WO2025051905A1

WO2025051905A1 - Polyethylene composition and uses thereof

Info

Publication number: WO2025051905A1
Application number: PCT/EP2024/074909
Authority: WO
Inventors: Eric Maziers; Kaitie GIFFIN; Virginie CIRRIEZ; Armelle SIGWALD
Original assignee: TotalEnergies Onetech SAS
Current assignee: TotalEnergies Onetech SAS
Priority date: 2023-09-08
Filing date: 2024-09-06
Publication date: 2025-03-13
Anticipated expiration: 2026-03-08

Abstract

The present invention relates to a metallocene-catalyzed polyethylene composition suitable for rotomolding applications, comprising: at least 15.0 % to at most 45.0 % by weight of metallocene-catalyzed ethylene polymer A having: a density ranging from at least 0.910 g/cm³ to at most 0.928 g/cm³; a molecular weight distribution M_w/M_n ranging from at least 3.0 to at most 6.5; a melt index ranging from an HLMI of at least 1.2 g/10 min to an MI₂ of at most 6.00 g/10 min; and a melt strength of X in Newtons, satisfying the following equations (1) and/or (2): (1) X is greater than - 0.026 ln(MI ₂) + 0.0498 (2) X is greater than - 0.026 ln(HLMI) + 0.1334 and at least 55.0 % to at most 85.0 % by weight of metallocene-catalyzed ethylene polymer B having: a density ranging from at least 0.950 g/cm3 to at most 0.965 g/cm³; and a melt index MI₂ of at least 3.00 to at most 10.00 g/10 min.

Description

Polyethylene composition and uses thereof

Field of invention

This invention relates to polyethylene compositions and articles made from such polyethylene composition, such as rotomolded articles, comprising said polyethylene composition. The present disclosure also relates to the processes to produce said polyethylene composition, and articles made therefrom.

Background of the invention

Polyethylene has been used in the production of various products, such as tanks and packaging. Examples of such products include bottles, drums, containers, and the like.

Polyethylene drums and tanks can easily be manufactured by rotomolding. The rotomolding process consists of adding a thermoplastic polymer into a mold, rotating the mold so that all the points of the internal surface of the mold are in contact with the polymer while heating the mold, so as to deposit the aforementioned molten polymer on the internal surface of the mold. Thereafter, a stage of cooling allows the solidification of the plastic article, which is then removed from the mold.

Rotational molding is advantageous because it avoids applying stress and strain to the plastic, which generally occurs in other transformations, for example in injection molding. Indeed, the plastic does not undergo malaxation or compaction as in an extruder or in injection molding. Rotational molding is particularly suitable for preparing large-sized articles, such as furniture, tanks, drums, reservoirs etc.

Often these drums and tanks are exposed to numerous stresses during their lifetime, and that exposure may result in cracks or breaks. Monomodal metallocene grades as well as some Ziegler-Natta metallocene polyethylene blends when used in rotomolding application suffer from lower impact performance, higher shrinkage, less stiffness/stress crack balance (more brittle break).

Tailoring the properties of polyolefins, such as polyethylene, to fit a desired applicability is therefore constantly ongoing.

There is thus still a need for polyethylene compositions that can achieve the best balance of properties to meet stiffness, impact, processability, and H2 permeability properties desired for rotomolding applications, such as fuel tanks and ^/Compressed natural gas (CNG) tanks.

SUMMARY OF THE INVENTION

The present invention aims at providing a solution to one or more of the aforementioned drawbacks and problems.

It is therefore an object of the present invention to provide polyethylene compositions suitable for rotomolding applications, preferably high-density polyethylene compositions suitable for rotomolding applications.

In a first aspect, the present invention provides a metallocene-catalyzed polyethylene composition comprising at least two metallocene-catalyzed ethylene polymers A and B, wherein the polyethylene composition comprises: at least 15.0 % to at most 45.0 % by weight of metallocene-catalyzed ethylene polymer A based on the total weight of the polyethylene composition, wherein metallocene-catalyzed ethylene polymer A has: a density ranging from at least 0.910 g/cm³ to at most 0.928 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; a molecular weight distribution M_w/M_n ranging from at least 3.0 to at most 6.5, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight; a melt index ranging from an HLMI of at least 1.2 g/10 min to an MI2 of at most 6.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm, and melt index HLMI is determined according to ISO 1133:2005 Method B, condition G, at a temperature 190 °C, and a 21.6 kg load using a die of 2.096 mm; and a melt strength of X in Newtons, as determined by Gbttfert Rheotens Melt Strength Apparatus, 190 °C, as described in the Experimental section, satisfying the following equations (1) and/or (2):

(1) X is greater than - 0.026 ln(/W/_2>) + 0.0498

(2) X is greater than - 0.026 \n(HLMI) + 0.1334 and at least 55.0 % to at most 85.0 % by weight of metallocene-catalyzed ethylene polymer B based on the total weight of the polyethylene composition, wherein metallocene-catalyzed ethylene polymer B has: a density ranging from at least 0.950 g/cm³ to at most 0.965 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; and a melt index MI2 of at least 3.00 to at most 10.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm.

According to a second aspect, the present invention provides an article comprising the metallocene-catalyzed polyethylene composition according to the first aspect.

In a third aspect, the present invention also encompasses a rotomolded or injected article comprising the metallocene-catalyzed polyethylene composition according to the first aspect.

The invention is particularly useful and provides polyethylene compositions that imparts stiffness, impact, processability, and permeability properties desired for rotomolding and injections applications, and to articles made therefrom, in particular rotomolded or injected articles, such as fuel tanks and (^/Compressed natural gas (CNG) tanks.

The independent and dependent claims set out particular and preferred features of the invention. Features from the dependent claims may be combined with features of the independent or other dependent claims as appropriate.

The present invention will now be further described. In the following passages, different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature or statement indicated as being preferred or advantageous may be combined with any other features or statements indicated as being preferred or advantageous.

Brief description of the figures

Figure 1 represents a graph plotting the ¹³C{¹H} NMR spectrum of a metallocene ethylene 1- hexene copolymer.

Figure 2 represents a rheometric dynamic analysis ("RDA") graph plotting viscosity (Pa.s) of tested compositions as a function of shear rate (Rad/s).

Figures 3A and 3B represent rheometric dynamic analysis ("RDA") graphs plotting storage modulus (G’) (in Pa) (Figure 3A) and loss modulus (G") (in Pa) (Figure 3B) of tested compositions as a function of shear rate (Rad/s).

Figure 4 represent a graph plotting the shear thinning characteristics (Tangent delta (Tan 8) vs angular frequency) of tested compositions and individual polymers thereof.

Figures 5, 6 and 7 represent graphs plotting the molecular weight distribution (weight fraction (area normalized) as a function of logarithm of molecular weight) of tested compositions, and individual polymers thereof.

Figure 8 represent a graph plotting the zero shear rate viscosity qO (Pa.s) versus molecular weight of tested compositions, and individual polymers thereof.

Figure 9 represents a graph plotting the impact energy for rotational molded samples with different peak internal air temperatures.

Figure 10 represents a graph plotting the impact energy for rotational molded samples of 3.0 mm wall thickness.

Figure 11 represents a graph plotting the impact energy for rotational molded samples of 4.5 mm wall thickness on different commercial machines with different peak internal air temperatures. Figure 12 represents a graph plotting the applied stress versus time-to-failure for samples.

Figure 13 represents a graph plotting the true stress-strain curve of rotomolded samples.

Figure 14 represents a graph plotting the creep i.e. , true deformation as a function of time for rotomolded sample subjected to a constant stress of 5MPa at 23 °C and 60 °C.

Figure 15 represents a graph plotting true strain values measured upon application on rotomolded sample of a stress of 5MPa at 60 °C.

Figure 16 represents a graph plotting true strain values measured upon application on rotomolded sample of a stress of 5MPa at 60 °C.

Detailed description of the invention

Before the present compositions, resins, polymers, processes, articles, and uses encompassed by the invention are described, it is to be understood that this invention is not limited to particular compositions, resins, polymers, processes, articles, and uses described, as such compositions, resins, polymers, processes, articles, and uses may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.

Unless otherwise defined, all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By means of further guidance, definitions for the terms used in the description are included to better appreciate the teaching of the present invention. When describing the polyethylene compositions, polymers, processes, articles, and uses of the invention, the terms used are to be construed in accordance with the following definitions, unless the context dictates otherwise.

As used herein, the singular forms "a", "an", and "the" include both singular and plural referents unless the context clearly dictates otherwise. By way of example, "a resin" means one resin or more than one resin.

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 can include 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 end points also includes the end point 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.

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 invention. Thus, appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics 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 invention, and form different embodiments, as would be understood by those in the art. For example, in the following claims and statements, any of the embodiments can be used in any combination.

Whenever the term “substituted” is used herein, it is meant to indicate that one or more hydrogen atoms on the atom indicated in the expression using “substituted” is replaced with a selection from the indicated group, provided that the indicated atom’s normal valence is not exceeded, and that the substitution results in a chemically stable compound, i.e. a compound that is sufficiently robust to survive isolation from a reaction mixture. Preferred substituents for the indenyl, tetrahydroindenyl, cyclopentadienyl and fluorenyl groups, can be selected from the group comprising alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)3, heteroalkyl; wherein each R¹⁰ is independently hydrogen, alkyl, or alkenyl. Preferably, substituents for the tetrahydroindenyl, cyclopentadienyl and fluorenyl groups, can be selected from the group comprising alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)3, heteroalkyl; wherein each R¹⁰ is independently hydrogen, alkyl, or alkenyl.

The term “halo” or “halogen” as a group or part of a group is generic for fluoro, chloro, bromo, iodo.

The term "alkyl" as a group or part of a group, refers to a hydrocarbyl group of formula C_nH2n+i wherein n is a number greater than or equal to 1. Alkyl groups may be linear or branched and may be substituted as indicated herein. Generally, alkyl groups of this invention comprise from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. For example, the term "Ci-2oalkyl", as a group or part of a group, refers to a hydrocarbyl group of formula -C_nH2n+i wherein n is a number ranging from 1 to 20. Thus, for example, “Cisalkyl” includes all linear or branched alkyl groups with between 1 and 8 carbon atoms, and thus includes methyl, ethyl, n-propyl, i-propyl, butyl and its isomers (e.g. n-butyl, i-butyl and t- butyl); pentyl and its isomers, hexyl and its isomers, etc. A “substituted alkyl" refers to an alkyl group substituted with one or more substituent(s) (for example 1 to 3 substituent(s), for example 1 , 2, or 3 substituent(s)) at any available point of attachment. When the suffix "ene" is used in conjunction with an alkyl group, i.e. “alkylene”, this is intended to mean the alkyl group as defined herein having two single bonds as points of attachment to other groups. As used herein, the term “alkylene” also referred as “alkanediyl”, by itself or as part of another substituent, refers to alkyl groups that are divalent, i.e., with two single bonds for attachment to two other groups. Alkylene groups may be linear or branched and may be substituted as indicated herein. Non-limiting examples of alkylene groups include methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH(CH3)-), 1-methyl-ethylene (-CH(CH3)- CH2-), n-propylene (-CH2-CH2-CH2-), 2-methylpropylene (-CH2-CH(CH3)-CH2-), 3- methylpropylene (-CH2-CH2-CH(CH3)-), n-butylene (-CH2-CH2-CH2-CH2-), 2-methylbutylene (- CH2-CH(CH₃)-CH2-CH₂-), 4-methylbutylene (-CH2-CH₂-CH2-CH(CH₃)-), pentylene and its chain isomers, hexylene and its chain isomers.

The term “alkenyl” as a group or part of a group, refers to an unsaturated hydrocarbyl group, which may be linear, or branched, comprising one or more carbon-carbon double bonds. Generally, alkenyl groups of this invention comprise from 3 to 20 carbon atoms, preferably from 3 to 10 carbon atoms, preferably from 3 to 8 carbon atoms. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. Examples of C3-2oalkenyl groups are ethenyl, 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl and its isomers, 2-hexenyl and its isomers, 2,4-pentadienyl, and the like. The term “alkoxy" or “alkyloxy”, as a group or part of a group, refers to a group having the formula -OR^b wherein R^b is alkyl as defined herein above. Non-limiting examples of suitable alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tertbutoxy, pentyloxy and hexyloxy.

The term “cycloalkyl”, as a group or part of a group, refers to a cyclic alkyl group, that is a monovalent, saturated, hydrocarbyl group having 1 or more cyclic structure, and comprising from 3 to 20 carbon atoms, more preferably from 3 to 10 carbon atoms, more preferably from 3 to 8 carbon atoms; more preferably from 3 to 6 carbon atoms. Cycloalkyl includes all saturated hydrocarbon groups containing 1 or more rings, including monocyclic, bicyclic groups or tricyclic. The further rings of multi-ring cycloalkyls may be either fused, bridged and/or joined through one or more spiro atoms. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. For example, the term “C3-2ocycloalkyl”, a cyclic alkyl group comprising from 3 to 20 carbon atoms. For example, the term “Cs- cycloalkyl”, a cyclic alkyl group comprising from 3 to 10 carbon atoms. For example, the term “Cs-scycloalkyl”, a cyclic alkyl group comprising from 3 to 8 carbon atoms. For example, the term “Cs-ecycloalkyl”, a cyclic alkyl group comprising from 3 to 6 carbon atoms. Examples of C3-i2cycloalkyl groups include but are not limited to adamantly, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicycle[2.2.1]heptan-2yl, (1S,4R)-norbornan-2-yl, (1 R,4R)-norbornan-2-yl, (1S,4S)-norbornan- 2-yl, (1 R,4S)-norbornan-2-yl.

When the suffix "ene" is used in conjunction with a cycloalkyl group, i.e. cycloalkylene, this is intended to mean the cycloalkyl group as defined herein having two single bonds as points of attachment to other groups. Non-limiting examples of "cycloalkylene" include 1 ,2- cyclopropylene, 1 ,1 -cyclopropylene, 1 ,1 -cyclobutylene, 1 ,2-cyclobutylene, 1 ,3-cyclopentylene, 1 ,1 -cyclopentylene, and 1 ,4-cyclohexylene.

Where an alkylene or cycloalkylene group is present, connectivity to the molecular structure of which it forms part may be through a common carbon atom or different carbon atom. To illustrate this applying the asterisk nomenclature of this invention, a C₃alkylene group may be for example *-CH₂CH₂CH₂-*, *-CH(-CH₂CH₃)-* or *-CH₂CH(-CH₃)-*. Likewise a C₃cycloalkylene group may be

The term “cycloalkenyl” as a group or part of a group, refers to a non-aromatic cyclic alkenyl group, with at least one site (usually 1 to 3, preferably 1) of unsaturation, namely a carboncarbon, sp2 double bond; preferably having from 5 to 20 carbon atoms more preferably from 5 to 10 carbon atoms, more preferably from 5 to 8 carbon atoms, more preferably from 5 to 6 carbon atoms. Cycloalkenyl includes all unsaturated hydrocarbon groups containing 1 or more rings, including monocyclic, bicyclic or tricyclic groups. The further rings may be either fused, bridged and/or joined through one or more spiro atoms. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. For example, the term “Cs-2ocycloalkenyl”, a cyclic alkenyl group comprising from 5 to 20 carbon atoms. For example, the term “Cs- cycloalkenyl”, a cyclic alkenyl group comprising from 5 to 10 carbon atoms. For example, the term “Cs-scycloalkenyl”, a cyclic alkenyl group comprising from 5 to 8 carbon atoms. For example, the term “Cs- ecycloalkyl”, a cyclic alkenyl group comprising from 5 to 6 carbon atoms. Examples include but are not limited to: cyclopentenyl (-C5H7), cyclopentenylpropylene, methylcyclohexenylene and cyclohexenyl (-CeHg). The double bond may be in the cis or trans configuration.

The term "cycloalkenylalkyl", as a group or part of a group, means an alkyl as defined herein, wherein at least one hydrogen atom is replaced by at least one cycloalkenyl as defined herein. The term “cycloalkoxy”, as a group or part of a group, refers to a group having the formula - OR^h wherein R^h is cycloalkyl as defined herein above.

The term “aryl”, as a group or part of a group, refers to a polyunsaturated, aromatic hydrocarbyl group having a single ring (i.e. phenyl) or multiple aromatic rings fused together (e.g. naphthyl), or linked covalently, typically containing 6 to 20 atoms; preferably 6 to 10, wherein at least one ring is aromatic. The aromatic ring may optionally include one to two additional rings (either cycloalkyl, heterocyclyl or heteroaryl) fused thereto. Examples of suitable aryl include Ce-2oaryl, preferably Ce- aryl, more preferably Ce-saryl. Non-limiting examples of aryl comprise phenyl, biphenylyl, biphenylenyl, or 1-or 2-naphthanelyl; 1-, 2-, 3-, 4-, 5- or 6-tetralinyl (also known as “1 ,2,3,4-tetrahydronaphtalene); 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-azulenyl, 4-, 5-, 6 or 7-indenyl; 4- or 5-indanyl; 5-, 6-, 7- or 8-tetrahydronaphthyl; 1 ,2,3,4-tetrahydronaphthyl; and 1 ,4- dihydronaphthyl; 1-, 2-, 3-, 4- or 5-pyrenyl. A “substituted aryl” refers to an aryl group having one or more substituent(s) (for example 1 , 2 or 3 substituent(s), or 1 to 2 substituent(s)), at any available point of attachment.

The term “aryloxy”, as a group or part of a group, refers to a group having the formula -OR^g wherein R^g is aryl as defined herein above.

The term "arylalkyl", as a group or part of a group, means an alkyl as defined herein, wherein at least one hydrogen atom is replaced by at least one aryl as defined herein. Non-limiting examples of arylalkyl group include benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl, 3- (2-naphthyl)-butyl, and the like.

The term “alkylaryl” as a group or part of a group, means an aryl as defined herein wherein at least one hydrogen atom is replaced by at least one alkyl as defined herein. Non-limiting examples of alkylaryl group include p-CH3-R^g-, wherein R^g is aryl as defined herein above.

The term “arylalkyloxy” or “aralkoxy” as a group or part of a group, refers to a group having the formula -O-R^a-R^g wherein R^g is aryl, and R^a is alkylene as defined herein above.

The term “heteroalkyl” as a group or part of a group, refers to an acyclic alkyl wherein one or more carbon atoms are replaced by at least one heteroatom selected from the group comprising O, Si, S, B, and P, with the proviso that said chain may not contain two adjacent heteroatoms. This means that one or more -CH3 of said acyclic alkyl can be replaced by -OH for example and/or that one or more -CR2- of said acyclic alkyl can be replaced by O, Si, S, B, and P.

The term “aminoalkyl” as a group or part of a group, refers to the group -R^j-NR^kR' wherein R^j is alkylene, R^k is hydrogen or alkyl as defined herein, and R¹ is hydrogen or alkyl as defined herein.

The term "heterocyclyl" as a group or part of a group, refers to non-aromatic, fully saturated or partially unsaturated cyclic groups (for example, 3 to 7 member monocyclic, 7 to 11 member bicyclic, or containing a total of 3 to 10 ring atoms) which have at least one heteroatom in at least one carbon atom-containing ring. Each ring of the heterocyclic group containing a heteroatom may have 1 , 2, 3 or 4 heteroatoms selected from N, S, Si, Ge, where the nitrogen and sulfur heteroatoms may optionally be oxidized and the nitrogen heteroatoms may optionally be quaternized. The heterocyclic group may be attached at any heteroatom or carbon atom of the ring or ring system, where valence allows. The rings of multi-ring heterocycles may be fused, bridged and/or joined through one or more spiro atoms.

Non limiting exemplary heterocyclic groups include aziridinyl, oxiranyl, thiiranyl, piperidinyl, azetidinyl, 2-imidazolinyl, pyrazolidinyl imidazolidinyl, isoxazolinyl, oxazolidinyl, isoxazolidinyl, thiazolidinyl, isothiazolidinyl, piperidinyl, succinimidyl, 3H-indolyl, indolinyl, isoindolinyl, 2H- pyrrolyl, 1 -pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, pyrrolidinyl, 4H-quinolizinyl, 2-oxopiperazinyl, piperazinyl, homopiperazinyl, 2-pyrazolinyl, 3-pyrazolinyl, tetrahydro-2H-pyranyl, 2H-pyranyl, 4H-pyranyl, 3,4-dihydro-2H-pyranyl, oxetanyl, thietanyl, 3-dioxolanyl, 1 ,4-dioxanyl, 2,5- dioximidazolidinyl, 2-oxopiperidinyl, 2-oxopyrrolodinyl, indolinyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydroquinolinyl, tetrahydroisoquinolin-1-yl, tetrahydroisoquinolin-2-yl, tetrahydroisoquinolin-3-yl, tetrahydroisoquinolin-4-yl, thiomorpholin-4-yl, thiomorpholin-4-ylsulfoxide, thiomorpholin-4-ylsulfone, 1 , 3-dioxolanyl, 1 ,4- oxathianyl, 1 ,4-dithianyl, 1 ,3,5-trioxanyl, 1 H-pyrrolizinyl, tetrahydro-1 ,1 -dioxothiophenyl, N- formylpiperazinyl, and morpholin-4-yl.

Whenever used in the present invention the term “compounds” or a similar term is meant to include the compounds of general formula (I) and/or (II) and any subgroup thereof, including all polymorphs and crystal habits thereof, and isomers thereof (including optical, geometric and tautomeric isomers) as hereinafter defined.

The compounds of formula (I) and/or (I I) or any subgroups thereof may comprise alkenyl group, and the geometric cis/trans (or Z/E) isomers are encompassed herein. Where structural isomers are interconvertible via a low energy barrier, tautomeric isomerism ('tautomerism') can occur. This can take the form of proton tautomerism in compounds of formula (I) containing, for example, a keto group, or so-called valence tautomerism in compounds which contain an aromatic moiety. It follows that a single compound may exhibit more than one type of isomerism.

Cis/trans isomers may be separated by conventional techniques well known to those skilled in the art, for example, chromatography and fractional crystallization.

Preferred statements (features) and embodiments of the compositions, processes, polymers, articles, and uses of this invention are set herein below. Each statement and embodiment of the invention so defined may be combined with any other statement and/or embodiment, unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other features or statements indicated as being preferred or advantageous. Hereto, the present invention is in particular captured by any one or any combination of one or more of the below numbered statements and embodiments, with any other aspect and/or embodiment.

1. A metallocene-catalyzed polyethylene composition comprising at least two metallocene- catalyzed ethylene polymers A and B, wherein the polyethylene composition comprises: at least 15.0 % to at most 45.0 % by weight of metallocene-catalyzed ethylene polymer A based on the total weight of the polyethylene composition, wherein metallocene-catalyzed ethylene polymer A has: a density ranging from at least 0.910 g/cm³ to at most 0.928 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; a molecular weight distribution M_w/M_n ranging from at least 3.0 to at most 6.5, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight; a melt index ranging from an HLMI of at least 1.2 g/10 min to an MI2 of at most 6.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm, and melt index HLMI is determined according to ISO 1133:2005 Method B, condition G, at a temperature 190 °C, and a 21.6 kg load using a die of 2.096 mm; and a melt strength of X in Newtons, as determined by Gbttfert Rheotens Melt Strength Apparatus, 190 °C, as described in the Experimental section, satisfying the following equations (1) and/or (2):

(1) X is greater than - 0.026 ln(/W/_2>) + 0.0498

(2) X is greater than - 0.026 \n(HLMI) + 0.1334 and at least 55.0 % to at most 85.0 % by weight of metallocene-catalyzed ethylene polymer B based on the total weight of the polyethylene composition, wherein metallocene-catalyzed ethylene polymer B has: a density ranging from at least 0.950 g/cm³ to at most 0.965 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; and a melt index MI2 of at least 3.00 to at most 10.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm. A metallocene-catalyzed polyethylene composition comprising: at least 15.0 % to at most 45.0 % by weight of a metallocene-catalyzed ethylene polymer A based on the total weight of the polyethylene composition, wherein metallocene- catalyzed ethylene polymer A has: a density ranging from at least 0.910 g/cm³ to at most 0.928 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; a molecular weight distribution M_w/M_n ranging from at least 3.0 to at most 6.5, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight; a melt index MI2 of at least 0.10 g/10 min to at most 6.00 g/10 min, wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm; and a melt strength of X in Newtons, as determined by Gbttfert Rheotens Melt Strength Apparatus, 190 °C, as described in the Experimental section, satisfying the following equation (1):

(1) X is greater than - 0.026 ln(/W/_2>) + 0.0498 and at least 55.0 % to at most 85.0 % by weight of a metallocene-catalyzed ethylene polymer B based on the total weight of the polyethylene composition, wherein metallocene- catalyzed ethylene polymer B has: a density ranging from at least 0.950 g/cm³ to at most 0.965 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; and a melt index MI2 of at least 3.00 to at most 10.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm.

3. A metallocene-catalyzed polyethylene composition comprising: at least 15.0 % to at most 45.0 % by weight of a metallocene-catalyzed ethylene polymer A based on the total weight of the polyethylene composition, wherein metallocene- catalyzed ethylene polymer A has: a density ranging from at least 0.910 g/cm³ to at most 0.928 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; a molecular weight distribution M_w/M_n ranging from at least 3.0 to at most 6.5, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight; a melt index ranging from an HLMI of at least 1.2 g/10 min to at most 150.0 g/10 min wherein melt index HLMI is determined according to ISO 1133:2005 Method B, condition G, at a temperature 190 °C, and a 21.6 kg load using a die of 2.096 mm; and a melt strength of X in Newtons, as determined by Gbttfert Rheotens Melt Strength Apparatus, 190 °C, as described in the Experimental section, satisfying the following equation (2): (2) X is greater than - 0.026 \n(HLMI) + 0.1334 and at least 55.0 % to at most 85.0 % by weight of a metallocene-catalyzed ethylene polymer B based on the total weight of the polyethylene composition, wherein metallocene- catalyzed ethylene polymer B has: a density ranging from at least 0.950 g/cm³ to at most 0.965 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; and a melt index MI2 of at least 3.00 to at most 10.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm.

4. The metallocene-catalyzed polyethylene composition according to any one of statements 1-3, wherein metallocene-catalyzed ethylene polymer A has a melt index ratio HLMI/MI2 (also referred as MI21/MI2) of at most 40.0, preferably at most 38.0, preferably at most 37.0, preferably at most 36.0, preferably at most 35.0, preferably at most 34.0, preferably at most 33.0, preferably at most 30.0.

5. The metallocene-catalyzed polyethylene composition according to any one of statements 1-4, wherein metallocene-catalyzed ethylene polymer A has a molecular weight distribution M_z/Mw of at most 3.6, preferably at most 3.5, preferably at most 3.4, preferably at most 3.3, preferably at most 3.2, preferably at most 3.1 , preferably at most 3.0, with M_z being the z average molecular weight and M_w being the weight-average molecular weight.

6. The metallocene-catalyzed polyethylene composition according to any one of statements 1-5, wherein metallocene-catalyzed ethylene polymer A has a molecular weight distribution Mz/Mw of at least 2.0, preferably at least 2.1 , preferably at least 2.2, preferably at least 2.3, with M_z being the z average molecular weight and M_w being the weight-average molecular weight.

7. The metallocene-catalyzed polyethylene composition according to any one of statements 1-6, wherein metallocene-catalyzed ethylene polymer A has a molecular weight distribution M_z/Mn of at least 7.0, preferably at least 7.1 , preferably at least 7.2, preferably at least 7.3, preferably at least 7.4, preferably at least 7.5, with M_z being the z average molecular weight and M_n being the number-average molecular weight.

8. The metallocene-catalyzed polyethylene composition according to any one of statements 1-7, wherein metallocene-catalyzed ethylene polymer A has a molecular weight distribution Mz/Mn of at most 20.0, preferably at most 18.0, preferably at most 15.0, with M_z being the z average molecular weight and M_n being the number-average molecular weight.

9. The metallocene-catalyzed polyethylene composition according to any one of statements 1-8, wherein metallocene-catalyzed ethylene polymer A has a M_z of at least 190000 Da, preferably at least 200000 Da, preferably at least 205000 Da, with M_z being the z average molecular weight.

10. The metallocene-catalyzed polyethylene composition according to any one of statements 1-9, wherein metallocene-catalyzed ethylene polymer A has a molecular weight distribution M_w/Mn of at least 3.0, preferably at least 3.1 , for example at least 3.2, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight.

11 . The metallocene-catalyzed polyethylene composition according to any one of statements 1-10, wherein metallocene-catalyzed ethylene polymer A has a molecular weight distribution M_w/M_n of at most 6.3, preferably at most 6.2, preferably at most 6.1 , preferably at most 6.0, preferably at most 5.5, preferably at most 5.3, preferably at most 5.0, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight.

12. The metallocene-catalyzed polyethylene composition according to any one of statements 1-11 , wherein metallocene-catalyzed ethylene polymer A has a molecular weight distribution M_w/M_n of at least 3.0 to at most 6.3, preferably at least 3.0 to at most 6.2, preferably at least 3.0 to at most 6.1 , preferably at least 3.1 to at most 6.0, preferably at least 3.1 to at most 5.5, preferably at least 3.1 to at most 5.0, with M_w being the weightaverage molecular weight and M_n being the number-average molecular weight.

13. The metallocene-catalyzed polyethylene composition according to any one of statements 1-12, wherein metallocene-catalyzed ethylene polymer A has a density of at most 0.925 g/cm³, preferably at most 0.924 g/cm³, preferably at most 0.923 g/cm³, preferably at most 0.922 g/cm³, preferably at most 0.921 g/cm³, preferably at most 0.920 g/cm³, preferably at most 0.919 g/cm³, preferably at most 0.918 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C.

14. The metallocene-catalyzed polyethylene composition according to any one of statements 1-13, wherein metallocene-catalyzed ethylene polymer A has a density of at least 0.910 g/cm³, preferably of at least 0.911 g/cm³, preferably of at least 0.912 g/cm³, preferably of at least 0.913 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C.

15. The metallocene-catalyzed polyethylene composition according to any one of statements 1-14, wherein metallocene-catalyzed ethylene polymerA has a melt index MI2 ranging from at least 0.10 g/10 min to at most 6.00 g/10 min, preferably at most 5.00 g/10 min, preferably at most 4.00 g/10 min, preferably at most 3.50 g/10 min, preferably at most 3.00 g/10 min, preferably at most 3.00 g/10 min, preferably at most 2.50 g/10 min, preferably at most 2.00 g/10 min, wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm. 16. The metallocene-catalyzed polyethylene composition according to any one of statements

1-15, wherein metallocene-catalyzed ethylene polymer A has a melt index MI2 from at least 0.10 g/10 min, preferably at least 0.20 g/10 min, preferably at least 0.30 g/10 min, preferably at least 0.40 g/10 min, preferably at least 0.50 g/10 min, preferably at least 0.80 g/10 min, preferably at least 1.00 g/10 min, preferably at least 1.10 g/10 min, preferably at least 1.20 g/10min, preferably at least 1.30 g/10 min, wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm.

17. The metallocene-catalyzed polyethylene composition according to any one of statements 1-16, wherein metallocene-catalyzed ethylene polymer A has a melt index HLMI ranging from at least 1.2 g/10 min to at most 150.0 g/10 min wherein melt index HLMI is determined according to ISO 1133:2005 Method B, condition G, at a temperature 190 °C, and a 21.6 kg load using a die of 2.096 mm, preferably an HLMI of at most 100.0 g/10 min, preferably an HLMI of at most 50.0 g/10 min, preferably an HLMI of at most 40.0 g/10 min.

18. The metallocene-catalyzed polyethylene composition according to any one of statements 1-17, wherein metallocene-catalyzed ethylene polymer A has a melt index HLMI from at least 1.2 g/10 min, wherein melt index HLMI is determined according to ISO 1133:2005 Method B, condition G, at a temperature 190 °C, and a 21.6 kg load using a die of 2.096 mm, preferably an HLMI of at least 5.0 g/10 min, preferably an HLMI of at least 10.0 g/10 min, preferably an HLMI of at least 15.0 g/10 min, preferably an HLMI of at least 20.0 g/10 min.

19. The metallocene-catalyzed polyethylene composition according to any one of statements 1-18, wherein metallocene-catalyzed ethylene polymerA has a melt index MI5 ranging from 0.50 g/10 min to 30.00 g/10 min, wherein MI5 is determined according to ISO 1133:2005 Method B, condition T, at a temperature 190 °C, and a 5 kg load using a die of 2.096 mm, preferably from 0.70 g/10 min to 20.00 g/10 min, preferably from 0.70 g/10 min to 15.00 g/10 min, preferably from 0.70 g/10 min to 12.00 g/10 min, preferably from 1.00 g/10 min to 10.00 g/10 min, preferably from 1.00 g/10 min to 5.00 g/10 min.

20. The metallocene-catalyzed polyethylene composition according to any one of statements 1-19, wherein metallocene-catalyzed ethylene polymer A has a melt index ratio HLMI/MI2 of at least 15.0; preferably at least 16.0, preferably at least 17.0, preferably at least 18.0.

21. The metallocene-catalyzed polyethylene composition according to any one of statements 1-20, wherein metallocene-catalyzed ethylene polymer A has a melt index ratio HLMI/MI5 of at most 20.0; preferably at most 15.0, preferably at most 12.0, preferably at most 11.0, for example at most 10.0, preferably a HLMI/MI5 of at least 5.0, preferably at least 6.0, preferably at least 7.0, preferably a HLMI/MI5 of at least 5.0 to at most 20.0, preferably at least 6.0 to at most 15.0, preferably at least 6.0 to at most 12.0, preferably at least 6.0 to at most 10.0.

22. The metallocene-catalyzed polyethylene composition according to any one of statements 1-21 , wherein metallocene-catalyzed ethylene polymer A has a melt index ratio MI5/MI2 of at most 10.0, preferably at most 7.0, preferably at most 5.0, preferably at most 4.0, preferably a MI5/MI2 of at least 1.0, preferably at least 1 .5, preferably at least 2.0, preferably at least 2.2, preferably a MI5/MI2 of at least 1.0 to at most 10.0, preferably at least 1.0 to at most 5.0, preferably at least 1.0 to at most 4.0, preferably at least 1.5 to at most 4.0.

23. The metallocene-catalyzed polyethylene composition according to any one of statements 1-22, wherein metallocene-catalyzed ethylene polymer A has at least one melting temperature T_m determined by DSC of at most 130.0 °C, for example at most 125.0 °C, for example at most 120.0 °C, preferably at most 115.0 °C, preferably in the range of at least 100.0 °C to at most 125.0 °C, more preferably in the range of at least 105.0 °C to at most 120.0 °C, still more preferably in the range of 105.0 °C to 115.0 °C.

24. The metallocene-catalyzed polyethylene composition according to any one of statements 1-23, wherein metallocene-catalyzed ethylene polymer A is an ethylene 1 -hexene copolymer that has a total 1 -hexene content, relative to the total weight of the ethylene polymer A of at least 5.0 % by weight, as determined by ¹³C NMR analysis, preferably at least 6.0 % by weight, preferably at least 6.5% by weight, preferably at least 6.9 % by weight, preferably at least 7.0 % by weight, preferably at least 7.4 % by weight.

25. The metallocene-catalyzed polyethylene composition according to any one of statements 1-24, wherein metallocene-catalyzed ethylene polymer A is an ethylene 1 -hexene copolymer that has a total 1 -hexene content, relative to the total weight of the ethylene polymer A of at most 15.0 % by weight, as determined by ¹³C NMR analysis, preferably at most 14.0 % by weight, preferably at most 13.0 % by weight, preferably at most 12.0 % by weight, preferably at most 11.0 % by weight, preferably at most 10.5 % by weight.

26. The metallocene-catalyzed polyethylene composition according to any one of statements 1-25, wherein metallocene-catalyzed ethylene polymer A is an ethylene 1 -hexene copolymer that has a total 1 -hexene content, relative to the total weight of the ethylene polymer A of at least 5.0 % by weight to at most 15.0 % by weight, as determined by ¹³C NMR analysis, preferably at least 6.0 % by weight to at most 12.0 % by weight, preferably at least 6.5% by weight to at most 12.0 % by weight, preferably at least 6.9 % by weight to at most 11.0 % by weight, preferably at least 7.0 % by weight to at most 11.5 % by weight.

27. The metallocene-catalyzed polyethylene composition according to any one of statements 1-26, wherein the metallocene used for polymer A is a dual metallocene catalyst composition comprising two metallocene catalysts, and an optional activator. 28. The metallocene-catalyzed polyethylene composition according to any one of statements

1-27, wherein the metallocene used for polymer A is a dual metallocene catalyst composition comprising a catalyst component A and a catalyst component B, an optional activator; an optional support; and an optional co-catalyst; wherein catalyst component A comprises a bridged metallocene compound with two groups independently selected from indenyl or tetrahydroindenyl, each group being unsubstituted or substituted; and catalyst component B comprises a bridged metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group.

29. The metallocene-catalyzed polyethylene composition according to any one of statements 1-28, wherein the metallocene used for polymer A is a dual metallocene catalyst composition comprising a catalyst component A and a catalyst component B, an optional activator; an optional support; and an optional co-catalyst; wherein the weight ratio of catalyst component A to catalyst component B is in a range of from 1 :4 to 4:1 , preferably 1 :3 to 3:1, preferably 1:2 to 2:1 , preferably 1 :1.

30. The metallocene-catalyzed polyethylene composition according to any one of statements 1-29, wherein metallocene-catalyzed ethylene polymer B has an MI2 of at most 9.0 g/10 min, preferably of at most 8.0 g/10 min, preferably of at most 7.0 g/10 min, as determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm.

31. The metallocene-catalyzed polyethylene composition according to any one of statements 1-30, wherein metallocene-catalyzed ethylene polymer B has a density of at least 0.952 g/cm³, preferably at least 0.954 g/cm³, preferably at least 0.955 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C.

32. The metallocene-catalyzed polyethylene composition according to any one of statements 1-31, wherein metallocene-catalyzed ethylene polymer B has a density of at most 0.964 g/cm³, preferably at most 0.962 g/cm³, preferably at most 0.960 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C.

33. The metallocene-catalyzed polyethylene composition according to any one of statements 1-32, wherein metallocene-catalyzed ethylene polymer B has a density ranging from at least 0.952 to at most 0.964 g/cm³; preferably from at least 0.954 to at most 0.962 g/cm³; and preferably from at least 0.955 to at most 0.960 g/cm³.

34. The metallocene-catalyzed polyethylene composition according to any one of statements 1-33, wherein metallocene-catalyzed ethylene polymer B is selected from a homopolymer or a copolymer of ethylene and one or more comonomer. The metallocene-catalyzed polyethylene composition according to any one of statements

1-34, wherein metallocene-catalyzed ethylene polymer B is a polymer which is made in the absence of comonomer or has a total comonomer content, relative to the total weight of the metallocene-catalyzed ethylene polymer B of at most 1 .0 % by weight of comonomer, preferably at most 0.5 % by weight, preferably at most 0.4 % by weight comonomer as determined by ¹³C-NMR analysis. The metallocene-catalyzed polyethylene composition according to any one of statements 1-35, wherein metallocene-catalyzed ethylene polymer B has a molecular weight distribution M_w/M_n of at least 2.0, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight, preferably at least 2.1 , preferably at least 2.3. The metallocene-catalyzed polyethylene composition according to any one of statements 1-36, wherein metallocene-catalyzed ethylene polymer B has a molecular weight distribution M_w/M_n of at most 4.0, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight, preferably at most 3.5, preferably at most 3.0. The metallocene-catalyzed polyethylene composition according to any one of statements 1-37, wherein metallocene-catalyzed ethylene polymer B has a molecular weight distribution M_w/M_n of at least 2.0 to at most 4.0, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight, preferably at least 2.0 to at most 3.5, preferably at least 2.0 to at most 3.0. The metallocene-catalyzed polyethylene composition according to any one of statements 1-38, comprising a physical blend of metallocene-catalyzed ethylene polymers A and B. The metallocene-catalyzed polyethylene composition according to any one of statements 1-39, comprising at least 20.0 % to at most 40.0 % by weight of metallocene-catalyzed ethylene polymer A based on the total weight of the metallocene-catalyzed polyethylene composition, preferably at least 25.0 % to at most 35.0 % by weight of metallocene- catalyzed ethylene polymer A. The metallocene-catalyzed polyethylene composition according to any one of statements 1-40, comprising at least 60.0 % to at most 80.0 % by weight of metallocene-catalyzed ethylene polymer B based on the total weight of the metallocene-catalyzed polyethylene composition, preferably at least 65.0 % to at most 75.0 % by weight of metallocene- catalyzed ethylene polymer B. The metallocene-catalyzed polyethylene composition according to any one of statements 1-41 , having a density ranging from at least 0.940 g/cm³ to at most 0.954 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C, for example from at least 0.940 g/cm³ to at most 0.953 g/cm³, for example from at least 0.940 g/cm³ to at most 0.952 g/cm³, for example from at least 0.940 g/cm³ to at most 0.950 g/cm³.

43. The metallocene-catalyzed polyethylene composition according to any one of statements 1-42, having a melt index MI2 of at least 2.0 to at most 6.0 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm; preferably at most 5.5 g/10min; preferably at most 5.0 g/10 min.

44. The metallocene-catalyzed polyethylene composition according to any one of statements 1-43, having a melt index ratio HLMI/MI2 (also referred as MI21/MI2) of at most 35.0, preferably at most 33.0, preferably at most 30.0, preferably at most 29.0, preferably at most 28.0, preferably at most 27.0, preferably at most 26.0, preferably at most 25.0, preferably a HLMI/MI2 of at least 10.0, preferably at least 15.0, preferably a HLMI/MI2 of at least 10.0 to at most 35.0, preferably at least 10.0 to at most 30.0, preferably at least 10.0 to at most 28.0, preferably at least 10.0 to at most 26.0.

45. The metallocene-catalyzed polyethylene composition according to any one of statements 1-44 having a molecular weight distribution M_w/M_n of at most 6.5, with M_w being the weightaverage molecular weight and M_n being the number-average molecular weight; preferably at most 6.0, preferably at most 5.5, preferably at most 5.0.

46. The metallocene-catalyzed polyethylene composition according to any one of statements 1-45, having a molecular weight distribution M_w/M_n of at least 2.0, with M_w being the weightaverage molecular weight and M_n being the number-average molecular weight; preferably at least 2.3, preferably at least 2.5, preferably at least 2.8.

47. The metallocene-catalyzed polyethylene composition according to any one of statements 1-46, having a molecular weight distribution M_w/M_n of at least 2.0 to at most 6.5, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight; preferably at least 2.3 to at most 6.0, preferably at least 2.5 to at most 5.5, preferably at least 2.5 to at most 5.0.

48. The metallocene-catalyzed polyethylene composition according to any one of statements 1-47, having a M_n of at least 18000 g/mol with M_n being the number-average molecular weight, preferably of at least 19000 g/mol.

49. The metallocene-catalyzed polyethylene composition according to any one of statements 1-48, having a molecular weight distribution M_z/M_n of at most 10.0, with M_z being the z average molecular weight and M_n being the number-average molecular weight; preferably at most 9.5, preferably at most 9.0, preferably at most 8.5, preferably at most 8.0, preferably a M_z/M_n of at least 3.0, preferably at least 4.0, preferably at least 3.0 to at most 10.0. The metallocene-catalyzed polyethylene composition according to any one of statements

1-49, having a zero shear viscosity q0 in Pa.s of at least 2900, preferably at least 3000, preferably at least 3200, preferably at least 3400, preferably at least 3500. A process for producing the metallocene-catalyzed polyethylene composition according to any one of statements 1-20, comprising the steps of providing at least 15.0 % to at most 45.0 % by weight of a metallocene-catalyzed ethylene polymer A based on the total weight of the polyethylene composition, wherein metallocene-catalyzed ethylene polymer A has: a density ranging from at least 0.910 g/cm³ to at most 0.928 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; a molecular weight distribution Mw/Mn ranging from at least 3.0 to at most 6.5, with Mw being the weight-average molecular weight and Mn being the numberaverage molecular weight; a melt index ranging from an HLMI of at least 1.2 g/10 min to an MI2 of at most 6.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm, and melt index HLMI is determined according to ISO 1133:2005 Method B, condition G, at a temperature 190 °C, and a 21.6 kg load using a die of 2.096 mm; and a melt strength of X in Newtons, as determined by Gbttfert Rheotens Melt Strength Apparatus, 190 °C, as described in the Experimental section, satisfying the following equations (1) and/or (2):

(1) X is greater than - 0.026 ln(MI2) + 0.0498

(2) X is greater than - 0.026 In(HLMI) + 0.1334 providing at least 55.0 % to at most 85.0 % by weight of a metallocene-catalyzed ethylene polymer B based on the total weight of the polyethylene composition, wherein metallocene-catalyzed ethylene polymer B has: a density ranging from at least 0.950 g/cm³ to at most 0.965 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; and a melt index MI2 of at least 3.00 to at most 10.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm; and blending metallocene-catalyzed ethylene polymer A and metallocene-catalyzed ethylene polymer B thereby producing said metallocene-catalyzed polyethylene composition.

52. An article comprising the metallocene-catalyzed polyethylene composition according to any one of statements 1-50.

53. An article comprising the metallocene-catalyzed polyethylene composition according to any one of statements 1-50, wherein the article is a rotomolded article or an injected article.

54. A rotomolded or an injection-molded article comprising the metallocene-catalyzed polyethylene composition according to any one of statements 1-50.

55. The rotomolded article according to any one of statements 53, 54, wherein the article is a tank, a drum, a container, a bin, a vat, a jerrycan, a can, a cistern, a bottle, boat or part thereof, float, buoy, a part of a car, or any other rotomolded component.

56. The injection-molded article according to any one of statements 53, 54, wherein the article is a tank, a drum, a container, a bin, a vat, a jerrycan, a can, a cistern, slosh baffle, a connector, a cap or closure, or any other injected component.

57. The rotomolded or injection-molded article according to any one of statements 53-56, wherein the article is a fuel tank, underground tank, hydrogen/Compressed natural gas (CNG) tanks.

58. A rotomolding process for preparing a rotomolded article according to any one of statements 53-57, comprising the steps of a) providing at least one metallocene-catalyzed polyethylene composition according to any one of statements 1-50, and b) rotomolding said at least one metallocene-catalyzed polyethylene composition into an article.

59. An injection-molding process for preparing an injection-molded article according to any one of statements 53-57, comprising the steps of a) providing at least one metallocene- catalyzed polyethylene composition according to any one of statements 1-50, and b) injection-molding said at least one metallocene-catalyzed polyethylene composition into an article.

60. Use of a metallocene-catalyzed polyethylene composition according to any one of statements 1-50, in rotomolding or injection molding applications.

As stated before, the present invention provides a metallocene-catalyzed polyethylene composition as defined herein (including all embodiments thereof as described herein), comprising metallocene-catalyzed ethylene polymers A and B, preferably a blend of polymers A and B, preferably a physical blend of metallocene-catalyzed ethylene polymers A and B.

In some embodiments, the metallocene-catalyzed polyethylene composition as defined herein (including all embodiments thereof as described herein), comprises: at least 15.0 % to at most 45.0 % by weight of metallocene-catalyzed ethylene polymer A based on the total weight of the polyethylene composition, preferably at least 20.0 % to at most 40.0 % by weight of metallocene-catalyzed ethylene polymer A, preferably at least 25.0 % to at most 35.0 % by weight of metallocene-catalyzed ethylene polymer A; wherein metallocene-catalyzed ethylene polymer A has: a density ranging from at least 0.910 g/cm³ to at most 0.928 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; preferably a density of at most 0.925 g/cm³, preferably at most 0.924 g/cm³, preferably at most 0.923 g/cm³, preferably at most 0.922 g/cm³, preferably at most 0.921 g/cm³, preferably at most 0.920 g/cm³, preferably at most 0.919 g/cm³, preferably at most 0.918 g/cm³, preferably of at least 0.911 g/cm³, preferably of at least 0.912 g/cm³, preferably of at least 0.913 g/cm³; a molecular weight distribution M_w/M_n ranging from at least 3.0 to at most 6.5, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight, preferably at least 3.1 , for example at least 3.2, preferably at most 6.3, preferably at most 6.2, preferably at most 6.1 , preferably at most 6.0, preferably at most 5.5, preferably at most 5.3, preferably at most 5.0, preferably at least 3.0 to at most 6.3, preferably at least 3.0 to at most 6.2, preferably at least 3.0 to at most 6.0, preferably at least 3.1 to at most 5.5, preferably at least 3.1 to at most 5.0; a melt index ranging from an HLMI of at least 1.2 g/10 min to an MI2 of at most 6.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm, and melt index HLMI is determined according to ISO 1133:2005 Method B, condition G, at a temperature 190 °C, and a 21.6 kg load using a die of 2.096 mm; preferably a melt index MI2 of at least 0.10 g/10 min to at most 6.00 g/10 min, preferably at most 5.00 g/10 min, preferably at most 4.00 g/10 min, preferably at most 3.50 g/10 min, preferably at most 3.00 g/10 min, preferably at most 3.00 g/10 min, preferably at most 2.50 g/10 min, preferably at most 2.00 g/10 min, preferably at least 0.20 g/10 min, preferably at least 0.30 g/10 min, preferably at least 0.40 g/10 min, preferably at least 0.50 g/10 min, preferably at least 0.80 g/10 min, preferably at least 1.00 g/10 min, preferably at least 1 .10 g/10 min, preferably at least 1 .20 g/1 Omin, preferably at least 1 .30 g/10 min, and/or preferably an HLMI of at least 1.2 g/10 min to at most 150.0 g/10 min, preferably an HLMI of at most 100.0 g/10 min, preferably an HLMI of at most 50.0 g/10 min, preferably an HLMI of at most 40.0 g/10 min, preferably an HLMI of at least 5.0 g/10 min, preferably an HLMI of at least 10.0 g/10 min, preferably an HLMI of at least 15.0 g/10 min, preferably an HLMI of at least 20.0 g/10 min; and a melt strength of X in Newtons, as determined by Gdttfert Rheotens Melt Strength Apparatus, 190 °C, as described in the Experimental section, satisfying the following equations (1) and/or (2):

(1) X is greater than - 0.026 ln(/W/₂) + 0.0498

(2) X is greater than - 0.026 \n(HLMI) + 0.1334 and at least 55.0 % to at most 85.0 % by weight of metallocene-catalyzed ethylene polymer B based on the total weight of the polyethylene composition, preferably at least 60.0 % to at most 80.0 % by weight of metallocene-catalyzed ethylene polymer B, preferably at least 65.0 % to at most 75.0 % by weight of metallocene-catalyzed ethylene polymer B; wherein metallocene-catalyzed ethylene polymer B has: a density ranging from at least 0.950 g/cm³ to at most 0.965 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C, preferably a density of at least 0.952 g/cm³, preferably at least 0.954 g/cm³, preferably at least 0.955 g/cm³, preferably a density of at most 0.964 g/cm³, preferably at most 0.962 g/cm³, preferably at most 0.960 g/cm³, preferably a density ranging from at least 0.952 to at most 0.964 g/cm³; preferably from at least 0.954 to at most 0.962 g/cm³; and preferably from at least 0.955 to at most 0.960 g/cm³; and a melt index MI2 of at least 3.00 to at most 10.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm, preferably an MI2 of at most 9.0 g/10 min, preferably of at most 8.0 g/10 min, preferably of at most 7.0 g/10 min.

Metallocene-catalyzed ethylene polymers A used herein can, in some aspects, have a non- conventional (reverse or inverse) co-monomer distribution, i.e., the higher molecular weight portions of the polymer have higher co-monomer incorporation than the lower molecular weight portions. Preferably, there is an increasing co-monomer incorporation with increasing molecular weight.

As used herein, the term “monomodal polyethylene” or “polyethylene with a monomodal molecular weight distribution” refers to polyethylene having one maximum in their molecular weight distribution curve, which is also defined as a unimodal distribution curve. As used herein, the term “polyethylene with a bimodal molecular weight distribution” or “bimodal polyethylene” it is meant, polyethylene having a distribution curve being the sum of two unimodal molecular weight distribution curves, and refers to a polyethylene product having two distinct but possibly overlapping populations of polyethylene macromolecules each having different weight average molecular weights. By the term “polyethylene with a multimodal molecular weight distribution” or “multimodal polyethylene” it is meant polyethylene with a distribution curve being the sum of at least two, preferably more than two unimodal distribution curves, and refers to a polyethylene product having two or more distinct but possibly overlapping populations of polyethylene macromolecules each having different weight average molecular weights. The multimodal polyethylene can have an “apparent monomodal” molecular weight distribution, which is a molecular weight distribution curve with a single peak and no shoulder. Nevertheless, the polyethylene will still be multimodal if it comprises two or more distinct populations of polyethylene macromolecules each having a different weight average molecular weights, as defined above, for example when the two distinct populations were prepared in different reactors and/or under different conditions and/or with different catalysts.

Preferably, the metallocene-catalyzed polyethylene composition as defined herein (including all embodiments thereof as described herein), comprises a blend, preferably a physical blend of metallocene-catalyzed ethylene polymer A and of metallocene-catalyzed ethylene polymer B.

As used herein, the terms “metallocene-catalyzed ethylene polymer", "ethylene polymer prepared using at least one metallocene catalyst composition", and the term "ethylene polymer prepared in the presence of at least one metallocene catalyst", are synonyms.

As used herein, the term “catalyst” refers to a substance that causes a change in the rate of a polymerization reaction. It is especially applicable to catalysts suitable for the polymerization of ethylene to polyethylene.

In some embodiment, the metallocene-catalyzed polyethylene composition as defined herein (including all embodiments thereof as described herein), is a blend of ethylene polymers A and B, each preferably prepared in the presence of at least one metallocene catalyst composition. As used herein, the terms “metallocene-catalyzed ethylene polymer”, and “metallocene- catalyzed polyethylene” are synonymous and used interchangeably and refers to an ethylene polymer prepared in the presence of a metallocene catalyst composition.

The term "metallocene catalyst" or “metallocene” for short is used herein to describe any transition metal complexes comprising metal atoms bonded to one or more ligands. The preferred 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 ligands composed of one or two groups of cyclopentadienyl, indenyl, fluorenyl or their derivatives. The structure and geometry of the metallocene can be varied to adapt to the specific need of the producer depending on the desired polymer. Metallocene catalysts typically comprise a single metal site, which allows for more control of branching and molecular weight distribution of the polymer. Monomers are inserted between the metal and the growing chain of polymer.

In some embodiments, the metallocene catalyst used for preparing the metallocene-catalyzed polymers is selected from a compound of formula (Al) or (All),

(Ar)₂MQ₂ (Al); or R”(Ar)₂MQ₂ (All), wherein the metallocene according to formula (Al) is a non-bridged metallocene and the metallocene according to formula (All) is a bridged metallocene; wherein said metallocene according to formula (Al) or (All) has two Ar bound to M which can be the same or different from each other; wherein Ar is an aromatic ring, group or moiety and wherein each Ar is independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, and fluorenyl, wherein each of said groups may be optionally substituted with one or more substituents each independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)3, heteroalkyl; wherein each R¹⁰ is independently hydrogen, alkyl, or alkenyl; wherein M is a transition metal selected from the group consisting of titanium, zirconium, hafnium, and vanadium; and preferably is zirconium; wherein each Q is independently selected from the group consisting of halogen, alkyl, - N(R¹¹)₂, alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R¹¹ is hydrogen or alkyl; and wherein R” is a divalent group or moiety bridging the two Ar groups and selected from the group consisting of -[CR⁸R⁹]h-, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl.

Illustrative examples of metallocene catalysts suitable for preparing metallocene catalyzed ethylene polymer B, comprise but are not limited to bis(cyclopentadienyl) zirconium dichloride (Cp₂ZrCI₂), bis(cyclopentadienyl) titanium dichloride (Cp₂TiCI₂), bis(cyclopentadienyl) hafnium dichloride (Cp₂HfCI₂); bis(tetrahydroindenyl) zirconium dichloride, bis(indenyl) zirconium dichloride, bis(n-butyl-cyclopentadienyl) zirconium dichloride; ethylenebis(4,5,6,7-tetrahydro- 1 -indenyl) zirconium dichloride, ethylenebis(1 -indenyl) zirconium dichloride, dimethylsilylene bis(2-methyl-4-phenyl-inden-1-yl) zirconium dichloride, diphenylmethylene (cyclopentadienyl)(fluoren-9-yl) zirconium dichloride, and dimethylmethylene [1-(4-tert-butyl-2- methyl-cyclopentadienyl)](fluoren-9-yl) zirconium dichloride.

In a preferred embodiment, the metallocene used for preparing metallocene-catalyzed polymer A is a dual metallocene catalyst composition comprising two metallocene catalysts, and an optional activator. Preferably, the metallocene catalyst composition comprises a dual catalyst which means a catalyst particle with two metallocene active sites on a single support. For example, catalyst “A” can produce short chains without co-monomer while catalyst “B” can produce longer chains with high concentration of co-monomer. The catalyst composition can be used in single reactor processes or even in multi-reactors processes.

In an embodiment, the dual metallocene catalyst composition for preparing metallocene- catalyzed ethylene polymer A comprises: at least one catalyst component A and at least one catalyst component B, an optional activator; an optional support; and an optional co-catalyst; wherein catalyst component A comprises a bridged metallocene compound with two groups independently selected from indenyl or tetrahydroindenyl, each group being unsubstituted or substituted; preferably catalyst component A comprises a bridged metallocene compound with two tetrahydroindenyl groups, each group being unsubstituted or substituted; catalyst component B comprises a bridged metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group.

In an embodiment, the metallocene which can be used for metallocene-catalyzed ethylene polymer A is a dual metallocene catalyst composition comprising a catalyst component A and a catalyst component B, an optional activator; an optional support; and an optional co-catalyst; wherein catalyst component A comprises a bridged metallocene compound with two tetrahydroindenyl groups, each group being unsubstituted or substituted; and catalyst component B comprises a bridged metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group.

In an embodiment, the metallocene which can be used for metallocene-catalyzed ethylene polymer A is a dual metallocene catalyst composition comprising a catalyst component A and a catalyst component B, an optional activator; an optional support; and an optional co-catalyst; wherein the weight ratio of catalyst component A to catalyst component B is in a range of from 1 :4 to 4: 1 , preferably 1 :3 to 3: 1 , preferably 1 :2 to 2: 1 , preferably 1 :1.

In an embodiment, the bridged metallocene compound of catalyst component B comprises at least one alkenyl, cycloalkenyl, or cycloalkenylalkyl substituent, preferably at least one C3- 2oalkenyl, Cs-2ocycloalkenyl, or C6-2ocycloalkenylalkyl substituent, more preferably at least one Cs-salkenyl, Cs-scycloalkenyl, or Ce-scycloalkenylalkyl substituent.

In one embodiment, the metallocene catalyst which can be used for preparing metallocene- catalyzed ethylene polymer A can be represented by formula (III) for catalyst A, and formula (IV) for catalyst B: wherein

L¹(Ar¹)₂M¹Q¹Q² (III),

L²(Ar²)(Ar³)M²Q³Q⁴ (IV), each Ar¹ is independently indenyl or tetrahydroindenyl, optionally substituted with one or more substituents each independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)3, heteroalkyl; wherein each R¹⁰ is independently hydrogen, alkyl, or alkenyl. Each indenyl or tetrahydroindenyl component may be substituted in the same way or differently from one another at one or more positions of either of the fused rings, each substituent can be independently chosen. Preferably, each Ar¹ is tetrahydroindenyl, optionally substituted with one or more substituents each independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)3, heteroalkyl; wherein each R¹⁰ is independently hydrogen, alkyl, or alkenyl;

Ar² is cyclopentadienyl, optionally substituted with one or more substituents each independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, or cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)3, heteroalkyl; wherein each R¹⁰ is independently hydrogen, alkyl, or alkenyl;

Ar³ is fluorenyl, optionally substituted with one or more substituents each independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, or cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)3, heteroalkyl; wherein each R¹⁰ is independently hydrogen, alkyl, or alkenyl; each of M¹ and M² is a transition metal selected from the group consisting of zirconium, hafnium, titanium, and vanadium; and preferably is zirconium;

Q¹ and Q² are each independently selected from the group consisting of halogen, alkyl, - N(R¹¹)₂, alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R¹¹ is hydrogen or alkyl;

Q³ and Q⁴ are each independently selected from the group consisting of halogen, alkyl, - N(R¹¹)₂, alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R¹¹ is hydrogen or alkyl;

L¹ is a divalent group or moiety bridging the two Ar¹ groups, preferably selected from -[CR⁸R⁹]h- , SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl; preferably L¹ is -[CR⁸R⁹]_h-;

L² is a divalent group or moiety bridging Ar² and Ar³ groups, preferably selected from -[CR⁸R⁹]h- , SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl.

In some embodiments, each Ar¹ is tetrahydroindenyl, optionally substituted with one or more substituents each independently selected from the group consisting of Ci-₂oalkyl, C3-2oalkenyl, C3-2ocycloalkyl, Cs-2ocycloalkenyl, C6-2ocycloalkenylalkyl, Cs-2oaryl, Ci-2oalkoxy, C?-2oalkylaryl, C7- 2oarylalkyl, halogen, Si(R¹⁰)3, and heteroCi-^alkyl; wherein each R¹⁰ is independently hydrogen, Ci-2oalkyl, or C3-2oalkenyl. Preferably each Ar¹ is tetrahydroindenyl, optionally substituted with one or more substituents each independently selected from the group consisting of Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Cs-scycloalkenylalkyl, Cs- i2aryl, Ci-salkoxy, C?-i2alkylaryl, C?-i2arylalkyl, halogen, Si(R¹⁰)3, and heteroCi-salkyl; wherein each R¹⁰ is independently hydrogen, Ci-salkyl, or Cs-salkenyl. Preferably each Ar¹ is tetrahydroindenyl, optionally substituted with one or more substituents each independently selected from the group consisting of Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, C6-i2aryl, and halogen.

In some embodiments, Ar² is cyclopentadienyl, optionally substituted with one or more substituents each independently selected from the group consisting of Ci-2oalkyl , C3-2oalkenyl, C3-2ocycloalkyl, Cs-2ocycloalkenyl, C6-2ocycloalkenylalkyl, Cs-2oaryl, Ci-2oalkoxy, C?-2oalkylaryl, C7- 2oarylalkyl, halogen, Si(R¹⁰)3, and heteroCi-^alkyl; wherein each R¹⁰ is independently hydrogen, Ci-2oalkyl, or C3-2oalkenyl. Preferably Ar² is cyclopentadienyl, optionally substituted with one or more substituents each independently selected from the group consisting of Ci- salkyl, Cs-salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Cs-scycloalkenylalkyl, C6-i2aryl, Ci-salkoxy, C7-i2alkylaryl, C7-i2arylalkyl, halogen, Si(R¹⁰)3, and heteroCi-salkyl; wherein each R¹⁰ is independently hydrogen, Ci-salkyl, or Cs-salkenyl. Preferably Ar² is cyclopentadienyl, optionally substituted with one or more substituents each independently selected from the group consisting of Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Cs-i2aryl, and halogen.

In some embodiments, Ar³ is fluorenyl, optionally substituted with one or more substituents each independently selected from the group consisting of Ci-2oalkyl, Cs-2oalkenyl, C3- 2ocycloalkyl, Cs-2ocycloalkenyl, Cs-2ocycloalkenylalkyl, Cs-2oaryl, Ci-2oalkoxy, C7-2oalkylaryl, C7- 2oarylalkyl, halogen, Si(R¹⁰)s, and heteroCi-isalkyl; wherein each R¹⁰ is independently hydrogen, Ci-2oalkyl , or Cs-2oalkenyl. Preferably Ar² is fluorenyl, optionally substituted with one or more substituents each independently selected from the group consisting of Ci-salkyl, Cs- salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Cs-scycloalkenylalkyl, Cs-i2aryl, Ci-salkoxy, C7- isalkylaryl, C7-i2arylalkyl, halogen, Si(R¹⁰)s, and heteroCi-salkyl; wherein each R¹⁰ is independently hydrogen, Ci-salkyl, or Cs-salkenyl. Preferably, Ar³ is fluorenyl, optionally substituted with one or more substituents each independently selected from the group consisting of Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Cs-i2aryl, and halogen.

In some embodiments, L¹ is -[CR⁸R⁹]h-, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, Ci-2oalkyl, Cs-2oalkenyl, Cs-2ocycloalkyl, Cs-2ocycloalkenyl, Cs- 2ocycloalkenylalkyl, Cs-isaryl, and C7-C2oarylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a Cs-2ocycloalkyl, Cs-2ocycloalkenyl or heterocyclyl. Preferably L¹ is - [CR⁸R⁹]h-, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, Ci-salkyl, C3- salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Cs-scycloalkenylalkyl, C6-i2aryl, and CyC^arylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a Cs-scycloalkyl, C5- scycloalkenyl or heterocyclyl. Preferably, L¹ is -[CR⁸R⁹]h-, or SiR⁸R⁹; wherein h is an integer selected from 1 , or 2; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Cs-scycloalkenylalkyl, and Ce-i2aryl. Preferably, L¹ is -[CR⁸R⁹]h-; wherein h is an integer selected from 1 , or 2; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, Ci-salkyl, preferably hydrogen.

In some embodiments, Q¹ and Q² are each independently selected from the group consisting of halogen, Ci-2oalkyl , -N(R¹¹)2, Ci-2oalkoxy, Cs-2ocycloalkoxy, C?-2oaralkoxy, Cs-2ocycloalkyl, Cs- 2oaryl, C?-2oalkylaryl, C?-2oaralkyl, and heteroCi-2oalkyl; wherein R¹¹ is hydrogen or Ci-2oalkyl. Preferably Q¹ and Q² are each independently selected from the group consisting of halogen, Ci-salkyl, -N(R¹¹)₂, Ci-salkoxy, Cs-scycloalkoxy, C7-i2aralkoxy, Cs-scycloalkyl, C6-i2aryl, C7- i2alkylaryl, C7-i2aralkyl, and heteroCi-salkyl; wherein R¹¹ is hydrogen or Ci-salkyl. Preferably, Q¹ and Q² are each independently selected from the group consisting of halogen, Ci-salkyl, - N(R¹¹)₂, Cs-i2aryl, and C7-i2aralkyl; wherein R¹¹ is hydrogen or Ci-salkyl, preferably Q¹ and Q² are each independently selected from the group consisting of Cl, F, Br, I, methyl, benzyl, and phenyl.

In some embodiments, L² is -[CR⁸R⁹]h-, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, Ci-2oalkyl, Cs-2oalkenyl, Cs-2ocycloalkyl, Cs-2ocycloalkenyl, Cs- 2ocycloalkenylalkyl, C6-i2aryl, and C7-C2oarylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a Cs-2ocycloalkyl, Cs-2ocycloalkenyl or heterocyclyl. Preferably L² is - [CR⁸R⁹]h-, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, Ci-salkyl, C3- salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Cs-scycloalkenylalkyl, C6-i2aryl, and C7-Ci2arylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a Cs-scycloalkyl, C5- scycloalkenyl or heterocyclyl. Preferably, L² is -[CR⁸R⁹]h-, or SiR⁸R⁹; wherein h is an integer selected from 1 , or 2; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Cs-scycloalkenylalkyl, and C₆-i2aryl.

In some embodiments, Q³ and Q⁴ are each independently selected from the group consisting of halogen, Ci-2oalkyl , -N(R¹¹)₂, Ci-2oalkoxy, C3-2ocycloalkoxy, C7-2oaralkoxy, C3-2ocycloalkyl, Cs- 2oaryl, C7-2oalkylaryl, C7-2oaralkyl, and heteroCi-2oalkyl; wherein R¹¹ is hydrogen or Ci-2oalkyl. Preferably Q³ and Q⁴ are each independently selected from the group consisting of halogen, Ci-salkyl, -N(R¹¹)₂, Ci-salkoxy, Cs-scycloalkoxy, C7-i2aralkoxy, Cs-scycloalkyl, Ce-^aryl, C7- i₂alkylaryl, C7-i2aralkyl, and heteroCi-salkyl; wherein R¹¹ is hydrogen or Ci-salkyl. Preferably, Q³ and Q⁴ are each independently selected from the group consisting of halogen, Ci-salkyl, - N(R¹¹)₂, Ce-i2aryl, and C7-i2aralkyl; wherein R¹¹ is hydrogen or Ci-salkyl, preferably Q¹ and Q² are each independently selected from the group consisting of Cl, F, Br, I, methyl, benzyl, and phenyl.

In some preferred embodiments, catalyst component A comprises a bridged metallocene catalyst of formula (la) or (lb), more preferably catalyst component A comprises a bridged metallocene catalyst of formula (la); wherein

each of R¹, and R³, are independently selected from the group comprising alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)s, and heteroalkyl; wherein each R¹⁰ is independently hydrogen, alkyl, or alkenyl; and m, p, are each independently an integer selected from 0, 1 , 2, 3, or 4; each of R², and R⁴, are independently selected from the group comprising alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)s, and heteroalkyl; wherein each R¹⁰ is independently hydrogen, alkyl, or alkenyl; and n, q are each independently an integer selected from 0, 1 , 2, 3, or 4;

L¹ is -[CR⁸R⁹]h-, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl;

M¹ is a transition metal selected from the group comprising zirconium, titanium, hafnium, and vanadium; and preferably M is zirconium; and

Q¹ and Q² are each independently selected from the group comprising halogen, alkyl, -N(R¹¹)₂, alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R¹¹ is hydrogen or alkyl.

In some embodiments, catalyst component A contains a -[CR⁸R⁹]h- bridging group; wherein h is an integer selected from 1 , 2, or 3; preferably 1 or 2, preferably 2, each of R⁸, and R⁹ are independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl, preferably hydrogen; or R⁸ and R⁹ together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl.

In some embodiments, catalyst component A comprises a bridged metallocene of formula (la), wherein

each of R¹, R³ are independently selected from the group comprising Ci-2oalkyl, C3-2oalkenyl, C3-2ocycloalkyl, Cs-2ocycloalkenyl, C6-2ocycloalkenylalkyl, Ce-2oaryl, Ci-2oalkoxy, C?-2oalkylaryl, C7- 2oarylalkyl, halogen, Si(R¹⁰)3, and heteroCi-^alkyl; wherein each R¹⁰ is independently hydrogen, Ci-2oalkyl, or C3-2oalkenyl; and m, p, are each independently an integer selected from 0, or 1 ; each of R², R⁴ are independently selected from the group comprising Ci-2oalkyl, C3-2oalkenyl, C3-2ocycloalkyl, Cs-2ocycloalkenyl, C6-2ocycloalkenylalkyl, Ce-2oaryl, Ci-2oalkoxy, C?-2oalkylaryl, C7- 2oarylalkyl, halogen, Si(R¹⁰)3, and heteroCi-^alkyl; wherein each R¹⁰ is independently hydrogen, Ci-2oalkyl, or C3-2oalkenyl; and n, q are each independently an integer selected from 0, or 1 ;

L¹ is -[CR⁸R⁹]h- wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group comprising hydrogen, Ci-2oalkyl, C3-2oalkenyl, C3-20 cycloalkyl, Cs-2ocycloalkenyl, C6-2ocycloalkenylalkyl, Ce- aryl, aminoCi-ealkyl, and C7- C2oarylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a C3- 2ocycloalkyl, Cs-2ocycloalkenyl or heterocyclyl;

Q¹ and Q² are each independently selected from the group consisting of halogen, Ci-2oalkyl, - N(R¹¹)₂, Ci-2oalkoxy, C3-2ocycloalkoxy, C7-2oaralkoxy, C3-2ocycloalkyl, Ce-2oaryl, C7-2oalkylaryl, C7- 2oaralkyl, and heteroCi-2oalkyl; wherein R¹¹ is hydrogen or Ci-2oalkyl.

In some embodiments, each of R¹, and R³ are independently selected from the group comprising Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Ce-scycloalkenylalkyl, Ce- aryl, Ciwalkoxy, C7-i2alkylaryl, C7-i2arylalkyl, halogen, Si(R¹⁰)3, and heteroCi-salkyl; wherein each R¹⁰ is independently hydrogen, Ci-salkyl, or Cs-salkenyl; and m, p, are each independently an integer selected from 0, or 1 ; each of R², and R⁴, are independently selected from the group comprising Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Cs-scycloalkenylalkyl, Ce-waryl, Ci-salkoxy, C?-i2alkylaryl, C7- warylalkyl, halogen, Si(R¹⁰)3, and heteroCi-8alkyl;wherein each R¹⁰ is independently hydrogen, Ci-salkyl, or Cs-salkenyl; and n, q are each independently an integer selected from 0, or 1 ;

L¹ is -[CR⁸R⁹]h-; wherein h is an integer selected from 1 , or 2; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, Ci-salkyl, preferably hydrogen; M¹ is a transition metal selected from the group comprising zirconium, titanium, hafnium, and vanadium; and preferably M is zirconium; and

Q¹ and Q² are each independently selected from the group comprising halogen, Ci-salkyl, - N(R¹¹)₂, Ci-salkoxy, Cs-scycloalkoxy, C7-i2aralkoxy, Cs-scycloalkyl, Ce- aryl, C7-i2alkylaryl, C7- waralkyl, and heteroCiwalkyl; wherein R¹¹ is hydrogen or Ci-salkyl.

In some embodiments, each of R¹, and R³ are independently selected from the group comprising Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Ce- aryl, and halogen; and m, p, are each independently an integer selected from 0, or 1 ; preferably 0; each of R², and R⁴, are independently selected from the group comprising Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Ce-waryl, and halogen; and n, q are each independently an integer selected from 0, or 1 ; preferably 0;

L¹ is -[CR⁸R⁹]h-; wherein h is an integer selected from 1 , or 2, preferably 2; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, Ci-salkyl, preferably hydrogen;

M¹ is a transition metal selected from zirconium, or hafnium; and preferably M is zirconium; and

Q¹ and Q² are each independently selected from the group comprising halogen, Ci-salkyl, - N(R¹¹)₂, Ce-waryl, and C7-waralkyl; wherein R¹¹ is hydrogen or Ci-salkyl, preferably Q¹ and Q² are each independently selected from the group comprising Cl, F, Br, I, methyl, benzyl, and phenyl.

In some embodiments, catalyst component A comprises a bridged metallocene of formula (Ic)

wherein R³, R⁴, L¹, M¹, Q¹, Q², p and q have the same meaning as that defined herein, preferably p and q are 0. In some embodiments, catalyst component A comprises bridged metallocene of formula (Id)

wherein L¹, M¹, Q¹, and Q², have the same meaning as that defined herein.

In some embodiments, catalyst component A comprises bridged metallocene of formula (le)

wherein M¹, Q¹, and Q², have the same meaning as that defined herein.

A bridged metallocene catalyst component can appear in two stereo-isomeric forms: a racemic form and a meso form. In some preferred embodiments, catalyst component A is a racemic bridged bis-tetrahydroindenyl metallocene compound, preferably component A has formula (la).

Non-limiting examples of catalyst A are shown below

Preferred examples of catalyst A are shown below

In some preferred embodiments, catalyst component B comprises a bridged metallocene catalyst of formula (II),

each of R⁵, R⁶, and R⁷, are independently selected from the group comprising alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R¹⁰)3, and heteroalkyl; wherein each R¹⁰ is independently hydrogen, alkyl, or alkenyl; and r, s, t are each independently an integer selected from 0, 1 , 2, 3, or 4;

L² is -[CR⁸R⁹]h-, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl;

M² is a transition metal selected from the group comprising zirconium, titanium, hafnium, and vanadium; and preferably is zirconium; and Q³ and Q⁴ are each independently selected from the group comprising halogen, alkyl, -N(R¹¹)2, alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R¹¹ is hydrogen or alkyl.

In some embodiments, catalyst component B comprises a bridged metallocene of formula (II), wherein

each of R⁵, R⁶, and R⁷, are independently selected from the group consisting of Ci-2oalkyl , C3- 2oalkenyl, C3-2ocycloalkyl, Cs-2ocycloalkenyl, Ce-2ocycloalkenylalkyl, Ce-2oaryl, Ciwalkoxy, C7- 2oalkylaryl, Cy-2oarylalkyl, halogen, Si(R¹⁰)3, and heteroCi-2oalkyl; wherein each R¹⁰ is independently hydrogen, Ci-2oalkyl, or C3-2oalkenyl; and r, s, tare each independently an integer selected from 0, 1 , 2, 3, or 4;

L² is -[CR⁸R⁹]h-, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group consisting of hydrogen, Ci-2oalkyl, C3- 2oalkenyl, C3-20 cycloalkyl, Cs-2ocycloalkenyl, C6-2ocycloalkenylalkyl, Ce-waryl, aminoCi-ealkyl, and C?-C2oarylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a C3- 2ocycloalkyl, Cs-2ocycloalkenyl or heterocyclyl;

M² is a transition metal selected from the group comprising zirconium, titanium, hafnium, and vanadium; and preferably is zirconium; and

Q³ and Q⁴ are each independently selected from the group comprising halogen, Ci-2oalkyl, - N(R¹¹)₂, Ci-2oalkoxy, C3-2ocycloalkoxy, C?-2oaralkoxy, C3-2ocycloalkyl, Ce-2oaryl, C?-2oalkylaryl, C7- 2oaralkyl, and heteroCi-2oalkyl; wherein R¹¹ is hydrogen or Ci-2oalkyl.

In some embodiments, each of R⁵, R⁶, and R⁷, are independently selected from the group comprising Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Ce-scycloalkenylalkyl, Ce- aryl, Ciwalkoxy, Cy-walkylaryl, Cy-warylalkyl, halogen, Si(R¹⁰)3, and heteroCi-salkyl; wherein each R¹⁰ is independently hydrogen, Ci-salkyl, or Cs-salkenyl; and r, s, t are each independently an integer selected from 0, 1 , 2, 3, or 4;

L² is -[CR⁸R⁹]h-, SiR⁸R⁹, GeR⁸R⁹, or BR⁸; wherein h is an integer selected from 1 , 2, or 3; each of R⁸, and R⁹ are independently selected from the group comprising hydrogen, Ci-salkyl, C3- salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Ce-scycloalkenylalkyl, Ce-waryl, aminoCi-ealkyl, and CrCwarylalkyl; or R⁸ and R⁹ together with the atom to which they are attached form a C3- scycloalkyl, Cs-scycloalkenyl or heterocyclyl;

M² is a transition metal selected from the group comprising zirconium, titanium, hafnium, and vanadium; and preferably is zirconium; and Q³ and Q⁴ are each independently selected from the group comprising halogen, Ci-salkyl, - N(R¹¹)₂, Ci-salkoxy, Cs-scycloalkoxy, C7-i2aralkoxy, Cs-scycloalkyl, Cs- aryl, C?-i2alkylaryl, C7- i₂aral kyl, and heteroCi-salkyl; wherein R¹¹ is hydrogen or Ci-salkyl.

In some embodiments, each of R⁵, R⁶, and R⁷, is independently selected from the group comprising Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Ce- aryl, and halogen; and r, s, t are each independently an integer selected from 0, 1 , 2, 3, or 4; preferably 0, 1 , 2, or 3, preferably 0, 1 , or 2; preferably 0, or 1 ;

L² is -[CR⁸R⁹]h-, or SiR⁸R⁹; wherein h is an integer selected from 1 , or 2; each of R⁸, and R⁹ are independently selected from the group comprising hydrogen, Ci-salkyl, Cs-salkenyl, C3- scycloalkyl; Cs-scycloalkenyl, Cs-scycloalkenylalkyl, and Ce- aryl;

M² is a transition metal selected from zirconium, or hafnium; and preferably zirconium; and

Q³ and Q⁴ are each independently selected from the group comprising halogen, Ci-salkyl, - N(R¹¹)₂, Ce-waryl, and C7-waralkyl; wherein R¹¹ is hydrogen or Ci-salkyl, preferably Q¹ and Q² are each independently selected from the group comprising Cl, F, Br, I, methyl, benzyl, and phenyl.

In some embodiments, catalyst component B comprises a bridged metallocene of formula (Ila),

wherein R⁵, R⁶, R⁷, L², M², Q³, Q⁴, and r have the same meaning as that defined herein, preferably each R⁶ and R⁷ is Ci-salkyl.

In some embodiments, catalyst component B comprises a bridged metallocene of formula (lib),

wherein R⁶, R⁷, L², M², Q³, Q⁴, have the same meaning as that defined herein, preferably each R⁶ and R⁷ is Ci-salkyl.

In some embodiments, catalyst component B comprises a bridged metallocene of formula (He),

wherein R⁶, R⁷, R⁸, R⁹, M², Q³, Q⁴, have the same meaning as that defined herein, preferably each R⁶ and R⁷ is Ci-salkyl.

Non-limiting examples of catalyst B are shown below:

Preferably the metallocene catalyst composition comprises dichloro[rac-ethylenebis(4,5,6- tetrahydro-1 -indenyl)]zirconium and (Butenyl)MeC(Cp)(2,7-tBii2-Flu)ZrCl2.

In a preferred embodiment, the weight ratio of catalyst component A to catalyst component B is in a range of from 1 :4 to 4:1, preferably 1 :3 to 3:1, preferably 1:2 to 2:1 , preferably 1 :1. The catalyst components A and B herein are preferably provided on a solid support, preferably both catalysts are provided on a single solid support, thereby forming a dual catalyst system.

The support for metallocene catalysts can be an inert organic or inorganic solid, which is chemically unreactive with any of the components of the conventional metallocene catalyst. Suitable support materials for the supported catalyst include solid inorganic oxides, such as silica, alumina, magnesium oxide, titanium oxide, thorium oxide, as well as mixed oxides of silica and one or more Group 2 or 13 metal oxides, such as silica-magnesia and silica-alumina mixed oxides. Silica, alumina, and mixed oxides of silica and one or more Group 2 or 13 metal oxides are preferred support materials. Preferred examples of such mixed oxides are the silica- aluminas. For example the solid oxide comprises titanated silica, silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof, preferably silica, titanated silica, silica treated with fluoride, silica-alumina, alumina treated with fluoride, sulfated alumina, silica-alumina treated with fluoride, sulfated silica-alumina, silica-coated alumina, silica treated with fluoride, sulfated silica-coated alumina, or any combination thereof. Most preferred is a titanated silica, or a silica compound. In a preferred embodiment, the bridged metallocene catalysts are provided on a solid support, preferably a titanated silica support, or a silica support. The support may be in granular, agglomerated, fumed or other form.

In some embodiments, the support is a porous support, and preferably a porous titanated silica, or silica support having a surface area comprised between 200 and 900 m²/g. In another embodiment, the support of the polymerization catalyst is a porous support, and preferably a porous titanated silica, or silica support having an average pore volume comprised between 0.5 and 4 mL/g. In yet another embodiment, the support of the polymerization catalyst is a porous support, and preferably a porous titanated silica, or silica support having an average pore diameter comprised between 50 and 300 A, and preferably between 75 and 220 A.

In some embodiments, the support has a D50 of at most 150 pm, preferably of at most 100 pm, preferably of at most 75 pm, preferably of at most 50 pm, preferably of at most 40 pm, preferably of at most 30 pm. The D50 is defined as the particle size for which fifty percent by weight of the particles has a size lower than the D50. The measurement of the particle size can be made according to the International Standard ISO 13320:2009 ("Particle size analysis -Laser diffraction methods"). For example, the D50 can be measured by sieving, by BET surface measurement, or by laser diffraction analysis. For example, Malvern Instruments' laser diffraction systems may advantageously be used. The particle size may be measured by laser diffraction analysis on a Malvern type analyzer. The particle size may be measured by laser diffraction analysis on a Malvern type analyzer after having put the supported catalyst in suspension in cyclohexane. Suitable Malvern systems include the Malvern 2000, Malvern MasterSizer (such as MasterSizer S), Malvern 2600 and Malvern 3600 series. Such instruments together with their operating manual meet or even exceed the requirements set- out within the ISO 13320:2009 Standard. The Malvern MasterSizer ( such as MasterSizer S) may also be useful as it can more accurately measure the D50 towards the lower end of the range e.g. for average particle sizes of less 8 pm, by applying the theory of Mie, using appropriate optical means.

Preferably, metallocene catalysts are activated by an activator. The activator can be any activator known for this purpose such as an aluminum-containing activator, a boron-containing activator, a fluorinated activator, an ionizing ionic compound, or any combination thereof. The aluminum-containing activator may comprise an alumoxane, an alkyl aluminum, a Lewis acid and/or a fluorinated catalytic support. Preferably, the activator comprises an alumoxane compound, preferably methyl alumoxane.

In some embodiments, alumoxane is used as an activator. The alumoxane can be used in conjunction with a catalyst in order to improve the activity of the catalyst during the polymerization reaction.

As used herein, the term “alumoxane” and “aluminoxane” are used interchangeably, and refer to a substance, which is capable of activating the bridged metallocene catalyst. In some embodiments, alumoxanes comprise oligomeric linear and/or cyclic alkyl alumoxanes. In a further embodiment, the alumoxane has formula (V) or (VI)

R^a-(AI(R^a)-O)_x-AIR^a2 (V) for oligomeric, linear alumoxanes; or

(-AI(R^a)-O-)_y (VI) for oligomeric, cyclic alumoxanes wherein x is 1-40, and preferably 10-20; wherein y is 3-40, and preferably 3-20; and wherein each R^a is independently selected from a Ci-salkyl, and preferably is methyl. In a preferred embodiment, the alumoxane is methylalumoxane (MAO).

The catalyst composition may comprise a co-catalyst. One or more aluminumalkyl represented by the formula AIR^b _x can be used as additional co-catalyst, wherein each R^b is the same or different and is selected from halogens or from alkoxy or alkyl groups having from 1 to 12 carbon atoms and x is from 1 to 3. Non-limiting examples are trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n- hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and any combination thereof. Especially suitable are trialkylaluminums, the most preferred being triisobutylaluminum (TIBAL) and triethylaluminum (TEAL).

In an embodiment, said metallocene is a metallocene catalyst composition comprising an alumoxane activator; and a titanated silica or silica solid support; and an optional co-catalyst. The metallocene-catalyzed ethylene polymers A and B can be prepared using a process comprising: contacting a catalyst composition with ethylene, an optional comonomer, and optionally hydrogen, and polymerizing the ethylene, the optional comonomer, in the presence of the at least one catalyst composition, and optionally hydrogen, thereby obtaining the ethylene polymer.

The terms “polyethylene” and “ethylene polymer” may be used synonymously. The term “polyethylene” encompasses ethylene homopolymer as well as ethylene copolymer resin 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 metallocene-catalyzed ethylene polymers A and B can be prepared out in bulk, gas, solution and/or slurry phase. The process can be conducted in one or more batch reactors, slurry reactors, gas-phase reactors, solution reactors, high pressure reactors, tubular reactors, autoclave reactors, or a combination thereof.

The polymerization can be carried out batchwise or in a continuous process. In a preferred embodiment of the present invention, the polymerization is carried out in a continuous process.

The term “continuous” means a system that operates without interruption or cessation. For example, a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn. By this it is meant herein that the reactors, when operating, are run in continuous mode, that is at least one feed stream is predominantly fed continuously to the reactor, while at least one stream is predominantly withdrawn continuously.

The metallocene-catalyzed ethylene polymer can be prepared out in gas, solution and/or slurry phase. The process can be conducted in one or more slurry loop reactors, gas-phase reactors, continuously stirred tank reactors or a combination thereof. Slurry polymerization is preferably used to prepare the ethylene polymers, preferably in a slurry loop reactor or a continuously stirred reactor.

As used herein, the terms “loop reactor” and “slurry loop reactor” may be used interchangeably herein. In certain embodiments, each loop reactor may comprise interconnected pipes, defining a reactor path. In certain embodiments, each loop reactor may comprise at least two vertical pipes, at least one upper segment of reactor piping, at least one lower segment of reactor piping, joined end to end by junctions to form a complete loop, one or more feed lines, one or more outlets, one or more cooling jackets per pipe, and one pump, thus defining a continuous flow path for a polymer slurry. The vertical sections of the pipe segments are preferably provided with cooling jackets. Polymerization heat can be extracted by means of cooling water circulating in these jackets of the reactor. The loop reactor preferably operates in a liquid full mode.

The term "slurry" or "polymerization slurry" or "polymer slurry", as used herein refers to substantially a multi-phase composition including at least polymer solids and a liquid phase, the liquid phase being the continuous phase. The solids may include the catalyst and polymerized monomer.

The catalyst is preferably added to the loop reactor as catalyst slurry. As used herein, the term “catalyst slurry” refers to a composition comprising catalyst solid particles and a diluent. The solid particles can be suspended in the diluent, either spontaneously or by homogenization techniques, such as mixing. The solid particles can be non-homogeneously distributed in a diluent and form sediment or deposit.

In some embodiments, the liquid phase comprises a diluent. As used herein, the term “diluent” refers to any organic diluent, which does not dissolve the synthesized polyolefin. As used herein, the term “diluent” refers to diluents in a liquid state, liquid at room temperature and preferably liquid under the pressure conditions in the loop reactor. Suitable diluents comprise but are not limited to hydrocarbon diluents such as aliphatic, cycloaliphatic and aromatic hydrocarbon solvents, or halogenated versions of such solvents. Preferred solvents are C12 or lower, straight chain or branched chain, saturated hydrocarbons, C5 to C9 saturated alicyclic or aromatic hydrocarbons or C2 to Ce halogenated hydrocarbons. Non-limiting illustrative examples of solvents are butane, isobutane, pentane, hexane, heptane, cyclopentane, cyclohexane, cycloheptane, methyl cyclopentane, methyl cyclohexane, isooctane, benzene, toluene, xylene, chloroform, chlorobenzenes, tetrachloroethylene, dichloroethane and trichloroethane, preferably isobutane or hexane.

The polymerization steps can be performed over a wide temperature range. In certain embodiments, the polymerization steps may be performed at a temperature from 20 °C to 125 °C, preferably from 60 °C to 110 °C, more preferably from 75 °C to 100 °C and most preferably from 78 °C to 98 °C. Preferably, the temperature range may be within the range from 75 °C to 100 °C and most preferably from 78 °C to 98 °C. Said temperature may fall under the more general term of polymerization conditions.

In certain embodiments, in slurry conditions, the polymerization steps may be performed at a pressure from about 20 bar to about 100 bar, preferably from about 30 bar to about 50 bar, and more preferably from about 37 bar to about 45 bar. Said pressure may fall under the more general term of polymerization conditions.

The term “metallocene-catalyzed ethylene polymer”, “ethylene polymer”, or “polyethylene” as used herein refers to the ethylene polymer fluff or powder that is extruded, and/or melted, and/or pelleted and can be prepared through compounding and homogenizing of the ethylene polymer as taught herein, for instance, with mixing and/or extruder equipment. Unless otherwise stated, all parameters used to define the metallocene-catalyzed ethylene polymer are as measured on ethylene polymer pellets.

The term “fluff” or “powder” as used herein refers to the ethylene polymer material with the solid catalyst particle at the core of each grain and is defined as the polymer material after it exits the polymerization reactor (or final polymerization reactor in the case of multiple reactors connected in series). The term “pellets” refers to the ethylene polymer that has been pelletized, for example through melt extrusion. As used herein, the terms “extrusion” or “extrusion process”, “pelletization” or “pelletizing” are used herein as synonyms and refer to the process of transforming ethylene polymer into a “polyolefin product” or into “pellets” after pelletizing. The process of pelletization preferably comprises several devices connected in series, including one or more rotating screws in an extruder, a die, and means for cutting the extruded filaments into pellets.

The metallocene catalyzed ethylene polymer A is preferably a copolymer of ethylene and one or more comonomer. Suitable comonomers comprise but are not limited to aliphatic C3-C20 alpha-olefins. Examples of suitable aliphatic C3-C20 alpha-olefins 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, most preferably 1 -hexene.

In some embodiments, the metallocene-catalyzed ethylene polymer A is an ethylene copolymer and comprises at least 5.0 % by weight of the one or more comonomers based on the total weight of the ethylene polymer A as determined by ¹³C-NMR analysis; preferably at least 6.0 % by weight; more preferably at least % by weight; even more preferably, at least 7.0 % by weight, preferably at least 7.5 % by weight; preferably at least 8.0 % by weight. Preferably the comonomer is 1 -hexene.

In some embodiments, the metallocene-catalyzed ethylene polymer A is an ethylene copolymer and comprises at most 15.0 % by weight of the one or more comonomers based on the total weight of the metallocene-catalyzed ethylene polymer A, as determined by ¹³C NMR analysis, preferably at most 14.0 % by weight, preferably at most 13.0 % by weight, preferably at most 12.0 % by weight, preferably at most 11.0 % by weight, preferably at most 10.5 % by weight. Preferably the comonomer is 1 -hexene.

The metallocene catalyzed ethylene polymer B can be selected from a homopolymer or a copolymer of ethylene and one or more comonomer. Suitable comonomers comprise but are not limited to aliphatic C3-C20 alpha-olefins. Examples of suitable aliphatic C3-C20 alpha-olefins 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.

The term homopolymer refers to a polymer which is made in the absence of comonomer or with less than 0.3 % by weight, relative to the total weight of the metallocene-catalyzed ethylene polymer B, more preferably less than 0.1 % by weight, less than 0.05 % by weight of comonomer. Preferably, the metallocene-catalyzed ethylene polymer B is a polymer which is made in the absence of comonomer or has a total comonomer content, relative to the total weight of the metallocene-catalyzed ethylene polymer B, of at most 1.0 % by weight of comonomer, preferably at most 0.5 % by weight, preferably at most 0.4 % by weight comonomer as determined by ¹³C-NMR analysis.

In some preferred embodiments, the metallocene-catalyzed polyethylene composition comprises: at least 15.0 % to at most 45.0 % by weight of metallocene-catalyzed ethylene polymer A based on the total weight of the polyethylene composition, wherein metallocene-catalyzed ethylene polymer A has: a density ranging from at least 0.910 g/cm³ to at most 0.928 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C, preferably a density of at most 0.925 g/cm³, preferably at most 0.924 g/cm³, preferably at most 0.923 g/cm³, preferably at most 0.922 g/cm³, preferably at most 0.921 g/cm³, preferably at most 0.920 g/cm³, preferably at most 0.919 g/cm³, preferably at most 0.918 g/cm³, preferably of at least 0.911 g/cm³, preferably of at least 0.912 g/cm³, preferably of at least 0.913 g/cm³; a molecular weight distribution M_w/M_n ranging from at least 3.0 to at most 6.5, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight, preferably at least 3.1 , for example at least 3.2, preferably at most 6.3, preferably at most 6.2, preferably at most 6.1 , preferably at most 6.0, preferably at most 5.5, preferably at most 5.3, preferably at most 5.0, preferably at least 3.0 to at most 6.3, preferably at least 3.0 to at most 6.2, preferably at least 3.0 to at most 6.0, preferably at least 3.1 to at most 5.5, preferably at least 3.1 to at most 5.0; a melt index ranging from an HLMI of at least 1.2 g/10 min to an MI2 of at most 6.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm, and melt index HLMI is determined according to ISO 1133:2005 Method B, condition G, at a temperature 190 °C, and a 21.6 kg load using a die of 2.096 mm; a melt strength of X in Newtons, as determined by Gbttfert Rheotens Melt Strength Apparatus, 190 °C, as described in the Experimental section, satisfying the following equations (1) and/or (2):

(1) X is greater than - 0.026 ln(/W/_2>) + 0.0498

(2) X is greater than - 0.026 \n(HLMI) + 0.1334 optionally a melt index ratio HLMI/MI2 (also referred as MI21/MI2) of at most 40.0, preferably at most 38.0, preferably at most 37.0, preferably at most 36.0; preferably at most 35.0, preferably at most 34.0, preferably at most 33.0, preferably at most 30.0, preferably a HLMI/MI2 of at least 15.0; preferably at least 16.0, preferably at least 17.0, preferably at least 18.0, for example a HLMI/MI2 of at least 15.0 to at most 40.0, for example of at least 16.0 to at most 37.0, for example of at least 17.0 to at most 36.0; optionally wherein said metallocene-catalyzed ethylene polymer A is an ethylene-1 - hexene copolymer; at least 55.0 % to at most 85.0 % by weight of metallocene-catalyzed ethylene polymer B based on the total weight of the polyethylene composition, wherein metallocene-catalyzed ethylene polymer B has: a density ranging from at least 0.950 g/cm³ to at most 0.965 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; a melt index MI2 of at least 3.00 to at most 10.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm; optionally a molecular weight distribution M_w/M_n ranging from at least 2.00 to at most 4.00, with M_w being the weight-average molecular weight and M_n being the numberaverage molecular weight; optionally wherein said metallocene-catalyzed ethylene polymer B has a total comonomer content, relative to the total weight of the metallocene-catalyzed ethylene polymer B of at most 1 .0 % by weight, as determined by ¹³C NMR analysis, preferably ranging from 0.0 % to at most 1 .0 % by weight; optionally wherein the metallocene-catalyzed polyethylene composition has a density ranging from at least 0.940 g/cm³ to at most 0.954 g/cm³, for example from at least 0.940 g/cm³ to at most 0.953 g/cm³, for example from at least 0.940 g/cm³ to at most 0.952 g/cm³, for example from at least 0.940 g/cm³ to at most 0.950 g/cm³as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; optionally a melt index MI2 of at least 2.0 to at most 6.0 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm, preferably at most 5.5 g/10min; preferably at most 5.0 g/10 min; optionally a melt index ratio HLMI/MI2 (also referred as MI21/MI2) of at most 35.0, preferably at most 33.0, preferably at most 30.0, preferably at most 29.0, preferably at most 28.0, preferably at most 27.0, preferably at most 26.0, preferably at most 25.0, preferably a HLMI/MI2 of at least 10.0, preferably at least 15.0, preferably a HLMI/Mi2 of at least 10.0 to at most 35.0, preferably at least 10.0 to at most 30.0, preferably at least 10.0 to at most 28.0, preferably at least 10.0 to at most 27.0; optionally a molecular weight distribution M_w/M_n of at most 6.50, preferably at most 6.0, preferably at most 5.5, preferably at most 5.0, preferably a M_w/M_n of at least 2.0, preferably at least 2.3, preferably at least 2.5, preferably at least 2.8, preferably a M_w/M_n of at least 2.0 to at most 6.5, preferably at least 2.3 to at most 6.0, preferably at least 2.5 to at most 5.5, preferably at least 2.5 to at most 5.0, with M_w being the weightaverage molecular weight and M_n being the number-average molecular weight; optionally a M_n of at least 18000 g/mol, preferably of at least 19000 g/mol with M_n being the number-average molecular weight; optionally a molecular weight distribution M_z/M_n of at most 10.0, preferably at most 9.5, preferably at most 9.0, preferably at most 8.5, preferably at most 8.0, preferably a M_z/M_n of at least 3.0, preferably at least 4.0, preferably at least 3.0 to at most 10.0, with M_z being the z average molecular weight and M_n being the number-average molecular weight; and optionally a zero shear viscosity q0 in Pa.s of at least 2900, preferably at least 3000, preferably at least 3200, preferably at least 3400, preferably at least 3500.

In some embodiments, the metallocene-catalyzed ethylene polymer A as defined herein (including all embodiments thereof as described herein) has a molecular weight distribution Mw/Mn ranging from at least 3.0 to at most 6.5, preferably at least 3.1 , for example at least 3.2, preferably a M_w/M_n of at most 6.3, preferably at most 6.2, preferably at most 6.1 , preferably at most 6.0, preferably at most 5.5, preferably at most 5.3, preferably at most 5.0, preferably a Mw/Mn of at least 3.0 to at most 6.3, preferably at least 3.0 to at most 6.0, preferably at least 3.0 to at most 5.5, preferably at least 3.1 to at most 5.5, preferably at least 3.1 to at most 5.0; optionally a melt index MI2 of at least 0.10 g/10 min to at most 6.00 g/10 min, preferably at most 5.00 g/10 min, preferably at most 4.00 g/10 min, preferably at most 3.50 g/10 min, preferably at most 3.00 g/10 min, preferably at most 3.00 g/10 min, preferably at most 2.50 g/10 min, preferably at most 2.00 g/10 min, preferably a MI2 of at least 0.20 g/10 min, preferably at least 0.30 g/10 min, preferably at least 0.40 g/10 min, preferably at least 0.50 g/10 min, preferably at least 0.80 g/10 min, preferably at least 1.00 g/10 min, preferably at least 1.10 g/10 min, preferably at least 1.20 g/10min, preferably at least 1.30 g/10 min, for example a MI2 ranging from at least 0.10 g/10 min to at most 5.00 g/10 min, for example ranging from at least 0.50 g/10 min to at most 4.00 g/10 min, for example ranging from at least 0.80 g/10 min to at most 3.00 g/10 min; optionally a molecular weight distribution M_z/M_w of at most 3.6, preferably at most 3.5, preferably at most 3.4, preferably at most 3.3, preferably at most 3.2, preferably at most 3.1 , preferably at most 3.0, preferably a M_z/M_w of at least 2.0, preferably at least 2.1 , preferably at least 2.2, preferably at least 2.3, for example a M_z/M_w of at least 2.0 to at most 3.6, for example at least 2.1 to at most 3.6, for example at least 2.2 to at most 3.6, for example at least 2.3 to at most 3.5; optionally a molecular weight distribution M_z/M_n of at least 7.0, preferably at least 7.1 , preferably at least 7.2, preferably at least 7.3, preferably at least 7.4, preferably at least 7.5, preferably a M_z/M_n of at most 20.0, preferably at most 18.0, preferably at most 15.0, for example a M_z/M_n of at least 7.0 to at most 20.0, for example at least 7.0 to at most 18.0, for example at least 7.0 to at most 15.0, for example at least 7.5 to at most 15.0; optionally a M_z of at least 190000 Da, preferably at least 200000 Da, preferably at least 205000 Da; optionally at least one melting temperature T_m determined by DSC of at most 130.0 °C, for example at most 125.0 °C, for example at most 120.0 °C, preferably at most 115.0 °C, preferably in the range of at least 100.0 °C to at most 125.0 °C, preferably in the range of at least 105.0 °C to at most 120.0 °C, preferably in the range of 105.0 °C to 115.0 °C.

In some embodiments, the metallocene-catalyzed ethylene polymer A as defined herein (including all embodiments thereof as described herein) has a molecular weight distribution M_w/Mn ranging from at least 3.0 to at most 6.5, preferably at least 3.1 , for example at least 3.2, preferably a M_w/M_n of at most 6.3, preferably at most 6.2, preferably at most 6.1 , preferably at most 6.0, preferably at most 5.5, preferably at most 5.3, preferably at most 5.0, preferably a Mw/Mn of at least 3.0 to at most 6.3, preferably at least 3.0 to at most 6.2, preferably at least 3.0 to at most 6.0, preferably at least 3.1 to at most 5.5, preferably at least 3.1 to at most 5.0; optionally an HLMI of at least 1.2 g/10 min to at most 150.0 g/10 min, preferably an HLMI of at most 100.0 g/10 min, preferably at most 50.0 g/10 min, preferably at most 40.0 g/10 min, preferably an HLMI of at least 5.0 g/10 min, preferably at least 10.0 g/10 min, preferably at least 15.0 g/10 min, preferably at least 20.0 g/10 min, for example an HLMI ranging from at least 1.2 g/10 min to at most 100.0 g/10 min, for example ranging from at least 5.0 g/10 min to at most 50.0 g/10 min, for example ranging from at least 10.0 g/10 min to at most 40.0 g/10 min, for example ranging from at least 15.0 g/10 min to at most 30.0 g/10 min; optionally a molecular weight distribution M_z/M_w of at most 3.6, preferably at most 3.5, preferably at most 3.4, preferably at most 3.3, preferably at most 3.2, preferably at most 3.1 , preferably at most 3.0, preferably a M_z/M_w of at least 2.0, preferably at least 2.1 , preferably at least 2.2, preferably at least 2.3, for example a M_z/M_w of at least 2.0 to at most 3.6, for example at least 2.1 to at most 3.6, for example at least 2.2 to at most 3.6, for example at least 2.3 to at most 3.5; optionally a molecular weight distribution M_z/M_n of at least 7.0, preferably at least 7.1 , preferably at least 7.2, preferably at least 7.3, preferably at least 7.4, preferably at least 7.5, preferably a M_z/M_n of at most 20.0, preferably at most 18.0, preferably at most 15.0, for example a M_z/M_n of at least 7.0 to at most 20.0, for example at least 7.0 to at most 18.0, for example at least 7.0 to at most 15.0, for example at least 7.5 to at most 15.0; optionally a M_z of at least 190000 Da, preferably at least 200000 Da, preferably at least 205000 Da; optionally at least one melting temperature T_m determined by DSC of at most 130.0 °C, for example at most 125.0 °C, for example at most 120.0 °C, preferably at most 115.0 °C, preferably in the range of at least 100.0 °C to at most 125.0 °C, more preferably in the range of at least 105.0 °C to at most 120.0 °C, still more preferably in the range of 105.0 °C to 115.0 °C.

In some embodiments, the metallocene-catalyzed ethylene polymer A as defined herein (including all embodiments thereof as described herein) has a molecular weight distribution M_w/Mn ranging from at least 3.0 to at most 6.5, preferably a M_w/M_n of at least 3.1 , for example at least 3.2, preferably a M_w/M_n of at most 6.3, preferably at most 6.2, preferably at most 6.1 , preferably at most 6.0, preferably at most 5.5, preferably at most 5.3, preferably at most 5.0, preferably a M_w/M_n of at least 3.0 to at most 6.3, preferably at least 3.0 to at most 6.2, preferably at least 3.0 to at most 6.0, preferably at least 3.1 to at most 5.5, preferably at least 3.1 to at most 5.0; optionally a melt index ratio HLMI/MI2 (also referred as MI21/MI2) of at most 40.0, preferably at most 38.0, preferably at most 37.0, preferably at most 36.0, preferably at most 35.0, preferably at most 34.0, preferably at most 33.0, preferably at most 30.0, preferably a HLMI/MI2 of at least 15.0; preferably at least 16.0, preferably at least 17.0, preferably at least 18.0, for example a HLMI/MI2 of at least 15.0 to at most 40.0, for example at least 16.0 to at most 37.0, for example at least 17.0 to at most 36.0; optionally a molecular weight distribution M_z/M_w of at most 3.6, preferably at most 3.5, preferably at most 3.4, preferably at most 3.3, preferably at most 3.2, preferably at most 3.1 , preferably at most 3.0, preferably a M_z/M_w of at least 2.0, preferably at least 2.1 , preferably at least 2.2, preferably at least 2.3, for example a M_z/M_w of at least 2.0 to at most 3.6, for example at least 2.1 to at most 3.6, for example at least 2.2 to at most 3.6, for example at least 2.3 to at most 3.5; optionally a molecular weight distribution M_z/M_n of at least 7.0, preferably at least 7.1 , preferably at least 7.2, preferably at least 7.3, preferably at least 7.4, preferably at least 7.5, preferably a M_z/M_n of at most 20.0, preferably at most 18.0, preferably at most 15.0, for example a M_z/M_n of at least 7.0 to at most 20.0, for example at least 7.0 to at most 18.0, for example at least 7.0 to at most 15.0, for example at least 7.5 to at most 15.0; optionally a M_z of at least 190000 Da, preferably at least 200000 Da, preferably at least 205000 Da; optionally at least one melting temperature T_m determined by DSC of at most 130.0 °C, for example at most 125.0 °C, for example at most 120.0 °C, preferably at most 115.0 °C, preferably in the range of at least 100.0 °C to at most 125.0 °C, more preferably in the range of at least 105.0 °C to at most 120.0 °C, still more preferably in the range of 105.0 °C to 115.0 °C.

In some embodiments, the metallocene-catalyzed ethylene polymer A as defined herein (including all embodiments thereof as described herein) has a molecular weight distribution M_w/Mn ranging from at least 3.0 to at most 6.5, preferably a M_w/M_n of at least 3.1 , for example at least 3.2, preferably a M_w/M_n of at most 6.3, preferably at most 6.2, preferably at most 6.1 , preferably at most 6.0, preferably at most 5.5, preferably at most 5.3, preferably at most 5.0, preferably a M_w/M_n of at least 3.0 to at most 6.3, preferably at least 3.0 to at most 6.2, preferably at least 3.0 to at most 6.0, preferably at least 3.1 to at most 5.5, preferably at least 3.1 to at most 5.0; optionally a melt index Mis ranging from 0.50 g/10 min to 30.00 g/10 min, wherein MI5 is determined according to ISO 1133:2005 Method B, condition T, at a temperature 190 °C, and a 5 kg load using a die of 2.096 mm, preferably from 0.70 g/10 min to 20.00 g/10 min, preferably from 0.70 g/10 min to 15.00 g/10 min, preferably from 0.70 g/10 min to 12.00 g/10 min, preferably from 1.00 g/10 min to 10.00 g/10 min, preferably from 1.00 g/10 min to 5.00 g/10 min; optionally a molecular weight distribution M_z/M_w of at most 3.6, preferably at most 3.5, preferably at most 3.4, preferably at most 3.3, preferably at most 3.2, preferably at most 3.1 , preferably at most 3.0, preferably a M_z/M_w of at least 2.0, preferably at least 2.1 , preferably at least 2.2, preferably at least 2.3, for example a M_z/M_w of at least 2.0 to at most 3.6, for example at least 2.1 to at most 3.6, for example at least 2.2 to at most 3.6, for example at least 2.3 to at most 3.5; optionally a molecular weight distribution M_z/M_n of at least 7.0, preferably at least 7.1 , preferably at least 7.2, preferably at least 7.3, preferably at least 7.4, preferably at least 7.5, preferably a M_z/M_n of at most 20.0, preferably at most 18.0, preferably at most 15.0, for example a M_z/M_n of at least 7.0 to at most 20.0, for example at least 7.0 to at most 18.0, for example at least 7.0 to at most 15.0, for example at least 7.5 to at most 15.0; optionally a M_z of at least 190000 Da, preferably at least 200000 Da, preferably at least 205000 Da; optionally at least one melting temperature T_m determined by DSC of at most 130.0 °C, for example at most 125.0 °C, for example at most 120.0 °C, preferably at most 115.0 °C, preferably in the range of at least 100.0 °C to at most 125.0 °C, more preferably in the range of at least 105.0 °C to at most 120.0 °C, still more preferably in the range of 105.0 °C to 115.0 °C.

In some embodiments, the metallocene-catalyzed ethylene polymer A as defined herein (including all embodiments thereof as described herein) has a molecular weight distribution M_w/Mn ranging from at least 3.0 to at most 6.5, preferably a M_w/M_n of at least 3.1 , for example at least 3.2, preferably a M_w/M_n of at most 6.3, preferably at most 6.2, preferably at most 6.1 , preferably at most 6.0, preferably at most 5.5, preferably at most 5.3, preferably at most 5.0, preferably a M_w/M_n of at least 3.0 to at most 6.3, preferably at least 3.0 to at most 6.2, preferably at least 3.0 to at most 6.0, preferably at least 3.1 to at most 5.5, preferably at least 3.1 to at most 5.0; optionally a melt index ratio HLMI/Mls of at most 20.0; preferably at most 15.0, preferably at most 12.0, preferably at most 11.0, preferably a HLMI/MI5 of at least 5.0, preferably at least 6.0, preferably at least 7.0, preferably a HLMI/MI5 of at least 5.0 to at most 20.0, preferably at least 5.0 to at most 15.0, preferably at least 6.0 to at most 12.0; optionally a molecular weight distribution M_z/M_w of at most 3.6, preferably at most 3.5, preferably at most 3.4, preferably at most 3.3, preferably at most 3.2, preferably at most 3.1 , preferably at most 3.0, preferably a M_z/M_w of at least 2.0, preferably at least 2.1 , preferably at least 2.2, preferably at least 2.3, for example a M_z/M_w of at least 2.0 to at most 3.6, for example at least 2.1 to at most 3.6, for example at least 2.2 to at most 3.6, for example at least 2.3 to at most 3.5; optionally a molecular weight distribution M_z/M_n of at least 7.0, preferably at least 7.1 , preferably at least 7.2, preferably at least 7.3, preferably at least 7.4, preferably at least 7.5, preferably a M_z/M_n of at most 20.0, preferably at most 18.0, preferably at most 15.0, for example a M_z/M_n of at least 7.0 to at most 20.0, for example at least 7.0 to at most 18.0, for example at least 7.0 to at most 15.0, for example at least 7.5 to at most 15.0; optionally a M_z of at least 190000 Da, preferably at least 200000 Da, preferably at least 205000

Da; optionally at least one melting temperature T_m determined by DSC of at most 130.0 °C, for example at most 125.0 °C, for example at most 120.0 °C, preferably at most 115.0 °C, preferably in the range of at least 100.0 °C to at most 125.0 °C, more preferably in the range of at least 105.0 °C to at most 120.0 °C, still more preferably in the range of 105.0 °C to 115.0 °C.

In some embodiments, the metallocene-catalyzed ethylene polymer A as defined herein (including all embodiments thereof as described herein) has a molecular weight distribution M_w/Mn ranging from at least 3.0 to at most 6.5, preferably a M_w/M_n of at least 3.1 , for example at least 3.2, preferably a M_w/M_n of at most 6.3, preferably at most 6.2, preferably at most 6.1 , preferably at most 6.0, preferably at most 5.5, preferably at most 5.3, preferably at most 5.0, preferably a M_w/M_n of at least 3.0 to at most 6.3, preferably at least 3.0 to at most 6.2, preferably at least 3.0 to at most 6.0, preferably at least 3.1 to at most 5.5, preferably at least 3.1 to at most 5.0; optionally a melt index ratio MI5/MI2 of at most 10.0, preferably at most 7.0, preferably at most 5.0, preferably at most 4.0, preferably a MI5/MI2 of at least 1.0, preferably at least 1.5, preferably at least 2.0, preferably at least 2.2, preferably a MI5/MI2 of at least 1.0 to at most 10.0, preferably at least 1 .0 to at most 5.0, preferably at least 1 .0 to at most 4.0, preferably at least 1.5 to at most 4.0; optionally a molecular weight distribution M_z/M_w of at most 3.6, preferably at most 3.5, preferably at most 3.4, preferably at most 3.3, preferably at most 3.2, preferably at most 3.1 , preferably at most 3.0, preferably a M_z/M_w of at least 2.0, preferably at least 2.1 , preferably at least 2.2, preferably at least 2.3, for example a M_z/M_w of at least 2.0 to at most 3.6, for example at least 2.1 to at most 3.6, for example at least 2.2 to at most 3.6, for example at least 2.3 to at most 3.5; optionally a molecular weight distribution M_z/M_n of at least 7.0, preferably at least 7.1 , preferably at least 7.2, preferably at least 7.3, preferably at least 7.4, preferably at least 7.5, preferably a M_z/M_n of at most 20.0, preferably at most 18.0, preferably at most 15.0, for example a M_z/M_n of at least 7.0 to at most 20.0, for example at least 7.0 to at most 18.0, for example at least 7.0 to at most 15.0, for example at least 7.5 to at most 15.0; optionally a M_z of at least 190000 Da, preferably at least 200000 Da, preferably at least 205000 Da; optionally at least one melting temperature T_m determined by DSC of at most 130.0 °C, for example at most 125.0 °C, for example at most 120.0 °C, preferably at most 115.0 °C, preferably in the range of at least 100.0 °C to at most 125.0 °C, more preferably in the range of at least 105.0 °C to at most 120.0 °C, still more preferably in the range of 105.0 °C to 115.0 °C.

In some embodiments, the metallocene-catalyzed ethylene polymer B as defined herein (including all embodiments thereof as described herein) has a density ranging from at least 0.950 g/cm³ to at most 0.965 g/cm³, preferably a density of at least 0.952 g/cm³, preferably at least 0.954 g/cm³, preferably at least 0.955 g/cm³, preferably a density of at most 0.964 g/cm³, preferably at most 0.962 g/cm³, preferably at most 0.960 g/cm³, preferably a density ranging from at least 0.952 to at most 0.964 g/cm³; preferably from at least 0.954 to at most 0.962 g/cm³; and preferably from at least 0.955 to at most 0.960 g/cm³; a melt index MI2 of at least 3.00 to at most 10.00 g/10 min, preferably an MI2 of at most 9.0 g/10 min, preferably of at most 8.0 g/10 min, preferably of at most 7.0 g/10 min; optionally a molecular weight distribution M_w/M_n of at least 2.0, preferably at least 2.1 , preferably at least 2.3, preferably a M_w/M_n of at most 4.0, preferably at most 3.5, preferably at most 3.0, for example a M_w/M_n of at least 2.0 to at most 4.0, preferably at least 2.0 to at most 3.5, preferably at least 2.0 to at most 3.0; and optionally metallocene-catalyzed ethylene polymer B is a polymer which is made in the absence of comonomer or has a total comonomer content, relative to the total weight of the metallocene-catalyzed ethylene polymer B of at most 1.0 % by weight of comonomer, preferably at most 0.5 % by weight, preferably at most 0.4 % by weight comonomer as determined by ¹³C-NMR analysis.

In some preferred embodiments, the metallocene-catalyzed polyethylene composition as defined herein (including all embodiments thereof as described herein), comprises: at least 15.0 % to at most 45.0 % by weight of metallocene-catalyzed ethylene polymer A based on the total weight of the polyethylene composition, preferably at least 20.0 % to at most 40.0 % by weight of metallocene-catalyzed ethylene polymer A, preferably at least 25.0 % to at most 35.0 % by weight of metallocene-catalyzed ethylene polymer A; wherein metallocene-catalyzed ethylene polymer A has: a density ranging from at least 0.910 g/cm³ to at most 0.928 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C, preferably a density of at most 0.925 g/cm³, preferably at most 0.924 g/cm³, preferably at most 0.923 g/cm³, preferably at most 0.922 g/cm³, preferably at most 0.921 g/cm³, preferably at most 0.920 g/cm³, preferably at most 0.919 g/cm³, preferably at most 0.918 g/cm³, preferably of at least 0.911 g/cm³, preferably of at least 0.912 g/cm³, preferably of at least 0.913 g/cm³; a molecular weight distribution M_w/M_n ranging from at least 3.0 to at most 6.5, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight, preferably a M_w/M_n of at least 3.1 , for example at least 3.2, preferably a Mw/Mn of at most 6.3, preferably at most 6.2, preferably at most 6.1 , preferably at most 6.0, preferably at most 5.5, preferably at most 5.3, preferably at most 5.0, preferably a M_w/M_n of at least 3.0 to at most 6.3, preferably at least 3.0 to at most 6.2, preferably at least 3.0 to at most 6.0, preferably at least 3.1 to at most 5.5, preferably at least 3.1 to at most 5.0; a melt index MI2 of at least 0.10 g/10 min to at most 6.00 g/10 min, preferably at most 5.00 g/10 min, preferably at most 4.00 g/10 min, preferably at most 3.50 g/10 min, preferably at most 3.00 g/10 min, preferably at most 3.00 g/10 min, preferably at most 2.50 g/10 min, preferably at most 2.00 g/10 min, preferably at least 0.20 g/10 min, preferably at least 0.30 g/10 min, preferably at least 0.40 g/10 min, preferably at least 0.50 g/10 min, preferably at least 0.80 g/10 min, preferably at least 1.00 g/10 min, preferably at least 1.10 g/10 min, preferably at least 1.20 g/10min, preferably at least 1.30 g/10 min, and/or an HLMI of at least 1.2 g/10 min to at most 150.0 g/10 min, preferably an HLMI of at most 100.0 g/10 min, preferably at most 50.0 g/10 min, preferably at most 40.0 g/10 min, preferably an HLMI of at least 5.0 g/10 min, preferably at least 10.0 g/10 min, preferably at least 15.0 g/10 min, preferably at least 20.0 g/10 min; a melt strength of X in Newtons, as determined by Gbttfert Rheotens Melt Strength Apparatus, 190 °C, as described in the Experimental section, satisfying the following equations (1) and/or (2):

(1) X is greater than - 0.026 ln(/W/_2>) + 0.0498

(2) X is greater than - 0.026 \n(HLMI) + 0.1334 optionally a melt index ratio HLMI/MI2 (also referred as MI21/MI2) of at most 40.0, preferably at most 38.0, preferably at most 37.0, preferably at most 36.0; preferably at most 35.0; preferably at most 34.0, preferably at most 33.0, preferably at most 30.0, preferably a HLMI/MI2 of at least 15.0; preferably at least 16.0, preferably at least 17.0, preferably at least 18.0, for example a HLMI/MI2 of at least 15.0 to at most 40.0, for example at least 16.0 to at most 37.0, for example at least 17.0 to at most 36.0; optionally a melt index MI5 ranging from at least 0.50 g/10 min to at most 30.00 g/10 min, wherein MI5 is determined according to ISO 1133:2005 Method B, condition T, at a temperature 190 °C, and a 5 kg load using a die of 2.096 mm, preferably from at least 0.70 g/10 min to at most 20.00 g/10 min, preferably from at least 0.70 g/10 min to at most 15.00 g/10 min, preferably from at least 0.70 g/10 min to at most 12.00 g/10 min, preferably from at least 1.00 g/10 min to at most 10.00 g/10 min, preferably from at least 1.00 g/10 min to at most 5.00 g/10 min; optionally a melt index ratio HLMI/Mls of at most 20.0; preferably at most 15.0, preferably at most 12.0, preferably at most 11 .0, preferably a HLMI/MI5 of at least 5.0, preferably at least 6.0, preferably at least 7.0, preferably a HLMI/MI5 of at least 5.0 to at most 20.0, preferably at least 5.0 to at most 15.0, preferably at least 6.0 to at most 12.0; optionally a melt index ratio MI5/MI2 of at most 10.0, preferably at most 7.0, preferably at most 5.0, preferably at most 4.0, preferably a MI5/MI2 of at least 1.0, preferably at least 1 .5, preferably at least 2.0, preferably at least 2.2, preferably a MI5/MI2 of at least 1.0 to at most 10.0, preferably at least 1.0 to at most 5.0, preferably at least 1.0 to at most 4.0, preferably at least 1 .5 to at most 4.0; optionally a molecular weight distribution M_z/M_w of at most 3.6, preferably at most 3.5, preferably at most 3.4, preferably at most 3.3, preferably at most 3.2, preferably at most 3.1 , preferably at most 3.0, preferably a M_z/M_w of at least 2.0, preferably at least 2.1 , preferably at least 2.2, preferably at least 2.3, for example a M_z/M_w of at least 2.0 to at most 3.6, for example at least 2.1 to at most 3.6, for example at least 2.2 to at most 3.6, for example at least 2.3 to at most 3.5; optionally a molecular weight distribution M_z/M_n of at least 7.0, preferably at least 7.1 , preferably at least 7.2, preferably at least 7.3, preferably at least 7.4, preferably at least 7.5, preferably a M_z/M_n of at most 20.0, preferably at most 18.0, preferably at most 15.0, for example a M_z/M_n of at least 7.0 to at most 20.0, for example at least 7.0 to at most 18.0, for example at least 7.0 to at most 15.0, for example at least 7.5 to at most 15.0; optionally a M_z of at least 190000 Da, preferably at least 200000 Da, preferably at least 205000 Da; optionally at least one melting temperature T_m determined by DSC of at most 130.0 °C, for example at most 125.0 °C, for example at most 120.0 °C, preferably at most 115.0 °C, preferably in the range of at least 100.0 °C to at most 125.0 °C, more preferably in the range of at least 105.0 °C to at most 120.0 °C, still more preferably in the range of 105.0 °C to 115.0 °C; optionally wherein said metallocene-catalyzed ethylene polymer A is an ethylene-1 - hexene copolymer; at least 55.0 % to at most 85.0 % by weight of metallocene-catalyzed ethylene polymer B based on the total weight of the polyethylene composition, preferably at least 60.0 % to at most 80.0 % by weight of metallocene-catalyzed ethylene polymer B, preferably at least 65.0 % to at most 75.0 % by weight of metallocene-catalyzed ethylene polymer B; wherein metallocene-catalyzed ethylene polymer B has: a density ranging from at least 0.950 g/cm³ to at most 0.965 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C, preferably a density of at least 0.952 g/cm³, preferably at least 0.954 g/cm³, preferably at least 0.955 g/cm³, preferably a density of at most 0.964 g/cm³, preferably at most 0.962 g/cm³, preferably at most 0.960 g/cm³, preferably a density ranging from at least 0.952 to at most 0.964 g/cm³; preferably from at least 0.954 to at most 0.962 g/cm³; and preferably from at least 0.955 to at most 0.960 g/cm³; a melt index MI2 of at least 3.00 to at most 10.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm, preferably an MI2 of at most 9.0 g/10 min, preferably of at most 8.0 g/10 min, preferably of at most 7.0 g/10 min; optionally a molecular weight distribution M_w/M_n ranging from at least 2.00 to at most 4.00, with M_w being the weight-average molecular weight and M_n being the numberaverage molecular weight, preferably at least 2.0 to at most 3.5, preferably at least 2.0 to at most 3.0; optionally metallocene-catalyzed ethylene polymer B is a polymer which is made in the absence of comonomer or has a total 1 -hexene content, relative to the total weight of the metallocene-catalyzed ethylene polymer B of at most 1.0 % by weight of 1-hexene, preferably at most 0.5 % by weight, preferably at most 0.4 % by weight 1-hexene as determined by ¹³C-NMR analysis; optionally wherein the metallocene-catalyzed polyethylene composition has a density ranging from at least 0.940 g/cm³ to at most 0.954 g/cm³, for example from at least 0.940 g/cm³ to at most 0.953 g/cm³, for example from at least 0.940 g/cm³ to at most 0.952 g/cm³, for example from at least 0.940 g/cm³ to at most 0.950 g/cm³as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; optionally a melt index MI2 of at least 2.0 to at most 6.0 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm, preferably at most 5.5 g/10min; preferably at most 5.0 g/10 min; optionally a melt index ratio HLMI/MI2 (also referred as MI21/MI2) of at most 35.0, preferably at most 33.0, preferably at most 30.0, preferably at most 29.0, preferably at most 28.0, preferably at most 27.0, preferably at most 26.0, preferably at most 25.0, preferably a HLMI/MI2 of at least 10.0, preferably at least 15.0, preferably a HLMI/MI2 of at least 10.0 to at most 35.0, preferably at least 10.0 to at most 30.0, preferably at least 10.0 to at most 28.0, preferably at least 10.0 to at most 26.0; optionally a molecular weight distribution M_w/M_n of at most 6.50, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight, preferably a M_w/M_n of at most 6.0, preferably at most 5.5, preferably at most 5.0, preferably a M_w/M_n of at least 2.0, preferably at least 2.3, preferably at least 2.5, preferably at least 2.8, preferably a M_w/M_n of at least 2.0 to at most 6.5, preferably at least 2.3 to at most 6.0, preferably at least 2.5 to at most 5.5, preferably at least 2.5 to at most 5.0; optionally a M_n of at least 18000 g/mol with M_n being the number-average molecular weight, preferably of at least 19000 g/mol; optionally a molecular weight distribution M_z/M_n of at most 10.0, with M_z being the z average molecular weight and M_n being the number-average molecular weight, preferably at most 9.5, preferably at most 9.0, preferably at most 8.5, preferably at most 8.0, preferably a M_z/M_n of at least 3.0, preferably at least 4.0, preferably at least 3.0 to at most 10.0; and optionally a zero shear viscosity q0 in Pa.s of at least 2900, preferably at least 3000, preferably at least 3200, preferably at least 3400, preferably at least 3500.

In some preferred embodiments, the metallocene-catalyzed polyethylene composition as defined herein (including all embodiments thereof as described herein), comprises: at least 20.0 % to at most 40.0 % by weight of metallocene-catalyzed ethylene polymer A based on the total weight of the polyethylene composition, preferably at least 25.0 % to at most 35.0 % by weight of metallocene-catalyzed ethylene polymer A; wherein metallocene- catalyzed ethylene polymer A has: a density ranging from at least 0.911 g/cm³ to at most 0.925 g/cm³, preferably at most 0.924 g/cm³, preferably at most 0.923 g/cm³, preferably at most 0.922 g/cm³, preferably at most 0.921 g/cm³, preferably at most 0.920 g/cm³, preferably at most 0.919 g/cm³, preferably at most 0.918 g/cm³, preferably of at least 0.912 g/cm³, preferably of at least 0.913 g/cm³; a molecular weight distribution M_w/M_n ranging from at least 3.0 to at most 6.0, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight, preferably a M_w/M_n of at least 3.1 , for example at least 3.2, preferably a Mw/Mn of at most 5.5, preferably at most 5.3, preferably at most 5.0, preferably a Mw/Mn of at least 3.0 to at most 5.5, preferably at least 3.1 to at most 5.0; a melt index MI2 of at least 0.10 g/10 min to at most 6.00 g/10 min, preferably at most 5.00 g/10 min, preferably at most 4.00 g/10 min, preferably at most 3.50 g/10 min, preferably at most 3.00 g/10 min, preferably at most 3.00 g/10 min, preferably at most 2.50 g/10 min, preferably at most 2.00 g/10 min, preferably at least 0.20 g/10 min, preferably at least 0.30 g/10 min, preferably at least 0.40 g/10 min, preferably at least 0.50 g/10 min, preferably at least 0.80 g/10 min, preferably at least 1.00 g/10 min, preferably at least 1.10 g/10 min, preferably at least 1.20 g/10min, preferably at least 1.30 g/10 min, and/or an HLMI of at least 1.2 g/10 min to at most 150.0 g/10 min, preferably an HLMI of at most 100.0 g/10 min, preferably at most 50.0 g/10 min, preferably at most 40.0 g/10 min, preferably an HLMI of at least 5.0 g/10 min, preferably at least 10.0 g/10 min, preferably at least 15.0 g/10 min, preferably at least 20.0 g/10 min; a melt strength of X in Newtons, as determined by Gbttfert Rheotens Melt Strength Apparatus, 190 °C, as described in the Experimental section, satisfying the following equations (1) and/or (2):

(1) X is greater than - 0.026 ln(/W/_2>) + 0.0498

(2) X is greater than - 0.026 \n(HLMI) + 0.1334 optionally a melt index ratio HLMI/MI2 (also referred as MI21/MI2) of at most 37.0, preferably at most 36.0; preferably at most 35.0; preferably at most 34.0, preferably at most 33.0, preferably at most 30.0, preferably a HLMI/MI2 of at least 15.0; preferably at least 16.0, preferably at least 17.0, preferably at least 18.0, for example a HLMI/MI2 of at least 15.0 to at most 40.0, for example at least 16.0 to at most 37.0, for example at least 17.0 to at most 36.0; optionally a melt index MI5 ranging from at least 0.50 g/10 min to a most 30.00 g/10 min, wherein MI5 is determined according to ISO 1133:2005 Method B, condition T, at a temperature 190 °C, and a 5 kg load using a die of at least 2.096 mm, preferably from at least 0.70 g/10 min to a most 20.00 g/10 min, preferably from 0.70 g/10 min to a most 15.00 g/10 min, preferably from at least 0.70 g/10 min to a most 12.00 g/10 min, preferably from at least 1.00 g/10 min to a most 10.00 g/10 min, preferably from at least 1 .00 g/10 min to a most 5.00 g/10 min; optionally a melt index ratio HLMI/MI5 of at most 20.0; preferably at most 15.0, preferably at most 12.0, preferably at most 11.0, preferably a HLMI/MI5 of at least 5.0, preferably at least 6.0, preferably at least 7.0, preferably a HLMI/MI5 of at least 5.0 to at most 20.0, preferably at least 5.0 to at most 15.0, preferably at least 6.0 to at most 12.0; optionally a melt index ratio MI5/MI2 of at most 10.0, preferably at most 7.0, preferably at most 5.0, preferably at most 4.0, preferably a MI5/MI2 of at least 1.0, preferably at least 2.0, preferably at least 2.2, preferably a MI5/MI2 of at least 1.0 to at most 10.0, preferably at least 1.0 to at most 5.0, preferably at least 1.0 to at most 4.0, preferably at least 1.5 to at most 4.0; optionally a molecular weight distribution M_z/M_w of at most 3.6, preferably at most 3.5, preferably at most 3.4, preferably at most 3.3, preferably at most 3.2, preferably at most 3.1 , preferably at most 3.0, preferably a M_z/M_w of at least 2.0, preferably at least 2.1 , preferably at least 2.2, preferably at least 2.3, for example a M_z/M_w of at least 2.0 to at most 3.6, for example at least 2.1 to at most 3.6, for example at least 2.2 to at most 3.6, for example at least 2.3 to at most 3.5; optionally a molecular weight distribution M_z/M_n of at least 7.0, preferably at least 7.1 , preferably at least 7.2, preferably at least 7.3, preferably at least 7.4, preferably at least 7.5, preferably a M_z/M_n of at most 20.0, preferably at most 18.0, preferably at most 15.0, for example a M_z/M_n of at least 7.0 to at most 20.0, for example at least 7.0 to at most 18.0, for example at least 7.0 to at most 15.0, for example at least 7.5 to at most 15.0; optionally a M_z of at least 190000 Da, preferably at least 200000 Da, preferably at least 205000 Da; optionally at least one melting temperature T_m determined by DSC of at most 130.0 °C, for example at most 125.0 °C, for example at most 120.0 °C, preferably at most 115.0 °C, preferably in the range of at least 100.0 °C to at most 125.0 °C, more preferably in the range of at least 105.0 °C to at most 120.0 °C, still more preferably in the range of 105.0 °C to 115.0 °C; optionally wherein said metallocene-catalyzed ethylene polymer A is an ethylene-1 - hexene copolymer; at least 60.0 % to at most 80.0 % by weight of metallocene-catalyzed ethylene polymer B based on the total weight of the polyethylene composition, preferably at least 65.0 % to at most 75.0 % by weight of metallocene-catalyzed ethylene polymer B; wherein metallocene- catalyzed ethylene polymer B has: a density ranging from at least 0.950 g/cm³ to at most 0.965 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C, preferably a density of at least 0.952 g/cm³, preferably at least 0.954 g/cm³, preferably at least 0.955 g/cm³, preferably a density of at most 0.964 g/cm³, preferably at most 0.962 g/cm³, preferably at most 0.960 g/cm³, preferably a density ranging from at least 0.952 to at most 0.964 g/cm³; preferably from at least 0.954 to at most 0.962 g/cm³; and preferably from at least 0.955 to at most 0.960 g/cm³; a melt index MI2 of at least 3.00 to at most 10.00 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm, preferably an MI2 of at most 9.0 g/10 min, preferably of at most 8.0 g/10 min, preferably of at most 7.0 g/10 min; optionally a molecular weight distribution M_w/M_n ranging from at least 2.00 to at most 4.00, with M_w being the weight-average molecular weight and M_n being the numberaverage molecular weight, preferably at least 2.0 to at most 3.5, preferably at least 2.0 to at most 3.0; optionally metallocene-catalyzed ethylene polymer B is a polymer which is made in the absence of comonomer or has a total 1 -hexene content, relative to the total weight of the metallocene-catalyzed ethylene polymer B of at most 1.0 % by weight of 1-hexene, preferably at most 0.5 % by weight, preferably at most 0.4 % by weight 1-hexene as determined by ¹³C-NMR analysis; optionally wherein the metallocene-catalyzed polyethylene composition has a density ranging from at least 0.940 g/cm³ to at most 0.954 g/cm³, for example from at least 0.940 g/cm³ to at most 0.953 g/cm³, for example from at least 0.940 g/cm³ to at most 0.952 g/cm³, for example from at least 0.940 g/cm³ to at most 0.950 g/cm³as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; optionally a melt index MI2 of at least 2.0 to at most 6.0 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm, preferably at most 5.5 g/10min; preferably at most 5.0 g/10 min; optionally a melt index ratio HLMI/MI2 (also referred as MI21/MI2) of at most 35.0, preferably at most 33.0, preferably at most 30.0, preferably at most 29.0, preferably at most 28.0, preferably at most 27.0, preferably at most 26.0, preferably at most 25.0, preferably a HLMI/MI2 of at least 10.0, preferably at least 15.0, preferably a HLMI/MI2 of at least 10.0 to at most 35.0, preferably at least 10.0 to at most 30.0, preferably at least 10.0 to at most 28.0, preferably at least 10.0 to at most 27.0; optionally a molecular weight distribution M_w/M_n of at most 6.50, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight, preferably a M_w/M_n of at most 6.0, preferably at most 5.5, preferably at most 5.0, preferably a M_w/M_n of at least 2.0, preferably at least 2.3, preferably at least 2.5, preferably at least 2.8, preferably a M_w/M_n of at least 2.0 to at most 6.5, preferably at least 2.3 to at most 6.0, preferably at least 2.5 to at most 5.5, preferably at least 2.5 to at most 5.0; optionally a M_n of at least 18000 g/mol with M_n being the number-average molecular weight, preferably of at least 19000 g/mol; optionally a molecular weight distribution M_z/M_n of at most 10.0, with M_z being the z average molecular weight and M_n being the number-average molecular weight, preferably at most 9.5, preferably at most 9.0, preferably at most 8.5, preferably at most 8.0, preferably a M_z/M_n of at least 3.0, preferably at least 4.0, preferably at least 3.0 to at most 10.0; and optionally a zero shear viscosity qO in Pa.s of at least 2900, preferably at least 3000, preferably at least 3200, preferably at least 3400, preferably at least 3500.

The present metallocene-catalyzed polyethylene composition as defined herein (including all embodiments thereof as described herein) can comprise one or more additives.

The metallocene-catalyzed polyethylene composition may be compounded with one or more additives, in particular additives such as, by way of example, processing aids, mold-release agents, anti-slip agents, primary and secondary antioxidants, light stabilizers, anti-UV agents, acid scavengers, flame retardants, fillers, nanocomposites, lubricants, antistatic additives, nucleating/clarifying agents, antibacterial agents, plasticizers, colorants/pigments/dyes, sealant resins and mixtures thereof. Illustrative pigments or colorants include titanium dioxide, carbon black, cobalt aluminum oxides such as cobalt blue, and chromium oxides such as chromium oxide green. Pigments such as ultramarine blue, phthalocyanine blue and iron oxide red are also suitable. Specific examples of additives include lubricants and mold-release agents such as calcium stearate, zinc stearate, SHT, antioxidants such as lrgafos®168, lrganox®1010, and lrganox®1076, anti-slip agents such as erucamide, light stabilizers such as Tinuvin®622, Tinuvin®326 and Cyasorb THT®4611 , ionomers such as those known under the tradenames of Surlyn® (DuPont), EEA Copolymer (ethylene-ethyl acrylate copolymer), Hycar® (Goodrich), lotek® (ExxonMobil), Priex® (Solvay Engineered Polymers), AClyn® (Honeywell International), Nation® (DuPont), and Thionic® (Uniroyal), and nucleating agents such as Milliken HPN20E™. An overview of useful additives is given in Plastics Additives Handbook, ed. H. Zweifel, 5^th edition, Hanser Publishers. These additives may be present in quantities generally between 0.01 and 10 weight % based on the weight of the polyethylene composition.

The present invention also encompasses articles comprising a metallocene-catalyzed polyethylene composition as defined herein (including all embodiments thereof as described herein).

Preferably the article is a rotomolded or injection-molded article.

The invention also encompasses the use of a metallocene-catalyzed polyethylene composition as defined herein (including all embodiments thereof as described herein), in rotomolding or injection-molding applications.

The articles obtained by rotomolding are generally hollow parts without any welding lines, such as tanks, drums, containers, bins, vats, jerrycans, cans, cisterns, boxes, bumpers, furniture (bathtubs), signs and ballards, planters, playground slides, car parts such as car doors, car bodies and car seats, airplane parts, nautical and aquatic equipment, buoys, floats, boards, planks and joints. In some embodiments, the rotomolded article is selected from the group comprising bottles, tanks, drums, containers, bins, vats, jerrycans, cans and cisterns, boat or parts thereof, and structural parts.

Rotomolded articles include single and multilayered constructions in the form of tanks, bottles, large hollow articles, rigid food containers and toys, for example.

The present invention also encompasses a rotomolding process for preparing a rotomolded article according to the invention, comprising the steps of a) providing at least one metallocene- catalyzed polyethylene composition as described herein (including all embodiments thereof as described herein); and b) rotomolding said metal locene-catalyzed polyethylene composition into an article. The article can be a mono-layered article only having one layer, or it can be multilayered such as a bi-layered or tri-layered rotomolded article.

These articles can have one or more openings and/or inserts of plastic or metal and/or “kiss offs” which are reinforcing junctions or bridges between two surfaces within the article.

Rotational molding is a process well-known to the person skilled in the art. The various processes of rotational molding can comprise the stages of a) loading of the mold; b) rotation of the mold; c) heating of the mold; d) cooling; and e) release from the mold. The mold can be made of any material known in the art for such a purpose. For example, the mold can be an aluminum mold or a Teflon mold. The mold may be then loaded with powder and/or micropellets comprising the metallocene-catalyzed polyethylene composition as described herein. The quantity of powder and/or of micropellets introduced into the mold depends on the size of the article and on the desired wall thickness. In some embodiments, the wall thickness of the article is of at least 1 .5 mm to at most 25 mm when the article comprises one or more layers, or at least 500 pm to at most 25 mm when the comprises a monolayer (single layer).

The rotation of the mold can be generally carried out around two perpendicular axes.

The heating step c) of the mold preferably occurs simultaneously with the rotation of the mold in step (b).

In some embodiments, the heating step can be carried out in an oven or by electric heating elements. In some other preferred embodiments heating can be carried out with a mold heated by an oil-filled heating jacket, as in for example, the Leonardo® rotomolding machine from Persico®. The heating temperature of the oven, electric heating elements or oil can vary from 150 °C to 350 °C, while the temperature of the air in the interior of the blow mold (peak internal air temperature) can vary from 165 °C to 215 °C. One generally uses a temperature of at least 10 °C higher, preferentially at least 20 °C higher, more preferentially at least 30 °C higher than the melting point of the layer that one wishes to mold. In another embodiment, heating can also be carried out by microwaves. The duration of the molding varies according to the dimensions and the thickness of the rotomolded article; it can range from 5 minutes to 600 minutes.

The duration and the time of the cooling step depends on the installation, on the dimensions of the article to be molded and on the type of article which one wishes to obtain. As mentioned previously, it is possible to cool the mold and/or the article contained in the mold. To cool the mold from the outside, one can use air at room temperature, water between 5 °C and 25 °C or oil between 5 °C and 80 °C. To cool the article from the inside of the mold, one can inject air and/or inert gas such as nitrogen and/or spray water (like a mist) within the interior of the mold, for example at a temperature of 25 °C. The time of cooling can vary between 5 minutes and 500 minutes depending on the thickness of the rotomolded article and the process used for cooling. When the article has a thickness of more than 10 mm, the mold can preferably be cooled from both the inside of the mold and the outside, preferably using Ar or inert gas such as nitrogen or a spray of water (mist).

Thereafter, the article can be released from the mold. Release of the article from the mold can be generally carried out when the article has sufficient rigidity. The release from the mold can be generally done at a temperature lower than 110°C.

According to another mode of realization, the cooling of the mold and/or article obtained can be done in just one step until a temperature ranging between room temperature and a temperature lower than 110 °C is obtained.

According to another mode of realization, the cooling of the mold and/or article comprises the following steps: i. cooling until a temperature ranging between 100 °C and 150 °C, preferably between 100 °C and 130 °C, is reached, ii. maintaining this temperature for 1 minute to 60 minutes, iii. cooling again until a temperature ranging between the room temperature and a temperature lower than 100 °C is reached.

Thereafter, the article can be released from the mold. Release of the article from the mold can be generally carried out when the article has sufficient rigidity.

The rotational molding can be carried out under inert gas in the absence of oxygen. In order to do so, one can for example add into the mold a compound which liberates carbon dioxide, such as dry ice. This can be for example together with the powder or pellets of the different components. Dry ice generates carbon dioxide during the heating and rotating steps of the molding process. One can also purge the mold with an inert gas, such as nitrogen, by injecting nitrogen after closing the mold. The walls of the articles can comprise one or more successive layers, at least one of which comprises a metallocene-catalyzed polyethylene composition as described herein. It is thus possible to manufacture articles with walls comprising for example two or more layers.

There are several known methods to manufacture multilayered rotomolded articles: by manual introduction of material during the rotomolding cycle, or by the use of a drop-box, or by a one- shot system wherein each layer has a different melting temperature and are introduced into the mold together.

In some embodiments, manual addition involves moving the mold from the oven, removing a vent tube or plug that creates an opening in the part and adding more material using a funnel or wand. This operation can be repeated for each additional layer.

In some embodiments, a drop-box typically comprises the material for a particular layer and it is an insulated container that holds material until it is released at the appropriate time during the cycle. The signal for release of material can be usually transmitted as a pressure pulse via the airline through the arm of the machine. The insulation can be kept cool to prevent the material inside the box from melting.

The present invention also discloses a method for rotomolding the articles according to the invention for one or more layers comprising the steps of (in no particular order) according to the process known to the skilled person: a) feeding at least one metallocene-catalyzed polyethylene composition as described herein for a first layer into a mold; b) placing the filled mold in pre-heated oven; c) rotating the filled mold about two perpendicular axes; d) optionally feeding a composition for a second layer; e) optionally feeding a composition for a third layer, followed by repeating steps (b) and (c); f)optionally feeding desired additional layers, each addition followed by repeating steps (b) and (c). g) cooling and retrieving the rotomolded article

Preferably, the process is carried out in the order described.

Articles obtained by the rotomolding process according to the invention do not have a point of weakness. They show homogeneous characteristics, such as for example a uniform thickness of the walls as well as very good surface aspects both internally and externally, without displaying any deformation, bubble or other defects.

The present invention also encompasses an injection-molding process for preparing an injection-molded article according to the invention, comprising the steps of a) providing at least one metallocene-catalyzed polyethylene composition as described herein (including all embodiments thereof as described herein); and b) injection-molding said metallocene- catalyzed polyethylene composition into an article.

The composition can be processed on conventional injection molding machines. The finish on the moldings obtained is homogeneous and can be improved further by increasing the rate of injection or raising the mold temperature.

The articles obtained by injection-molding include tanks, drums, containers, bins, vats, jerrycans, cans, cisterns, boxes, and other components such as connectors, caps or closures, or any other injected components etc. In some preferred embodiment, said injection-molded article can be a container, in particular a tank, such as automotive fuel tanks, SCR (Selective Catalytic Reduction) or AdBlue® tanks. Such injection-molded article can also be an inner part of a tank e.g. a slosh baffle, a connector, a pillar, and the like.

In addition, the metal locene-catalyzed polyethylene composition as defined herein, for use in the processes, presents little or no sagging behavior during the rotomolding. In particular, the articles obtained therewith display low warpage, and low deformation. They also benefit from improved stiffness and rigidity; as well as good tensile properties. When the article is obtained by sealing together two injection-molded half shells, the very low warpage of the composition is particularly advantageous, because said half shells result to be easily sealable due to their good planarity.

The invention will now be illustrated by the following, non-limiting illustrations of particular embodiments of the invention.

EXAMPLES

Test methods

The properties cited herein and cited below were determined in accordance with the following test procedures. Where any of these properties is referenced in the appended claims, it is to be measured in accordance with the specified test procedure.

Density

The density of the polyolefin was measured according to the method of standard ISO 1183- 1 :2012 method A at a temperature of 23 °C (weight of displaced fluid (Buoyancy) at 23°C in isopropanol).

Melt flow index

The melt flow index MI2 was determined according to ISO 1133:2005 Method B, condition D, at a temperature of 190 °C, and a 2.16 kg load using a die of 2.096 mm.

The melt flow rate MI5 was determined according to ISO 1133:2005, Method B, condition T, at 190 °C and under a load of 5 kg, using a die of 2.096 mm.

The high load melt flow index (HLMI) or MI21 was determined according to ISO 1133:2005 Method B, condition G, at a temperature of 190 °C, and a 21.6 kg load using a die of 2.096 mm.

Molecular weight, molecular distribution

The molecular weight (M_n (number average molecular weight), M_w (weight average molecular weight) and molecular weight distributions D (M_w/M_n), and D’ (M_z/M_w) were determined by size exclusion chromatography (SEC) and in particular by IR-detected gel permeation chromatography (GPC) at high temperature (145 °C). Briefly, a GPC-IR5MCT from Polymer Char was used: 8 mg polymer sample was dissolved at 160 °C in 8 mL of trichlorobenzene stabilized with 1000 ppm by weight of butylhydroxytoluene (BHT) for 1 hour (h). Injection volume: about 400 pl, automatic sample preparation and injection temperature: 160 °C. Column temperature: 145 °C. Detector temperature: 160 °C. Column set: 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) to collect all C-H bonds and two narrow band filters tuned to the absorption region assigned to CH3 and CH2 groups. Calibration: narrow standards of polystyrene (PS) (commercially available). Calculation of molecular weight Mj of each fraction i of eluted polymer is based on the Mark-Houwink relation (log (MpE) = 0.965909 x log10(Mps) - 0.28264) (cut off on the low molecular weight end at M_PE = 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 form the calculated Mi:

Here Nj and are the number and weight, respectively, of molecules having molecular weight Mj. 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.

Differential Scanning Calorimetry (DSC) for Determination of Melting Temperatures.

Melting temperature (T_m) was determined via Differential Scanning according to ISO 11357- 3:2018 on a DSC Q2000 instrument by TA Instruments, calibrated with indium and using T zero mode. To erase any prior thermal and crystallization history the samples were first heated to 220 °C at a heating rate of 10°C/min and kept at 220 °C for 5 minutes. The polymer was then cooled with a constant cooling rate of -10 °C/min up to 0 °C and kept isothermal at 0 °C for 5 minutes. The polymer was then heated to 220 °C at a constant heating rate of 10 °C/min. and the melting temperature was 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. In some cases, the thermogram can present two melting peaks. The extremum associated to the lowest temperature is labelled as T_mi and the extremum associated to the highest temperature is labelled as T_m2.

Comonomer content

The 1 -hexene content (wt.% C6-) relative to the total weight of the ethylene copolymer was determined from a ¹³C{¹H} NMR spectrum.

The sample was 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 internal standard. To give an example, about 220 mg of polymer were dissolved in 2.0 mL of TCB, followed by addition of 0.5 mL of CeDe and 2 to 3 drops of HMDS.

¹³C{¹H} NMR signal was recorded on a Bruker 500 MHz with a 10 mm probe (or 10mm cryoprobe) with the following conditions:

Pulse angle: 90°

Pulse repetition time: 30s

Spectral width: 25000 Hz centered at 95 ppm

Data points: 64K

Temperature: 130 °C +1-2 °C

Rotation: 15 Hz

Scan numbers: 2000 - 4000 (240 scans with 10 mm cryoprobe)

Decoupling sequence: inverse-gated decoupling sequence to avoid NOE effect

¹³C{¹H} NMR spectrum was obtained by Fourier Transform on 131 K points after a light Gaussian multiplication. Spectrum was phased, baseline corrected, and chemical shift scale was referenced to the internal standard HMDS at 2.03 ppm.

Chemical shifts of signals were peak picked, and peaks were integrated as mentioned on Figure 1 and in the following Table A.

Table A: integration regions of ¹³C{¹H} NMR spectrum

Small adjustments on integration limits can be applied if necessary.

Chemical shifts are given at ± 0.05 ppm.

The wt.% C6- contents are obtained by the following areas (A) combinations:

AC3 = 0.5 X AcH2(a) B1 AC4 = ACH3 B2

AC6 = ACH2(2) B4

AC2 = 0.5 X (ATV1 + ATV2 + ATV3 + Avinylidenel + Avinylidene2 + 0.5 X AcH2(a) B1 + ATS3 + 2X ATS2 + AcH2n ' AC6⁺ AcH2(b) )

Dynamic rheometry analyses (RDA)

Dynamic shear viscosity (or complex viscosity) as a function of frequency was determined by small-amplitude oscillatory shear (SAOS) rheology. Complex viscosity is measured at 190 °C over an angular frequency range from 0.1 to 300 rad/s using the procedure described below using Small Amplitude Oscillatory Shear (SAOS) testing. From the data generated by such a test, it is possible to determine the phase or loss angle 5, which is the inverse tangent of the ratio of G" (the loss modulus) to G' (the storage modulus). For a typical linear polymer, the loss angle at low frequencies (or long times) approaches 90° making the loss modulus much larger than the storage modulus. As frequencies increase, more of the chains relax too slowly to absorb energy during the oscillations, and the storage modulus grows relative to the loss modulus. Eventually, the storage and loss moduli become equal and the loss angle reaches 45°. In contrast, a branched chain polymer relaxes very slowly. Such branched polymers never reach a state where all its chains can relax during an oscillation, and the loss angle never reaches 90° even at the lowest frequency, co, of the experiments. The loss angle is also relatively independent of the frequency of the oscillations in the SAOS experiment; another indication that the chains cannot relax on these timescales.

In a plot of the phase angle 5 versus the measurement frequency co, polymers that have long chain branches exhibit a plateau in the function of b(co), whereas linear polymers do not have such a plateau. According to Garcia-Franco et al. (34(10) Macromolecules 3115-3117 (2001)), the plateau in the aforementioned plot will shift to lower phase angles 5 when the amount of long chain branching occurring in the polymer sample increases.

The zero shear viscosity qO in Pa.s is obtained from a frequency sweep experiment, and taking the usual assumption of equivalence of angular frequency (rad/s) and shear rate; wherein zero shear viscosity qO is estimated by fitting with Garreau-Yasuda flow curve (q-W) at a temperature of 190°C, obtained by oscillatory shear rheology on ARES-G2 equipment (manufactured by TA Instruments) in the linear viscoelasticity domain; wherein circular frequency (W in rad/s) varies from 0.1 rad/s to 300 rad/s, and the shear strain is typically 10 %.

Melt strength

The melt strength (also referred as strength at break) was measured with a Gdttfert Rheotens Melt Strength device, model 71-97, in combination with Rheograph Gdttfert RG50, both manufactured by Gdttfert under the following testing conditions: Rheograph Gdttfert (RG50)= Die geometry (L/D): 30 mm/2 mm, 180° entrance angle; barrel + die temperature: 190 °C; Piston diameter 12 mm, Piston speed: 0.25 mm/s. Rheotens (model 71-97) Wheels: standard (ridged wheels); Wheel gap: 0.4 mm; Wheel acceleration: 2 mm/s², Strand length: 100.0 mm, Wheel initial speed Vo: 9.0 mm/s. In the Rheotens test, the tensile force required for extension/stretching of an extruded melt filament exiting a capillary die was measured as a function of the wheel take-up velocity that increased continuously at a constant acceleration speed. The tensile force typically increased as the wheel (roller) velocity was increased and above a certain take-up velocity the force remained constant until the filament (strand) broke.

For each material, Rheotens curves were generated to verify data reproducibility. Polymer was loaded into the barrel and allowed to melt for 360 seconds at 190 °C before beginning the testing. In fact, the complete amount of material present in the barrel of the Rheograph was extruded through the die and was being picked up by the wheels of the Rheotens device. The strand was let to stabilize between the wheels turning at 9 mm/s, once the strand was stabilized, the force was calibrated to 0 N and the acceleration of the wheels was started. Once the test was started, the speed of the wheels was increased with a 2.0 mm/s² acceleration and the tensile force was measured for each given speed. After each strand break, or strand slip between the wheels, the measurement was stopped and the material was placed back between the wheels for a new measurement. A new Rheotens curve was recorded. Measuring continued until all material in the barrel was consumed. In this invention, the average of the tensile force vs. draw ratio for each material was reported.

Impact properties of rotomolded samples

Unless otherwise specified, the impact properties of the rotomolded articles were measured using the method of standard test ISO 6603-2:2023 at a temperature of - 40 °C. This is a falling weight test that gives the resistance to shock. The tests were carried out at temperatures of -40 °C and a speed of the falling mass of 4.43 m/s. The test results were obtained on an average of at least 5 samples. Modes of failure during impact testing fall into two categories: brittle and ductile. With brittle failure, a crack initiates and propagates prior to any bulk yielding of the specimen and hence the point of failure lies on the initial rising portion of the I oad/d eformation curve. In the case of ductile failure, considerable yielding takes place and the failure occurs well after the maximum on the load/deformation curve. As the area under the load/deformation curve is a measure of the fracture energy, it follows that brittle failure is associated with very low absorbed energy as compared to ductile failure. The ductility index is defined by the ratio Eprop/Etot, in % (i.e. (Eprop/Etot)*100), wherein total energy Etot is the sum of peak energy Epeak and propagation energy Eprop. The samples used for impact tests were all taken from the same side of each trial molding so that the results were made comparable to the molding conditions. They were cut with a bandsaw into squares of 65 mmx65 mm, the edges were cleaned of burrs and the thickness at the center of each sample was noted. The machine used was the-INSTRON 9450.

In some cases, an alternative impact method was used as described in Association of Rotational Molding International. Low Temperature Impact Test. Version 4.0 - July 2003, procedure D.

Catalysts:

1. Metallocene 1 : Dichloro[rac-ethylenebis(4,5,6-tetrahydro-1-indenyl)]zirconium (Met1)

Dichloro[rac-ethylenebis(4,5,6-tetrahydro-1-indenyl)]zirconium was purchased from Boulder Scientific Company (CAS 100163-29-9).

2. Metallocene 2: (Butenyl)MeC(Cp)(2,7-tBu2-Flu)ZrCl2 (Met2)

Metallocene 2 was prepared as described below, following the synthesis described in Journal of Organometallic Chemistry vol. 553, 1998, p. 205-220:

Into a 200 mL 3-neck flask equipped with a gas inlet tube and a magnetic stirring bar was charged, under nitrogen, 2.5 eq of freshly cracked cyclopentadiene and 1 eq of 5-hexene-2- one in 60 mL of methanol. Then, 2 eq of pyrrolidine was added dropwise at 0 °C and the mixture was stirred overnight at room temperature. The reaction was quenched with 50 mL of HCI 1 M and extracted with Et20 (3 x 50 mL). Organic fractions were dried over MgSO4 and solvent was removed under reduced pressure. The fulvene was obtained as a yellow oil and used without further purification (Yield = 65%).

Step 2:

In a 3-neck flask, 1 eq of di-tert-butylfluorene was added under flow of nitrogen and dissolved in 70 mL of Et20. 1.1 eq of n-BuLi (1.6 M in hexane) was added dropwise at O °C to this solution and the mixture was stirred overnight at room temperature. A solution of 3.5 g of fulvene prepared in the previous step, dissolved in 30 mL of Et20 was added dropwise. The reaction mixture was allowed to stir overnight. The reaction was quenched with water and extracted with Et20 (3 x 50 mL). Combined organic fractions were dried over MgSCL and solvent was removed under reduced pressure. The product was crystallized in pentane/MeOH at 0 °C to afford a white solid (Yield = 85%).

Step 3:

In a round-bottomed flask, 1 g of ligand was introduced and dissolved in 40 mL of Et20. 2.1 eq. of nBuLi was added dropwise and the mixture was stirred overnight at room temperature. Solvent was removed under vacuum and 40 mL of dry pentane was added. Then 1 eq of ZrCL was added in small portions at room temperature. The reaction was stirred over 2 days and filtered. The resulting precipitate was diluted in DCM and centrifuged to eliminate lithium chloride. Solvent was removed under vacuum to afford a pink-red powder (Yield = 70%).

¹H N MR (500 MHz, CD₂CI₂) 5 1.34 (s, 9 H, CH₃ tBu); 1.36 (s, 9 H, CH₃ tBu); 2.30 (m, CH₂ alk); 2.43 (s, 3 H, CH₃); 2.55 (m, 1 H, CH₂ alk.); 2.65 (m, 1 H, CH₂ alk.); 3.25 (m, 1 H, CH₂ alk.); 5.13 (m; 1 H, CHvinyl); 5.18 (m; 1 H, CHvinyl); 5.70 (m, 2 H, CHcp); 6.10 (m; 1 H, CHvinyl); 6.29 (m, 2 H, CHcp); 7.55 (s, 1 H, CHflu), 7.63-7.68 (m, 2 H, CHflu); 7.72 (s, 1 H, CHflu); 8.00- 8.04 (m, 2 H, CHflu)

3. Synthesis of supported catalysts

All catalyst and co-catalyst experimentations were carried out in a glove box under nitrogen atmosphere. Methylaluminoxane (30 wt%) (MAO) in toluene from Albemarle was used as the activator. Supported metallocene catalysts were prepared in two steps using the following method:

1. Impregnation of MAO on silica:

Ten grams of dry silica (dried at 450 °C under nitrogen during 6 h) was introduced into a round- bottomed flask equipped with a mechanical stirrer and a slurry was formed by adding 100 ml of toluene. MAO (21 ml) was added dropwise with a dropping funnel. The reaction mixture was stirred at 110 °C for 4 hours. The reaction mixture was filtered through a glass frit (POR3) and the powder was washed with dry toluene (3 x 20 ml) and with dry pentane (3 x 20 ml). The powder was dried under reduced pressure overnight to obtain a free flowing grey powder.

2. Deposition of metallocene on silica/MAO support:

Silica/MAO (10 g) was suspended in toluene (100 ml) under nitrogen. Metallocene catalysts 1 and 2 (total amount of metallocene = 0.2 g) were introduced and the mixture was stirred 2 hours at room temperature. The reaction mixture was filtered through a glass frit and the powder was washed with dry toluene (3 x 20 ml) and with dry pentane (3x 20 ml). The powder was dried under reduced pressure overnight to obtain a free flowing grey powder.

The catalyst composition prepared is shown in Table 1.

Table 1

Metallocene-catalyzed ethylene polymers

Polymerization reaction for preparing metallocene-catalyzed ethylene polymer A used herein was performed using the dual catalyst composition 1 shown in Table 1 , in a slurry single loop reactor with isobutane as diluent. The polymerization was performed under the operating conditions depicted in Table 2. Table 2

The ethylene polymers used for preparing compositions according to the invention and comparative compositions are shown in Table 3.

Polyethylene HD 6081 is a commercial high density Ziegler-Natta polyethylene commercially available from TotalEnergies Refining and Chemicals.

Polyethylene Lumicene® mPE M 1810 EP is a commercial metallocene linear low density polyethylene with 1 -hexene as comonomer commercially available from TotalEnergies Refining and Chemicals. Polyethylene Lumicene® mPE M 6040 is a commercial metallocene high density Polyethylene commercially available from TotalEnergies Refining and Chemicals.

Table 3

Compositions

Compositions were compounded in a twin screw extruder (Coperion ZSK) using the following conditions: Screw diameter: 133 mm, L/D: 44, Throughput: 2000 kg/h, Barrel-temperature: 20- 220 °C, Temperature at die-plate: 260°C, Screw-Speed: 310 +/- 20 rpm, Melt screen with 300 pm and under water granulation.

The compounded compositions are shown in Table 4a. Their properties are shown in Table 4b. SLIRLYN™ 1650 Ionomer is an ionomer of ethylene acid copolymer commercially available from Dow. Polyether block amide Pebax® MH 1657 resin is a thermoplastic elastomer made of flexible polyether and rigid polyamide commercially available from Arkema. CYASORB THT® 4611 (UV stabilizing performance and thermal protection) is commercially available from Solvay. Zinc Stearate DA FLAKE is commercially available from FACI. Irganox® B 225 is a processing and long-term thermal stabilizer system commercially available from BASF. C16 (PEB7300) is a concentrate of a high color carbon black in an LDPE carrier commercially available from Hubron. CYASORB CYNERGY SOLUTIONS® R333 is a stabilizer commercially available from Solvay. CYANOX® 2777 by Solvay is an antioxidant commercially available from Solvay.

Table 4a

Table 4b

NM: not measured

RDA analyses were performed. The results are shown in Figure 2, which plots viscosity (Pa.s) of each composition as a function of shear rate (Rad/s); and in Figures 3A and 3B, which plot the storage modulus (G’) (Figure 3A) and loss modulus (G") (Figure 3B) of each composition as a function of shear rate (Rad/s). Figure 4 represent a graph plotting the shear thinning characteristics (Tangent delta (Tan 8) vs angular frequency) of tested compositions.

The molecular weight distribution curves of the prepared compositions, and individual polymers, as determined by Gel Permeation Chromatography (GPC), are shown in Figures 5, 6 and 7.

Figure 8 represent a graph plotting the zero shear rate viscosity qO (Pa.s) as a function of molecular weight of tested compositions, and individual polymers thereof. The “Linear” power and rectangles in Figure 8 represent the dependence of zero shear viscosity for commercially available linear metallocene-catalyzed ethylene polymers when plotted against the weight average molecular weight.

Rotomolded articles:

Rotomolded bottles were manufactured. The composition used were ground into rotomolding powder (average particle size 300pm) using as pulverizing system. The samples were evaluated on 7 L bottles prepared by rotomolding using a commercial rotomolding equipment. A carousel oven machine was used. Cooling of the molds was obtained via external air cooling only. Air was used at room temperature (between 20 °C to 25 °C). For each bottle, composition powder was loaded in the mold, followed by manufacturing the bottle by rotational molding.

1 - Permeation to hydrogen and methane

For the permeation test, the samples were rotomolded using the following parameters of the rotomolding cycle:

Heating of the oven to a temperature of about 310 °C;

PIAT (peak internal air temperature): about 220 °C;

Thickness of wall of bottles: 3.0 mm;

Removed from the oven at 200 °C (internal air temperature).

Hydrogen and methane permeability has been tested according to the method of standard ISO 15105-1 :2007 method A at a temperature of 23 °C and 0 % of relative humidity.

The test time were 11 days for hydrogen and 25 days for methane. The results for hydrogen and methane permeability test are shown in Table 5.

Table 5

Table 5 shows that the rotomolded sample made with composition E1 has lower hydrogen (17.3 % lower) permeability and lower methane permeability (15.7 % lower) than the sample made with comparative composition CE1. The rotomolded article prepared with E1 composition therefore outperformed the comparative example prepared with CE1 and showed lower H2 and CH4 permeability.

2- Impact properties as a function of PIAT: 6.5 mm wall thickness

For the impact test as a function of PIAT, the samples were rotomolded using the following parameters of the rotomolding cycle:

Heating of the oven to a temperature of about 310 °C;

PIAT (peak internal air temperature): ranging from 190 to 220 °C;

Thickness of wall of bottles: 6.5 mm;

The impact test were performed as described in Association of Rotational Molding International. Low Temperature Impact Test. Version 4.0 - July 2003, procedure D. The impact results as a function of peak internal air temperature recorded are reported in Table 6 and in Figure 9.

Table 6

Figure 9 illustrates the impact energy of rotomolded parts made with compositions according to the invention versus comparative compositions. As seen, the rotomolded part that was formulated with composition E1 achieves the higher impact energy at a shorter rotational molding time interval (given by peak internal air temperature) compared to the rotomolded part that was formulated with either comparative compositions CE1 and CE2. Furthermore, the rotomolded part formulated with composition E1 unexpectedly retains an impact energy at longer oven times than do the rotomolded parts formulated with either the comparatives compositions CE1 and CE2. The rotomolded article prepared with E1 composition outperformed the comparative examples prepared with CE1 and CE2 in terms of improved impact properties (see Figure 9).

3 - Impact properties 3.0 mm wall thickness

For the impact test at PIAT 220 °C, the samples were rotomolded using a ROBOMOULD® Electrical Machine:

Heating of the Mold to a temperature of about 240 °C; PIAT (peak internal air temperature): 220 °C;

Thickness of wall of bottles: 3.0 mm;

The impact results (ISO 6603 Method) recorded are reported in Figure 10. The division between ductile and brittle is around 27 J. The rotomolded article prepared with E1 composition outperformed the comparative example prepared with CE1 in terms of improved impact properties (see Figure 10).

4 - Impact properties as a function of PIAT: 4.5 mm wall thickness

For this impact test, the samples were rotomolded using the following parameters of the rotomolding cycle: the samples were rotomolded using a Smart® Electrical Machine from Persico:

Heating of the Mold to a temperature of about 180 to 270° °C;

PIAT (peak internal air temperature): range from 170 °C to 250 °C

The impact results (ISO 6603 Method) recorded are reported in Figure 11. The division between ductile and brittle is around 80 J. The rotomolded article prepared with E4 composition outperformed the comparative example prepared with CE1 (see Figure 11).

5 -Full notch creep test (FNCT)

The tests performed were Full Notch Creep Test (FNCT) as per ISO 16770, testing at 50°C in a 10% Caflon NP9 Solution.

Compression molded plaques of nominal thickness 6 mm for FNCT specimens were prepared. The molding conditions for 6 mm plaques were: • Melt temperature: 200 °C • Pre-heat time: 25 minutes with 20 minutes under low pressure and 5 minutes at high pressure. • Cooling rate: from 200 °C to 20 °C at 15 °C/min.

FNCT was undertaken according to ISO 16770. Specimens were machined from the 6 mm plaques to nominal dimensions of 6 x 6 x 80 mm. A hydraulic jig was used to introduce a notch of 1 mm depth circumferentially around the center of the specimen using a blade of notch tip radius of ~10 pm. The specimens were placed into the test grips with one end attached to a lever arm and the other to a location pin in the test bath. This ensured complete submergence in the 10% Caflon solution at 50 °C. Target stresses, between 4 and 6 MPa, were applied to the specimen by lowering a load using a scissor jack onto the lever arm. An automatic timer was used to record the time to failure and the ligament of the failed sample was measured using a travelling microscope to determine the true applied stress. The results were plotted on a time to fail (hours) vs calculated stress (MPa) graph. A best fit line was plotted through the data points and the time to fail value at 4.5 MPa was calculated.

Lumicene® mPE M3583 UV is a second generation metallocene medium density polyethylene (mMDPE) grade with hexene as the comonomer commercially available from Total Energies Refining and Chemicals.

Lumicene® mPE M 4041 UV is a new generation metallocene medium density polyethylene (mMDPE) with hexene as comonomer commercially available from TotalEnergies Refining and Chemicals.

The time to failure of the tested compositions for a range of applied stresses are reported in Figure 12. The rotomolded article prepared with E1 composition outperformed the comparative example prepared with CE1 and showed improved environmental stress crack (see Figure 12).

6 - Tensile test

For this test, the samples were rotomolded using the following parameters of the rotomolding cycle:

Heating of the oven to a temperature of about 310 °C;

PIAT (peak internal air temperature): about 220 °C;

Thickness of wall of bottles: 4.5 mm;

The tensile properties of cut bars from rotomolded bottles were measured using the methodology of Accelerated Characterization for long-term creep Prediction (MACcreeP) as described in Rotoworld magazines (www.rotoworldmag.com) Volume XIII, issue 6, December 2020-January 2021 pages 38-43; Volume XVII, issue 1 , March-April 2021 pages 44-48; Volume XVII, issue 2, June-July 2021 , pages 46-51. Tensile and creep tensile tests were performed on a testing machine equipped with a 500N load cell. The tests were performed at an isothermal temperature and the specimens were conditioned stress-free at the set temperature until stabilization. The true strains were computed from the displacement of four markers on the surface of the specimen. The tensile test were performed as a constant strain of 10'³ s’¹, at 23°C using a video traction apparatus. The longitudinal and transversal deformations were measured; each essay was repeated 6 times.

Table 7 and Figure 13 depicts the results of this test.

Table7

The rotomolded article prepared with E1 composition outperformed the comparative example prepared with CE1 higher stiffness for compositions with the same final density (Figure 13).

7 - Creep and recovery test

For this test, the samples were rotomolded using the following parameters of the rotomolding cycle: Heating of the oven to a temperature of about 310 °C;

PIAT (peak internal air temperature): about 220 °C;

Thickness of wall of bottles: 4.5 mm.

The creep properties of cut bars from rotomolded bottles were measured using the methodology of Accelerated Characterization for long-term creep Prediction (MACcreeP) as described in Rotoworld magazines (www.rotoworldmag.com) Volume XIII, issue 6, December 2020-January 2021 pages 38-43; Volume XVII, issue 1 , March-April 2021 pages 44-48; Volume XVII, issue 2, June-July 2021, pages 46-51. Creep tensile tests were performed on a testing machine equipped with a 500N load cell. The tests were performed at isothermal temperature and the specimens were conditioned stress-free at the set temperature until stabilization. Figure 14 depicts the results of this Creep test using 5MPa at 23 °C and 60 °C. Figures 15 and 16 depicts the results of this Creep test using 5MPa at 60 °C. The rotomolded article prepared with E1 composition outperformed the comparative example prepared with CE1 and showed lower shrinkage (Figures 14, 15, and 16).

Claims

(1) X is greater than - 0.026 ln(/W/_2>) + 0.0498

2. The metallocene-catalyzed polyethylene composition according to claim 1 , wherein metallocene-catalyzed ethylene polymer A has a melt index ratio HLMI/MI2 (also referred as MI21/MI2) of at most 40.0, preferably at most 38.0, preferably at most 37.0, preferably at most 36.0, preferably at most 35.0, preferably at most 34.0, preferably at most 33.0, preferably at most 30.0.

3. The metallocene-catalyzed polyethylene composition according to any one of claims 1-2, wherein metallocene-catalyzed ethylene polymer A has a molecular weight distribution M_z/Mn of at least 8.0 preferably a M_z/M_n of at least 8.5, preferably a M_z/M_n of at least 9.0, with M_z being the z average molecular weight and M_n being the number-average molecular weight.

4. The metallocene-catalyzed polyethylene composition according to any one of claims 1-3, wherein metallocene-catalyzed ethylene polymer A has a molecular weight distribution M_z/Mn of at most 20.0, preferably at most 18.0, preferably at most 15.0, with M_z being the z average molecular weight and M_n being the number-average molecular weight.

5. The metallocene-catalyzed polyethylene composition according to any one of claims 1-4, wherein metallocene-catalyzed ethylene polymer A has a M_z of at least 190000 Da, preferably at least 200000 Da, preferably at least 210000 Da, with M_z being the z average molecular weight.

6. The metallocene-catalyzed polyethylene composition according to any one of claims 1-5, wherein metallocene-catalyzed ethylene polymer B has a molecular weight distribution M_w/Mn of at least 2.0 to at most 4.0, with M_w being the weight-average molecular weight and M_n being the number-average molecular weight, preferably at least 2.0 to at most 3.5, preferably at least 2.0 to at most 3.0.

7. The metallocene-catalyzed polyethylene composition according to any one of claims 1-6, having a density ranging from at least 0.940 g/cm³ to at most 0.954 g/cm³, as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C, for example from at least 0.940 g/cm³ to at most 0.953 g/cm³, for example from at least 0.940 g/cm³ to at most 0.952 g/cm³, for example from at least 0.940 g/cm³ to at most 0.950 g/cm³.

8. The metallocene-catalyzed polyethylene composition according to any one of claims 1-7, having a melt index MI2 of at least 2.0 to at most 6.0 g/10 min wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm; preferably at most 5.5 g/10min; preferably at most 5.0 g/10 min.

9. The metallocene-catalyzed polyethylene composition according to any one of claims 1-8, having a M_n of at least 18000 g/mol with M_n being the number-average molecular weight, preferably of at least 19000 g/mol, preferably at least 20000 g/mol.

10. The metallocene-catalyzed polyethylene composition according to any one of claims 1-9, having a molecular weight distribution M_z/M_n of at most 10.0, with M_z being the z average molecular weight and M_n being the number-average molecular weight; preferably at most

9.5, preferably at most 9.0, preferably at most 8.5, preferably at most 8.0.

11 . The metal locene-catalyzed polyethylene composition according to any one of claims 1-10, having a zero shear viscosity q0 in Pa.s of at least 2900, preferably at least 3000, preferably at least 3200, preferably at least 3400, preferably at least 3500.

12. An article comprising the metallocene-catalyzed polyethylene composition according to any one of claims 1-11.

13. An article comprising the metallocene-catalyzed polyethylene composition according to any one of claims 1-11 , wherein the article is a rotomolded article or an injected article.

14. A rotomolded or an injection-molded article comprising the metallocene-catalyzed polyethylene composition according to any one of claims 1-11.

15. Use of a metallocene-catalyzed polyethylene composition according to any one of claims 1-11 , in rotomolding or injection molding applications.