalcohol (B) accounts for 0.01% to 100% by weight of the active ingredients contained in article (F).

[0068] The 33rd paragraph provides the method of the 27th or 29th paragraph, wherein the total amount of active ingredients in the polymer processing aid is 50% by weight or less of the total polymer processing aid, preferably less than 30% by weight, more preferably less than 20% by weight, even more preferably 10% by weight or less, preferably more than 0.1% by weight, more preferably more than 0.5% by weight, and polyalcohol (B) accounts for 0.01% to 100% by weight of the active ingredients contained in the polymer processing aid.

[0069] Paragraph 34 provides the method of paragraph 29, wherein the polyalcohol (B) is provided in the form of one or more polymer processing aids specified in paragraphs 1 to 19.

[0070] Paragraph 35 provides the method of paragraph 27 or 29, wherein the thermoplastic polymer is a polyolefin.

[0071] Item 36 provides the method of Item 27 or 29, wherein the melting point of polyalcohol (B) is below the melting temperature.

[0072] Paragraph 37 provides the method of paragraph 27 or 29 for reducing or eliminating melt fracture during melt processing of a thermoplastic polymer composition.

[0073] Paragraph 38 provides the use of one or more processing aids specified in paragraphs 1 through 19 to reduce melt fracture in the melt processing of thermoplastic polymers.

[0074] Paragraph 39 provides the use of a polymer processing aid containing polyalcohol (B) for melt processing of polyolefin polymers. [Modes for carrying out the invention]

[0075] All percentages and ratios are based on weight unless otherwise specified.

[0076] The term "polymer processing aid," also known as "extruder" or "PPA," refers to an additive used to reduce quality defects such as melt fracture and die rolls that form during the melt processing of thermoplastic polymers. The term "fluoropolymer-free polymer processing aid" or "FFPA" refers to a polymer processing aid that does not contain fluoropolymers.

[0077] The term "diluent" as used in this invention may refer to a solvent. The term "diluent" means a solvent or thermoplastic polymer (also called a carrier polymer) that is combined with the active ingredient to produce a masterbatch. The diluent in this invention is not fluorinated. The diluent does not contain fluorine. The term "solvent" refers to a liquid used to disperse or dissolve the active ingredient, which becomes a liquid or paste once dispersed or dissolved. The term "polymer" refers to a compound or mixture of compounds formed by polymerization and having repeating structural units. The term "carrier polymer" refers to diluent (A), which is polymerizable and preferably a polyolefin polymer. The term "thermoplastic polymer" refers to a type of polymer that can be softened by heating and then melt-processed using methods such as extrusion, injection molding, thermoforming, and blow molding. Thermoplastic polymers harden when cooled and can often be melt-processed multiple times.

[0078] The term "polymer processing aid," also known as "extruder" or "PPA," refers to an additive used to reduce quality defects such as melt fracture and die rolls that form during melt processing. The term "active ingredient" refers to the component of the polymer processing aid that plays a role in reducing quality defects in thermoplastic polymer extruded articles such as article F. As used herein, the terms "performance" and "performance characteristics" are used to describe the ability to eliminate quality defects known as melt fracture, unless otherwise expressed. The term "melt fracture" is a quality defect on the surface of an article that is reduced or eliminated by adding a polymer processing aid to melt processing. The term "die roll" is a quality defect caused by the deposition of material on the extrusion die, which is corrected by the addition of a polymer processing aid.

[0079] The term "polyalcohol" refers to an organic component containing two or more hydroxyl groups. The polyalcohol (B) of the present invention includes all stereoisomers and constituent isomers and is not polymerizable. The term "sugar alcohol" refers to a polyalcohol also called a polyhydric alcohol, polyalcohol, alditol, or glycitol, which is typically derived from sugars and contains one hydroxyl group (-OH) bonded to each carbon atom. As used herein, the term "ring structure" refers to a cyclic carbon chain structure in which carbon chains form a ring, and the carbon chain contains at least one additional element other than carbon, such as an oxygen atom or a nitrogen atom, as a member of the ring.

[0080] The term "masterbatch" refers to a "polymer processing aid masterbatch," which is a composition containing an active ingredient dispersed in a diluent (A). The term "extrudeable compound" refers to a thermoplastic polymer composition containing a thermoplastic polymer and one or more active ingredients, the active ingredients reducing the number of quality defects formed during melt processing.

[0081] The term "synergistic agent," also called an "interfacial agent," is considered an active ingredient if, when combined with other active ingredients, it performs better than when either active ingredient is used alone. The term "fluoropolymer" refers to a polymer containing fluorinated monomer units and is commonly used as an active ingredient in polymer processing aids. The term "fluoropolymer" includes thermoplastic fluoropolymers and fluoroelastomers, as well as polyvinylidene fluoride copolymers such as poly(vinylidene fluoride-co-hexafluoropropylene) copolymers. The term "melt index," "melt flow index," or MFR refers to the melt viscosity of a material, with a higher MFR value indicating lower melt viscosity. The melt flow index value is obtained using the procedure specified in ASTM D1238. The melting point is obtained by DSC with a second heat, according to ASTM D3418.

[0082] The term "rapid" in relation to PPA performance is used herein to describe PPA that can eliminate melt fracture within 30 minutes. The term "efficient" in relation to PPA performance is used herein to describe PPA that can eliminate melt fracture using PPA of 400 ppm or less.

[0083] Composition and form of polymer processing aids The present invention relates to a polymer processing aid (C) used to reduce or eliminate surface defects arising from the melt extrusion of thermoplastic polymers, particularly polyolefin polymers. The polymer processing aid (C) of the present invention comprises at least one polyalcohol (B), preferably one or more of the following: (i) Processing aid additives, (ii) Alternative polymer processing aids.

[0084] The present invention relates to a polymer processing aid masterbatch (D) used to reduce or eliminate surface defects arising from the melt extrusion of thermoplastic polymers, particularly polyolefin polymers. The masterbatch (D) of the present invention comprises at least one polyalcohol (B) and a diluent (A), and may contain one or more of the following: (iii) Processing aid additives, (iv) Alternative polymer processing aids.

[0085] Polymer processing aids (C) can be used to produce masterbatches (D), extrudeable compounds (E), or articles (F). When polymer processing aid (C) of the present invention is produced without the addition of fluorinated polymers, it can be a fluorinated polymer-free polymer processing aid (FFPA), and the diluents and other active ingredients of the present invention do not contain fluorinated monomer units.

[0086] polyalcohol Polyalcohol (B), processing aid additives, and alternative polymer processing aids are considered active ingredients, but diluent (A) is not an active ingredient of polymer processing aid (C).

[0087] The total amount of active ingredients in polymer processing aid (C) can account for more than 50% by weight of the total polymer processing aid (C), preferably 95% by weight or more, preferably 99% or more, and most preferably 100% by weight. Polyalcohol (B) can account for 0.1% to 100% by weight of the total amount of active ingredients contained in polymer processing aid (C).

[0088] The polyalcohol (B) of the present invention can be any polyhydric alcohol containing two or more hydroxyl groups, with one hydroxyl group (-OH) bonded to each carbon atom, and is also called a sugar alcohol. Polyalcohol (B) may be a single polyalcohol or a blend of two or more polyalcohols. Examples of polyalcohols (B), sometimes called sugar alcohols, include, but are not limited to, glycerin (glycerol), erythritol, slaytol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fusitol, iditol, inositol, boremitol, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, polyglycitol, and all other related isomer forms.

[0089] Polyalcohol (B) does not contain a ring structure, is not a monosaccharide, disaccharide, or polysaccharide, is not polymerizable, and does not contain polymerized diols. The melting point of polyalcohol (B) of the present invention is 240°C or less, preferably less than 230°C, most preferably less than 220°C, preferably in the range of 240 to 10°C, more preferably 230 to 20°C, even more preferably 220 to 50°C, even more preferably 210 to 80°C, and most preferably in the range of 200 to 110°C. Polyalcohol (B) can be in a liquid state at room temperature, glycerin being one example. Preferred polyalcohol (B) includes D-mannitol.

[0090] Polyalcohols are often produced from sugars and are therefore considered a biorenewable resource. They are typically produced by the hydrogenation of monosaccharides such as fructose and glucose. More specifically, polyalcohols are commonly produced by either the electrolytic reduction or transition metal-catalyzed hydrogenation of sugar solutions, or by fermentation of sugars or sugar alcohols using the yeast Zygosaccharomyces rouxii, or by pure culture fermentation of sugars using the non-pathogenic and non-toxic bacterium Lactobacillus intermedius (fermentum).

[0091] The melt processing of polyolefins such as LLDPE is typically carried out at a melt processing temperature of less than 250°C, ideally in the range of 200 to 230°C. It is preferable to select a polyalcohol with a melting point lower than the melt processing temperature of the thermoplastic polymer being processed.

[0092] In some embodiments of the present invention, the melting point of polyalcohol (B) is below the melting temperature of the thermoplastic polymer being melted, preferably about 10 to 70°C lower than the melting temperature used, and more preferably 20 to 50°C lower than the melting temperature used. For example, the melting point of polyalcohol D-mannitol is 166 to 167°C, which is about 25 to 35°C lower than the typical melting temperature for blow film extrusion of polyolefin polymers. Without being bound by any theory, it is thought that polyalcohol is effective only at temperatures above its melting point, and that delaying the melting of the polyalcohol until later in the extrusion process allows the polyalcohol to be effective when needed. Ideally, the polyalcohol remains unactivated until it reaches the metering zone of the single-screw extruder, and then maintains its activity as it passes through the extrusion die.

[0093] The polyalcohol (B) of the present invention can be described as biorenewable if it is derived from biological and renewable resources.

[0094] It is known in the art that eutectic blends can be produced by combining different sugar alcohols, and that the melting point of the blend can be adjusted by changing the ratio of these sugar alcohols. One aspect of the present invention is to produce a PPA having a target melting point lower than the melting temperature used. The target melting point can be obtained by adjusting the composition of two or more polyalcohols that make up the blend.

[0095] Diluent In the present invention, the term "diluent" refers to a thermoplastic polymer or solvent that is combined with an active ingredient to produce a polymer processing aid. The diluent (A) of the present invention is not fluorinated. The diluent (A) does not contain fluorine. If the diluent (A) is thermoplastic and contains and is used partially to deliver a polyalcohol (B), the diluent (A) may be called a carrier polymer. The diluent (A) may also be a solvent. In some embodiments, the solvent is water.

[0096] The diluent (A) of the present invention is sometimes called a carrier polymer, but is preferably a polyolefin polymer. In some embodiments of the present invention, the diluent (A) is a thermoplastic polymer having a lower molecular weight than the thermoplastic polymer being melt-processed. In another embodiment of the present invention, the diluent (A) has the same composition as the thermoplastic polymer being melt-processed. In yet another embodiment of the present invention, the diluent (A) is a solvent.

[0097] The diluent (A) of the present invention is preferably a polyolefin polymer, and more preferably a polyolefin containing ethylene monomer units. The diluent (A) may be a polyethylene polymer containing or consisting of low-density polyethylene (LDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), or ultra-high-density polyethylene (UHDPE), or a combination thereof. This may be polyethylene obtained using a metallocene catalyst, a "single-site" catalyst, a Phillips catalyst, or a Ziegler-Natta catalyst. This can be ethylene copolymers, including but not limited to ethylene vinyl acetate, ethylene methacrylic acid, ethylene methacrylate, ethylene-propylene, and ethylene-α-olefins; functionalized polyolefins; ethylene copolymers containing any non-fluorinated monomer; polypropylene, particularly isotactic or syndiotactic polypropylene; polybutene (obtained from 1-butene); poly(3-methylbutene) or poly(4-methylpentene); and blends or alloys of two or more polyolefins, such as a blend of LLDPE and LDPE. In some embodiments of the present invention, the diluent (A) is a polyolefin composition containing a copolymer, such as ethylene acrylate or ethylene vinyl acetate. In some embodiments of the present invention, the polyolefin is preferably also a carrier polymer having a molecular weight less than or equal to that of the thermoplastic polymer to be melt-processed.

[0098] When used in a masterbatch (D), the diluent (A) of the present invention is preferably a carrier polymer, selected to be compatible with the thermoplastic polymer to be melt-processed, and preferably having a melt index greater than or equal to the melt index of the thermoplastic polymer to be melt-processed. The melt index of the diluent (A) as a carrier polymer is measured according to ASTM D 1238 with a load of 2.16 kg and at 190°C and is 0.1 to 100 g / 10 min, preferably 0.5 to 60 g / 10 min, more preferably 0.75 to 20 g / 10 min, and most preferably 1.0 to 10 g / 10 min.

[0099] The diluent (A) may be the same polymer as the thermoplastic polymer being melt-processed, or a different polymer. The thermoplastic polymer being melt-processed constitutes the majority by weight % of the extrudeable compound (E) or article (F), and preferably, the thermoplastic polymer being melt-processed accounts for more than 90% by weight of the extrudeable compound (E) or article (F).

[0100] Processing aid additives Polymer processing aid (C) may optionally include one or more "processing aid additives" selected from the group consisting of aliphatic polyesters such as polybutylene adipate, polylactic acid, and polycaprolactone (PCL) such as polycaprolactone diol; aromatic polyesters such as diisobutyl phthalate; polyethers such as polyether polyols; amine oxides such as octyldimethylamine oxide; carboxylic acids such as hydroxybutanediic acid; and fatty acid esters such as sorbitan monolaurate. When combined with alternative polymer processing aids or polyalcohols (B), the processing aid additives are considered active ingredients.

[0101] Alternative polymer processing aids A polymer processing aid (C), masterbatch (D), extrudeable compound (E), or article (F) may optionally contain one or more "alternative polymer processing aids" selected from the group consisting of fluoropolymers, silicones; silicone-polyether copolymers, polyethylene glycol (PEG), polyamides and polyether block amides (PEBA), and combinations thereof. The PEBA polyamides and block polyamides may be selected from PA6, PA10, PA11, PA12, PA66, PA610, PA612, PA1010, PA1012, PA1212, or copolyamides PA6 / 12, PA6 / 11, PA6 / 1010, PA6 / 66, PA6 / 66 / 12, PA6 / 66 / 11, PA6 / 66 / 610, PA6 / 612 / 11, or any combination thereof.

[0102] Optionally, the polymer processing aid (C) of the present invention may contain other additive components, stabilizers, and other liquids, solids, and polymers, including but not limited to fillers, organic and inorganic pigments, dyes, colorants, ultraviolet absorbers, nucleating agents, reinforcing agents, antiblocking agents, antioxidants, lubricants (including but not limited to metal soaps, fatty acid esters, hydrocarbon waxes, ester waxes, and amide waxes), and low molecular weight lubricants more appropriately classified as plasticizers. The filler may include dispersed organic or inorganic particles. Examples of inorganic fillers include silica, alumina, zeolite, titanium dioxide, carbonates (e.g., sodium carbonate or potassium carbonate), hydrotalcite, talc, zinc oxide, magnesium oxide, or calcium oxide, diatomaceous earth, carbon black, and the like.

[0103] Composition and form of masterbatch (D) The masterbatch (D) of the present invention comprises at least one polyalcohol (B) and a diluent (A), and may optionally contain one or more of the following: i) processing aid additives, and ii) alternative polymer processing aids. The polyalcohol (B), processing aid additives, and alternative polymer processing aids are all active ingredients, but the diluent (A) is not an active ingredient. The active ingredients in the masterbatch (D) may account for 50% by weight or less, preferably less than 30% by weight, more preferably less than 20% by weight, even more preferably 10% by weight or less, more than 1% by weight, and more preferably more than 1.5% by weight, as a weight percentage of the total masterbatch (D). The polyalcohol (B) accounts for 0.01% to 100% by weight of the active ingredients contained in the masterbatch (D). The diluent (A) may be a thermoplastic polymer, a solvent, or water. In many cases, the diluent is a polyolefin polymer and is often referred to as a carrier polymer.

[0104] In one embodiment, the diluent (A) is combined with a polyalcohol (B) to produce a masterbatch (D), and if the diluent (A) is a thermoplastic polymer, it is often referred to as the carrier polymer in the masterbatch (D). In one embodiment, the masterbatch (D) comprises (i) the diluent (A) (preferably containing a polyolefin polymer) and (ii) at least one active ingredient comprising the polyalcohol (B), and optionally contains other additives.

[0105] The amount of diluent (A) in the masterbatch (D) depends on the intended use and the manufacturing process, and may be in the range of 0.2 to 99% by weight, more preferably 0.5 to 98% by weight, even more preferably 1 to 95% by weight, even more preferably 1.5 to 80% by weight, and most preferably 2 to 75% by weight, relative to the total weight of the masterbatch (D).

[0106] In some embodiments, the amount of polyalcohol (B) in the masterbatch (D) is 25% by weight or less, preferably 20% by weight or less, or 10% by weight or less, more than 0.5% by weight, and more preferably more than 1% by weight, relative to the total weight of the masterbatch. When polyalcohol (B) is the sole active ingredient in the masterbatch (D), it accounts for more than 1% of the total masterbatch (D).

[0107] The masterbatch (D) can be produced by extrusion compounding, compression compounding, or any process known in the art for blending components. The components of the masterbatch (D) can be combined by dry blending, dissolution in a solvent, extrusion compounding, or any combination thereof. When using extrusion compounding, it is achieved using any means known in the art, including the use of a single-screw extruder, a Banbury mixer, a continuous mixer, more preferably a twin-screw extruder or a cone kneader. The masterbatch (D) can be in solid form, preferably in powder form, or in compressed form such as pellets, or in compressed and ground form into granular powder, or in dispersion in a solvent such as water. The masterbatch (D) can also be in liquid or paste form, preferably in dissolved form in a solvent, more preferably in dissolved form in water.

[0108] The masterbatch (D) of the present invention can be produced by combining a polyalcohol (B) and a diluent (A), and may contain one or more of the following: i) processing aid additives, ii) alternative polymer processing aids.

[0109] The masterbatch (D) of the present invention can be used to produce an extrudeable compound (E) or article (F). When the masterbatch (D) of the present invention is produced without the addition of fluoropolymers or other fluorinated materials, it can be a fluoropolymer-free masterbatch.

[0110] The polymer processing aid (C) and / or masterbatch (D) may be in solid form, preferably in powder form, compressed into pellets or the like, compressed and pulverized into granular powder form, or dispersed in a solvent such as water. The polymer processing aid (C) and / or masterbatch (D) may also be in liquid or paste form, preferably dissolved in a solvent, more preferably dissolved in water.

[0111] Composition and form of extrudeable compound (E) The extrudeable compound (E) of the present invention contains a polyalcohol (B) in a thermoplastic polymer (most preferably a polyolefin). The extrudeable compound (E) may further contain one or more of the following: i) processing aid additives, ii) alternative polymer processing aids. The polyalcohol (B) in the extrudeable compound (E) accounts for 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, 5000 ppm or less, preferably 3000 ppm or less, more preferably 2000 ppm or less, and most preferably 1000 ppm or less, based on the total weight of the extrudeable compound (E). In some embodiments, the active ingredient (from PPA) in the extrudeable compound (E) is 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, 75 ppm or more, based on the total weight of the extrudeable compound (E), and accounts for 0.5% by weight or less, preferably 0.3% by weight or less, most preferably 0.25% by weight or less, or 0.1% by weight or less. Polyalcohol (B) accounts for 0.01% to 100% by weight of the active ingredient contained in the extrudeable compound (E). In some embodiments, the amount of active ingredient in the extrudeable compound (E) can be between 1 ppm and 5000 ppm. In some embodiments, the amount of active ingredient in the extrudeable compound (E) can be between 10 ppm and 3000 ppm. The diluent (A) used to produce the extrudeable compound (E) is often a thermoplastic polymer, more often a polyolefin polymer.

[0112] The extrudeable compound (E) of the present invention can be produced by extrusion compounding, compression compounding, or any process known in the art to combine the components of the extrudeable compound (E). The polyalcohol (B) can be introduced into the extrudeable compound (E) in various forms, including but not limited to liquids, pastes, powders, and pellets. The extrudeable compound (E) can be in different forms, such as pellets and powders, or any form known in the art. The extrudeable compound (E) can be prepared by combining a thermoplastic polymer, preferably a polyolefin, with the polyalcohol (B). The polyalcohol (B) may be in the form of a polymer processing aid (C), a masterbatch (D), or any combination thereof, and may contain one or more of the following: i) processing aid additives, ii) alternative polymer processing aids.

[0113] The polyolefin of the extrudeable compound (E) may be functionalized, unfunctionalized, or a mixture thereof. For example, the polyolefin may be polyethylene; examples include, but are not limited to, low-density polyethylene (LDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), or ultra-high-density polyethylene (UHDPE), or combinations thereof. The polyolefin of the extrudeable compound (E) may be polyethylene obtained using a metallocene catalyst, more commonly a "single-site" catalyst, a Phillips catalyst, or a Ziegler-Natta catalyst; polypropylene, isotactic polypropylene, or syndiotactic polypropylene; polybutene (obtained from 1-butene); poly(3-methylbutene) or poly(4-methylpentene).

[0114] In some embodiments, the extrudeable compound (E) contains, based on the total weight of the thermoplastic polymer, at least 10 ppm of polyalcohol (B), 10 ppm to 0.5% by weight, preferably 25 ppm to 0.3% by weight, more preferably 50 ppm to 0.25% by weight, even more preferably 75 ppm to 0.5% by weight, and most preferably 100 ppm to 2000 ppm of polyalcohol (B).

[0115] In some embodiments of the present invention, the extrudeable compound (E) comprises a thermoplastic polymer and a polyalcohol (B) in an amount of 5 ppm to 0.5% by weight, preferably 10 ppm to 0.25% by weight, based on the total weight of the extrudeable compound (E).

[0116] The extrudeable compound (E) of the present invention can be used to manufacture an article (F). In some embodiments, the extrudeable compound (E) does not contain a fluoropolymer or any other fluorinated material.

[0117] Composition and form of article (F) The present invention also relates to an article (F) comprising a polyalcohol (B) and a thermoplastic polymer, preferably polyethylene. Article (F) may include an extrudeable compound or can be manufactured from an extrudeable compound. In some preferred embodiments, the thermoplastic polymer of the extrudeable compound is a polyolefin, which may be functionalized, unfunctionalized, or a mixture thereof. As an example, the thermoplastic polymer of the present invention may be polyethylene such as low-density polyethylene (LDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), or ultra-high-density polyethylene (UHDPE), or a combination thereof. This may be polyethylene obtained using a metallocene catalyst, more commonly a "single-site" catalyst, a Phillips catalyst, or a Ziegler-Natta catalyst; polypropylene, isotactic polypropylene, or syndiotactic polypropylene; polybutene (obtained from 1-butene); poly(3-methylbutene) or poly(4-methylpentene).

[0118] Article (F) may optionally contain one or more of the following: i) processing aid additives, and ii) alternative polymer processing aids. The active ingredients in Article (F) are present in an amount of 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, and 75 ppm or more, relative to the total weight of Article (F), and account for 0.5% or less by weight, preferably 0.3% or less by weight, and most preferably 0.25% or less by weight. Polyalcohol (B) accounts for 0.01% to 100% by weight of the active ingredients contained in Article (F). The thermoplastic polymer used to manufacture Article (F) is often a polyolefin polymer.

[0119] A polyalcohol (B) can be introduced into a thermoplastic polymer in the form of a polymer processing aid (C) or a masterbatch (D), and then melt-processed to form an article (F). The article (F) can be formed by melt-processing an extrudeable compound (E). The thermoplastic polymer is preferably a polyolefin polymer.

[0120] In some embodiments, article (F) comprises at least 10 ppm of polyalcohol (B) based on the weight of the thermoplastic polymer in article (F), and may contain 10 ppm to 0.5% by weight, preferably 25 ppm to 0.25% by weight, more preferably 50 ppm to 0.1% by weight, even more preferably 75 ppm to 0.5% by weight, and most preferably 100 ppm to 2000 ppm of polyalcohol (B) based on the weight of the thermoplastic polymer.

[0121] In some embodiments of the present invention, article (F) comprises a thermoplastic polymer, preferably a polyolefin, and a polyalcohol (B) in an amount of 5 ppm to 0.5% by weight, preferably 10 ppm to 0.1% by weight, based on the total weight of article (F).

[0122] Article (F) of the present invention can be manufactured by extrusion or molding, or by any other means of melting an extrudeable compound. In some embodiments, article (F) is in the form of a film, tube, pipe, sheet, rod, fiber, filament, shaped extruded article, molded part or molded component, wire coating, multilayer structure, and cable sheathing or insulation, or a part or component selected from these.

[0123] In some embodiments, the article (F) of the present invention is produced by injecting a liquid polyalcohol (B) into a thermoplastic polymer during melt processing. An example is to produce an extrudeable compound (in situ) in which the polyalcohol (B) is properly dispersed in the melting process and acts as a polymer processing aid, by dissolving the polyalcohol (B) in water and then injecting it into an extruder containing the thermoplastic polymer.

[0124] The masterbatch (D), extrudeable compound (E), or article (F) may contain one or more other additives selected from the group consisting of fillers, pigments, dyes, antioxidants, UV absorbers and light stabilizers, nucleating agents, and reinforcing agents. The fillers may include dispersed organic or inorganic particles. Examples of inorganic fillers include silica, alumina, zeolite, titanium dioxide, carbonates (e.g., sodium carbonate, potassium carbonate), hydrotalcite, talc, zinc oxide, magnesium oxide, or calcium oxide, diatomaceous earth, carbon black, etc. The pigments may be inorganic or organic. The diluent (A) of the present invention may also be a liquid, preferably water. In some embodiments of the present invention, the polyalcohol (B) is completely dissolved in the diluent.

[0125] Processes used Any process known in the art for combining and / or blending individual components can be used to produce polymer processing aids (C), masterbatches (D), or extrudeable compounds (E). Typically, extrusion processes are used, more commonly melt extrusion processes, but compression processes may also be used. Unlike extrusion processes, compression processes are typically carried out below the melting temperature of the components being combined.

[0126] The present invention also relates to the production of an article (F) using any process known in the art for producing thermoplastic articles, including extrusion and molding. In one embodiment of the present invention, the article (F) is produced by an extrusion process that forms a film, tube, pipe, sheet, rod, multilayer structure, cable sheath, or insulator. The polyalcohol (B) can be added directly to the thermoplastic polymer to be melt-worked, or it can be introduced into the thermoplastic polymer to be melt-worked in the form of a polymer processing aid (C) or a masterbatch (D). The article (F) can be formed by processing an extrudeable compound (E). Preferably, the thermoplastic polymer of the present invention is a polyolefin polymer. [Examples]

[0127] experiment All experiments described herein were performed using masterbatches prepared with the components shown in the table below. The carrier polymer used in all masterbatches is 1MI linear low-density polyethylene from Ineos Inc. The fluoropolymer identified as PVDF1 is a PVDF-HFP copolymer used in commercially available PPA formulations. The polyalcohols used were identified as D-mannitol, D-dalcitol, and glycerin. The polycaprolactone (PCL1) surfactant is Capa® 2403D6 manufactured by Ingevity. The polyethylene glycol (PEG) is Carbowax® Sentry PEG8000 powder from Dow Chemical Company. The polyamides used are long-chain polyamides identified as polyamide 11 (PA11) and polyamide 12 (PA12).

[0128] Polymer processing aids were manufactured by twin-screw compounding. The polymer processing aids were prepared using a Leistritz 18mm twin-screw designed for good mixing and dispersion. The carrier polymer used was a barefoot 1MI LLDPE polymer manufactured by Ineos. The active ingredient was added to the carrier polymer at 2.5% by weight, based on the total weight of the polymer processing aid to be manufactured. The carrier polymer and active ingredient were fed into the feed throat of the twin-screw using individual weight-reducing feeders. The barrel temperature and feed rate were adjusted to maintain the melting temperature at approximately 200°C. Volatile substances were removed using a vacuum vent. The polymer processing aids were discharged from the twin-screw through a strand die, cooled using a water bath, dried by passing through an air knife, and then pelletized using a strand cutter.

[0129] Polymer processing aids were evaluated by performing flat die extrusion tests. Flat die extrusion tests involve extruding strips or ribbons using a flat profile die. Flat die extrusion tests were performed using a 1.5-inch Davis Standard extruder with a compression ratio of 3:1 and an L / D metering screw of 24:1. The flat die, also called a slot die, had dimensions of 50 mm × 0.5 mm, a 10 mm land, and a tapered feed section. The flat die was equipped with heater bands for temperature control on the die body and die lip. The extruder and flat die were positioned downward at an angle of 20-30 degrees to prevent the extruded material from contacting the die surface.

[0130] The flat die test is initiated by purging for 25 minutes using Dow Purge® purge compound (manufactured by Dow Inc.). The extruder and die are purged with all temperature zones set to 392°F and the screw speed to 60 rpm. This is followed by purging with 1.0 MI of LLDPE until a steady-state pressure is achieved and uniform melt fracture is observed. Then, the screw speed is adjusted to 21.3 rpm for 300 seconds until a steady state is achieved (typically 20-30 minutes) and the extruded ribbon visually shows uniform 100% melt fracture on all surfaces. -1 Achieve the calculated shear rate.

[0131] After reaching a steady state, a flat die test can be performed. The thermoplastic polymer is pellet-blended with a polymer processing aid to achieve the desired target level of the active ingredient. Subsequently, after removing any remaining purged material from the extruder hopper, the pellet blend is extruded. The thermoplastic polymer is 1.0 MI LLDPE, and the active ingredient was tested at several different levels, including 200 ppm, 250 ppm, 400 ppm, 475 ppm, 500 ppm, or 1000 ppm of the total composition under test.

[0132] The flat die test measures the time until melt fracture is eliminated from the extruded surface. The test begins when the thermoplastic polymer containing the polymer processing aid is added to the extruder hopper. The test ends when melt fracture is eliminated. The decrease in melt pressure is measured, which is the difference between the initial melt pressure and the melt pressure after melt fracture (due to the introduction of the polymer processing aid) is eliminated. A melt pressure transducer attached to the die was used to monitor and record the pressure.

[0133] The data is reported as a percentage reduction in melt fracture, determined by visual inspection of the extruded material during testing. The test is started at 100% melt fracture, and after adding the thermoplastic polymer containing PPA, visible melt fracture is recorded as a function of time until melt fracture is eliminated. For most useful polymer processing aids, at levels ranging from 200 ppm to 400 ppm, melt fracture is eliminated within one hour after PPA addition.

[0134] In the following examples, melt failure reduction is expressed as 1%, 2%, or 3% melt failure, in accordance with established practices for conducting these tests. The levels of melt failure can be further described as follows: The presence of "1% melt failure" indicates that melt failure is completely eliminated from the extruded surface, except for the edges. "1% melt failure" is considered to be the complete elimination of melt failure in this test. The presence of "2% melt failure" indicates that melt failure is present in 1% of the extruded surface plus at the edges. The presence of "3% melt failure" indicates that melt failure is present in 2% of the extruded surface plus at the edges. The presence of 2% and 3% melt failure is very close to the complete elimination of melt failure.

[0135] Example 1 Example 1 describes the use of glycerin as an active ingredient in a polymer processing aid. Glycerin is a polyalcohol that is liquid at room temperature and has a melting point of 18.2°C. A polymer processing aid containing 2.5% glycerin and 97.5% carrier resin was prepared using a twin-screw compounder. The carrier resin used in the polymer processing aid was barefoot 1 MI LLDPE polymer. Next, this polymer processing aid was pelletized and blended with barefoot 1 MI LLDPE thermoplastic polymer, with a target glycerin level of 250 ppm in the pellet blend. A performance test was performed on the pellet blend containing 250 ppm glycerin using the method described above. It was found that glycerin acted as a polymer processing aid and eliminated melt fracture in 63 minutes. Glycerin also reduced the melt pressure. No charring or color change was observed.

[0136] [Table 1]

[0137] Example 2 Example 2 describes the use of D-dalcitol as an active ingredient in a polymer processing aid. D-dalcitol is a polyalcohol with a melting point in the range of 98-100°C. A polymer processing aid containing 2.0% D-dalcitol and 98.0% carrier resin was manufactured using a twin-screw compounder. The carrier resin used in the polymer processing aid was barefoot 1 MI LLDPE polymer. Next, this polymer processing aid was pellet-blended with barefoot 1 MI LLDPE thermoplastic polymer, and the target D-dalcitol level in the pellet blend was set to 200 ppm. A performance test was performed on the pellet blend containing 200 ppm D-dalcitol using the method described above. D-dalcitol acted as a polymer processing aid, reducing melt fracture to a 6% level in 60 minutes, and requiring 90 minutes to eliminate melt fracture. D-dalcitol also reduced the melt pressure. No charring or discoloration was observed.

[0138] [Table 2]

[0139] Example 3 Example 3 describes the use of D-mannitol as an active ingredient in a polymer processing aid. D-mannitol is a polyalcohol with a melting point of 164-169°C. A polymer processing aid containing 2.0% D-mannitol and 98.0% carrier resin was prepared using a twin-screw compounder. The carrier resin used in the polymer processing aid was barefoot 1 MI LLDPE polymer. Next, this polymer processing aid was pelletized and blended with barefoot 1 MI LLDPE thermoplastic polymer, with target D-mannitol levels of 200 ppm and 400 ppm in the pelletized blend. Performance tests were performed on the LLDPE blends containing 200 ppm and 400 ppm D-mannitol using the method described above. D-mannitol acted as a polymer processing aid and was found to rapidly and efficiently eliminate melt fracture in 20 minutes at both levels tested. D-mannitol also reduced the melt pressure. No charring or discoloration was observed in the LLDPE blends containing D-mannitol.

[0140] [Table 3]

[0141] Example 4 Example 4 describes a blended PPA masterbatch comprising two separate masterbatches, one containing a fluoropolymer (PVDF1) and the other containing a polyalcohol (D-mannitol). The fluoropolymer-containing masterbatch contained 2.5% PVDF1 and 97.5% LLDPE carrier resin. The polyalcohol-containing masterbatch contained 2.0% D-mannitol and 98.0% LLDPE carrier resin. Both PPA masterbatches were manufactured using a twin-screw compounder. The blended PPA masterbatch was manufactured by combining the PVDF1 masterbatch and the D-mannitol masterbatch in a 3:1 ratio. Next, the blended PPA masterbatches were added to barefoot 1 MI LLDPE to produce an LLDPE composition containing 375 ppm PVDF1 and 100 ppm D-mannitol relative to the total composition. The LLDPE composition was subjected to performance testing using the method described above. An LLDPE composition containing 375 ppm PVDF1 and 100 ppm D-mannitol eliminated melt fracture more quickly than a composition containing PVDF1 alone at a similar level of active ingredients. The melt pressure reduction was similar for both compositions.

[0142] [Table 4]

[0143] Example 4 Example 4 describes a blended PPA masterbatch comprising two separate masterbatches, one containing a fluoropolymer and a synergistic agent (PVDF2), and the other containing a polyalcohol (D-mannitol). The fluoropolymer-containing masterbatch (PVDF2) contained 1.375% PVDF1, 1.125% PEG 8000, and 97.5% LLDPE carrier resin. The polyalcohol-containing masterbatch contained 2.0% D-mannitol and 98.0% LLDPE carrier resin. Both PPA masterbatches were manufactured using a twin-screw compounder. The blended PPA masterbatch was manufactured by combining the PVDF2 masterbatch and the D-mannitol masterbatch in a 3:1 ratio. The blended PPA masterbatches were then added to barefoot 1 MI LLDPE to produce an LLDPE composition containing 375 ppm PVDF2 and 100 ppm D-mannitol relative to the total composition. The LLDPE compositions were subjected to performance tests using the method described above. LLDPE compositions containing 375 ppm PVDF2 and 100 ppm D-mannitol eliminated melt fracture faster than compositions containing PVDF2 alone at similar levels of active ingredients. The decrease in melt pressure was similar for both compositions. No charring or discoloration was observed.

[0144] [Table 5]

[0145] Example 5 Example 5 describes a blended PPA masterbatch comprising two separate masterbatches, one containing PEG (PEG8000) and the other containing polyalcohol (D-mannitol). The PEG-containing masterbatch (PEG8000) contained 2.0% PEG8000 and 98.0% LLDPE carrier resin. The polyalcohol-containing masterbatch contained 2.0% D-mannitol and 98.0% LLDPE carrier resin. Both PPA masterbatches were manufactured using a twin-screw compounder. The blended PPA masterbatch was manufactured by combining the PEG8000 masterbatch and the D-mannitol masterbatch in ratios of 9:1 and 3:1, respectively. A blended PPA masterbatch was added to barefoot 1 MI LLDPE to produce two LLDPE compositions: one containing 900 ppm PEG 8000 and 100 ppm D-mannitol relative to the total composition, and the other containing 300 ppm PEG 8000 and 100 ppm D-mannitol relative to the total composition. Performance tests were performed on the LLDPE compositions using the method described above. The melt fracture exclusion performance of PEG 8000 was significantly improved by the addition of D-mannitol. The reduction in melt pressure was also improved by adding D-mannitol to PEG 8000. No charring or color change was observed.

[0146] [Table 6]

[0147] Example 6 Example 6 describes a blended PPA masterbatch comprising two separate masterbatches, one containing polyamide 12 (PA12) and the other containing polyalcohol (D-mannitol). The polyamide-containing masterbatch (PA12) contained 2.0% PA12 and 98.0% LLDPE carrier resin. The polyalcohol-containing masterbatch contained 2.0% D-mannitol and 98.0% LLDPE carrier resin. Both PPA masterbatches were manufactured using a twin-screw compounder. The blended PPA masterbatch was manufactured by combining the PA12 masterbatch and the D-mannitol masterbatch in ratios of 7:1, 1:1, and 1:7, respectively. A blended PPA masterbatch was added to barefoot 1 MI LLDPE to produce three LLDPE compositions: one containing 350 ppm PA12 and 50 ppm D-mannitol, another containing 200 ppm PA12 and 200 ppm D-mannitol, and another containing 50 ppm PA12 and 350 ppm D-mannitol. Performance tests were conducted on the LLDPE compositions using the method described above. The melt fracture exclusion performance of PA12 was significantly improved by the addition of D-mannitol. The reduction in melt pressure was also improved by the addition of D-mannitol to PA12. No charring or color change was observed.

[0148] [Table 7]

[0149] Example 7 Example 7 describes a blended PPA masterbatch comprising two separate masterbatches, one containing polyamide 11 (PA11) and the other containing polyalcohol (D-mannitol). The polyamide-containing masterbatch (PA11) contained 2.0% PA11 and 98.0% LLDPE carrier resin. The polyalcohol-containing masterbatch contained 2.0% D-mannitol and 98.0% LLDPE carrier resin. Both PPA masterbatches were manufactured using a twin-screw compounder. The blended PPA masterbatch was manufactured by combining the PA11 masterbatch and the D-mannitol masterbatch in a 3:1 ratio. Next, the blended PPA masterbatches were added to barefoot 1 MI LLDPE to produce an LLDPE composition containing 300 ppm PA11 and 100 ppm D-mannitol relative to the total composition. The LLDPE composition was subjected to performance testing using the method described above. LLDPE compositions containing 300 ppm PA11 and 100 ppm D-mannitol eliminated melt fracture in a relatively short time of 31 minutes. In contrast, 400 ppm PA11 failed to eliminate melt fracture, and 75% melt fracture was observed even after a 60-minute test. No charring or discoloration was observed.

[0150] [Table 8]

[0151] Comparative Example 1 Comparative Example 1 describes the use of glucose as an active ingredient in a polymer processing aid. Glucose is a monosaccharide, not a polyalcohol, and has a melting point of approximately 146°C. A polymer processing aid containing 2.5% glucose and 97.5% carrier resin was manufactured using a twin-screw compounder. The carrier resin used in the polymer processing aid was barefoot 1 MI LLDPE polymer. Next, this polymer processing aid was pelletized and blended with barefoot 1 MI LLDPE thermoplastic polymer, with a target glucose level of 400 ppm in the blend. Performance tests were performed on the LLDPE blend containing 400 ppm glucose using the method described above. Glucose did not act as a polymer processing aid and did not result in a reduction of melt fracture or a decrease in pressure. Significant darkening of the LLDPE blend containing glucose was observed, which is thought to be due to the combustion of glucose.

[0152] Comparative Example 2 Comparative Example 2 describes the use of sucrose as an active ingredient in a polymer processing aid. Sucrose is a disaccharide, not a polyalcohol, and has a melting point of 185-187°C. A polymer processing aid containing 2.5% sucrose and 97.5% carrier resin was manufactured using a twin-screw compounder. The carrier resin used in the polymer processing aid was barefoot 1 MI LLDPE polymer. Next, this polymer processing aid was pelletized and blended with barefoot 1 MI LLDPE thermoplastic polymer, with a target sucrose level of 400 ppm in the blend. Performance tests were performed on the LLDPE blend containing 400 ppm sucrose using the method described above. Sucrose did not act as a polymer processing aid and did not result in a reduction of melt fracture or a decrease in pressure. Significant blackening was observed in the LLDPE blend containing sucrose, which is thought to be due to the combustion of sucrose.

[0153] Comparative Example 3 Comparative Example 3 describes the use of cyclohexane 1,2,3,4,5,6-hexol as an active ingredient in a polymer processing aid. Cyclohexane 1,2,3,4,5,6-hexol is a cyclic polyalcohol with a melting point of 252°C. A polymer processing aid containing 2.5% cyclohexane 1,2,3,4,5,6-hexol and 97.5% carrier resin was manufactured using a twin-screw compounder. The carrier resin used in the polymer processing aid was barefoot 1 MI LLDPE polymer. Next, this polymer processing aid was pelletized and blended with barefoot 1 MI LLDPE thermoplastic polymer, with a target cyclohexane 1,2,3,4,5,6-hexol level of 400 ppm in the blend. Performance tests were performed on the LLDPE blend containing 400 ppm cyclohexane 1,2,3,4,5,6-hexol using the method described above. Cyclohexane 1,2,3,4,5,6-hexol did not act as a polymer processing aid, nor did it reduce melt fracture or pressure. No charring or discoloration was observed.

Claims

1. It contains one or more polyalcohols (B), and optionally one or more of the following: a. Processing aid additives selected from the group consisting of aliphatic polyesters such as polybutylene adipate, polylactic acid, and polycaprolactone (PCL) such as polycaprolactone diol; aromatic polyesters such as diisobutyl phthalate; polyethers such as polyether polyols; amine oxides such as octyldimethylamine oxide; carboxylic acids such as hydroxybutanediic acid; and fatty acid esters such as sorbitan monolaurate. b. A polymer processing aid (C) comprising an alternative polymer processing aid selected from the group consisting of silicones, silicone-polyether copolymers, fluoropolymers, polyamides, polyether block amides (PEBA), polyethylene glycol, and silicone polyalkylene oxides such as polyethylene glycol (PEG), The polyalcohol (B) is not a polymer, but a polymer processing aid with a melting point of 240°C or lower.

2. The polymer processing aid according to claim 1, wherein the polyalcohol (B) contains a polyhydric alcohol and has two or more hydroxyl groups, and each carbon has a single hydroxyl group.

3. The polymer processing aid according to claim 1, wherein the polyalcohol (B) is selected from the group consisting of ethylene glycol, glycerin (glycerol), erythritol, sreitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fusitol, iditol, inositol, boremitol, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, polyglycitol, and combinations thereof.

4. The polymer processing aid according to claim 1, wherein the polyalcohol (B) contains D-mannitol.

5. The polymer processing aid according to claim 1, wherein the polyalcohol (B) contains sorbitol.

6. The polymer processing aid according to claim 1, wherein the polyalcohol (B) has a melting point of 230°C or less, preferably less than 220°C.

7. The polymer processing aid according to any one of claims 1 to 6, wherein the polyalcohol (B) comprises at least two different polyalcohols.

8. The polymer processing aid according to claim 7, wherein the polyalcohol forms a eutectic blend.

9. A polymer processing aid according to any one of claims 1 to 8, further comprising an additive selected from the group consisting of fillers, colorants, antiblocking agents, antioxidants, lubricants, stabilizers, synergists, and combinations thereof.

10. The polymer processing aid according to any one of claims 1 to 9, wherein the amount of the polyalcohol (B) in the polymer processing aid (C) is in the range of more than 0.1% by weight to 99% by weight, preferably 1.0 to 99.9% by weight, more preferably 5 to 99% by weight, and even more preferably 50 to 98.5% by weight, based on the total weight of the polymer processing aid (C).

11. The polymer processing aid according to any one of claims 1 to 9, wherein the total amount of active components in the polymer processing aid (C) is more than 50% by weight, preferably 95% by weight or more, preferably 99% by weight or more, and most preferably 100% by weight, and the polyalcohol (B) accounts for 0.1% by weight to 100% by weight of the total amount of active components in the polymer processing aid (C).

12. A polymer processing aid according to any one of claims 1 to 9, further comprising a diluent (A) to form a masterbatch (D).

13. The polymer processing aid according to claim 12, wherein the total amount of active ingredients in the polymer processing aid is 50% by weight or less of the total polymer processing aid, preferably less than 30% by weight, more preferably less than 20% by weight, even more preferably 10% by weight or less, preferably more than 0.1% by weight, more preferably more than 0.5% by weight, and the polyalcohol (B) accounts for 0.01% to 100% by weight of the active ingredients contained in the polymer processing aid.

14. The polymer processing aid according to claim 13, wherein the diluent (A) contains one or more polyolefins.

15. The polymer processing aid according to claim 13, wherein the diluent (A) contains a polyethylene polymer.

16. The polymer processing aid according to claim 13, wherein the diluent (A) comprises at least one of a polypropylene homopolymer or a polypropylene copolymer.

17. The polymer processing aid according to claim 13, wherein the diluent (A) is selected from the group consisting of LDPE, HDPE, LLDPE, and functionalized polyolefins.

18. The polymer processing aid according to claim 13, wherein the diluent (A) comprises an ethylene copolymer selected from the group consisting of ethylene vinyl acetate, ethylene methacrylic acid, ethylene methacrylate, ethylene-propylene, ethylene-α-olefin, and combinations thereof.

19. The polymer processing aid according to claim 13, wherein the diluent (A) comprises a solvent, preferably water.

20. An extrudeable compound (E) comprising a polyalcohol (B) and a thermoplastic polymer, preferably the thermoplastic polymer being a polyolefin.

21. An extrudeable compound (E) comprising a polymer processing aid according to any one of claims 1 to 19.

22. An extrudeable compound (E) according to claim 21, comprising a polyalcohol (B) in an amount from 10 ppm to 2000 ppm, preferably up to 1000 ppm, and most preferably up to 750 ppm, based on the weight of the thermoplastic polymer.

23. The extrudeable compound (E) according to claim 21, comprising 1 ppm or more, preferably 5 ppm or more, most preferably 10 ppm or more, and 0.5% by weight or less, preferably 0.25% by weight or less, most preferably 0.1% or less of the total weight of the active ingredients in the extrudeable compound (E), wherein the polyalcohol (B) accounts for 0.01% to 100% by weight of the active ingredients contained in the extrudeable compound (E).

24. An article (F) comprising a polymer processing aid according to any one of claims 1 to 19.

25. An article (F) comprising an extrudeable compound (E) according to any one of claims 20 to 23.

26. Article (F) according to claim 24 or 25, wherein the thermoplastic polymer is a polyolefin.

27. A method for melt processing thermoplastic polymers, a) A step of combining a polymer processing aid according to any one of claims 1 to 19 with a thermoplastic polymer, preferably a polyolefin polymer, wherein the amount of polyalcohol (B) is 1 ppm to less than 1% by weight, preferably less than 5000 ppm, based on the total weight of the thermoplastic polymer. b) A step of heating the polyalcohol (B) at a temperature higher than its melting point, c) A step of melting the thermoplastic polymer composition by extrusion or molding, A method that includes this.

28. The method according to claim 27, wherein the amount of the polyalcohol (B) is 10 ppm to 0.25% by weight.

29. The following steps: a) A step of producing a thermoplastic polymer composition by combining a polyalcohol (B) and a thermoplastic polymer, preferably a polyolefin polymer, in an amount of 1 ppm to 5000 ppm based on the total weight of the thermoplastic polymer, and then b) A step of heating the thermoplastic polymer composition in an extruder, molding machine, or other melting apparatus at a temperature higher than the melting point of the thermoplastic polymer, and c) A process of manufacturing an article (F) by extrusion, molding, or melt processing, The present invention provides a method for manufacturing an article (F) by melting, including the following:

30. Next step: a) A step of providing an extrudeable compound (E) according to any one of claims 20 to 23, comprising 1 ppm to 5000 ppm of polyalcohol (B) based on the total weight of the thermoplastic polymer, and thereafter b) A step of producing an article (F) by heating and melting the extrudeable compound (E) composition at a temperature higher than the melting point of the thermoplastic polymer, A method for manufacturing an article (F) by melting, including the following.

31. The method according to claim 27, 29, or 30, wherein the amount of the polyalcohol (B) is at least 10 ppm and up to 5000 ppm, more preferably up to 2000 ppm, even more preferably up to 1000 ppm, and most preferably up to 750 ppm, based on the weight of the thermoplastic polymer.

32. The method according to claim 27, 29, or 30, wherein the amount of the active ingredient is 1 ppm or more, preferably 5 ppm or more, most preferably 10 ppm or more, and 0.5% by weight or less, preferably 0.25% by weight or less, and most preferably 0.1% or less, of the total weight of the active ingredient in the article (F), and the polyalcohol (B) accounts for 0.01% to 100% by weight of the active ingredient contained in the article (F).

33. The method according to claim 27, 29, or 30, wherein the total amount of active ingredients in the polymer processing aid is 50% by weight or less of the total polymer processing aid, preferably less than 30% by weight, more preferably less than 20% by weight, even more preferably 10% by weight or less, preferably more than 0.1% by weight, more preferably more than 0.5% by weight, and the polyalcohol (B) accounts for 0.01% to 100% by weight of the active ingredients contained in the polymer processing aid.

34. The method according to claim 29, wherein the polyalcohol (B) is provided in the form of a polymer processing aid according to any one of claims 1 to 19.

35. The method according to claim 27, 29, or 30, wherein the thermoplastic polymer is a polyolefin.

36. The method according to claim 27, 29, or 30, wherein the melting point of the polyalcohol (B) is less than the melting temperature.

37. The method according to claim 27, 29, or 30, wherein melt fracture is reduced or eliminated during the melt processing of the thermoplastic polymer composition.

38. Use of a polymer processing aid according to any one of claims 1 to 19 for reducing melt fracture in the melt processing of thermoplastic polymers.

39. Use of a polymer processing aid containing polyalcohol (B) for melt processing of polyolefin polymers.

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