EP4698573A1 - Polyalcohol as polymer processing aids - Google Patents

Abstract

The invention relates to composition comprising polyalcohol used to reduce or eliminate surface defects arising from melt extrusion of thermoplastics polymers.

Description

POLYALCOHOL AS POLYMER PROCESSING AIDS

[0001] This Application take priority from US provisional application 63/461 ,101 filed April 21 , 2023, its entire contents herein incorporated by reference.

[0002] FIELD OF THE INVENTION

[0003] The present invention relates to a polymer processing aid (“PAA”) comprising a polyalcohol.

BACKGROUND OF THE INVENTION

[0004] In a melt extrusion process, a solid polymer, normally in the form of pellets or powder, is fed into an extruder and heated to a temperature above the melting point of the solid polymer to produce a polymer melt. The polymer melt is then conveyed through an extrusion die located at the end of the extruder and formed into a desired shape such as a tube, sheet, rod, film, or other profile.

[0005] During the extrusion process, the polymer melt is subjected to shear stresses that can cause surface defects, with the most common being melt fracture. Melt fracture appears as a surface haze often described as a “matt" finish, and under magnification, visually appears as a rough saw tooth pattern. Melt fracture is considered an unacceptable quality problem that adversely affects optical and visual characteristics and may also adversely affects physical and mechanical properties. Polymer processing aids are known to reduce and most often eliminate melt fracture. In most cases, polymer processing aids (PPA) contain a fluoropolymer which is the active component responsible for eliminating melt fracture. For polymer processing aids containing a fluoropolymer and a synergist, both the fluoropolymer and synergist are considered active components for eliminating melt fracture.

[0006] When performing melt fracture elimination studies, in many cases, lower levels of active components are used to better observe melt fracture elimination over a longer period. By slowing down melt fracture elimination, better performance differentiation between tests can be obtained.

[0007] Additives such as mineral fillers (contained in many polymer compounds) can further promote melt fracture. It is understood that the presence of such fillers reduces the ability of a PPA comprising a fluoropolymer to eliminate melt fracture. When this occurs, PPA levels are typically increased.

[0008] The relative performance of a polymer process aid is normally related to the ability of the PPA to eliminate melt fracture. One means of evaluating PPA performance is to study the time needed for a PPA to eliminate melt fracture. A typical test starts by setting up extrusion conditions favorable for melt fracture formation. Once melt fracture formation is obtained, and the process is stable, PPA is then added, and the time to eliminate melt fracture recorded. In this test, a better performing PPA is one that eliminates melt fracture in less time. As an example, in such a test, if one PPA is found able to eliminate melt fracture in 30 minutes and a second PPA able to eliminate melt fracture in 60 minutes, and they both use the same addition levels and process conditions, then the PPA able to eliminate melt fracture in 30 minutes is said to be a better performing PPA.

[0009] The relative performance of a polymer process aid can also be evaluated by varying the amount of PPA needed to achieve similar melt fracture elimination performance. As an example, in such a study, if one PPA is found effective at 300 ppm and a second PPA found similarly effective at 500 ppm, the PPA found effective at 300 ppm is said to be a better performing PPA.

[0010] There is a direct correlation between the ability to eliminate melt fracture quickly and the ability to eliminate melt fracture using lower PPA addition levels. In general, PPA’s found able to eliminate melt fracture quickly also perform better at lower addition levels. Lower PPA addition levels provide several benefits including lower production costs and less negative effects on final product properties.

[0011] Many commercial polymer process aids containing fluoropolymers also contain synergists to improve melt fracture elimination performance. In such a polymer processing aid, the fluoropolymer and synergist are both active components that work together to eliminate melt fracture better than if either component were used individually. Common PPA synergists combined with fluoropolymers are described in several patents. As an example, in EP1976927B1 .

[0012] Polymer processing aids comprising fluoropolymers are known to be highly effective and historically have been used almost exclusively when extruding polyolefin polymers. It is generally understood by those knowledgeable about polyolefin extrusion that polymer processing aids containing fluoropolymers outperform those without fluoropolymers.

[0013] There is currently a worldwide effort to reduce or eliminate the use of fluorinated chemicals including fluoropolymers in many applications. More specific to this invention, industry efforts are underway to replace fluoropolymers in polymer processing aids with alternative nonfluorinated chemistries. Due to these efforts, effective polymer processing aids without fluoropolymers are needed. More specifically, there is a need for PPA’s without fluoropolymers able to eliminate melt fracture as efficiently as those containing fluoropolymers. Prior to this invention, effective fluoropolymer free polymer processing aids having comparable performance to those containing fluoropolymers were unknown. [0014] A PPA produced without a fluoropolymer can be referred to as a Fluoropolymer Free polymer Processing Aid or FFPA. As noted, a highly effective FFPA for melt fracture elimination was unknown prior to this discovery. For a fluoropolymer free polymer processing aid (FFPA) to be useful, several performance characteristics need to be met. Of importance, the FFPA needs to provide an acceptable level of melt fracture elimination at traditional addition levels. Preferably, the FFPA is a drop-in replacement for the fluoropolymer containing PPA providing similar performance characteristics at similar addition levels. In addition, in many applications, it is preferable that the FFPA meets applicable requirements for food and water contact. The active components of this invention identified as polyalcohols are commonly used as food additives.

[0015] Prior to this discovery, PPA’s comprising fluoropolymers were the primary means of eliminating melt fracture quickly, especially when low addition levels were considered necessary. The discovery of a fluoropolymer free process aid composition able to provide melt fracture elimination performance equivalent too, and in many cases, better than polymer process aids containing fluoropolymers was surprising.

[0016] The invention described herein provides a polymer process aid comprising one or more polyalcohol as active components. The addition of a fluoropolymer or a synergist is not needed for this invention to perform effectively as a PPA. Polymer process aids comprising one or more polyalcohol were found to effectively eliminate melt fracture during melt extrusion. The primary active component of this invention is not a fluoropolymer, and instead is a polyalcohol, and more specifically, a “polyhydric” or “sugar” alcohol. Besides not containing fluorine, the polyalcohol of this invention also differs from currently used polymer processing aids by not being polymeric.

[0017] The inventors have found that Polyalcohol (B) of this invention can be used as a polymer processing aid for the elimination of melt fracture in a polymer melt extrusion process. The polyalcohol (B) of this invention may also provide other polymer processing aid benefits known in the art including but not limited to die drool reduction and lowering melt process pressure in addition to reducing quality defects such as melt fracture. The invention also includes the combination of polyalcohol and other active components to produce polymer processing aid compositions.

BRIEF DESCRIPTION OF THE INVENTION

[0018] The invention relates to a composition comprising polyalcohol used to reduce or eliminate surface defects arising from melt extrusion of thermoplastic polymers, particularity useful in polyolefins. The composition of the invention comprising polyalcohol can optionally contain other commercially available polymer processing aids and other components known in the art to reduce quality defects such as melt fracture. [0019] The polymer processing aid (C) of this invention comprises at least one polyalcohol (B). The polymer processing aid (C) may contain one or more of the following: ii) a “processing aid additive” iii) an alternative polymer processing aid. The polyalcohol (B), process aid additive and alternative polymer processing aid are all active components.

[0020] The polyalcohol (B) can be combined with an alternative polymer processing aid to provide performance better than when the alternative polymer processing aid is used alone.

[0021] In the case that the polymer processing aid comprises more than one component, the polymer processing aid (C) can be produced by extrusion compounding, compression compounding, or any process known in the art to blend the components to produce a polymer processing aid. The polymer processing aid (C) can be in different forms including pellet, powder, liquid, or any form known in the art to produce a polymer processing aid.

[0022] Polyalcohol (B) can be added directly during a polymer melt extrusion process or used as a component in an extrudable compound (E), or as a component in a masterbatch (D), or as a component in a polymer processing aid (C) or in an article (F) produced therefrom.

[0023] The process of producing an extrudable compound (E), or a masterbatch (D), or a polymer processing aid (C) or an article (F) containing Polyalcohol (B) for the purposes of reducing quality defects in a thermoplastic that has been melt processed is included as part of this invention.

[0024] The masterbatch (D) of this invention comprises a polyalcohol (B) and a diluent (A). The polyalcohol (B) may comprise 50 wt.% or less, preferably 10% or less, and greater than 0.1 % or above 0.5 wt.%, of the total composition of the masterbatch (D). In the event that polyalcohol (B) is the only active component of masterbatch (D) then it comprises greater than 1 % of the total masterbatch (D). In some embodiments the diluent A is preferably a thermoplastic polymer (also referred to as a carrier polymer and can be used in part to contain and deliver the active components.

[0025] The masterbatch (D) can be produced by extrusion compounding, compression compounding, or any process known in the art to blend the components to produce a masterbatch (D). The masterbatch (D) can be in different forms including pellet, powder, liquid, or any form known in the art to produce a polymer processing aid.

[0026] The invention includes the processes and methods used to produce polymer processing aid (C), masterbatch (D), an extrudable compound (E), and articles (F), which contain polyalcohol (B) and can contain one or more of the following: i) a processing aid additive, ii) an alternative polymer processing aid, and can also contain other components including but not limited to additives, fillers, colorants, anti-block agents, antioxidants, lubricants, stabilizers, and other components.

[0027] A preferred embodiment of this invention is identified as “fluoropolymer-free” and does not contain any fluorinated polymers or fluorinated compounds in its composition. This embodiment can be referred to as a fluoropolymer-free polymer processing aid (FFPA) and can contain other active components including other polymer processing aids, synergists, lubricants, and other additives provided they are fluorine free.

[0028] A preferred embodiment of this invention contains a polyalcohol (B) that is derived from a biorenewable resource and can contain one or more additional active components that are also derived from natural and renewable resources. For this embodiment, ideally, the totality of all active components is derived from natural and renewable resources.

[0029] In some embodiments of the invention, the polymer processing aid (C), or the masterbatch (D) or the extrudable compound (E) or the article (F) comprises a fluoropolymer.

[0030] In some embodiments of the invention, the polymer processing aid (C), or the masterbatch (D) or the extrudable compound (E) or the article (F) comprises polyethylene glycol (PEG)

[0031] In some embodiments of the invention, the polymer processing aid (C), or the masterbatch (D) or the extrudable compound (E) or the article (F) comprises polyethylene glycol, a fluoropolymer and combinations thereof.

[0032] In some embodiments of the invention, the polymer processing aid (C), or the masterbatch (D) or the extrudable compound (E) or the article (F) comprises a polyamide.

[0033] In some embodiments of the invention, the polymer processing aid (C), or the masterbatch (D) or the extrudable compound (E) or the article (F) comprises another component that when added to polyethylene resin reduces melt fracture.

[0034] This invention is useful in the melt processing of thermoplastic polymers, more preferably the melt processing of polyolefin polymers. Melt processes in which this 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.

[0035] The invention provides for a method for the melt processing of thermoplastic polymers comprises the steps of a) combining the polymer processing aid (C) with a thermoplastic polymer, preferably a polyolefin polymer, wherein the amount of polyalcohol (B) is from 1 ppm to less than 1 wt.%, preferably less than 5000ppm based on total weight of thermoplastic polymer, b) heating to above the melting point of the polyalcohol (B), and c) melt processing the thermoplastic polymer composition by extruding or molding. The polymer processing aid (C) can be any of the various embodiments of polymer processing aid (C) described herein. The polyalcohol B can be introduced into the thermoplastic polymers in the form of any of the polymer processing aids (C), or masterbatches (D) described herein.

[0036] The invention provides for many embodiments of the invention. Some Preferred Clauses of the Invention include:

[0037] Clause 1 of the invention provides for a polymer processing aid (C) comprising one or more polyalcohols (B) and optionally containing one or more of: a. a processing aid additive selected from the group consisting of; aliphatic polyesters such as polybutylene adipate, polylactic acid and polycaprolactones (PCL) such as polycaprolactone diols; aromatic polyesters such as the diisobutyl ester of phthalic acid; polyether’s such as polyether polyols amine oxides such as octyldimethylamine oxide; carboxylic acids such as hydroxy-butanedioic acid; and fatty acid esters such as Sorbitan monolaurate; and/or b. alternative Polymer processing aids selected from the group consisting of silicones; silicone-polyether copolymers fluoropolymer, polyamide, polyether block amide (PEBA), polyethylene glycol and silicones polyalkylene oxides such as polyethylene glycol (PEG) and wherein polyalcohol (B) is not polymeric and has a melting point 240°C or below.

[0038] Clause 2 provides for the processing aid of Clause 1 , wherein the polyalcohol (B) comprises a polyhydric alcohol and has 2 or more hydroxyl groups and has a single hydroxyl group on each carbon.

[0039] Clause 3 provides for the processing aid of Clause 1 , wherein the polyalcohol (B) is selected from the group consisting of ethylene glycol, glycerin (glycerol), erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, polyglycitol and combinations thereof.

[0040] Clause 4 provides for the processing aid of Clause 1 , wherein the polyalcohol (B) comprises D- Mannitol.

[0041] Clause 5 provides for the processing aid of Clause 1 , wherein the polyalcohol (B) comprises Sorbitol. [0042] Clause 6 provides for the processing aid of Clause 1 , wherein the polyalcohol (B) has a melting point 230°C or below, preferably below 220°C. The melting point may be above 30°C, preferably above 40°C or above 50°C or above 60°C.

[0043] Clause 7 provides for the processing aid of any one or more of Clauses 1 to 6, wherein polyalcohol (B) comprises at least 2 different polyalcohols.

[0044] Clause 8 provides for the processing aid of Clause 7, wherein the polyalcohols forms a eutectic blend.

[0045] Clause 9 provides for the processing aid of any one or more of Clauses 1 to 8, further containing additives selected from the group consisting of fillers, colorants, antiblock agents, antioxidants, lubricants, stabilizers, synergists, and combinations thereof.

[0046] Clause 10 provides for the processing aid of any one or more of Clauses 1 to 9, wherein the amount of polyalcohol (B) in the polymer processing aid is in the range of from greater than 0.1 to 99.9 wt.%, preferably 1 .0 to 99 wt.%, even more preferably 5 to 99wt%, and even more preferably 50 to 98.5wt%, based on the total weight of the polymer processing aid (C).

[0047] Clause 1 1 provides for the processing aid of any one or more of Clauses 1 to 9, where in the total amount of active components in polymer processing aid (C) comprise greater than 50 wt%, preferably 95 wt.% or more, preferably 99 wt.% or more and most preferably 100 wt.% of the total polymer processing aid (C), wherein the polyalcohol (B) comprises 0.1 wt.% up to 100wt% of the total amount of active components in polymer processing aid (C).

[0048] Clause 12 provides for the polymer processing aid of any one or more of Clauses 1 to 9 further comprising a diluent (A) to form Masterbatch (D).

[0049] Clause 13 provides for the polymer processing aid of Clause 12, wherein the total amount of active components in the polymer processing aid are less than or equal to 50 wt.%, preferably less than 30 wt.%, more preferably less than 20 wt.% and even more preferably equal to or less than 10 wt.% and preferably above 0.1 wt.%, more preferably above 0.5 wt.% of the total polymer processing aid. The polyalcohol (B) comprises from 0.01 wt.% up to 100% of the active components contained in polymer processing aid.

[0050] Clause 14 provides for the processing aid of Clause 13, wherein the diluent (A) comprises one or more polyolefins.

[0051] Clause 15 provides for the processing aid of Clause 13, wherein the diluent (A) comprises a polyethylene polymer.

[0052] Clause 16 provides for the processing aid of Clause 13, wherein the diluent (A) comprises at least one of polypropylene homopolymer or a polypropylene copolymer.

[0053] Clause 17 provides for the processing aid of Clause 13, wherein the diluent (A) is selected from the group consisting of LDPE, HDPE, LLDPE, and functionalized polyolefin. The diluent (A) may also be any combination of a medium density polyethylene (MDPE), a polypropylene (PP). Any mixture of any of LDPE, MDPE HDPE, LLDPE, PP and functionalized polyolefin.

[0054] Clause 18 provides for the processing aids of Clause 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 alpha-olefins and combination thereof. [0055] Clause 19 provides for the processing aid of Clauses 13, wherein the diluent (A) comprises a solvent, preferably water.

[0056] Clause 20 provides for an extrudable compound (E) comprising polyalcohol (B) and a thermoplastic polymer, preferably the thermoplastic polymer is a polyolefin.

[0057] Clause 21 provides for an extrudable compound (E) comprising the polymer processing aid of any one or more of Clauses 1 -19.

[0058] Clause 22 provides for the extrudable compound (E) of Clause 21 , comprising from 10 ppm up to 2000 ppm, preferably up to 1000 ppm, and most preferably up to 750 ppm of polyalcohol (B) based on weight of thermoplastic polymer.

[0059] Clause 23 provides for the extrudable compound (E) of Clause 21 comprising 1 ppm or more, preferably 5 ppm or more, most preferably 10 ppm or more and 0.5 wt.% or less, preferably 0.25 wt.% or less, most preferably 0.1% or less of the total weight of the active component in the extrudable compound E, wherein the polyalcohol (B) comprises from 0.01 wt. % up to 100% of the active components contained in the extrudable compound (E).

[0060] Clause 24 provides for an Article (F) comprising the polymer processing aid of any one or more of Clauses 1 -19.

[0061] Clause 25 provides for an Article (F) comprising the extrudable compound (E) of any one or more of Clauses 20-23.

[0062] Clause 26 provides for the Article (F) of Clause 24 or 25, wherein the thermoplastic polymer is a polyolefin.

[0063] Clause 27 provides for a method of melt processing a thermoplastic polymer comprising: a) combining the polymer processing aid of any one or more of Clauses 1 -19 with a thermoplastic polymer, preferably a polyolefin polymer, wherein the amount of polyalcohol (B) is from 1 ppm up to less than 1 wt.%, preferably 5000ppm or less based on total weight of thermoplastic polymer, b) heating to above the melting point of the polyalcohol (B), and c) melt processing the thermoplastic polymer composition by extruding or molding.

[0064] Clause 28 provides for the method of Clause 27 where the amount of polyalcohol (B) is from 10 ppm up to 0.25 wt.%.

[0065] Clause 29 provides for a method of producing article (F) by melt processing comprising the steps of: a) combine polyalcohol (B) and a thermoplastic polymer, preferably a polyolefin polymer, wherein the amount of polyalcohol (B) is from 1 ppm up to 5000ppm based on total weight of thermoplastic polymer to make a thermoplastic polymer composition, and then, b) heating the thermoplastic polymer composition above the melting point of the thermoplastic polymer in an extruder, molder, or other melt processing equipment, and c) extrude or mold or melt process to produce article (F).

[0066] Clause 30 provides for a method of article (F) by melt processing comprising the steps of: a) providing the extrudable compound (E) of any one or more of Clauses 20-23, wherein extrudable compound (E) comprises polyalcohol(B) in an amount of from 1 ppm up to 5000ppm based on total weight of thermoplastic polymer and then b) heating and melt process the extrudable compound (E) composition above the melting point of the thermoplastic polymer to produce article (F). [0067] Clause 31 provides for the method of Clauses 27 or 29 wherein the wherein the amount of polyalcohol (B), comprises 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..

[0068] Clause 32 provides for the method of Clauses 27 or 29 wherein the amount of active component comprises 1 ppm or more, preferably 5 ppm or more, most preferably 10 ppm or more and 0.5 wt.% or less, preferably 0.25 wt.% or less, most preferably 0.1 % or less of the total weight of the active component in the article (F), wherein the polyalcohol (B) comprises from 0.01 wt. % up to 100% of the active components contained in article (F).

[0069] Clause 33 provides for the method of Clauses 27 or 29 wherein the total amount of active components in the polymer processing aid are less than or equal to 50 wt.%, preferably less than 30 wt.%, more preferably less than 20 wt.% and even more preferably equal to or less than 10 wt.% and preferably above 0.1 wt.%, more preferably above 0.5 wt.% of the total polymer processing aid, wherein the polyalcohol (B) comprises from 0.01 wt.% up to 100% of the active components contained in polymer processing aid.

[0070] Clause 34 provides for the methods of Clause 29 wherein the polyalcohol (B) is provided in the form of the polymer processing aid of any one or more of Clauses 1 - 19.

[0071] Clause 35 provides for the methods of Clauses 27 or 29 wherein the thermoplastic polymer is a polyolefin.

[0072] Clause 36 provides for the methods of Clauses 27 or 29 wherein the melting point of polyalcohol (B), is less than the melt processing temperature.

[0073] Clause 37 provides for the methods of Clauses 27 or 29 wherein melt fracture is reduced or eliminated during the melt processing of the thermoplastic polymer composition.

[0074] Clause 38 provides for the use of the processing aid of any one or more of Clauses 1 to 19 to reduce melt fracture in the melt processing of a thermoplastic polymer.

[0075] Clause 39 provides for the use of polymer processing aid comprising polyalcohol (B) for melt processing a polyolefin polymer.

DETAILED DESCRIPTION OF THE INVENTION

[0076] All percentage and ratios are by weight unless otherwise indicated.

[0077] The term ‘polymer processing aid”, also referred to as an “extrusion agent” or “PPA”, refers to an additive used to reduce quality defects such as melt fracture and die drool that form during melt processing of a thermoplastic polymer. The term “fluoropolymer-free polymer processing aid” or “FFPA” refers to a polymer processing aid that does not contain any fluoropolymer.

[0078] The term “diluent” as used in the present invention can be a solvent. The term “diluent” means a solvent or a thermoplastic polymer (also referred to as a carrier polymer) that is combined with the active component to produce a Masterbatch. The diluent of the present invention is not fluorinated. The diluents are fluorine free. The term “solvent” refers to a liquid used to disperse or dissolve the active component and once dispersed or dissolved, will be in the form of a liquid or paste. The term “polymer" refers to a chemical compound or mixture of compounds formed by polymerization and having repeated structural units. The term “carrier polymer" refers to a diluent (A) that is polymeric and preferably a polyolefin polymer. The term “thermoplastic polymer” refers to a class of polymers that can be softened through heating and then melt processed using methods such as extrusion, injection molding, thermoforming, and blow molding. A thermoplastic polymer will harden once cooled and often can be melt processed multiple times.

[0079] The term “polymer processing aid”, also referred to as an “extrusion agent” or “PPA”, refers to an additive used to reduce quality defects such as melt fracture and die drool that form during melt processing. The term “active component” refers to the component of a polymer processing aid responsible for reducing quality defects in a thermoplastic polymeric extruded article such as Article F. The terms “performance” and “performance characteristics” as used herein, unless expressed otherwise, are used to describe the ability to eliminate quality defects known as melt fracture. The term “melt fracture” is a quality defect on the surface of an article that is reduced or eliminated with the addition of a polymer processing aid to the melt processing. The term “die drool” is a quality defect that is caused by material build up on an extrusion die that is corrected with the addition of a polymer processing aid. [0080] The term “polyalcohol” refers to an organic component containing two or more hydroxyl groups. Polyalcohol (B) of this invention include all stereoisomers and constitutional isomers and are not polymeric. The term “sugar alcohols" are polyalcohols also referred to as polyhydric alcohols, polyalcohols, alditols or glycitols, and typically derived from sugars, and contain one hydroxyl group (- OH) attached to each carbon atom. The term “ring structure” when used herein means a cyclic carbon chain structure in which the carbon chain forms a ring, and the carbon chain contains at least one additional element in the chain other than carbon as a member of the ring, as for example an oxygen or nitrogen atom.

[0081] The term “masterbatch”, which is a “polymer processing aid master batch”, refers to a composition comprising an active component dispersed in a diluent (A). The term “extrudable compound” refers to a thermoplastic polymer composition comprising a thermoplastic polymer and one or more active component, and the active component reduces the number of quality defects that form during melt processing.

[0082] The term “synergist”, also referred to as an “interfacial agent”, is considered an active component when combined with another active component, the performance is better than when using either active component alone. The terms “fluoropolymer” are polymers containing fluorinated monomer units and are commonly used as active components in polymer process aids. The term fluoropolymer includes thermoplastic fluoropolymers and fluoroelastomers and includes polyvinylidene fluoride copolymers such as Poly(vinylidene fluoride-co-hexafluoropropylene) copolymers. The term “melt index” or “melt flow index” or MFR refers to the melt viscosity of the material with a higher MFR value indicating a lower melt viscosity. Melt flow index values are obtained using procedures defined in ASTM D1238. Melting points are obtained by DSC per ASTM D3418, second heat.

[0083] The term “quickly" in reference to PPA performance is used herein to describe a PPA able to eliminate melt fracture in 30 minutes or less. The term “efficient” in reference to PPA performance is used herein to describe a PPA able to eliminate melt fracture using 400 ppm or less PPA.

COMPOSITION AND FORM OF POLYMER PROCESSING AID

[0084] The invention relates to a polymer process aid (C) used to reduce or eliminate surface defects arising from melt extrusion of thermoplastic polymers, specifically polyolefin polymers. The polymer process aid (C) of this invention comprises at least one polyalcohol (B) preferably contains one or more of the following: i. A processing aid additive, ii. Alternative polymer processing aid.

[0085] The invention relates to a polymer process aid masterbatch (D) used to reduce or eliminate surface defects arising from melt extrusion of thermoplastic polymers, specifically polyolefin polymers. The masterbatch (D) of this invention comprises at least one polyalcohol (B) and a diluent (A) may contain one or more of the following:

Hi. A processing aid additive, iv. Alternative polymer processing aid.

[0086] The polymer processing aid (C) can be used to produce a masterbatch (D), an extrudable compound (E) or an article (F). The polymer process aid (C) of this invention can be a fluoropolymer free polymer processing aid (FFPA) when produced without the addition of a fluoropolymer, and the diluent and other active components of this invention do not contain any fluorinated monomer units.

[0087] POLYALCOHOL

[0088] The polyalcohol (B), process aid additive and alternative polymer processing aid are considered active components whereas diluent (A) is not an active component in the polymer processing aid (C). [0089] The total amount of active components in polymer processing aid (C) may comprise greater than 50wt% but preferably greater than 95 wt.% or more, preferably 99% or more and most preferably 100 wt.% of the total polymer processing aid (C). The polyalcohol (B) can comprise as little as 0.1 wt.% up to 100% of the total amount of active components contained in polymer processing aid (C).

[0090] The polyalcohol (B) of this invention can be any polyhydric alcohol containing 2 or more hydroxyl groups and one hydroxyl group (-OH) attached to each carbon atom, are also referred to as sugar alcohols. The polyalchohol (B) can be a singular polyalcohol or a blend of two or more polyalcohols. Polyalcohol (B), which can be referred to as sugar alcohol, include but are not limited to glycerin (glycerol), erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, polyglycitol and including all other related isomeric forms.

[0091] The polyalcohol (B) does not contain a ring structure, is not a monosaccharide, disaccharide, or polysaccharide, is not polymeric and does not include polymeric diols. The melting point of the polyalcohol (B) of this invention is 240°C or below, preferably below 230°C, and most preferably below 220°C, preferably ranging from 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 200 to 1 10°C. Polyalcohol (B) can be in the form of a liquid at room temperature, with glycerin being an example. A preferred polyalcohol (B) comprises D-Mannitol.

[0092] Polyalcohols are most often produced from sugars and therefore considered a bio-renewable resource. Polyalcohols are commonly produced by hydrogenation of simple sugars such as fructose and glucose. More specifically, the polyalcohol is commonly produced by either electrolytic reduction or transition metal catalytic hydrogenation of sugar solutions, or by the fermentation of sugars or sugar alcohols using the yeast Zygosaccharomyces rouxii'. or pure culture fermentation of sugars using the nonpathogenic, nontoxicogenic bacterium Lactobacillus intermedius {fermentum).

[0093] Melt processing of polyolefins such as LLDPE are typically performed using melt processing temperatures below 250°C, and ideally in the range of 200 to 230°C. It is preferred that the melting point of the polyalcohols are selected to be below the melt processing temperature of the thermoplastic polymer being melt processed.

[0094] In some embodiments of this invention the melting temperature of the polyalcohol (B) is below the melt processing temperature of the thermoplastic polymer being melt processed, preferably about 10 to 70°C below the melt processing temperature being used, more preferably 20 to 50°C below the melt processing temperature being used. For example, the polyalcohol D-Mannitol has a melting point of 166 to 167°C, which is about 25 to 35°C below a typical melt processing temperature for blown film extrusion of a polyolefin polymer. Without being bound by any theory, it is believed that the polyalcohol is only effective at temperatures above its melting point, and that by delaying melting of the polyalcohol until late in the extrusion process, we believe the polyalcohol will be effective when needed. Ideally, the polyalcohol would not become active until reaching the metering zone of a single screw extruder and then remaining active as it passes through the extrusion die.

[0095] The polyalcohols (B) of this invention can be described as bio-renewable if derived from biological and renewable resources.

[0096] It is known in the art that different sugar alcohols can be combined to produce eutectic blends, and the ratio of these sugar alcohols can be changed to adjust the melting point of the blend. One aspect of this invention is to produce a PPA having a lower and targeted melting point relative to the melt processing temperature being used. The targeted melting point can be obtained by adjusting the composition of two or more polyalcohols comprising the blend.

[0097] DILUENT

[0098] The term "diluent” as used in the present invention refers to a thermoplastic polymer or a solvent that is combined with the active component to produce a polymer processing aid. The diluent (A) of the present invention is not fluorinated. Diluent (A) is fluorine free. Diluent (A) can be referred to as a carrier polymer if the diluent (A) is a thermoplastic and used in part to contain and deliver the polyalcohol (B). The diluent (A) can also be a solvent. In some embodiments the solvent is water.

[0099] The diluent (A) of the invention, sometimes referred to as a carrier polymer, is preferably a polyolefin polymer. In some embodiments of this invention, the diluent (A) is a thermoplastic polymer having a lower molecular weight than the thermoplastic polymer being melt processed. In another embodiment of this invention, the diluent (A), is the same composition as the thermoplastic polymer being melt processed. In still another embodiment of this invention, the diluent (A) is a solvent.

[0100] The diluent (A) of the invention is preferably a polyolefin polymer, more preferably a polyolefin comprising ethylene monomer units. The diluent (A) can be a polyethylene polymer that comprises or consists of low-density polyethylene (LDPE), a high-density polyethylene (HOPE), a linear low-density polyethylene (LLDPE), a medium-density polyethylene (MDPE), or ultra-high-density polyethylene (UHDPE) or combinations thereof. It can be a polyethylene obtained using a catalyst of the metallocene type or ‘single-site' catalyst, a catalyst of Phillips type or a catalyst of Ziegler-Natta. It can be an ethylene copolymer polymer including but not limited to an ethylene vinyl acetate, ethylene methacrylic acid, ethylene methacrylate, ethylene-propylene, and ethylene alpha-olefins; functionalized polyolefins; ethylene copolymers comprising any nonfluorinated monomer; a polypropylene, in particular an iso- or syndiotactic polypropylene; a polybutene (obtained from 1 -butene); a poly(3-methylbutene) or a poly(4- methylpentene); and blends or alloys of two or more polyolefins, for example a blend of LLDPE with LDPE. In some embodiments of the invention, the diluent (A) are polyolefin compositions comprising a copolymer, for example, ethylene acrylate or ethylene vinyl acetate. In some embodiments of this invention, the polyolefin is also a carrier polymer preferably having a lower molecular weight equal to or lower than the thermoplastic polymer being melt processed.

[0101] The diluent (A) of the invention is preferably a carrier polymer when used in the masterbatch (D) and selected to be compatible with the thermoplastic polymer to be melt processed and preferred to have a melt index equal to or higher than the melt index of the thermoplastic polymer being melt processed. The melt index of the diluent (A) as a carrier polymer may be from 0.1 to 100 g/1 Omin, preferably from 0.5 to 60 g/10 min, and more preferably from 0.75 to 20 g/1 Omin and most preferably from 1.0 to 10 g/10 min measured with a 2.16 kg weight and 190°C per ASTM D 1238.

[0102] Diluent (A) can be the same polymer or a different polymer from the thermoplastic polymer being melt processed. Thermoplastic polymer being melt processed forms the majority weight % of Extrudable Compound (E) or Article (F), preferably the thermoplastic polymer being melt processed makes up greater than 90% by weight of the Extrudable Compound (E) or Article (F).

[0103] Processing Aid Additive

[0104] The polymer process aid (C) can optionally contain one or more “processing aid additive” selected from the group consisting of; aliphatic polyesters such as polybutylene adipate, polylactic acid and polycaprolactones (PCL) such as polycaprolactone diols; aromatic polyesters such as the diisobutyl ester of phthalic acid; polyether’s such as polyether polyols; amine oxides such as octyldimethylamine oxide; carboxylic acids such as hydroxy-butanedioic acid; and fatty acid esters such as Sorbitan monolaurate. Processing aid additives are considered active components when in combination with alternative polymer processing aids or with polyalcohol (B).

[0105] Alternative Polymer Processing Aids

[0106] The polymer process aid (C), the masterbatch (D), the extrudable compound (E) or the 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), and polyamides and polyether block amides (PEBA) and combinations thereof. The polyamide and block polyamide of PEBA can be selected from is PA6, PA10, PA1 1 , PA12, PA66, PA 610, PA612, PA1010, PA1012, PA 1212, or a copolyamide PA 6/12, PA 6/1 1 , PA 6/1010, PA 6/66, PA 6/66/12, PA 6/66/1 1 , PA 6/66/610, PA 6/612/1 1 , or any combination thereof.

[0107] Optionally, the polymer process aid (C) of this invention can contain other additive components including but not limited to fillers, organic and inorganic pigments, dyes, colorants, UV absorbers, nucleating agents, reinforcing agents, antiblock agents, antioxidants, lubricants including but not limited to metal soaps, fatty acid esters, hydrocarbon waxes, ester waxes, amide waxes and include lower molecular weight lubricants better classified as plasticizers, stabilizers and other liquids, solids, and polymers. The filler can comprise dispersed organic or inorganic particles. An inorganic filler can be, for example, a silica, an alumina, a zeolite, a titanium oxide, a carbonate (for example, sodium carbonate or potassium carbonate), hydrotalcite, talc, a zinc oxide, a magnesium oxide or a calcium oxide, a diatomaceous earth, carbon black, and the like.

COMPOSITION AND FORM OF THE MASTERBATCH (D)

[0108] The masterbatch (D) of this invention comprises at least one polyalcohol (B) and a diluent (A) and can optionally contain one or more of the following: i) a processing aid additive, ii) an alternative polymer processing aid. The polyalcohol (B), process aid additive and alternative polymer processing aid are all active components whereas diluent (A) is not an active component. The active components in the masterbatch (D) may comprises less than or equal to 50 wt.%, preferably less than 30 wt.%, more preferably less than 20 wt.% and even more preferably equal to or less than 10 wt.% and above 1 wt.%, more preferably above 1 .5 wt.% of the total masterbatch (D). The polyalcohol (B) comprises from 0.01 wt.% up to 100% of the active components contained in masterbatch (D). The diluent (A) can be a thermoplastic polymer, or a solvent or water. Most often the diluent is a polyolefin polymer, and often referred to as a carrier polymer.

[0109] In one embodiment, Diluent (A) is combined with polyalcohol (B) to produce masterbatch (D), When Diluent (A) is a thermoplastic polymer, it is often referred to as a carrier polymer in masterbatch (D). In one embodiment, the masterbatch (D) comprises (i) diluent (A), preferably comprises a polyolefin polymer and (II) at least one active component comprising a polyalcohol (B) and optionally contains other additives. [0110] The amount of diluent (A) in masterbatch (D) is dependent on the application and manufacturing processes being used and may range from 0.2 to 99 wt.%, more preferably 0.5 to 98 wt.%, even more preferably 1 to 95 wt.%, and even more preferably 1 .5 to 80 wt.%, and most preferably 2 to 75% of the total weight of the masterbatch(D).

[0111] In some embodiments, the amount of polyalcohol (B) in the masterbatch (D) is equal to or below 25 wt.% , preferably equal to or below 20 wt.%, or equal to or below 10 wt.%, and above 0.5 wt.%, and more preferably above 1 wt.% of the total weight of the masterbatch. In the event that polyalcohol (B) is the only active component of masterbatch (D) then it comprises greater than 1% of the total masterbatch (D).

[0112] The masterbatch (D) can be produced by extrusion compounding, compression compounding, or any process known in the art that blends components. The components of the masterbatch (D) can be combined by dry blending, by dissolving in a solvent, by extrusion compounding, or any combination thereof. When extrusion compounding is used, it is accomplished using any means known in the art including a single screw extruder, a Banbury mixer, a continuous mixer and more preferably using either a twin-screw extruder or co-kneader. The masterbatch (D) can be in the form of a solid, preferably in the form of a powder or compressed into a shape such as a pellet, or compacted and milled into a granular powder, or dispersed in a solvent such as water. The masterbatch (D) can also be in the form of a liquid or paste, preferably dissolved in a solvent, more preferably dissolved in water.

[0113] The masterbatch (D) of this invention can be produced by combining polyalcohol (B) and a diluent (A) and may contain one or more of the following: i) a processing aid additive, ii) an alternative polymer processing aid.

[0114] The masterbatch (D) of this invention can be used to produce an extrudable compound (E) or an article (F). The masterbatch (D) of this invention can be a fluoropolymer free masterbatch when produced without the addition of a fluoropolymer or any other fluorinated materials.

[0115] The polymer processing aid (C) and or the masterbatch (D) can be in the form of a solid, preferably in the form of a powder or compressed into a shape such as a pellet, or compacted and milled into a granular powder, or dispersed in a solvent such as water. The polymer processing aid (C) and or the masterbatch (D) can also be in the form of a liquid or paste, preferably dissolved in a solvent, more preferably dissolved in water.

[0116] COMPOSITION AND FORM OF EXTRUDABLE COMPOUND (E)

[0117] The extrudable compound (E) of this invention comprises a polyalcohol (B), in a thermoplastic polymer most preferably a polyolefin. The extrudable compound (E) may further contain one or more of the following: i) a processing aid additive, ii) an alternative polymer processing aid. The polyalcohol (B) in the extrudable compound (E) comprises 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more and 5000ppm or less, 3000ppm or less, preferably 2000 ppm or less, most preferably 10OOppm or less by weight of the total weight of the extrudable compound (E). In some embodiments, the active components (from the PPA) in the extrudable compound (E) comprise 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, 75 ppm or more and 0.5 wt.% or less, preferably 0.3 wt.% or less, most preferably 0.25wt% or less or 0.1 wt % or less based on the total weight of the extrudable compound (E). The polyalcohol (B) comprises from 0.01 wt.% up to 100% of the active components contained in extrudable compound (E). In some embodiments, the amount of active components in extrudable compound (E) can comprise from 1 ppm or more to 5000ppm or less. In some embodiments, the amount of active components in extrudable compound (E) can comprise from 10 ppm or more to 3000 ppm or less. The diluent (A) used to produce extrudable compound (E) is often a thermoplastic polymer and more often a polyolefin polymer. [0118] The extrudable compound (E) of this invention can be produced by extrusion compounding, compression compounding, or any process known in the art to combine the components of the extrudable compound (E). The polyalcohol (B) can be introduced into the extrudable compound (E) in different forms including but not limited to a liquid, paste, powder, and pellet. The extrudable compound (E) can be in different forms including pellet and powder or any form known in the art. The extrudable compound (E) can be prepared by combining a thermoplastic polymer, preferably 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) a processing aid additive, ii) an alternative polymer processing aid.

[0119] The polyolefin of the extrudable compound (E) may be functionalized, non-functionalized, or a mixture thereof. As an example, the polyolefin can be a polyethylene; examples include but are not limited to a low-density polyethylene (LDPE), a high-density polyethylene (HDPE), a linear low-density polyethylene (LLDPE), a medium-density polyethylene (MDPE), or ultra-high-density polyethylene (UHDPE) or combinations thereof. The polyolefin of the extrudable compound (E) can be a polyethylene obtained using a catalyst of the metallocene type or more generally a 'single-site' catalyst, a catalyst of Phillips type or a catalyst of Ziegler-Natta type; a polypropylene, an iso- or syndiotactic polypropylene; a polybutene (obtained from 1 -butene); a poly(3-methylbutene) or a poly(4-methylpentene.

[0120] In some embodiments the extrudable compound (E) comprising at least 10 ppm of polyalcohol

(B), from 10 ppm to 0.5 wt.%, preferably from 25 ppm to 0.3 wt.%, more preferably from 50 ppm to 0.25 wt.%, even more preferably from 75 ppm to 0.5 wt.%, and most preferably from 100 ppm to 2000 ppm of polyalcohol (B) based on the total weight of the thermoplastic polymer.

[0121] In some embodiments of the invention, the extrudable compound (E) is comprised of a thermoplastic polymer and from 5 ppm up to 0.5 wt.%, preferably 10 ppm up to 0.25 wt.% of polyalcohol (B) based of the total weight of the extrudable compound (E).

[0122] The extrudable compound (D) of this invention can be used to produce an article (F). In some embodiments, the extrudable compound (D) is free of fluoropolymer or any other fluorinated materials.

COMPOSITION AND FORM OF ARTICLE (F)

[0123] The invention also relates to an article (F) comprising polyalcohol (B) and a thermoplastic polymer, preferably a polyethylene. Article (F) can comprise or be made from the extrudable compound. In some preferred embodiments, the thermoplastic polymer of the extrudable compound is a polyolefin, which may be functionalized, non-functionalized, or a mixture thereof. As an example, the thermoplastic polymer of this invention can be a polyethylene, such as a low-density polyethylene (LDPE), a high-density polyethylene (HDPE), a linear low-density polyethylene (LLDPE), a medium-density polyethylene (MDPE), or ultra-high-density polyethylene (UHDPE) or combinations thereof. It can be a polyethylene obtained using a catalyst of the metallocene type or more generally a 'single-site' catalyst, a catalyst of Phillips type or a catalyst of Ziegler-Natta type; a polypropylene, an iso- or syndiotactic polypropylene; a polybutene (obtained from 1 -butene); a poly(3-methylbutene) or a poly(4-methylpentene).

[0124] Article (F) may optionally contain one or more of the following: i) a processing aid additive, ii) an alternative polymer processing aid. The active components in article (F) comprise 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, 75 ppm or more and 0.5 wt.% or less , preferably 0.3 wt.% or less, most preferably 0.25% or less of the total weight of articles (F). The polyalcohol (B) comprises from 0.01 wt.% up to 100% of the active components contained in article (F). The thermoplastic polymer used to produce article (F) is often a polyolefin polymer.

[0125] Polyalcohol (B) can be introduced into the thermoplastic polymer in the form of a polymer processing aid (C) or a Masterbatch (D) and then melt process to form article (F). Article (F) can be formed by melt processing the extrudable compound (E). The thermoplastic polymer is preferably a polyolefin polymer.

[0126] In some embodiments, article (F) comprises at least 10 ppm of polyalcohol (B) based on weight of thermoplastic polymer in the article (F) and) can comprise from 10 ppm to 0.5 wt.%, preferably from 25 ppm to 0.25 wt.%, more preferably from 50 ppm to 0.1 wt.%, even more preferably from 75 ppm to 0.5 wt.%, and most preferably from 100 ppm to 2000 ppm of a polyalcohol (B) based on weight of thermoplastic polymer.

[0127] In some embodiments of the invention articles (F) comprises thermoplastic polymer, preferably polyolefin, and 5 ppm up to 0.5 wt.%, preferably 10 ppm up to 0.1 wt.% of polyalcohol (B) based on the total weight of the article (F).

[0128] The article (F) of this invention can be produced by extrusion or molding or any other means of melt processing the extrudable compound. In some embodiments, the article (F) is in a form selected from a film, a tube, a pipe, a sheet, a rod, a fiber, a filament, a profile, a filament a molded part or a molded component, a wire coating, a multilayered structure, and a cable jacketing or insulation, or part or component.

[0129] In some embodiments, the article (F) of this invention is produced by injecting the polyalcohol (B) in liquid form into the thermoplastic polymer during melt processing. An example would include dissolving the polyalcohol (B) in water and then injecting it into the extruder containing thermoplastic polymer, thereby producing an extrudable compound (in situ), in the melt process that allows the polyalcohol (B) to properly disperse and act as a polymer processing aid.

[0130] The masterbatch (D), the extrudable compound (E) or the article (F) may include one or more other additives selected from the group consisting of fillers, pigments, dyes, antioxidants, UV absorbers and light stabilizers, nucleating agents, reinforcing agents. The filler can comprise dispersed organic or inorganic particles. An inorganic filler can be, for example, a silica, an alumina, a zeolite, a titanium oxide, a carbonate (for example, sodium carbonate or potassium carbonate), hydrotalcite, talc, a zinc oxide, a magnesium oxide or a calcium oxide, a diatomaceous earth, carbon black, and the like. The pigments may be inorganic or organic. The diluent (A) of the invention can also be a liquid, preferably water. In some embodiments of this invention, the polyalcohol (B) is completely dissolved in the diluent.

PROCESSES USED

[0131] Any processes known in the art for combining and/or blending individual components can be used to produce a polymer process aid (C), or Masterbatch (D) or extrudable compound (E). Typically, an extrusion process is used, more typically a melt extrusion process, but can also be done using a compaction process. A compaction process differs from an extrusion process in that it is typically performed below the melt temperature of the components being combined.

[0132] The invention also relates to preparing an article (F) using any process known in the art for producing thermoplastic articles including extrusion and molding. In one embodiment of this invention, the article (F) is produced by an extrusion process to form of a film, a tube, a pipe, a sheet, a rod, a multilayered structure, a cable jacket, or insulation. The polyalcohol (B) can be added to the thermoplastic polymer being melt processed directly or introduced into the thermoplastic polymer being melt processed in the form of a polymer processing aid (C) or a masterbatch (D). Article (F) can be formed by processing the extrudable compound (E). Preferably the thermoplastic polymer of the invention is a polyolefin polymer.

EXPERIMENTAL [0133] All experiments described herein were performed using masterbatch’s prepared with the components indicated in the tables below. The carrier polymer used in all masterbatch’s is 1 Ml linear low-density polyethylene from Ineos Inc. The fluoropolymer identified as PVDF1 is a commercially available PVDF-HFP copolymer used in commercial PPA formulations. The polyalcohols used were identified as D-Mannitol, D-Dulcitol and glycerin. The polycaprolactone (PCL1 ) interfacial agents is Capa® 2403D6 produced by Ingevity. The polyethylene glycol (PEG) is Carbowax® Sentry PEG 8000 powder from Dow Chemical Company. The polyamides used are long chain polyamides identified as polyamide 1 1 (PA1 1 ) and polyamide 12 (PA12).

[0134] The polymer process aids were produced by twin-screw compounding. A Leistritz 18 mm twin- screw designed for good mixing and dispersion was used to prepare the polymer processing aids. The carrier polymer used was a barefoot 1 Ml LLDPE polymer produced by Ineos. The active ingredients were added to the carrier polymer at 2.5 wt.% based on the total weight of the polymer processing aid being produced. Individual loss in weight feeders were used to feed the carrier polymer and active components into the twin-screw feed throat. Barrel temperatures and feed rates were adjusted to maintain the melt temperature near 200°C. Vacuum venting was used to remove volatiles. The polymer processing aid exited the twin-screw through a strand die, cooled utilizing a water bath, passed through an air knife to facilitate drying, and then pelletized using a strand cutter.

[0135] The polymer processing aids were evaluated by performing flat die extrusion tests. A flat die extrusion test involves extrusion of a strip or ribbon using a flat profile die. Flat die extrusion studies were performed using a 1 ,5-inch Davis Standard extruder having a 3/1 compression ratio and a 24 to 1 L/D metering screw. The flat die, also referred to as a slot die, had dimensions of 50 mm by 0.5 mm and with a 10 mm land and contained a tapered feed section. The flat die contained heater bands on the die body and die lip for temperature control. The extruder and flat die were positioned downward at an angle of 20 to 30 degree to prevent the extrudate from contacting die surfaces.

[0136] A flat die study is started by performing a 25-minute purge using Dow Purge® purging compound (from Dow Inc.). Purging is performed through the extruder and die with all temperature zones set at 392°F and a screw speed of 60 rpm. This is followed by purging using 1 .0 Ml LLDPE until a steady state pressure is achieved and a uniform melt fracture observed. The screw speed is then adjusted to 21 .3 rpm to achieve a calculated shear rate of 300 s-1 run until the extruded ribbon visually displays a uniform 100% melt fracture on all surfaces and steady state achieved (20 to 30 minutes typical).

[0137] A flat die study can be performed once steady state is reached. The thermoplastic polymer is pellet blended with the polymer processing aid to achieve a desired target level for the active components. The pellet blend is then added to the extruder after removal of any remaining purge material from the extruder hopper. The thermoplastic polymer was 1 .0 Ml LLDPE, and the active components were tested at several different levels including 200, 250, 400, 475, 500 or 1000 ppm of the total composition being tested.

[0138] The flat die test measures the time to eliminate melt fracture on the surface of the extrudate and the test starts when the thermoplastic polymer containing the polymer processing aid is added into the extruder hopper. The test ends once melt fracture is eliminated. Melt pressure reduction is measured and is the difference between the starting melt pressure and melt pressure once melt fraction has been eliminated (from introducing the polymer processing aid). A melt pressure transducer mounted on the die was used to monitor and record pressure.

[0139] Data is reported as % melt fracture reduction and is determined through visual examination of the extrudate during the test. The test starts at 100% melt fracture, and after addition of a thermoplastic polymer containing a PPA, visible melt fracture is recorded as a function of time until melt fracture is eliminated. For most useful polymer processing aid, at levels in the range of 200 to 400 ppm, melt fracture is eliminated within an hour after addition of the PPA. [0140] In the examples to follow, melt fracture reduction is expressed as either 1 %, 2% or 3% melt fracture in accordance with practices established for performing these tests. The levels of melt fracture can be further described as follows: The presence of “1 % melt fracture” indicates complete elimination of melt fracture on the extrudate surface but excluding the edges. “1% melt fracture” is considered complete elimination of melt fracture in this test. The presence of “2% melt fracture” indicates the presence of melt fracture on 1% of extrudate surface plus on the edges. The presence of “3% melt fracture” indicates the presence of melt fracture on 2% of the extrudate surface plus on the edges. The presence of 2% and 3% melt fracture is very close to complete elimination of melt fracture.

Example 1

[0141] Example 1 describes the use of glycerin as the active component 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 was produced comprised of 2.5% glycerin and 97.5% carrier resin using a twin- screw compounder. The carrier resin used in the polymer processing aid was a barefoot 1 Ml LLDPE polymer. The polymer processing aid was then pellet blended with a barefoot 1 Ml LLDPE thermoplastic polymer to achieve a target glycerin level of 250 ppm in the pellet blend. Performance testing was performed on the pellet blend containing 250 ppm glycerin using the methods previously described. Glycerin was found to act as a polymer processing aid and eliminated melt fracture in 63 minutes. Glycerin also lowered melt pressure. No burning or color change was observed.

Example 2

[0142] Example 2 describes the use of D-Dulcitol as the active component in a polymer processing aid. D-Dulcitol is a polyalcohol having a melting point in the range of 98 to 100°C. A polymer processing aid was produced comprised of 2.0% D-Dulcitol and 98.0% carrier resin using a twin-screw compounder. The carrier resin used in the polymer processing aid was a barefoot 1 Ml LLDPE polymer. The polymer processing aid was then pellet blended with a barefoot 1 Ml LLDPE thermoplastic polymer to achieve a target D-Dulcitol level of 200 ppm in the pellet blend. Performance testing was performed on the pellet blend containing 200 ppm D-Dulcitol using the methods previously described. D-Dulcitol was found to act as a polymer processing aid and was able to reduce melt fracture to the 6% level in 60 minutes and required 90 minutes to eliminate melt fracture. D-Dulcitol also lowered melt pressure. No burning or color change was observed.

Example 3

[0143] Example 3 describes the use of D-Mannitol as the active component in a polymer processing aid. D-Mannitol is a polyalcohol having a melting point of from 164 to 169°C. A polymer processing aid was produced comprised of 2.0% D-Mannitol and 98.0% carrier resin using a twin-screw compounder. The carrier resin used in the polymer processing aid was a barefoot 1 Ml LLDPE polymer. The polymer processing aid was then pellet blended with barefoot 1 Ml LLDPE thermoplastic polymer to achieve target D-Mannitol levels of 200 ppm and 400 ppm in the pellet blends. Performance testing was performed on the LLDPE blends containing 200 ppm and 400 ppm D-Mannitol using the methods previously described. D-Mannitol was found to act as a polymer processing aid and was able to eliminate melt fracture quickly and efficiently in 20 minutes at both levels tested. D-Mannitol also lowered melt pressure. No burning or discoloration of the LLDPE blends containing D-Mannitol was observed.

Example 4

[0144] Example 4 describes a blended PPA masterbatch comprised of two individual masterbatch’s with one masterbatch containing a fluoropolymer (PVDF1 ), and the other containing a polyalcohol (D- Mannitol). The fluoropolymer containing masterbatch was comprised of 2.5% PVDF1 and 97.5% LLDPE carrier resin. The polyalcohol containing masterbatch was comprised of 2.0% D-Mannitol and 98.0% LLDPE carrier resin. The PPA masterbatches were both produced using a twin-screw compounder. The blended PPA masterbatch was produced by combining PVDF1 and D-Mannitol masterbatch’s at a ratio of 3/1 , respectively. The blended PPA masterbatch was then added to barefoot 1 Ml LLDPE to produce a LLDPE composition comprising 375 ppm PVDF1 and 100 ppm D-Mannitol of the total composition. Performance testing was performed on the LLDPE composition using the methods previously described. The LLDPE composition containing 375 ppm PVDF1 , and 100 ppm D-Mannitol eliminated melt fracture quicker than a similar composition containing only PVDF1 at similar levels of active components. Melt Pressure drop was similar for the two compositions.

Example 4

[0145] Example 4 describes a blended PPA masterbatch comprised of two individual masterbatch’s with one masterbatch containing a fluoropolymer and synergist (PVDF2), and the other containing a polyalcohol (D-Mannitol). The fluoropolymer containing masterbatch (PVDF2) was comprised of 1 .375% PVDF1 , 1 .125% PEG 8000 and 97.5% LLDPE carrier resin. The polyalcohol containing masterbatch was comprised of 2.0% D-Mannitol and 98.0% LLDPE carrier resin. The PPA masterbatches were both produced using a twin-screw compounder. The blended PPA masterbatch was produced by combining PVDF2 and D-Mannitol masterbatch’s at a ratio of 3/1 , respectively. The blended PPA masterbatch was then added to barefoot 1 Ml LLDPE to produce a LLDPE composition comprising 375 ppm PVDF2 and 100 ppm D-Mannitol of the total composition. Performance testing was performed on the LLDPE composition using the methods previously described. The LLDPE composition containing 375 ppm PVDF2, and 100 ppm D-Mannitol eliminated melt fracture quicker than from a similar composition containing only PVDF2 at similar levels of active components. Melt Pressure drop was similar for the two compositions. No burning or color change was observed.

Example 5

[0146] Example 5 describes a blended PPA masterbatch comprised of two individual masterbatch’s with one masterbatch containing PEG (PEG 8000), and the other containing a polyalcohol (D-Mannitol). The PEG containing masterbatch (PEG 8000) was comprised of 2.0% PEG 8000 and 98.0% LLDPE carrier resin. The polyalcohol containing masterbatch was comprised of 2.0% D-Mannitol and 98.0% LLDPE carrier resin. The PPA masterbatches were both produced using a twin-screw compounder.

The blended PPA masterbatch was produced by combining PEG 8000 and D-Mannitol masterbatch’s at ratios of 9/1 and 3/1 . The blended PPA masterbatch was added to barefoot 1 Ml LLDPE to produce two LLDPE compositions with one comprising 900 ppm PEG 8000 and 100 ppm D-Mannitol and the other comprising 300 ppm PEG 8000 and 100 ppm D- Mannitol of the total composition. Performance testing was performed on the LLDPE composition using the methods previously described. Melt fracture elimination performance of PEG 8000 was significantly improved with the addition of D-Mannitol. Melt pressure reduction was also improved by adding D-Mannitol to PEG 8000. No burning or color change was observed.

Example 6

[0147] Example 6 describes a blended PPA masterbatch comprised of two individual masterbatch’s with one masterbatch containing a polyamide 12 (PA12), and the other containing a polyalcohol (D- Mannitol). The polyamide containing masterbatch (PA12) was comprised of 2.0% PA12 and 98.0% LLDPE carrier resin. The polyalcohol containing masterbatch was comprised of 2.0% D-Mannitol and 98.0% LLDPE carrier resin. The PPA masterbatches were both produced using a twin-screw compounder. The blended PPA masterbatch’s were produced by combining PA12 and D-Mannitol masterbatch’s at ratios of 7/1 , 1 /1 and 1/7. The blended PPA masterbatch’s were added to barefoot 1 Ml LLDPE to produce three (3) LLDPE compositions with one comprising 350 ppm PA12 and 50 ppm D- Mannitol, one comprising 200 ppm PA12 and 200 ppm D-Mannitol, and one comprising 50 ppm PA12 and 350 ppm D-Mannitol. Performance testing was performed on the LLDPE compositions using the methods previously described. Melt fracture elimination performance of PA12 was significantly improved with the addition of D-Mannitol. Melt pressure reduction was also improved by adding D- Mannitol to PA12. No burning or color change was observed.

Example 7

[0148] Example 7 describes a blended PPA masterbatch comprised of two individual masterbatch’s with one masterbatch containing a polyamide 1 1 (PA1 1), and the other containing a polyalcohol (D- Mannitol). The polyamide containing masterbatch (PA11 ) was comprised of 2.0% PA1 1 and 98.0% LLDPE carrier resin. The polyalcohol containing masterbatch was comprised of 2.0% D-Mannitol and 98.0% LLDPE carrier resin. The PPA masterbatches were both produced using a twin-screw compounder. The blended PPA masterbatch was produced by combining PA1 1 and D-Mannitol masterbatch’s at a ratio of 3/1 , respectively. The blended PPA masterbatch was then added to barefoot 1 Ml LLDPE to produce a LLDPE composition comprising 300 ppm PA1 1 and 100 ppm D-Mannitol of the total composition. Performance testing was performed on the LLDPE composition using the methods previously described. The LLDPE composition containing 300 ppm PA1 1 , and 100 ppm D-Mannitol eliminated melt fracture relatively quickly at 31 minutes. Conversely, 400 ppm PA11 was unable to eliminate melt fracture with 75% melt fracture still observed after 60 minutes of testing. No burning or color change was observed.

Comparative 1

[0149] Comparative 1 describes the use of Glucose as the active component in a polymer processing aid. Glucose is not a polyalcohol and instead is a monosaccharide and having a melting point of ~146°C. A polymer processing aid was produced comprised of 2.5% Glucose and 97.5% carrier resin using a twin-screw compounder. The carrier resin used in the polymer processing aid was a barefoot 1 Ml LLDPE polymer. The polymer processing aid was then pellet blended with a barefoot 1 Ml LLDPE thermoplastic polymer to achieve a target Glucose level of 400 ppm in the blend. Performance testing was performed on the LLDPE blend containing 400 ppm Glucose using the methods previously described. Glucose did not act as a polymer processing aid and provided no melt fracture reduction and no pressure drop. Significant darkening of the LLDPE blend containing Glucose was noted and attributed to burning of the Glucose.

Comparative 2

[0150] Comparative 2 describes the use of Sucrose as the active component in a polymer processing aid. Sucrose is not a polyalcohol and instead is a disaccharide and having a melting point of 185 to 187°C. A polymer processing aid was produced comprised of 2.5% Sucrose and 97.5% carrier resin using a twin-screw compounder. The carrier resin used in the polymer processing aid was a barefoot 1 Ml LLDPE polymer. The polymer processing aid was then pellet blended with a barefoot 1 Ml LLDPE thermoplastic polymer to achieve a target Sucrose level of 400 ppm in the blend. Performance testing was performed on the LLDPE blend containing 400 ppm Sucrose using the methods previously described. Sucrose did not act as a polymer processing aid and provided no melt fracture reduction and no pressure drop. Significant darkening of the LLDPE blend containing Sucrose was noted and attributed to burning of the Sucrose.

Comparative 3

[0151] Comparative 3 describes the use of Cyclohexane 1 ,2, 3, 4, 5, 6 - Hexol as the active component in a polymer processing aid. Cyclohexane 1 ,2, 3, 4, 5, 6 - Hexol is a cyclic polyalcohol having a melting point of 252°C. A polymer processing aid was produced comprised of 2.5% Cyclohexane 1 ,2, 3, 4, 5, 6 - Hexol and 97.5% carrier resin using a twin-screw compounder. The carrier resin used in the polymer processing aid was a barefoot 1 Ml LLDPE polymer. The polymer processing aid was then pellet blended with a barefoot 1 Ml LLDPE thermoplastic polymer to achieve a target Cyclohexane 1 ,2, 3, 4, 5, 6 - Hexol level of 400 ppm in the blend. Performance testing was performed on the LLDPE blend containing 400 ppm Cyclohexane 1 ,2, 3, 4, 5, 6 - Hexol using the methods previously described. Cyclohexane 1 ,2, 3, 4, 5, 6 - Hexol did not act as a polymer processing aid and provided no melt fracture reduction and no pressure drop. No burning or color change was observed.

Claims

Claims

1. A polymer processing aid (C) comprising one or more polyalcohols (B) and optionally containing one or more of the following: a. A processing aid additive selected from the group consisting of; aliphatic polyesters such as polybutylene adipate, polylactic acid and polycaprolactones (PCL) such as polycaprolactone diols; aromatic polyesters such as the diisobutyl ester of phthalic acid; polyether’s such as polyether polyols amine oxides such as octyldimethylamine oxide; carboxylic acids such as hydroxy-butanedioic acid; and fatty acid esters such as Sorbitan monolaurate, b. Alternative Polymer processing aids selected from the group consisting of silicones; siliconepolyether copolymers fluoropolymer, polyamide, polyether block amide (PEBA), polyethylene glycol and silicones polyalkylene oxides such as polyethylene glycol (PEG) and wherein polyalcohol (B) is not polymeric and has a melting point 240°C or below.

2. The processing aid of Claim 1 , wherein the polyalcohol (B) comprises a polyhydric alcohol and has 2 or more hydroxyl groups and has a single hydroxyl group on each carbon.

3. The processing aid of Claim 1 , wherein the polyalcohol (B) is selected from the group consisting of ethylene glycol, glycerin (glycerol), erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, polyglycitol and combinations thereof.

4. The processing aid of Claim 1 , wherein the polyalcohol (B) comprises D-Mannitol.

5. The processing aid of Claim 1 , wherein the polyalcohol (B) comprises Sorbitol.

6. The processing aid of Claim 1 , wherein the polyalcohol (B) has a melting point 230°C or below, preferably below 220°C.

7. The processing aid of any one or more of Claims 1 to 6, wherein polyalcohol (B) comprises at least 2 different polyalcohols.

8. The processing aid of Claim 7, wherein the polyalcohols forms a eutectic blend.

9. The processing aid of any one or more of claims 1 to 8, further containing additives selected from the group consisting of fillers, colorants, antiblock agents, antioxidants, lubricants, stabilizers, synergists, and combinations thereof.

10. The processing aid of any one or more of Claims 1 to 9, wherein the amount of polyalcohol (B) in the polymer processing aid is in the range of from greater than 0.1 to 99 wt.%, preferably 1 .0 to 99.9 wt.%, even more preferably 5 to 99wt%, and even more preferably 50 to 98.5wt%, based on the total weight of the polymer processing aid (C).

11. The processing aid of any one or more of Claims 1 to 9, where in the total amount of active components in polymer processing aid (C) comprise greater than 50 wt%, preferably 95 wt.% or more, preferably 99 wt.% or more and most preferably 100 wt.% of the total polymer processing aid (C), wherein the polyalcohol (B) comprises 0.1 wt.% up to 100wt% of the total amount of active components in polymer processing aid (C).

12. The polymer processing aid of any one or more of claims 1 to 9 further comprising a diluent (A) to form Masterbatch (D).

13. The polymer processing aid of Claim 12, wherein the total amount of active components in the polymer processing aid are less than or equal to 50 wt.%, preferably less than 30 wt.%, more preferably less than 20 wt.% and even more preferably equal to or less than 10 wt.% and preferably above 0.1 wt.%, more preferably above 0.5 wt.% of the total polymer processing aid. The polyalcohol (B) comprises from 0.01 wt.% up to 100% of the active components contained in polymer processing aid.

14. The processing aid of Claim 13, wherein the diluent (A) comprises one or more polyolefins.

15. The processing aid of Claim 13, wherein the diluent (A) comprises a polyethylene polymer.

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

17. The processing aid of Claim 13, wherein the diluent (A) is selected from the group consisting of LDPE, HDPE, LLDPE, and functionalized polyolefin.

18. The processing aids 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 alpha-olefins and combination thereof.

19. The processing aid of Claims 13, wherein the diluent (A) comprises a solvent, preferably water.

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

21. An extrudable compound (E) comprising the polymer processing aid of any one or more of claims 1 - 19.

22. The extrudable compound (E) of Claim 21 , comprising from 10 ppm up to 2000 ppm, preferably up to 1000 ppm, and most preferably up to 750 ppm of polyalcohol (B) based on weight of thermoplastic polymer.

23. The extrudable compound (E) of Claim 21 comprising 1 ppm or more, preferably 5 ppm or more, most preferably 10 ppm or more and 0.5 wt.% or less, preferably 0.25 wt.% or less, most preferably 0.1% or less of the total weight of the active component in the extrudable compound E, wherein the polyalcohol (B) comprises from 0.01 wt. % up to 100% of the active components contained in the extrudable compound (E).

24. An Article (F) comprising the polymer processing aid of any one or more of claims 1 -19.

25. An Article (F) comprising the extrudable compound (E) of any one or more of claims 20-23.

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

27. A method of melt processing a thermoplastic polymer comprising: a) combining the polymer processing aid of any one or more of claims 1 -19 with a thermoplastic polymer, preferably a polyolefin polymer, wherein the amount of polyalcohol (B) is from 1 ppm up to less than 1 wt.%, preferably less than 5000ppm based on total weight of thermoplastic polymer, b) heating to above the melting point of the polyalcohol (B), and c) melt processing the thermoplastic polymer composition by extruding or molding .

28. The method of Claim 27 where the amount of polyalcohol (B) is from 10 ppm up to 0.25 wt.%.

29. A method of producing article (F) by melt processing comprising the steps of: a) combine polyalcohol (B) and a thermoplastic polymer, preferably a polyolefin polymer, in an amount from 1 ppm up to 5000ppm based on total weight of thermoplastic polymer to make a thermoplastic polymer composition, and then, b) heating the thermoplastic polymer composition above the melting point of the thermoplastic polymer in an extruder, molder, or other melt processing equipment, and c) extrude or mold or melt process to produce article (F).

30. A method of producing article (F) by melt processing comprising the steps of: a) providing the extrudable compound (E) of any one or more of Claims 20-23, wherein extrudable compound (E) comprises polyalcohol (B) in an amount of from 1 ppm up to 5000ppm based on total weight of thermoplastic polymer and then, b) heating and melt process the extrudable compound (E) composition above the melting point of the thermoplastic polymer to produce article (F).

31. The method of Claims 27, 29 or 30 wherein the wherein the amount of polyalcohol (B), comprises 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 of Claims 27, 29 or 30 wherein the amount of active component comprises 1 ppm or more, preferably 5 ppm or more, most preferably 10 ppm or more and 0.5 wt.% or less, preferably 0.25 wt.% or less, most preferably 0.1 % or less of the total weight of the active component in the article (F), wherein the polyalcohol (B) comprises from 0.01 wt. % up to 100% of the active components contained in article (F).

33. The method of Claims 27, 29 or 30 wherein the total amount of active components in the polymer processing aid are less than or equal to 50 wt.%, preferably less than 30 wt.%, more preferably less than 20 wt.% and even more preferably equal to or less than 10 wt.% and preferably above 0.1 wt.%, more preferably above 0.5 wt.% of the total polymer processing aid, wherein the polyalcohol (B) comprises from 0.01 wt.% up to 100% of the active components contained in polymer processing aid.

34. The methods of Claim 29 wherein the polyalcohol (B) is provided in the form of the polymer processing aid of any one or more of claims 1 - 19.

35. The methods of Claims 27, 29 or 30 wherein the thermoplastic polymer is a polyolefin.

36. The methods of Claims 27, 29 or 30 wherein the melting point of polyalcohol (B), is less than the melt processing temperature.

37. The methods of Claims 27, 29 or 30 wherein melt fracture is reduced or eliminated during the melt processing of the thermoplastic polymer composition.

38. Use of the processing aid of any one or more of Claims 1 to 19 to reduce melt fracture in the melt processing of a thermoplastic polymer.

39. The use of polymer processing aid comprising polyalcohol (B) for melt processing a polyolefin polymer.