WO2025149673A1

WO2025149673A1 - Pfas-free polymer composition

Info

Publication number: WO2025149673A1
Application number: PCT/EP2025/050691
Authority: WO
Inventors: Mazad KHAN-JEAUDEEN; Christian PENU; Antoine CRÉPIN
Original assignee: TotalEnergies Onetech SAS
Current assignee: TotalEnergies Onetech SAS
Priority date: 2024-01-11
Filing date: 2025-01-13
Publication date: 2025-07-17
Anticipated expiration: 2026-07-11

Abstract

A PFAS-free polymer processing aids mixture, comprising from 2.0 to 40.0 wt.% of one or more inorganic agents based on the total weight of the PFAS-free polymer processing aids mixture wherein the one or more inorganic agents are selected from the group consisting of montmorillonite, zeolite, silica, barium sulfate, calcium silicate, calcium sulfide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, neodymium oxide, and boron nitride; and two or more organic metal salts selected from calcium stearate, zinc stearate, barium stearate, aluminum monostearate, potassium stearate, magnesium stearate, sodium stearate, zinc acetate, sodium acetate, sodium caprylate, sodium laurate, sodium behenate, sodium 1-decane sulfonate, and sodium dodecyl sulfate.

Description

PFAS-FREE POLYMER COMPOSITION

TECHNICAL FIELD

The disclosure relates to polymer compositions, such as polyethylene compositions, suitable for blow molding film application.

TECHNICAL BACKGROUND

Polymer processing aids (PPA) are used to improve processability in several polymer compositions. For example, the presence of PPA in a polymer composition for blown film applications and grass yarn allow the reduction and elimination of melt fracture.

Melt fracture can be present in polymers with relatively low polydispersity index (below 4-5), such as metallocene-catalyzed polymers, with low melt index in blown film applications, due to their narrow molecular weight distribution (MWD) and their high viscosity.

However, most existing PPA compositions are or comprise per- and polyfluoroalkyl substances (PFAS).

PFAS are a large class of synthetic chemicals that are increasingly detected as environmental pollutants and some are linked to negative effects on human health. The restriction of their use under the chemical legislation (REACH) should come into force. PFAS in the scope of this restriction are defined as fluorinated substances that contain at least one aliphatic carbon atom that is both, saturated and fully fluorinated, i.e. any chemical with at least one perfluorinated methyl group (-CF3) or at least one perfluorinated methylene group (-CF2-), including fluoropolymers and fluorinated side chain polymers.

W02023/056207A1 discloses a polymer composition comprising a polymer and a surfactant. The surfactant can serve as a polymer processing aid (PPA) and can include a sorbitan ester and/or a polysorbate. The polymer can be a C2-C6 olefin homopolymer or a copolymer of two or more C2-C20 alpha-olefins. The polymer composition can be free or substantially free of fluorine.

W02023/056208A1 discloses a polymer composition comprising a polymer and a polyethylene glycol-based polymer processing aid (PPA). The polymer can be a C2-C6 olefin homopolymer or a copolymer of two or more C2-C20 alpha-olefins. The polymer composition can be free or substantially free of fluorine.

W02023/056210A1 , WO2023/056212A1 , and US02230031000A1 disclose a polymer composition comprising a polymer and a polymer processing aid (PPA) comprising at least two of (i) polyethylene glycol, (ii) surfactant comprising a sorbitan ester or a polysorbate; and (iii) a metal salt of a fatty acid. The polymer can be a C2-C6 olefin homopolymer or a copolymer of two or more C2-C20 alpha-olefins. The polymer composition can be free or substantially free of fluorine.

WO2023/056213A1 discloses a polymer composition comprising a polymer and a polyethylene glycol-based polymer processing aid (PPA). The polyethylene glycol can have a molecular weight of less than 40,000 g/mol. The polymer can be a C2-C6 olefin homopolymer or a copolymer of two or more C2-C20 alpha-olefins and can have a melt index ratio (MIR) of 20 or less. The polymer composition can be free or substantially free of fluorine.

WO2023/056214A1 discloses polymer compositions and methods of making them, including blending a polymer and a polyethylene glycol (PEG) masterbatch. The PEG masterbatch can include one or more PEGs each having a molecular weight of less than 40,000 g/mol. The polymer can be a C2-C6 olefin homopolymer or a copolymer of two or more C2-C20 alphaolefins. The polymer composition can be free or substantially free of fluorine.

WO2023/285888A1 discloses fluoropolymer-free polymer processing aids comprising a polyalkylene glycol such as polyethylene glycol together with high-pressure low-density polyethylene (LDPE). The composition shows reduced melt defects in a thermoplastic polyolefin such as linear low-density polyethylene (LLDPE).

US7491762B2 discloses compositions comprising hexahydrophthalate (HHPA) metal salts may be useful as nucleating agents in polyolefins. Masterbatch compositions containing such salts and silica and/or hydrotalcite are useful in reducing haze and improving properties of manufactured polyolefin articles or film. Such compositions may be dispersed effectively and efficiently into resin during manufacturing operations in the form of a masterbatch.

US2022056250A1 discloses polyethylene-based compositions suitable for packaging applications, films, and articles. In one aspect, a polyethylene-based composition suitable for packaging applications comprises (a) at least 97% by weight, based on the total weight of the polyethylene-based composition, of a polyethylene composition comprising: (i) from 25 to 37 percent by weight of a first polyethylene fraction having a density in the range of 0.935 to 0.947 g/cm3 and a melt index (I2) of less than 0.1 g/10 minutes; and (ii) from 63 to 75 percent by weight of a second polyethylene fraction; and (b) 90 to 540 ppm, based on the total weight of the polyethylene-based composition of a calcium salt of 1 ,2-cyclohexanedicarboxylic acid; wherein the polyethylene composition has less than 0.10 branches per 1 ,000 carbon atoms when measured using ¹³C NMR, wherein the density of the polyethylene-based composition is at least 0.965 g/cm³, and wherein the melt index (I2) of the polyethylene-based composition is 0.5 to 10 g/10 minutes. CN104387655A discloses medical nano-zinc oxide antibacterial PE and a preparation method thereof. The method comprises the following steps: weighing PE, calcium carbonate, cerium oxide, HDPE, nano-zinc oxide, DCP, an antioxidant, calcium stearate, EBS, POE, a coupling agent, CPE, barium stearate, stearic acid and zinc stearate according to the parts by weight; mixing evenly; and then extruding and pelletizing, so as to prepare medical nano-zinc oxide antibacterial PE.

US2003013785A1 discloses a stabilizer mixture containing (A) a sterically hindered amine compound, (B) an organic salt of Ca or an inorganic salt of Ca and (C) an organic salt of Mg, an inorganic salt of Mg, an organic salt of Zn or an inorganic salt of Zn; with the proviso that component (C) is Mg-hydroxide-carbonate, Zn-hydroxide-carbonate or dolomite, when component (B) is calcium stearate.

US2015315355A1 discloses a composition comprising a blend of high-density polyethylene (HDPE) and a nucleating component, with optional additives, in amounts effective to provide reduced shrinkage of the extruded composition and components made from the composition.

However, there is still a need to find PPA mixtures being PFAS-free PPA mixtures, that can, when present in a polymer composition, achieve similar or improved melt fracture behavior by comparison of PFAS-containing PPA compositions. In particular, there is a need for PPA mixtures being PFAS-free PPA mixtures, that can, when present in a polymer composition, achieve similar or improved melt fracture behavior by comparison of PFAS-containing PPA compositions while maintaining the optical and mechanical properties.

SUMMARY

It has now been found that one or more of the aforementioned needs can be fulfilled with a PFAS-free polymer processing aids mixture comprising two or more organic metal salts and one or more inorganic agents.

According to a first aspect, the disclosure provides a PFAS-free polymer processing aids mixture, remarkable in that it comprises:

- from 2.0 to 40.0 wt.% one or more inorganic agents based on the total weight of the PFAS-free polymer processing aids mixture wherein the one or more inorganic agents are selected from the group consisting of montmorillonite, zeolite, silica, barium sulfate, calcium silicate, calcium sulfide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, neodymium oxide, and boron nitride; and

- two or more organic metal salts selected from calcium stearate, zinc stearate, barium stearate, aluminum monostearate, potassium stearate, magnesium stearate, sodium stearate, zinc acetate, sodium acetate, sodium caprylate, sodium laurate, sodium behenate, sodium 1 -decane sulfonate, and sodium dodecyl sulfate.

Indeed, it was found that it was possible to achieve the same level of melt fracture properties in a polymer composition, such as a polyethylene composition, with a PFAS-free polymer processing aids mixture comprising inorganic agents in addition to two or more organic metal salts; such as two or more organic metal salts of fatty acids. Surprisingly, as demonstrated by the examples, a synergetic effect has been found between the components of the PFAS-free polymer processing aids mixture when two different organic metal salts are combined with an inorganic agent.

Melt fracture phenomena are illustrated by a surface modification of the film surface leading to bad aspects of the film. Consequently, a melt fracture clearance additive should restore the good film aspect by clearing the melt fracture. However, such an additive should not significantly change the other properties of the film such as optical properties (haze, gloss, transparency...), mechanical properties (impact resistance, tear resistance, E modulus...), or thermal properties (crystallization temperature, melt temperature...).

In a preferred embodiment, the two or more organic metal salts comprises calcium stearate and/or zinc stearate.

In one or more embodiments, the PFAS-free polymer processing aids mixture is devoid of sterically hindered amine compounds and/or siloxane-based components.

In one or more embodiments, the PFAS-free polymer processing aids mixture comprises at least one organic metal salt of a first metal and at least one organic metal salt of a second metal wherein the first metal and the second metal are different. With preference, the first and second metal are selected from calcium, zinc, barium, aluminum, potassium, magnesium and sodium.

In one or more embodiments, the PFAS-free polymer processing aids mixture comprises at least one organic metal salt of a first metal and at least one organic metal salt of a second metal wherein the first metal and the second metal are different; wherein the second metal is zinc and wherein the at least one organic metal salt of zinc is present in the PFAS-free polymer processing aids mixture at a content lower than the at least one organic metal salt of a first metal.

In one or more embodiments, the one or more inorganic agents are selected from aluminum oxide, magnesium oxide, and zinc oxide. With preference, the one or more inorganic agents are or comprise zinc oxide. In one or more embodiments, the PFAS-free polymer processing aids mixture comprises from 3.0 to 30.0 wt.% one or more inorganic agents based on the total weight of the PFAS-free polymer processing aids mixture; preferably from 10.0 to 30.0 wt.%.

The disclosure also aims to provide polymer compositions suitable for blown film applications and grass yarn that are PFAS-free but achieve the same level of melt fracture properties in the polymer composition. In particular, the disclosure aims to provide polymer compositions suitable for blown film applications and grass yarn that are PFAS-free but achieve the same level of melt fracture properties as the PFAS based additives together with reduced die deposit while maintaining optical and mechanical properties.

Thus, according to second aspect the disclosure provides for polymer composition remarkable in that it comprises:

- a component (A) comprising one or more polymers selected from C2-C6 alpha-olefin homopolymers, and copolymers of two or more C2-C20 alpha-olefins; and

- a component (B) being a PFAs-free polymer processing aids mixture according to the first aspect.

In one or more embodiments, the component (A) is or comprises one or more polyethylenes selected from ethylene homopolymers and/or one or more copolymers of ethylene and one or more comonomers selected from C3-C20 alpha-olefins; and/or the component (A) is metallocene catalyzed.

In one or more embodiments, the component (A) is or comprises one or more polyethylenes selected from linear low-density polyethylenes (LLDPE), low-density polyethylenes (LDPE), medium-density polyethylenes (MDPE), and high-density polyethylenes (HDPE); with preference, the component (A) is or comprises one or more LLDPE and/or one or more HDPE.

In one or more embodiments, the component (A) is one or more polyethylenes, wherein one or more of the following is true: the component (A) has a melt index ranging from 0.1 to 5.0 g/10 min as determined according to ISO 1133-2005 at 190°C under a load of 2.16 kg; the component (A) has a density ranging from 0.900 to 0.970 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at a temperature of 23 °C; the component (A) has a molecular weight distribution ranging from 2.0 to 12.0.

In one or more embodiments, the polymer composition comprises from 1 ,000 to 5,000 ppm of the PFAS-free polymer processing aids mixture (i.e. the component B); preferably from 1 ,000 to 4,500 ppm; more preferably, from 1 ,500 to 4,000 ppm; even more preferably from 1 ,500 to 3,000 ppm; most preferably from 1 ,500 to 2,500 ppm. In one or more embodiments, the component (B) comprises one or more organic metal salt of a second metal selected from zinc stearate and magnesium stearate ; and the one ore more organic metal salt of a second metal are present in the polymer composition at a content ranging from 100 to 1 ,000 ppm based on the total weight of the polymer composition; preferably at a content ranging from 200 to 800 ppm based on the total weight of the polymer composition.

In a preferred embodiment, the polymer composition comprises both zinc oxide and zinc stearate wherein their cumulated content based on the total weight of the polymer composition is at most 2,000 ppm; preferably at most 1 ,800 ppm; more preferably at most 1 ,500 ppm; and even more preferably at most 1250 ppm.

In a preferred embodiment, the one or more organic metal salt of a first metal are or comprise calcium stearate ; and the one or more organic metal salt of a second metal are present in the polymer composition at a content ranging from 500 to 2,000 ppm based on the total weight of the polymer composition; preferably from 700 to 1 ,600 ppm.

In one or more embodiments, the component (B) is provided at a content suitable for the polymer composition to comprise from 100 to 2,000 ppm of the one or more inorganic agents.

In one or more embodiments, the component (B) is devoid of siloxane-based components

It is understood that to be qualified as being a PFAS-free polymer processing aids, the component (B) is devoid of polyethylene glycol and/or is devoid of a chemical with at least one perfluorinated methyl group (-CF3) or at least one perfluorinated methylene group (-CF2-).

According to a third aspect, the disclosure provides for a process to produce a polymer composition, the process comprising the following step: a) providing a component (A) comprising one or more polymers selected from C2-C6 alpha-olefin homopolymers, and copolymers of two or more C2-C20 alpha-olefins; b) providing a component (B) being a PFAS-free polymer processing aids mixture comprising two or more organic metal salts and one or more inorganic agents; c) blending the components (A) and (B) to form a polymer composition according to the second aspect.

According to a fourth aspect, the disclosure provides for an article made from a material that is or comprises at least one polymer composition remarkable in that at least the polymer composition is according to the second aspect or produced according to the third aspect; with preference, the article is selected from a film or a yarn; more preferably the article is a blown film. According to a fifth aspect, the disclosure provides for the use of a PFAS-free polymer processing aids mixture, remarkable in that said PFAS-free polymer processing aids mixture is according to the fifth aspect.

DESCRIPTION OF THE FIGURES

Figure 1 represents the evolution of the melt fracture content of the film (100% meaning that all the film surface is covered with melt fracture and 0% meaning that all the film surface is free of melt fracture)

DETAILED DESCRIPTION

For the purpose of the disclosure, the following definitions are given.

The terms "comprising", "comprises" and "comprised of' as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. The terms "comprising", "comprises" and "comprised of" also include the term “consisting of”.

The recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g., 1 to 5 includes 1 , 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements). The recitation of endpoints also includes the recited endpoint values themselves (e.g., from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.

The reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure. The particular features, structures, characteristics, or embodiments may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the disclosure and form different embodiments, as would be understood by those in the art.

Unless otherwise defined, all terms used in disclosing the disclosure, including technical and scientific terms, have the meaning as commonly understood by one skilled in the art to which this disclosure belongs. By means of further guidance, definitions for the terms used in the description are included to better appreciate the teaching of the present disclosure. As used herein, the terms “melt blending” involves the use of shear force, extensional force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy or combinations comprising at least one of the foregoing forces or forms of energy and is conducted in a processing equipment wherein the aforementioned forces are exerted by a single screw, multiple screws, intermeshing co-rotating or counter-rotating screws, non-intermeshing corotating or counter-rotating screws, reciprocating screws, screws with pins, barrels with pins, rolls, rams, helical rotors, or combinations comprising at least one of the foregoing. Melt blending may be conducted in machines such as single or multiple screw extruders, Buss kneaders, Eirich mixers, Henschel, helicones, Ross mixers, Banbury, roll mills, moulding machines such as injection moulding machines, vacuum forming machines, blow moulding machines, or the like, or combinations comprising at least one of the foregoing machines. It is generally desirable during melt or solution blending of the composition to impart a specific energy of about 0.01 to about 10 kilowatt-hours/kilogram (kW h/kg) of the composition. In a preferred embodiment, melt blending is performed in a twin-screw extruder, such as a Brabender co-rotating twin-screw extruder.

The terms “polyethylene” (PE) and “ethylene polymer” may be used synonymously. The term “polyethylene” encompasses homopolymer of ethylene as well as copolymer of ethylene which can be derived from ethylene and one or more comonomers selected from the group consisting of C3-C20 alpha-olefins, such as propylene, 1 -butene, 1 -pentene, 4-methyl-1 -pentene, 1- hexene, 1 -octene, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene and 1- eicosene.

The terms “polyethylene resin”, as used herein, refer to polyethylene fluff or powder that is extruded, and/or melted and/or pelletized and can be produced through compounding and homogenizing of the polyethylene resin as taught herein, for instance, with mixing and/or extruder equipment. As used herein, the term “polyethylene” that can be used as a shorthand for “polyethylene resin”. The terms “fluff” or “powder” as used herein refer to polyethylene material with the hard catalyst particle at the core of each grain and is defined as the polymer material after it exits the polymerization reactor (or the final polymerization reactor in the case of multiple reactors connected in series).

Under normal production conditions in a production plant, it is expected that the melt index (MI2, HLMI, Mis) will be different for the fluff than for the polyethylene resin. Under normal production conditions in a production plant, it is expected that the density will be slightly different for the fluff, than for the polyethylene resin. Unless otherwise indicated, density and melt index for the polyethylene resin refer to the density and melt index as measured on the polyethylene resin as defined above. The terms “virgin polyethylene” is used to denote a polyethylene directly obtained from an ethylene polymerization plant. The terms “directly obtained” is meant to include that the polyethylene may optionally be passed through a pelletization step or an additivation step or both.

The terms “Post Consumer Resin”, which may be abbreviated as “PCR”, is used to denote the component of domestic waste, household waste or end of life vehicle waste. The terms “Post Industrial Resin”, which may be abbreviated as “PIR”, is used to denote the component of industrial waste.

The terms “polyethylene post-consumer resin” (PCR-PE) is a recycled material that is a compound made of high-density polyethylene, low-density polyethylene, linear low-density polyethylene and may contain one or more other polymer such as polypropylene.

Ziegler-Natta catalyst systems are generally formed from the combination of a metal component (i.e., a catalyst precursor) with one or more additional components, such as a catalyst support, a co-catalyst and/or one or more electron donors.

Metallocene catalysts are compounds of Group IV transition metals of the Periodic Table such as titanium, zirconium, hafnium, etc., and have a coordinated structure with a metal compound and a ligand composed of one or two groups of cyclopentadienyl, indenyl, fluorenyl or their derivatives.

Chromium catalysts are known to the person skilled in the art. For example, chromium catalyst can be prepared by impregnating high surface area silica gel with chromium trioxide or related chromium compounds. The solid precatalyst is then calcined in air to give the active catalyst. EP2004704B1 provides a more detailed process of production of a suitable chromium catalyst.

As used herein, "blend", "polymer blend" and like terms refer to a composition of two or more compounds, for example, two or more polymers or one polymer with at least one other compound.

The particular features, structures, characteristics, or embodiments may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments.

The disclosure provides for a PFAS-free polymer processing aids mixture, remarkable in that it comprises:

The polymer processing aids mixture is said PFAS-free because it is devoid of a chemical with at least one perfluorinated methyl group (-CF3) or at least one perfluorinated methylene group (-CF2-).

The disclosure also provides for a polymer composition comprising a component (A) comprising one or more polymers selected from C2-C6 alpha-olefin homopolymers, and copolymers of two or more C2-C20 alpha-olefins; and a component (B) being a PFAS-free polymer processing aids mixture as defined above, i.e. a PFAS-free polymer processing aids mixture comprising

The disclosure also provides for a process to produce a polymer composition comprising the steps of:

1. providing a component (A) comprising one or more polymers selected from C2-C6 alpha-olefin homopolymers, and copolymers of two or more C2-C20 alpha-olefins;

2. providing a component (B) being a PFAS-free polymer processing aids mixture as defined above, i.e. a PFAS-free polymer processing aids mixture comprising

■ from 2.0 to 40.0 wt.% one or more inorganic agents based on the total weight of the PFAS-free polymer processing aids mixture wherein the one or more inorganic agents are selected from the group consisting of montmorillonite, zeolite, silica, barium sulfate, calcium silicate, calcium sulfide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, neodymium oxide, and boron nitride; and

• two or more organic metal salts selected from calcium stearate, zinc stearate, barium stearate, aluminum monostearate, potassium stearate, magnesium stearate, sodium stearate, zinc acetate, sodium acetate, sodium caprylate, sodium laurate, sodium behenate, sodium 1 -decane sulfonate, and sodium dodecyl sulfate.

3. blending the components (A) and (B) to form a polymer composition.

The PFAS-free polymer processing aids mixture, the polymer composition and the process to produce the polymer composition will be jointly described.

The component (A) of the polymer composition

According to the disclosure, the component (A) comprises one or more polymers selected from C2-C6 alpha-olefin homopolymers, and copolymers of two or more C2-C20 alpha-olefins.

In various embodiments, the component (A) is or comprises one or more homopolymers of C2-C6 alpha-olefin. The term “copolymer” refers to a polymer that is made by linking ethylene and at least one comonomer in the same polymer chain. The term homopolymer refers to a polymer that is made in the absence of comonomer or with less than 0.1 wt.% as determined by ¹³C-NMR, more preferably less than 0.05 wt.% of comonomer. In an embodiment, the component (A) is or comprises one or more ethylene homopolymers and/or one or more propylene homopolymers.

In various embodiments, the component (A) is or comprises one copolymers of two or more C2-C20 alpha-olefins. For example, the component (A) includes one or more copolymers of ethylene and one or more comonomers selected from C3-C20 alpha-olefins and/or one or more copolymers of propylene and one or more comonomers selected from ethylene and C4- C20 alpha-olefins. In case the polymer is a copolymer, it comprises at least 0.1 wt.% of comonomer, preferably at least 1 wt.%. The copolymer comprises up to 20 wt.% of comonomer as determined by ¹³C-NMR more preferably up to 15 wt.%, even more preferably up to 10 wt.%. and most preferably up to 9 wt.%. With preference, the component (A) includes one or more copolymers of ethylene and one or more comonomers selected from C3-C20 alphaolefins.

In a preferred embodiment, the component (A) is or comprises one or more polyethylenes selected from ethylene homopolymers and/or one or more copolymers of ethylene and one or more comonomers selected from C3-C20 alpha-olefins. Suitable comonomers comprise but are not limited to aliphatic C3-C20 alpha-olefins. Examples of suitable aliphatic C3-C20 alphaolefins include propylene, 1 -butene, 1 -pentene, 4-methyl-1 -pentene, 1 -hexene, 1 -octene, 1- decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene and 1-eicosene. With preference, the one or more comonomers are selected from propylene, 1 -butene, 1 -hexene, and 1 -octene. With preference, the one or more comonomers are selected from propylene, 1- butene, and 1 -hexene. More preferably the comonomer is 1 -butene and/or 1 -hexene.

For example, the component (A) is one or more polyethylenes and has a density ranging from 0.900 to 0.970 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at a temperature of 23 °C; preferably from 0.905 to 0.965 g/cm³; more preferably from 0.910 to 0.960 g/cm³.

For example, the one or more polyethylenes are selected from linear low-density polyethylenes (LLDPE), low-density polyethylenes (LDPE), medium density polyethylenes (MDPE), and high- density polyethylenes (HDPE). In a preferred embodiment, the component (a) is or comprises one or more LLDPE and/or one or more HDPE.

For example, the one or more LLDPE are copolymers of ethylene and one or more comonomers selected from propylene, 1 -butene, 1 -hexene, and 1 -octene. For example, at least one LLDPE or the single LLDPE is a copolymer of ethylene and 1 -hexene.

The one or more LLDPE may have a density of at least 0.910 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at 23°C; preferably of at least 0.912 g/cm³, or at least 0.915 g/cm³; more preferably of at least 0.920 g/cm³, or at least 0.923 g/cm³; even more preferably of at least 0.925 g/cm³, or at least 0.928 g/cm³; and most preferably of at least 0.930 g/cm³, or at least 0.935 g/cm³.

The one or more LLDPE may have a density of at most 0.940 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at 23°C; preferably at most 0.938 g/cm³; more preferably at most 0.936 g/cm³; and most preferably at most 0.935 g/cm³.

The one or more HDPE may have a density of at least 0.940 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at 23°C; preferably of at least 0.942 g/cm³, or at least 0.945 g/cm³; more preferably of at least 0.946 g/cm³, or at least 0.948 g/cm³; most preferably at least 0.950 g/cm³ and even most preferably at least 0.952 g/cm³.

The one or more HDPE may have a density of at most 0.970 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at 23°C; preferably at most 0.9 g/cm³, more preferably at most 0.965 g/cm³, even more preferably at most 0.963 g/cm³. For example, the component (A) is one or more polyethylenes and has a melt index ranging from 0.1 to 5.0 g/10 min as determined according to ISO 1133-2005 at 190°C under a load of 2.16 kg; preferably from 0.1 to 4.0 g/10 min; more preferably from 0.1 to 3.0 g/10 min; even more preferably from 0.2 to 2.5 g/10 min; most preferably from 0.3 to 2.0 g/10 min and even most preferably from 0.4 to 1.8 g/10 min or from 0.5 to 1.5 g/10 min or from 0.2 to 1.2 g/10 min.

The one or more polyethylenes can be produced can be produced using a chromium catalyst, a Ziegler-Natta catalyst or a metallocene catalyst. With preference, the component (A) is or comprise one or more metallocene-catalyzed polyethylenes. For example, the component (A) is or comprises one or more polyethylene and has a molecular weight distribution ranging from has a molecular weight distribution ranging from 2.0 to 12.0; preferably from 2.2 to 11.0; more preferably from 2.5 to 10.0; even more preferably from 2.8 to 9.0; most preferably from 3.0 to 8.0 or from 3.2 to 7.0; and even most preferably from 3.5 to 6.0 or from 3.8 to 5.8.

In an embodiment, the polymer composition comprises one or more metallocene-catalyzed polyethylenes and has a density ranging from 0.930 to 0.940 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at a temperature of 23 °C.

Examples of suitable metallocene-catalyzed polyethylenes are commercially available at TotalEnergies upon the commercial name Lumicene ® M5510 EP, Lumicene ® M4707EP, Lumicene ® M6012EP, Lumicene ® Supertough 32ST05 and Lumicene ® Supertough 40ST05.

The PFAS-free polymer processing aids mixture (i.e. the component (B) of the polymer composition)

According to the disclosure, the PFAS-free polymer processing aids mixture comprises:

- from 2.0 to 40.0 wt.% one or more inorganic agents based on the total weight of the PFAS-free polymer processing aids mixture wherein the one or more inorganic agents are selected from the group consisting of montmorillonite, zeolite, silica, barium sulfate, calcium silicate, calcium sulfide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, neodymium oxide, and boron nitride; and two or more organic metal salts selected from calcium stearate, zinc stearate, barium stearate, aluminum monostearate, potassium stearate, magnesium stearate, sodium stearate, zinc acetate, sodium acetate, sodium caprylate, sodium laurate, sodium behenate, sodium 1 -decane sulfonate, and sodium dodecyl sulfate the component (B) is PFAS-free polymer processing aids mixture comprising two or more organic metal salts and one or more inorganic agents. The PFAS-free polymer processing aids mixture of the disclosure is used as the component (B) of the polymer composition.

When used as component (B), the different components of the PFAS-free polymer processing aids mixture can be dry blended and added jointly as a mixture, or can be added to the polymer composition separately.

The content of the component (B) in the polymer composition, and of each of the inorganic agents and each of the organic metal salts in the component (B) corresponds to the content added during the process to produce a polymer composition. It is nevertheless noted that, if needed, the person skilled in the art can assess the presence of metals in the polymer composition by inductively coupled plasma atomic emission spectroscopy (ICP-AES). ICP- AES can also be used to determine the content of each metal in the polymer composition. The content of fatty acids such as the stearate content can be assessed by gas chromatographymass spectrometry. Both techniques are well known to the person skilled in the art.

The polymer composition may comprise from 500 to 5,000 ppm of the PFAS-free polymer processing aids mixture (i.e., the component (B)) based on the total weight of the polymer composition; preferably from 800 to 4,800 ppm; more preferably from 1 ,000 to 4,500 ppm; even more preferably from 1 ,200 to 4,200 ppm; most preferably from 1 ,500 to 4,000 ppm or from 1 ,500 to 3,800 ppm; even most preferably from 1 ,500 to 3,800 ppm or from 1 ,500 to 3,500 ppm; preferably from 1 ,500 to 3,000 ppm; preferably from 1 ,500 to 2,800 ppm, preferably from 1 ,500 to 2,500 ppm ; preferably from 1 ,800 to 2,500 ppm; preferably from 1 ,900 to 2,500 ppm; preferably from 2,000 to 2,500 ppm.

PFAS-free polymer processing aids mixture (i.e., the component (B)) comprises two or more organic metal salts selected from calcium stearate, zinc stearate, barium stearate, aluminum monostearate, potassium stearate, magnesium stearate, sodium stearate, zinc acetate, sodium acetate, sodium caprylate, sodium laurate, sodium behenate, sodium 1 -decane sulfonate, and sodium dodecyl sulfate.

In some embodiments, the metal salt is a metal salt of a carboxylic acid or a sulfonic acid. Carboxylic acids and sulfonic acids may be monofunctional or multifunctional (e.g., difunctional) and may be aliphatic or aromatic. In other words, the carbonyl carbon or sulfonyl sulfur may be attached to an aliphatic group or aromatic ring. Aliphatic carboxylic acids and sulfonic acids may be saturated or unsaturated. In addition to the one or more -C(O)O' or - S(O)2O' anions (i.e., carboxylate or sulfonate groups, respectively), the aliphatic or aromatic group may also be substituted by other functional groups including halogen (i.e., fluoro, chloro, bromo, and iodo), hydroxyl, and alkoxy groups, and aromatic rings may also be substituted by alkyl groups. In some embodiments, the carboxylic acid or sulfonic acid is monofunctional or difunctional and aliphatic, without any further substituents on the aliphatic chain.

In some embodiments, the metal salt is a metal salt of a carboxylic acid. In some embodiments, the carboxylic acid useful for providing the metal salt is represented by the formula RCOOH, wherein R is alkyl or alkenyl. For example, the carboxylic acid is acetic acid.

In preferred embodiments, the carboxylic acid is a fatty acid, for example, having an alkyl or alkenyl group with about 8 to 30 (in some embodiments, 8 to 26 or 8 to 22) carbon atoms. The common names of the fatty acids having from 8 to 26 carbon atoms are caprylic acid (C8), capric acid (C10), lauric acid (C12), myristic acid (C14), palmitic acid (C16), stearic acid (C18), arachidic acid (C20), behenic acid (C22), lignoceric acid (C24), and cerotic acid (C26). Fatty acid metal salts of these acids may be caprylate, caprate, laurate, myristate, palmitate, stearate, arachidate, behenate, lignocerate, and cerotate salts, in some embodiments. For example, the carboxylic acid is stearic acid.

In some embodiments, the metal salt is a metal salt of a sulfonic acid. In some embodiments, the sulfonic acid useful for providing the metal salt is represented by formula RS(O)2OH, wherein R is alkyl or alkenyl. The alkyl or alkenyl group has about 8 to 30 (in some embodiments, 8 to 26 or 8 to 22) carbon atoms.

In some embodiments, the metal salt is a metal salt of an alkyl sulfate. In addition to the one or more -OS(O)2O' anions (i.e., sulfate groups), the alkyl group may also be substituted by other functional groups including, hydroxyl, and alkoxy groups. In some embodiments, the alkyl group includes no further substitution. The acid useful for providing the metal salt is typically represented by formula R'OS(O)2OH, wherein R' is alkyl having about 8 to 30 (in some embodiments, 8 to 26 or 8 to 22) carbon atoms. According to the disclosure, the alkyl group is not substituted by a functional group including a halogen (i.e., fluoro, chloro, bromo, and iodo).

Examples of useful metal cations in the metal salt of a carboxylic acid, sulfonic acid, or alkylsulfate include aluminum (Al), calcium (Ca), magnesium (Mg), zinc (Zn), barium (Ba), lithium (Li), sodium (Na), and potassium (K). In some embodiments, the metal salt is a sodium or potassium salt. In preferred embodiments, the metal salt is a zinc or calcium salt.

Many metal salts of a carboxylic acid, sulfonic acid, or alkylsulfate are available from a variety of commercial sources, and others can be made by conventional methods. In some embodiments, the metal salt of a carboxylic acid, sulfonic acid, or alkylsulfate can be formed in situ. In these embodiments, typically a first component containing the metal cation and a second component containing the carboxylic acid, sulfonic acid, or alkylsulfate can both be added to the component (A). For example, zinc oxide and stearic acid may be added to a composition to form zinc stearate.

The presence of metal salts of a carboxylic acid, sulfonic acid, or alkylsulfate is useful for thermally stabilizing the polymer composition.

In a preferred embodiment, at least one of the two or more organic metal salts of the component (B) is a metal salt of fatty acids; preferably, at least two organic metal salts of the component (B) are metal salt of fatty acids; more preferably all the organic metal salts of the component (B) are metal salt of fatty acids.

In a preferred embodiment, the component (B) comprises two organic metal salts of fatty acids. With preference, the component (B) comprises calcium stearate and/or zinc stearate.

In some embodiments, component (B) comprises at least two organic metal salts having a difference in melting point of at least 5°C; preferably at least 8°C, more preferably at least 10 °C, even more preferably at least 12°C, most preferably at least 15°C.

The melting points of organic metal salts are known to the person skilled in the art. For example, the melting point of calcium stearate is 145-155°C, of zinc stearate is 120-130°C, of barium stearate is >225°C, of aluminum monostearate is about 155°C, of potassium stearate is 235-245°C, of magnesium stearate 85-90°C, of sodium stearate is 245-255°C, of sodium acetate is 320-325°C, of sodium laurate is about 245°C, and of sodium dodecyl sulfate is about 206°C.

The polymer composition may comprise from 400 to 3,000 ppm of the two or more organic metal salts based on the total weight of the polymer composition; preferably from 800 to 2,800 ppm; more preferably from 1 ,000 to 2,500 ppm; even more preferably from 1 ,100 to 2,200 ppm; most preferably from 1 ,200 to 2,000 ppm; and even most preferably from 1 ,300 to 1 ,900 ppm or from 1 ,400 to 1 ,800 ppm

The component (B) may comprise from 18.0 to 98.0 wt.% of the two or more organic metal salts based on the total weight of the component (B); preferably from 20.0 to 97.6 wt.%; more preferably from 22.0 to 97.0 wt.%; even more preferably from 24.0 to 96.4 wt.%; most preferably from 26.0 to 96.0 wt.%; and even most preferably from 28.0 to 80.0 wt.% or from 30.0 to 60.0 wt.%.

In a preferred embodiment the component (B) comprises two or more organic metal salts of two or more different metals. For example, the component (B) comprises at least one organic metal of a first metal and at least one organic metal of a second metal wherein the first metal and the second metal are different; with preference the first and second metal are selected from calcium, zinc, barium, aluminum, potassium, magnesium and sodium.

With preference, the one or more organic metal salts of the first metal are selected from calcium stearate, barium stearate, aluminum monostearate, potassium stearate, sodium stearate, sodium acetate, sodium laurate, and sodium dodecyl sulfate; more preferably, the one or more organic metal salts of the first metal are or comprise calcium stearate.

For example, the polymer composition comprises from 500 to 2,000 ppm of the one or more organic metal salts of the first metal based on the total weight of the polymer composition as; preferably from 550 to 1 ,900 ppm; more preferably from 600 to 1 ,800 ppm; even more preferably from 650 to 1 ,700 ppm; most preferably from 700 to 1 ,600 ppm; and even most preferably from 750 to 1 ,500 ppm or from 800 to 1 ,400 ppm; or from 800 to 1 ,300 ppm.

In a preferred embodiment, the polymer composition comprises from 500 to 2,000 ppm of calcium stearate based on the total weight of the polymer composition; preferably from 550 to 1 ,900 ppm; more preferably from 600 to 1 ,800 ppm; even more preferably from 650 to 1 ,700 ppm; most preferably from 700 to 1 ,600 ppm; and even most preferably from 750 to 1 ,500 ppm or from 800 to 1 ,400 ppm; or from 800 to 1 ,300 ppm.

In an embodiment, the one or more organic metal salts of the first metal is calcium stearate and the polymer composition comprises at most 1 ,300 ppm based on the total weight of the polymer composition; preferably at most 1 ,200 ppm; more preferably at most 1 ,100 ppm; even more preferably at most 1 ,000 ppm; most preferably at most 900 ppm; and even most preferably at most 800 ppm.

With preference, the one or more organic metal salts of the second metal are selected from zinc stearate and magnesium stearate provided that the metal is different from the first metal; more preferably, the one or more organic metal salts of the second metal are or comprise zinc stearate.

For example, the polymer composition comprises from 100 to 1 ,000 ppm of the one or more organic metal salts of the second metal based on the total weight of the polymer composition as; preferably from 120 to 950 ppm; more preferably from 150 to 900 ppm; even more preferably from 180 to 850 ppm; most preferably from 200 to 800 ppm; and even most preferably from 200 to 750 ppm or from 200 to 700 ppm; or from 200 to 650 ppm; or from 200 to 600 ppm.

For example, the polymer composition comprises from 100 to 1 ,000 ppm of zinc stearate based on the total weight of the polymer composition; preferably from 120 to 950 ppm; more preferably from 150 to 900 ppm; even more preferably from 180 to 850 ppm; most preferably from 200 to 800 ppm; and even most preferably from 200 to 750 ppm or from 200 to 700 ppm; or from 200 to 650 ppm; or from 200 to 600 ppm.

In one or more embodiments, the PFAS-free polymer processing aids mixture comprises at least one organic metal salt of a first metal and at least one organic metal salt of a second metal wherein the first metal and the second metal are different; wherein the second metal is zinc and wherein the at least one organic metal salt of zinc is present in the PFAS-free polymer processing aids mixture at a content lower than the at least one organic metal salt of a first metal. Indeed, for food contact applications it is important to limit the overall content of zinc in the polymer composition.

The PFAS-free polymer processing aids mixture (i.e. the component (B)) comprises from 2.0 to 40.0 wt.% based on the total weight of the PFAS-free polymer processing aids mixture of one or more inorganic agents selected from the group consisting of montmorillonite, zeolite, silica, barium sulfate, calcium silicate, calcium sulfide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, neodymium oxide, and boron nitride.

Although the organic metal salts can be considered agents, it is understood in the context of the disclosure that the one or more inorganic agents are different from the two or more metal salts.

In an embodiment, the one or more inorganic agents are or comprise one or more selected from aluminum oxide, magnesium oxide, and zinc oxide. Even more preferably, the one or more inorganic agents are or comprise zinc oxide.

Indeed, zinc oxide was found useful to prevent die built up.

The one or more inorganic agents specifically excludes talc (i.e. magnesium silicate), kaolinite, mica, clay, graphite, carbon black, calcium carbonate, calcium titanate, and titanium oxide; as they significantly modify the film transparency.

The polymer composition mays comprise from 100 to 2,000 ppm of the one or more inorganic agents based on the total weight of the polymer composition; preferably from 120 to 1 ,800 ppm; more preferably from 150 to 1 ,500 ppm; even more preferably from 180 to 1 ,300 ppm; most preferably from 200 to 1 ,000 ppm; and even most preferably from 200 to 800 ppm or from 200 to 600 ppm

In a preferred embodiment, the polymer composition comprises from 100 to 2,000 ppm of zinc oxide based on the total weight of the polymer composition; preferably from 120 to 1 ,800 ppm; more preferably from 150 to 1 ,500 ppm; even more preferably from 180 to 1 ,300 ppm; most preferably from 200 to 1 ,000 ppm; and even most preferably from 200 to 800 ppm or from 200 to 600 ppm.

The component (B) may comprise from 2.0 to 40.0 wt.% of the one or more inorganic agents based on the total weight of the component (B); preferably from 2.4 to 36.0 wt.%; more preferably from 3.0 to 30.0 wt.%; even more preferably from 3.6 to 26.0 wt.%; most preferably from 4.0 to 20.0 wt.%; and even most preferably from 4.0 to 16.0 wt.% or from 4.0 to 12.0 wt.%.

In a preferred embodiment, the component (B) comprises from 2.0 to 40.0 wt.% of zinc oxide based on the total weight of the component (B); preferably from 2.4 to 36.0 wt.%; more preferably from 3.0 to 30.0 wt.%; even more preferably from 3.6 to 26.0 wt.%; most preferably from 4.0 to 20.0 wt.%; and even most preferably from 4.0 to 16.0 wt.% or from 4.0 to 12.0 wt.%.

The disclosure also provides for an article made from a material that is or comprises at least one polymer composition remarkable in that at least the polymer composition is as described above or produced according to the process described above; with preference, the article is selected from a film or a yarn; more preferably the article is a blown film.

The disclosure provides for the use of a PFAS-free polymer processing aids mixture, remarkable in that said PFAS-free polymer processing aids mixture is as described above.

With preference, the polymer composition comprises one or more metallocene-catalyzed polyethylenes and has a density ranging from 0.930 to 0.940 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at a temperature of 23 °C; and the film show a haze of at most 20% as determined according to ISO 14782:2021 at the thickness of 43 pm; preferably at most 18 %; more preferably at most 15 %; even more preferably at most 12 %; and most preferably at most 10 %.

With preference, the polymer composition comprises one or more metallocene-catalyzed polyethylenes and has a density ranging from 0.930 to 0.940 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at a temperature of 23 °C; and the film show a gloss at 45° of at least 55 as determined according to ASTM D 2457-21 ; preferably at least 58; more preferably at least 60; even more preferably at least 62; and most preferably at least 65. With preference, the polymer composition comprises one or more metallocene-catalyzed polyethylenes and has a density ranging from 0.930 to 0.940 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at a temperature of 23 °C; and the film show a dart of at least 80 g at the thickness of 43 pm as determined according to ISO 7765-1 :1988 ; preferably at least 90 g; more preferably at least 100 g; even more preferably at least 110 g; and most preferably at least 120 g.

With preference, the polymer composition comprises one or more metallocene-catalyzed polyethylenes and has a density ranging from 0.930 to 0.940 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at a temperature of 23 °C; and the film show an Elmendorf MD of at least 20 N/mm according to ISO 6383-2:2004 ; preferably at least 25 N/mm; more preferably, at least 30 N/mm.

With preference, the polymer composition comprises one or more metallocene-catalyzed polyethylenes and has a density ranging from 0.930 to 0.940 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at a temperature of 23 °C; and the film show an Elmendorf TD of at least 90 N/mm according to ISO 6383-2:2004 ; preferably at least 100 N/mm; more preferably, at least 105 N/mm.

Test methods

The melt flow index MI2 of the polyethylene is determined according to ISO 1133-1 :2022 at 190°C under a load of 2.16 kg.

The density was measured according to the method of standard ISO 1183-1 :2012 (immersion method) at a temperature of 23 °C.

The Mn, Mw, Mz, Mw/Mn and Mz/Mw: The molecular weight (M_n (number average molecular weight), M_w (weight average molecular weight) and molecular weight distributions D (Mw/Mn) were determined by size exclusion chromatography (SEC) and in particular by gel permeation chromatography (GPC). Briefly, a GPC-IR5 from Polymer Char was used: 10 mg polyethylene sample was dissolved at 160°C in 10 ml of trichlorobenzene for 1 hour. Injection volume: about 400 pl, automatic sample preparation and injection temperature: 160°C. Column temperature: 145°C. Detector temperature: 160°C. Two Shodex AT-806MS (Showa Denko) and one Styragel HT6E (Waters) columns were used with a flow rate of 1 ml/min. Detector: Infrared detector (2800-3000 cm^-1). Calibration: narrow standards of polystyrene (PS) (commercially available). Calculation of molecular weight Mi of each fraction i of eluted polyethylene is based on the Mark-Houwink relation (log (MpE) = 0.965909 x log (Mps) - 0.28264) (cut off on the low molecular weight end at MPE = 1000). The molecular weight averages used in establishing molecular weight/property relationships are the number average (M_n), weight average (M_w) and z average (M_z) molecular weight. These averages are defined by the following expressions and are determined from the calculated Mi:

Here Nj and Wj are the number and weight, respectively, of molecules having molecular weight Mi. The third representation in each case (farthest right) defines how one obtains these averages from SEC chromatograms, hi is the height (from baseline) of the SEC curve at the i_th elution fraction and Mj is the molecular weight of species eluting at this increment.

The molecular weight distribution (MWD) is then calculated as Mw/Mn.

The ¹³C-NMR is performed using a 400 MHz or 500 MHz Bruker NMR spectrometer under conditions such that the signal intensity in the spectrum is directly proportional to the total number of contributing carbon atoms in the sample. Such conditions are well-known to the skilled person and include, for example, sufficient relaxation time etc. In practice, the intensity of a signal is obtained from its integral, i.e., the corresponding area. The data are acquired using proton decoupling, 2000 to 4000 scans per spectrum with 10 mm room temperature through or 240 scans per spectrum with a 10 mm cryoprobe, a pulse repetition delay of 11 seconds and a spectral width of 25000 Hz (+/- 3000 Hz). The sample is prepared by dissolving a sufficient amount of polymer in 1 ,2,4-trichlorobenzene (TCB, 99%, spectroscopic grade) at 130°C and occasional agitation to homogenize the sample, followed by the addition of hexadeuterobenzene (CeDe, spectroscopic grade) and a minor amount of hexamethyldisiloxane (HMDS, 99.5+ %), with HMDS serving as an internal standard. To give an example, about 200 mg to 600 mg of polymer is dissolved in 2.0 ml of TCB, followed by the addition of 0.5 mL of CeDe and 2 to 3 drops of HMDS.

Following data acquisition, the chemical shifts are referenced to the signal of the internal standard HMDS, which is assigned a value of 2.03 ppm.

The comonomer content in polyethylene is determined by ¹³C-NMR analysis of pellets according to the method described by G.J. Ray et al. (Macromolecules, 1977, 10, (4), 773- 778). Crystallisation temperature (Tc) and Melting temperature (Tm) are determined according to ISO 11357-3:2018 on a DSC Q2000 instrument by TA Instruments. To erase the thermal history the samples are first heated to 220°C and kept at 220°C for 3 minutes. Then the polymer is cooled at -20°C/min. up to 20°C and kept at 20°C for 3 minutes. The crystallization temperature is determined during this cooling step. The crystallization temperature Tc corresponds to the temperature of the extremum of the spectrogram presenting the heat flux associated with the polymer as a function of the temperature during its cooling. The polymer is then melted up to 220°C at 20°C/min. and the melting temperature is determined during this heating step. The melting temperature corresponds to the temperature of the extremum of the spectrogram presenting the heat flux associated with the polymer as a function of the temperature during its melting.

Quantification of metals using Inductively coupled plasma atomic emission spectroscopy (ICP- AES).

The principle of ICP-AES is to send droplets of a sample in solution form into a plasma, where the energy is used to move atoms or ions into an excited state. On returning to the ground state, the amount of light emitted at different wavelengths from an element of interest (in our case, Ca and Zn) is measured. The concentration of the element present in solution is a function of the intensity of the signal emitted by the element itself.

The polymer sample is calcinated in an automatic furnace at 600°C. The ashes obtained are dissolved with acids before the ICP analysis.

To calibrate the ICP-AES, solutions containing known amounts of each element are measured. From this data, a calibration curve is created.

External control solutions are read on these calibration curves. The control results are used to calculate the LQ (limit of quantification) of each element analyzed and to validate the results.

The calibration solutions and the control solutions are made with the same acid matrix used to dissolve the ashes of the calcinated samples.

Quantification of fatty acids using GC-MS

The stearate quantification was performed in two steps. In the first one, a liquid extraction was made under a sufficient quantity of solvent with microwave of not. The solvent could be one of them or a combination of them, methanol, ethanol, heptane, methylene chloride, toluene. A internal standard is added during the extraction step. The appropriate one should be a free fatty acid such as pentadecanoic acid or heptadecanoic acid. Then, the aliquot is derivatized with a trimethyl sylil agent, such as MSTFA, and injected in a GC-MS/FID for the identification and the quantification step. The GC condition are well known to the skilled person. GC was equipped with a conventional SSL injector (260°C) and an apolar column with Helium as carrier gas. The MS part is performed under ionization energy of 70 eV, ion source temperature of 230°C, the scan range of 35-400 m/z and a solvent delay depending on the solvent extraction. Identifications were performed with the NIST library.

Examples

The following non-limiting examples illustrate the disclosure.

Example 1 - Preparation of polymer compositions

Several polymer compositions comprising a 2000 ppm of a PPA composition have been tested.

We perform Melt Fracture Tests on our Monolayer Blown film Macchi Line.

The first step is to generate Melt Fracture by using a reference resin without adding any PPA. Once 100% Melt Fracture is observed on the line, we then replace the material in the hopper with the recipe to be tested (RE 1 , CE 3, CE 4, IE 1 , IE 2 and IE 3) and observe how long it takes for each of this recipe to clear out the Melt Fracture.

A film sample is taken every 10 minutes to be visually observed for Melt Fracture. Each band of Melt Fracture along the width of the film is measured using a ruler and we calculate the percentage of the Melt Fracture along the whole width of the film.

This is done until a time of 120 minutes has been completed. We then plot the percentage of Melt Fracture remaining against time as shown in Figure 1.

This trend line provides an indication of the efficiency of each solution to clear out Melt Fracture. The faster the Melt Fracture disappears, the more efficient is the solution.

After 2 hours of continuous running on the line, we also observed the die lips to check if die build up is observed or not. This is done by visual inspection. For all the recipes tested, no die build up was observed after 2 hours of continuous running.

Selection of the materials

The polymer used was a fluff metallocene catalyzed polyethylene having a density of 0.934 g/cm³ and a melt index of 0.9 g/10 min (2.16 kg - 190°C).

The compositions have been produced by blending the M3410 fluff with the additives in a twin- screw extruder.

ZnO was provided in the form of a masterbatch. ZnSt and CaSt were provided in powder form. Table 1 : Polymer Processing Aids mixtures

RE1 is the refence with Fluoropolymer based PPA (Contains PFAS)

Melt fracture performance was assessed by visual assessment Table 2 - Results on melt fracture

It can be seen that the inventive examples show a clear improvement in the melt fracture performance with melt fracture being assessed to be less than 5 % at 120 min. In addition, the inventive compositions show reduced deposits by comparison to reference example 1 (RE1). Example 2

New formulations were tested

CE5 was prepared using the following additive mixture

- HPN20E: 5,000 ppm

Silica: 2,500 ppm

Hydrotalcite: 840 ppm CE6 was prepared using the following additive mixture

CaSt; 1 ,000 ppm

- Znst; 1 ,000 ppm

TiCh; 5,000 ppm ;

Steric hindered Amine (HALS): 1 ,000 ppm

CE7 was prepared using the following additive mixture

- HPN20E: 5,000 ppm

CaCO: 10,000 ppm

The Steric hindered Amine (HALS) was the commercial product TINUVIN 622

The silica was the commercial product HTTP 1C

Optical properties

Optical properties were tested and reported in Table 3 below wherein they were compared to

IE3

Table 3

Haze was determined according to ISO 14782:2021 at the thickness of the film.

Gloss at 45° was determined according toASTM D 2457-21.

Mechanical properties on the IE3 were determined. Dart of IE3 was determined according to ISO 7765-1 :1988 at the thickness of the film (i.e. 43 pm) and was 121 g. Elmendorf MD/TD was determined according to ISO 6383-2:2004 and was 30 N/mm in the machine direction (MD) and 108 N/mm in the transvers direction (TD).

Melt fracture performance was assessed by visual assessment and reported in Table 3 below wherein they were compared to IE4.

Table 4 - Results on melt fracture

Melt fracture phenomena are illustrated by a surface modification of the film surface leading to bad aspects of the film. Consequently, a melt fracture clearance additive should restore the good film aspect by clearing the melt fracture. Clearance of melt fracture cannot be obtained in CE6 because of a loss of the optical properties causing the film to be white. This might result from the presence of TiC>2 in the additive mixture.

Claims

1 . A PFAS-free polymer processing aids mixture, characterized in that it comprises:

- from 2.0 to 40.0 wt.% of one or more inorganic agents based on the total weight of the PFAS-free polymer processing aids mixture wherein the one or more inorganic agents are selected from the group consisting of montmorillonite, zeolite, silica, barium sulfate, calcium silicate, calcium sulfide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, neodymium oxide, and boron nitride; and

2. The PFAS-free polymer processing aids mixture according to claims 1 is characterized in that two or more organic metal salts comprises calcium stearate and/or zinc stearate.

3. The PFAS-free polymer processing aids mixture according to any one of claims 1 or 2 is characterized in that it comprises at least one organic metal salt of a first metal and at least one organic metal salt of a second metal wherein the first metal and the second metal are different.

4. The PFAS-free polymer processing aids mixture according to claim 3 is characterized in that the first and second metal are selected from calcium, zinc, barium, aluminum, potassium, magnesium and sodium.

5. The PFAS-free polymer processing aids mixture according to any one of claims 1 to 4 is characterized in that the one or more inorganic agents are selected from aluminum oxide, magnesium oxide, and zinc oxide.

6. The PFAS-free polymer processing aids mixture according to claim 5 is characterized in that the one or more inorganic agents are or comprise zinc oxide.

7. The PFAS-free polymer processing aids mixture according to any one of claims 1 to 6 is characterized in that it comprises from 3.0 to 30.0 wt.% one or more inorganic agents based on the total weight of the PFAS-free polymer processing aids mixture; preferably from 10.0 to 30.0 wt.%.

8. A polymer composition characterized in that it comprises: a component (A) comprising one or more polymers selected from C2-C6 alphaolefin homopolymers, and copolymers of two or more C2-C20 alpha-olefins; and a component (B) being a PFAs-free polymer processing aids mixture according to any one of claims 1 to 7.

9. The polymer composition according to claim 8 is characterized in that the component (A) is or comprises one or more polyethylenes selected from ethylene homopolymers and/or one or more copolymers of ethylene and one or more comonomers selected from C3-C20 alpha-olefins.

10. The polymer composition according to claim 8 or 9 is characterized in that the component (A) is metallocene catalyzed.

11 . The polymer composition according to any one of claims 8 to 10 is characterized in that the component (A) is or comprises one or more polyethylenes selected from linear low- density polyethylenes (LLDPE), low-density polyethylenes (LDPE), medium density polyethylenes (MDPE), and high-density polyethylenes (HDPE).

12. The polymer composition according to claim 11 is characterized in that, the component (A) is or comprises one or more LLDPE and/or one or more HDPE.

13. The polymer composition according to any one of claims 8 to 12 is characterized in that the component (A) is one or more polyethylenes, wherein the component (A) has a melt index ranging from 0.1 to 5.0 g/10 min as determined according to ISO 1133-2005 at 190°C under a load of 2.16 kg.

14. The polymer composition according to any one of claims 8 to 13 is characterized in that the component (A) is one or more polyethylenes, wherein the component (A) has a density ranging from 0.900 to 0.970 g/cm³ as determined according to ISO 1183-1 :2012 (immersion method) at a temperature of 23 °C.

15. The polymer composition according to any one of claims 8 to 14 is characterized in that the component (A) has a molecular weight distribution ranging from 2.0 to 12.0.

16. The polymer composition according to any one of claims 8 to 15 is characterized in that it comprises from 1 ,000 to 4,500 ppm of the PFAS-free polymer processing aids mixture based on the total weight of the polymer composition; preferably from 1 ,500 to 4,000 ppm.

17. The polymer composition according to any one of claims 8 to 16 is characterized in that the component (B) comprises one or more organic metal salt of a second metal selected from zinc stearate and magnesium stearate ; and the one or more organic metal salt of a second metal are present in the polymer composition at a content ranging from 100 to 1 ,000 ppm based on the total weight of the polymer composition; preferably at a content ranging from 200 to 800 ppm based on the total weight of the polymer composition.

18. The polymer composition according to any one of claims 8 to 17 is characterized in that the polymer composition comprises both zinc oxide and zinc stearate wherein their cumulated content, based on the total weight of the polymer composition, is at most 2,000 ppm; preferably at most 1250 ppm.

19. The polymer composition according to any one of claims 8 to 18 is characterized in that the one or more inorganic agents of the component (B) are present in the polymer composition at a content ranging from 100 to 2,000 ppm based on the total weight of the polymer composition.

20. The polymer composition according to any one of claims 8 to 19 is characterized in that the one or more organic metal salt of a first metal are or comprise calcium stearate ; and the one or more organic metal salt of a second metal are present in the polymer composition at a content ranging from 500 to 2,000 ppm based on the total weight of the polymer composition; preferably from 700 to 1 ,600 ppm.

21. A process to produce a polymer composition characterized in that it comprises the steps of a) providing a component (A) comprising one or more polymers selected from C2- C6 alpha-olefin homopolymers, and copolymers of two or more C2-C20 alphaolefins; b) providing a component (B) being a PFAs-free polymer processing aids mixture comprising two or more organic metal salts and one or more inorganic agents; c) blending the components (A) and (B) to form a polymer composition according to any one of claim 8 to 20.

22. An article made from a material that is or comprises at least one polymer composition characterized in that at least one polymer composition is according to any one of claims 8 to 20 or produced according to claim 21 .

23. The article according to claim 22 is characterized in that it is selected from a film or a yarn; more preferably the article is a blown film.

24. The use of the PFAS-free polymer processing aids mixture in a blown film characterized in that said PFAS-free polymer processing aids mixture is according to any one of claim 1 to 7.