FIELD OF INVENTION

The invention relates to the new dual catalyst compositions, in particular dual site catalyst compositions for polymerization reactions. This invention also relates to new ethylene polymers and to articles comprising said ethylene polymers.

BACKGROUND OF THE INVENTION

In the field of polymer, constant mechanical properties improvement is mandatory. It was achieved in the last few years using metallocene catalyst combined with cascade reactor to make tailor made bimodal resins. However, the requirement of multiple reactors leads to increased costs for both construction and operation, and this can be overcome using dual-site catalyst composition in a single reactor.

In the prior art, the first obvious strategy was multiple separate catalyst injection. Although, this process showed high flexibility, several drawbacks can be highlighted: multiple catalysts injections lead to increased costs and polymer homogeneity was difficult to achieve.

The strategy of using a dual-site catalyst in a single reactor seemed therefore to be a good alternative. However, this technology suffers from the difficulty to control properly the heterogenization and more importantly the activation. This might be related to the different behavior of metallocene during the heterogenization process typically leading to a dominating structure while others seem inactive. Moreover, in several examples in the literature, some combinations suffer of a lack of reactivity or works only in specific conditions or in a specific process. The challenge is to find the right combination of metallocenes to avoid these drawbacks.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a new dual catalyst avoiding the above-mentioned drawbacks.

The present invention provides dual catalyst composition containing a bridged bis-indenyl metallocene having meso stereoisomer geometry, each indenyl being independently substituted with one or more substituents, preferably wherein at least one of the substituents is on position 3 and/or 5 of each indenyl, preferably on position 3 of each indenyl, and a second metallocene with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group. The new compositions of the present invention give polyethylene products with unique molecular architectures and high density splits in a one reactor configuration. In a first aspect, the present invention provides a catalyst composition comprising: catalyst component A comprising the meso form of a bridged metallocene compound with two indenyl groups each indenyl being independently substituted with one or more substituents, wherein at least one of the substituents is an aryl or heteroaryl; wherein the meso/rac ratio of the meso form of the bridged metallocene compound of catalyst component A is 95:5 or greater, as determined using ¹ H NMR; preferably wherein at least one of the substituents is on position 3 and/or 5 of each indenyl, preferably wherein the aryl or heteroaryl substituent is on the 3-position of each indenyl; catalyst component B comprising a bridged metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; an optional activator; an optional support; and an optional co-catalyst.

In a second aspect, the present invention provides an olefin polymerization process, the process comprising: contacting at least one catalyst composition according to the first aspect, with an olefin monomer, optionally hydrogen, and optionally one or more olefin comonomers; and polymerizing the monomer, and the optionally one or more olefin comonomers, in the presence of the at least one catalyst composition, and optional hydrogen, thereby obtaining a polyolefin.

In a third aspect, the present invention provides, an olefin polymer at least partially catalyzed by at least one catalyst composition according to the first aspect or produced by the process according to the second aspect of the invention.

In a fourth aspect, the present invention provides a metal locene-catalyzed ethylene polymer, preferably prepared using a continuous process, and at least one metallocene catalyst composition, said metallocene-catalyzed ethylene polymer having: a melt index MI2 ranging from 0.1 g/10 min to 12.0 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; a molecular weight distribution M _w /M _n ranging from 4.0 to 12.0, with M _w being the weightaverage molecular weight and M _n being the number-average molecular weight; a rheology long chain branching index g _r heo of at least 0.90, preferably at least 0.93, preferably at least 0.95; and preferably at least 0.30 % by weight of ethyl branching with regard to the total weight of the ethylene polymer measured by ¹³ C NMR, with the proviso that said ethyl branching content is not generated from 1 -butene incorporation as comonomer.

The present invention also encompasses an article comprising the olefin polymer according to the third aspect, and/or the metallocene-catalyzed ethylene polymer according to the fourth aspect.

The invention overcomes the drawbacks of the aforementioned strategies. The invention provides a composition comprising a dual catalyst composition which means a catalyst particle with two metallocene active sites on a single carrier.

Such catalyst compositions can be used to produce, for example, ethylene-copolymers having broad molecular weight distributions, ideal comonomer incorporation to improve mechanical properties and a higher activity compared to other systems. The catalysts used in the present composition provide control for the targeted molecular architecture and afford an inverse comonomer distribution (comonomers concentrated in the higher molecular weight chains). For the co-polymerization of ethylene with an a-olefin, the dual catalyst composition provides a higher density split between the lower molecular weight and the higher molecular weight fractions (very low comonomer incorporation in the shorter chains versus the longer chains), in addition to very high catalyst activities. The lower molecular weight component can improve the product processability, while the high molecular weight component can enhance the mechanical properties.

Catalyst component A has very low comonomer incorporation and provides a low molecular weight high density product, while catalyst component B generates a low density, high molecular weight product with a low number of long chain branches.

The dual catalyst composition can provide polyethylene products with novel broad/bimodal molecular weight distributions, the desirable inverse comonomer incorporation, and improved processing/mechanical properties.

The catalyst composition can be used in single reactor processes (slurry loop and/or gas phase) or even in multimodal processes.

The present invention also provides ethylene polymers having broad molecular weight distributions, ideal co-monomer incorporation and improved processing and mechanical properties.

After the polymer is produced, it may be formed into various articles, including but not limited to, film products, caps and closures, liners, rotomoulding, grass yarn, etc.

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 ¹³ C{ ¹ H} NMR spectrum of a metallocene ethylene polymer.

Figure 2 represents a graph plotting the ¹ H NMR spectrum of meso-Met 1 (mMetl).

Figure 3 represents a graph plotting the GPC traces (i.e., the molecular weight distribution (logarithm of molecular weight)) of the polymers obtained with mMet1/Met2 compositions with varying weight ratio of each catalyst.

Figure 4 represents a graph plotting the log of the complex viscosity (| q*| Pa.s) as a function of the log of the angular frequency (co, rad/s) for the polymers obtained with mMet1/Met2 composition with varying weight ratio of each catalyst. Shear strain (y) 10 %, angular frequencies (co) expressed in log scale from -1 to 2.477 (i.e., from 0.1 to 300 s ^-1 ).

Figure 5 represents the van Gurp-Palmen plots of polymers obtained with mMet1/Met2 composition with varying weight ratio of each catalyst.

Figure 6 represents a graph plotting the productivity of resins A to I.

Figure 7 represents a graph plotting the melt index of resins A to I as a function of hydrogen/ethylene feed concentration.

Figure 8 represents a graph plotting the density of resins A to I as a function of 1- hexene/ethylene feed concentration.

Figure 9 represents a graph plotting the GPC traces of resins A to D.

Figure 10 represents a graph plotting the GPC traces of resins E to I.

Figure 11 represents a graph plotting the ratio CH3/CH2 (GPC-IR) as a function of the logarithm of molecular weight of resins E to I.

Figure 12 represents a graph plotting the log of the complex viscosity (|n*l Pa.s) as a function of the log of the angular frequency (co, rad/s) for resins A to D. Shear strain (y) 10 %, angular frequencies (co) expressed in log scale from -1 to 2.477 (i.e., from 0.1 to 300 s ^-1 ).

Figure 13 represents a graph plotting the log of the complex viscosity (|n*l Pa.s) as a function of the log of the angular frequency (co, rad/s) for resins E to I. Shear strain (y) 10 %, angular frequencies (co) expressed in log scale from -1 to 2.477 (i.e., from 0.1 to 300 s ^-1 ).

Figure 14 represents the van Gurp-Palmen plots of resins A to D. Figure 15 represents the van Gurp-Palmen plots of resins E to I.

Figure 16 represents a graph plotting the melt strength measured for resins A to D.

Figure 17 represents a graph plotting the melt strength measured for resins E to I.

Figure 18 represents a graph plotting the TREF (temperature rising elution fractionation) profile of resins E, F, H, I.

DETAILED DESCRIPTION OF THE INVENTION

Before the present compositions, compounds, 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, compounds, polymers, processes, articles, and uses described, as such compositions, compounds, 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 compounds, 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 polymer" means one polymer or more than one polymer.

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, cyclopentadienyl and fluorenyl groups, can be selected from the group comprising alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R ¹⁰ )3, heteroalkyl; wherein each R ¹⁰ is independently hydrogen, alkyl, or alkenyl. Preferably, each indenyl is substituted with at least one aryl or heteroaryl, more preferably aryl; preferably wherein the aryl or heteroaryl substituent is on the 3-position of each indenyl; the indenyl can be further substituted with one or more substituents selected from the group comprising alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R ¹⁰ )3, heteroalkyl; wherein each R ¹⁰ 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 _n H2n+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 _n H2n+i wherein n is a number ranging from 1 to 20. Thus, for example, “Ci- salkyl” 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 (-CH ₂ -), ethylene (-CH ₂ -CH ₂ -), methylmethylene (-CH(CH ₃ )-), 1-methyl-ethylene (-CH(CH ₃ )- CH ₂ -), n-propylene (-CH ₂ -CH ₂ -CH ₂ -), 2-methylpropylene (-CH ₂ -CH(CH ₃ )-CH ₂ -), 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 C3-20alkenyl 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, tert- butoxy, 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 “C _3-20 cycloalkyl”, a cyclic alkyl group comprising from 3 to 20 carbon atoms. For example, the term “C _3-10 cycloalkyl”, a cyclic alkyl group comprising from 3 to 10 carbon atoms. For example, the term “C _3-8 cycloalkyl”, a cyclic alkyl group comprising from 3 to 8 carbon atoms. For example, the term “C ₃ .6cycloalkyl”, 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 C ₃ alkylene group may be for example *-CH ₂ CH ₂ CH ₂ -*, *-CH(-CH ₂ CH ₃ )-* or *-CH ₂ CH(-CH ₃ )-*. Likewise, a C ₃ cycloalkylene 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 “C5-2ocycloalkenyl”, a cyclic alkenyl group comprising from 5 to 20 carbon atoms. For example, the term “Cs-iocycloalkenyl”, 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 C _6-20 aryl, preferably C _6-10 aryl, more preferably C _6-8 aryl. 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 example 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 ^k R ^l wherein R ^j is alkylene, R ^k is hydrogen or alkyl as defined herein, and R ^l 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 membered monocyclic group, 7 to 10 membered bicyclic group) preferably 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 multiring 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 catalyst composition comprising: catalyst component A comprising the meso form of a bridged metallocene compound with two indenyl groups each indenyl being independently substituted with one or more substituents, wherein at least one of the substituents is an aryl or heteroaryl, preferably wherein the meso/rac ratio of the meso form of the bridged metallocene compound of catalyst component A is preferably 95:5 or greater, as determined using ¹ H NMR; preferably wherein at least one of the substituents is aryl; preferably wherein at least one of the substituents is on position 3 and/or 5 of each indenyl, preferably each indenyl has one substituent on position 3, preferably each indenyl has one substituent on position 5, yet more preferably each indenyl has one substituent on position 3 and one substituent on position 5 of each indenyl, preferably the aryl or heteroaryl substituent is on 3-position of each indenyl; catalyst component B comprising a bridged metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; an optional activator; an optional support; and an optional co-catalyst.

2. A catalyst composition comprising: catalyst component A comprising the meso form of a bridged metallocene compound with two indenyl groups each indenyl being independently substituted with one or more substituents, wherein at least one of the substituents is an aryl or heteroaryl, preferably wherein the meso/rac ratio of the meso form of the bridged metallocene compound of catalyst component A is preferably 95:5 or greater, as determined using ¹ H NMR; preferably wherein at least one of the substituents is aryl; preferably wherein at least one of the substituents is on position 3 and/or 5 of each indenyl, preferably each indenyl has one substituent on position 3, preferably each indenyl has one substituent on position 5, yet more preferably each indenyl has one substituent on position 3 and one substituent on position 5 of each indenyl, preferably the aryl or heteroaryl substituent is on 3-position of each indenyl; catalyst component B comprising a bridged metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; an activator; a support; and an optional co-catalyst. The catalyst composition according to any one of statements 1-2, wherein the meso/rac ratio of the meso form of the bridged metallocene compound of catalyst component A is preferably 95:5 or greater, as determined using ¹ H NMR. The composition according to any one of statements 1-3, wherein the weight ratio of catalyst component A to catalyst component B is in a range of from 10/90 to 90/10, preferably in the range of from 15/85 to 80/20, preferably in the range of from 20/80 to 70/30, preferably in the range of from 20/80 to 60/40, preferably in the range of from 20/80 to 50/50, preferably in the range of from 20/80 to 40/60, more preferably in the range of from 25/75 to 35/65, preferably 28/72 to 33/67, preferably 29/71 to 32/68, preferably 29/71 to 31/69, preferably 30/70. The composition according to any one of statements 1-4, wherein the bridged metallocene compound of catalyst component B comprises at least one alkenyl, cycloalkenyl, or cycloalkenylalkyl substituent, preferably at least one C3-2oalkenyl, C5-2ocycloalkenyl, or Ce- 2ocycloalkenylalkyl substituent, more preferably at least one Cs-salkenyl, Cs-scycloalkenyl, or Ce-scycloalkenylalkyl substituent. The composition according to any one of statements 1-5, wherein the bridged metallocene compound of catalyst component B comprises at least one alkenyl, cycloalkenyl, or cycloalkenylalkyl substituent on the bridge; preferably at least one C3-2oalkenyl, Cs- 2ocycloalkenyl, or C6-2ocycloalkenylalkyl substituent, more preferably at least one C3- salkenyl, Cs-scycloalkenyl, or Ce-scycloalkenylalkyl substituent. The composition according to any one of statements 1-6, wherein catalyst component A contains a Si, or C bridging atom, optionally substituted with a one or two substituents each independently selected from alkyl, alkenyl, cycloalkyl, or cycloalkenyl. The composition according to any one of statements 1-7, wherein catalyst component B contains a C, Si, B or Ge bridging atom. The composition according to any one of statements 1-8, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof, preferably wherein the activator comprises an alumoxane compound. The composition according to any one of statements 1-9, wherein the activator comprises at least one alumoxane compound of formula (V) or (VI) R ^a -(AI(R ^a )-O) _x -AIR ^a 2 (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. The composition according to any one of statements 1-10, wherein the activator is methyl alumoxane. The composition according to any one of statements 1-11 wherein the catalyst composition comprises a co-catalyst. The composition according to any one of statements 1-12 wherein the catalyst composition comprises an organoaluminum co-catalyst. The composition according to any one of statements 1-13, wherein the catalyst composition comprises an organoaluminum co-catalyst selected from the group comprising 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. The composition according to any one of statements 1-14, wherein the support comprises a solid oxide, preferably a solid inorganic oxide, preferably, 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. The composition according to any one of statements 1-15, wherein the support has a D50 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 particle size may be measured by laser diffraction analysis on a Malvern type analyzer. The composition according to any one of statements 1-16, comprising an alumoxane activator; and a titanated silica or silica solid support; and an optional co-catalyst. The composition according to any one of statements 1-17, wherein catalyst component A comprises the meso form of a bridged metallocene catalyst of formula (I), wherein each of R ¹ , and R ³ , are independently selected from the group comprising alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R ¹⁰ )3, and heteroalkyl; wherein at least one of R ¹ or R ³ is aryl, wherein each R ¹⁰ is independently hydrogen, alkyl, or alkenyl; and m, p, are each independently an integer selected from 0, 1 , 2, 3, or 4, wherein at least one of m or p is at least 1 ; each of R ² , and R ⁴ , are independently selected from the group comprising alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R ¹⁰ )3, and heteroalkyl; wherein at least one of R ² or R ⁴ is aryl, wherein each R ¹⁰ is independently hydrogen, alkyl, or alkenyl; and n, q are each independently an integer selected from 0, 1 , 2, 3, or 4, wherein at least one of n or q is at least 1 ;

L ¹ is SiR ⁸ R ⁹ , -[CR ⁸ R ⁹ ]h-, GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1 , 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl;

M ¹ is a transition metal selected from the group comprising zirconium, titanium, hafnium, and vanadium; and preferably M is zirconium; and

Q ¹ and Q ² are each independently selected from the group comprising halogen, alkyl, - N(R ¹¹ ) ₂ , alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R ¹¹ is hydrogen or alkyl. The composition according to any one of statements 1-18, wherein the catalyst component A contains a SiR ⁸ R ⁹ , or -[CR ⁸ R ⁹ ]h- bridging group; preferably a SiR ⁸ R ⁹ bridging group; wherein h is an integer selected from 1 , 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl, preferably alkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl. 20. The composition according to any one of statements 1-19, wherein catalyst component A comprises the meso form of a bridged metallocene of formula (I), wherein each of R ¹ , R ³ are independently selected from the group comprising C1-20alkyl, C3- 20alkenyl, C3-20cycloalkyl, C5-20cycloalkenyl, C6-20cycloalkenylalkyl, C6-20aryl, C1-20alkoxy, C7- alkylaryl, C arylalkyl, halo ¹⁰ 1 20 7-20 gen, Si(R )3, and heteroC1-12alkyl; wherein at least one of R or R ³ is C6-20aryl, preferably phenyl; wherein each R ¹⁰ is independently hydrogen, C1-20alkyl, or C3-20alkenyl; and m, p, are each independently an integer selected from 0, 1, 2, 3, or 4, wherein at least one of m or p is at least 1; each of R ² , R ⁴ are independently selected from the group comprising C1-20alkyl, C3- 20alkenyl, C3-20cycloalkyl, C5-20cycloalkenyl, C6-20cycloalkenylalkyl, C6-20aryl, C1-20alkoxy, C7- alkylaryl, C arylalkyl, halogen, Si(R ¹⁰ ) , and heteroC al 2 20 7-20 3 1-12 kyl; wherein at least one of R or R ⁴ is C6-20aryl, preferably phenyl; wherein each R ¹⁰ is independently hydrogen, C1-20alkyl, or C3-20alkenyl; and n, q are each independently an integer selected from 0, 1, 2, 3, or 4, wherein at least one of n or q is at least 1; L ¹ is SiR ⁸ R ⁹ , -[CR ⁸ R ⁹ ]h-, GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1, 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C _{1- 20} alkyl, C _3-20 alkenyl, C ₃ - ₂₀ cycloalkyl, C _5-20 cycloalkenyl, C _6-20 cycloalkenylalkyl, C _6-10 aryl, aminoC _1-6 alkyl, and C ₇ -C ₂₀ arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a C _3-20 cycloalkyl, C _5-20 cycloalkenyl or heterocyclyl; preferably L ¹ is SiR ⁸ R ⁹ ; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C _{1- 20} alkyl, C _3-20 alkenyl, C ₃ - ₂₀ cycloalkyl, C _5-20 cycloalkenyl, C _6-20 cycloalkenylalkyl, C _6-10 aryl, aminoC _1-6 alkyl, and C ₇ -C ₂₀ arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a C _3-20 cycloalkyl, C _5-20 cycloalkenyl or heterocyclyl; preferably each of R ⁸ , and R ⁹ are independently C _1-6 alkyl; M ¹ is a transition metal selected from the group comprising zirconium, titanium, hafnium, and vanadium; and preferably M is zirconium; and Q ¹ and Q ² are each independently selected from the group consisting of halogen, C _1-20 alkyl, -N(R ¹¹ ) ₂ , C _1-20 alkoxy, C _3-20 cycloalkoxy, C _7-20 aralkoxy, C _3-20 cycloalkyl, C _6-20 aryl, C _{7- 20} alkylaryl, C _7-20 aralkyl, and heteroC _1-20 alkyl; wherein R ¹¹ is hydrogen or C _1-20 alkyl. 21. The composition according to any one of statements 18-20, wherein each of R ¹ , and R ³ are independently selected from the group comprising C _1-8 alkyl, C _{3- 8} alkenyl, C _3-8 cycloalkyl, C _5-8 cycloalkenyl, C _6-8 cycloalkenylalkyl, C _6-10 aryl, C _1-8 alkoxy, C _{7- 12} alkylaryl, C _7-12 arylalkyl, halogen, Si(R ¹⁰ ) ₃ , and heteroC _1-8 alkyl; wherein at least one of R1 or R ³ is C _6-10 aryl, preferably phenyl; wherein each R ¹⁰ is independently hydrogen, C _1-8 alkyl, or C _3-8 alkenyl; and m, p, are each independently an integer selected from 0, 1, 2, 3, or 4, wherein at least one of m or p is at least 1; each of R ² , and R ⁴ , are independently selected from the group comprising C _1-8 alkyl, C _{3- 8} alkenyl, C _3-8 cycloalkyl, C _5-8 cycloalkenyl, C _6-8 cycloalkenylalkyl, C _6-10 aryl, C _1-8 alkoxy, C _{7- 12} alkylaryl, C _7-12 arylalkyl, halogen, Si(R ¹⁰ ) ₃ , and heteroC _1-8 alkyl; wherein at least one of R ² or R ⁴ is C6-10aryl, preferably phenyl; wherein each R ¹⁰ is independently hydrogen, C1-8alkyl, or C3-8alkenyl; and n, q are each independently an integer selected from 0, 1, 2, 3, or 4, wherein at least one of n or q is at least 1; L ¹ is SiR ⁸ R ⁹ , -[CR ⁸ R ⁹ ]h-, GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1, 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C1- 8alkyl, C3-8alkenyl, C3-8cycloalkyl, C5-8cycloalkenyl, C6-8cycloalkenylalkyl, C6-10aryl, aminoC1-6alkyl, and C7-C12arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a C3-8cycloalkyl, C5-8cycloalkenyl or heterocyclyl; preferably L ¹ is SiR ⁸ R ⁹ ; preferably each of R ⁸ , and R ⁹ are independently selected from hydrogen, or C1-8alkyl; M ¹ is a transition metal selected from the group comprising zirconium, titanium, hafnium, and vanadium; and preferably M is zirconium; and Q ¹ and Q ² are each independently selected from the group comprising halogen, C1-8alkyl, -N(R ¹¹ )2, C1-8alkoxy, C3-8cycloalkoxy, C7-12aralkoxy, C3-8cycloalkyl, C6-10aryl, C7-12alkylaryl, C7-12aralkyl, and heteroC1-8alkyl; wherein R ¹¹ is hydrogen or C1-8alkyl. 22. The composition according to any one of statements 18-21, wherein each of R ¹ , and R ³ are independently selected from the group comprising C1-8alkyl, C3- 8alkenyl, C3-8cycloalkyl, C6-10aryl, and halogen; wherein at least one of R ¹ or R ³ is C6-10aryl, preferably phenyl; and m, p, 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, wherein at least one of m or p is at least 1; each of R ² , and R ⁴ , are independently selected from the group comprising C _1-8 alkyl, C _{3- 8} alkenyl, C _3-8 cycloalkyl, C _6-10 aryl, and halogen; wherein at least one of R ² or R ⁴ is C _6-10 aryl, preferably phenyl; and n, q 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, wherein at least one of n or q is at least 1; L ¹ is SiR ⁸ R ⁹ , or -[CR ⁸ R ⁹ ] _h -; wherein h is an integer selected from 1, or 2; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C _1-8 alkyl, C _3-8 alkenyl, C ₃ - ₈ cycloalkyl; C _5-8 cycloalkenyl, C _6-8 cycloalkenylalkyl, and C _6-10 aryl; preferably L ¹ is SiR ⁸ R ⁹ ; preferably each of R ⁸ , and R ⁹ are independently selected from hydrogen, or C _1-8 alkyl; M ¹ is a transition metal selected from zirconium, or hafnium; and preferably M is zirconium; and Q ¹ and Q ² are each independently selected from the group comprising halogen, C _1-8 alkyl, -N(R ¹¹ ) ₂ , C _6-10 aryl, and C _7-12 aralkyl; wherein R ¹¹ is hydrogen or C _1-8 alkyl, preferably Q ¹ and Q ² are each independently selected from the group comprising Cl, F, Br, I, methyl, benzyl, and phenyl. 23. The composition according to any one of statements 1-22, wherein catalyst component A comprises the meso form of bridged metallocene of formula (Ia) wherein R ¹ , R ² , R ³ , R ⁴ , L ¹ , M ¹ , Q ¹ , Q ² , p and q have the same meaning as that defined in any one of statements 18-22, preferably wherein R ¹ and R ² are each independently C6- 1 ₀ aryl. 24. The composition according to any one of statements 1-23, wherein catalyst component A comprises the meso form of bridged metallocene of formula (Ib) wherein R ¹ , R ² , R ³ , R ⁴ , L ¹ , M ¹ , Q ¹ , and Q ² , have the same meaning as that defined in any one of statements 18-22, preferably wherein R ¹ and R ² are each independently C6-10aryl. The composition according to any one of statements 1-24, wherein catalyst component A comprises meso bridged metallocene of formula (Ic) The composition to any one of statements 1-25, wherein catalyst component B comprises a bridged metallocene of formula (II), wherein each of R ⁵ , R ⁶ , and R ⁷ , are independently selected from the group comprising alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R ¹⁰ )3, and heteroalkyl; wherein each R ¹⁰ is independently hydrogen, alkyl, or alkenyl; and r, s, t are each independently an integer selected from 0, 1 , 2, 3, or 4;

L ² is -[CR ⁸ R ⁹ ]h-, SiR ⁸ R ⁹ , GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1 , 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl;

M ² is a transition metal selected from the group comprising zirconium, titanium, hafnium, and vanadium; and preferably is zirconium; and

Q ³ and Q ⁴ are each independently selected from the group comprising halogen, alkyl, - N(R ¹¹ ) ₂ , alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R ¹¹ is hydrogen or alkyl. The composition according to any one of statements 1-26, wherein catalyst component B comprises a bridged metallocene of formula (II), wherein each of R ⁵ , R ⁶ , and R ⁷ , are independently selected from the group consisting of C _1-20 alkyl, C _3-20 alkenyl, C _3-20 cycloalkyl, C _5-20 cycloalkenyl, C _6-20 cycloalkenylalkyl, C _6-20 aryl, C _1-20 alkoxy, C _7-20 alkylaryl, C _7-20 arylalkyl, halogen, Si(R ¹⁰ ) ₃ , and heteroC _1-20 alkyl; wherein each R ¹⁰ is independently hydrogen, C _1-20 alkyl, or C _3-20 alkenyl; and r, s, t are each independently an integer selected from 0, 1, 2, 3, or 4; L ² is -[CR ⁸ R ⁹ ]h-, SiR ⁸ R ⁹ , GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1, 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group consisting of hydrogen, C1- 20alkyl, C3-20alkenyl, C3-20 cycloalkyl, C5-20cycloalkenyl, C6-20cycloalkenylalkyl, C6-10aryl, aminoC1-6alkyl, and C7-C20arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a C3-20cycloalkyl, C5-20cycloalkenyl or heterocyclyl; M ² is a transition metal selected from the group comprising zirconium, titanium, hafnium, and vanadium; and preferably is zirconium; and Q ³ and Q ⁴ are each independently selected from the group comprising halogen, C1-20alkyl, -N(R ¹¹ )2, C1-20alkoxy, C3-20cycloalkoxy, C7-20aralkoxy, C3-20cycloalkyl, C6-20aryl, C7- 20alkylaryl, C7-20aralkyl, and heteroC1-20alkyl; wherein R ¹¹ is hydrogen or C1-20alkyl. 28. The composition according to any one of statements 26-27, wherein each of R ⁵ , R ⁶ , and R ⁷ , are independently selected from the group comprising C1-8alkyl, C3- 8alkenyl, C3-8cycloalkyl, C5-8cycloalkenyl, C6-8cycloalkenylalkyl, C6-10aryl, C1-8alkoxy, C7- 12alkylaryl, C7-12arylalkyl, halogen, Si(R ¹⁰ )3, and heteroC1-8alkyl; wherein each R ¹⁰ is independently hydrogen, C1-8alkyl, or C3-8alkenyl; and r, s, t are each independently an integer selected from 0, 1, 2, 3, or 4; L ² is -[CR ⁸ R ⁹ ]h-, SiR ⁸ R ⁹ , GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1, 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C1- 8alkyl, C3-8alkenyl, C3-8cycloalkyl, C5-8cycloalkenyl, C6-8cycloalkenylalkyl, C6-10aryl, aminoC1-6alkyl, and C7-C12arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a C _3-8 cycloalkyl, C _5-8 cycloalkenyl or heterocyclyl; M ² is a transition metal selected from the group comprising zirconium, titanium, hafnium, and vanadium; and preferably is zirconium; and Q ³ and Q ⁴ are each independently selected from the group comprising halogen, C _1-8 alkyl, -N(R ¹¹ ) ₂ , C _1-8 alkoxy, C _3-8 cycloalkoxy, C _7-12 aralkoxy, C _3-8 cycloalkyl, C _6-10 aryl, C _7-12 alkylaryl, C _7-12 aralkyl, and heteroC _1-8 alkyl; wherein R ¹¹ is hydrogen or C _1-8 alkyl. 29. The composition according to any one of statements 26-28, wherein each of R ⁵ , R ⁶ , and R ⁷ , is independently selected from the group comprising C _1-8 alkyl, C _{3- 8} alkenyl, C _3-8 cycloalkyl, C _6-10 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; L ² is -[CR ⁸ R ⁹ ] _h -, or SiR ⁸ R ⁹ ; wherein h is an integer selected from 1, or 2; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C1-8alkyl, C3-8alkenyl, C3-8cycloalkyl; C5-8cycloalkenyl, C6-8cycloalkenylalkyl, and C6-10aryl; M ² is a transition metal selected from zirconium, or hafnium; and preferably zirconium; and Q ³ and Q ⁴ are each independently selected from the group comprising halogen, C1-8alkyl, -N(R ¹¹ )2, C6-10aryl, and C7-12aralkyl; wherein R ¹¹ is hydrogen or C1-8alkyl, preferably Q ¹ and Q ² are each independently selected from the group comprising Cl, F, Br, I, methyl, benzyl, and phenyl. 30. The composition according to any one of statements 1-29, wherein catalyst component A comprises a bridged metallocene of formula (IIa), wherein R ⁵ , R ⁶ , R ⁷ , L ² , M ² , Q ³ , Q ⁴ , and r have the same meaning as that defined in any one of statements 26-29, preferably each R ⁶ and R ⁷ is C _1-8 alkyl. 31. The composition according to any one of statements 1-30, wherein catalyst component B comprises a bridged metallocene of formula (IIb), wherein R ⁶ , R ⁷ , L ² , M ² , Q ³ , Q ⁴ , have the same meaning as that defined in any one of statements 26-29, preferably each R ⁶ and R ⁷ is C _1-8 alkyl. 32. The composition according to any one of statements 1-31, wherein catalyst component B comprises a bridged metallocene of formula (IIc), wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ , M ² , Q ³ , Q ⁴ , have the same meaning as that defined in any one of statements 26-29, preferably each R ⁶ and R ⁷ is C _1-8 alkyl. 33. The composition according to any one of statements 1-32, wherein catalyst component B comprises a bridged metallocene of formula (IId), 34. The composition according to any one of statements 1-33, wherein the meso/rac ratio of the meso form of the bridged metallocene compound of catalyst component A is 95:5 or greater, and the weight ratio of catalyst component A to catalyst component B is in a range of from 20/80 to 50/50, preferably in the range of from 20/80 to 40/60, preferably in the range of from 25/75 to 35/65, preferably 28/72 to 33/67, preferably 29/71 to 32/68, preferably 29/71 to 31/69, preferably 30/70. 35. The composition according to any one of statements 1-34, wherein the meso/rac ratio of the meso form of the bridged metallocene compound of catalyst component A is 90: 10 or greater, preferably 95:5 or greater, and wherein the weight ratio of catalyst component A to catalyst component B is in a range of from preferably in the range of from 25/75 to 35/65, preferably 28/72 to 33/67, preferably 29/71 to 32/68, preferably 29/71 to 31/69, preferably 30/70.

36. An olefin polymerization process, the process comprising: contacting a catalyst composition according to any one of statements 1-35, with an olefin monomer, optionally hydrogen, and optionally one or more olefin comonomers; and polymerizing the monomer, and the optionally one or more olefin comonomers, in the presence of the at least one catalyst composition, and optional hydrogen, thereby obtaining a polyolefin.

37. The process according to statement 36, wherein the process is performed in the slurry phase or gas phase or liquid phase, preferably in the slurry phase.

38. The process according to any one of statements 36-37, wherein the process is 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.

39. The process according to any one of statements 36-38, wherein the process is conducted in a single reaction zone.

40. The process according to any one of statements 36-39, wherein the polymerization can be carried out batchwise or in a continuous process.

41. The process according to any one of statements 36-40, wherein the polymerization is carried out in a continuous process.

42. The process according to any one of statements 36-41 , wherein the olefin monomer is ethylene, and the olefin comonomer comprises propylene, 1 -butene, 2-butene, 3-methyl- 1 -butene, isobutylene, 1 -pentene, 2-pentene, 3-methyl-l-pentene, 4-methyl-1 -pentene, 1- hexene, 2-hexene, 3-ethyl-1 -hexene, 1 -heptene, 2-heptene, 3-heptene, 1 -octene, 1- decene, styrene, or a mixture thereof; preferably the olefin comonomer is 1 -hexene.

43. The process according to any one of statements 36-41 , wherein the olefin monomer is propylene, and the olefin comonomer comprises ethylene, 1 -butene, 2-butene, 3-methyl- 1 -butene, isobutylene, 1 -pentene, 2-pentene, 3-methyl-1 -pentene, 4-methyl-1 -pentene, 1- hexene, 2-hexene, 3-ethyl-l-hexene, 1 -heptene, 2-heptene, 3-heptene, 1 -octene, 1- decene, styrene, or a mixture thereof.

44. The process according to any one of statements 36-42, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a molecular weight distribution M _w /M _n ranging from 4.0 to 12.0, preferably from 4.0 to 10.0, preferably from 4.0 to 9.0, preferably from 4.0 to 8.5, preferably 4.1 to 8.0, preferably from 4.1 to 7.6, preferably from 4.1 to 7.0, preferably from 4.0 to 6.5, preferably from 4.0 to 6.0, preferably from 4.0 to 5.8, with M _w being the weight-average molecular weight and M _n being the number-average molecular weight. The process according to any one of statements 36-42, 44, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a molecular weight distribution M _z /M _w of at most 7.0, with M _z being the z average molecular weight, preferably at most 6.0, preferably at most 5.5, preferably at most 4.0, preferably at most 3.5, preferably at least 2.0, preferably at least 2.5. The process according to any one of statements 36-42, 44-45, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a molecular weight distribution M _z /M _n of at least 8.0, with M _z being the z average molecular weight and M _n being the number-average molecular weight, preferably at least 9.0, preferably at least 9.5, preferably at least 10.0, preferably at least 10.5, preferably at most 25.0, preferably at most 22.5, preferably at most 20.0. The process according to any one of statements 36-42, 44-46, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having at least 0.30 % by weight of ethyl branching with regard to the total weight of the ethylene polymer, as determined by ¹³ C NMR analysis, preferably at least 0.31 % by weight of ethyl branching, preferably at least 0.32 % by weight of ethyl branching, preferably at least 0.33 % by weight of ethyl branching, preferably at least 0.34 % by weight of ethyl branching, preferably at least 0.35 % by weight of ethyl branching, preferably at most 1.20 % by weight of ethyl branching, preferably at most 1.10 % by weight of ethyl branching, preferably at most 1.00 % by weight of ethyl branching, preferably at most 0.98 % by weight of ethyl branching, with the proviso that said ethyl branching is not generated from 1 -butene comonomer incorporation; and/or with the proviso that the optional comonomer used in the process is not 1 -butene. The process according to any one of statements 36-42, 44-47, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a total comonomer content, for example 1 -hexene content, relative to the total weight of the ethylene polymer ranging from 0.0 % by weight to 15.0 % by weight, as determined by ¹³ C NMR analysis, preferably from 0.0% by weight to 10.0 % by weight, preferably from 0.0% by weight to 9.0 % by weight. The process according to any one of statements 36-42, 44-48, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a melt index MI2 ranging from 0.1 g/10 min to 12.0 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 from 0.2 g/10 min to 11.0 g/10 min, preferably from 0.3 g/10 min to 10.0 g/10 min. The process according to any one of statements 36-42, 44-49, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a melt index HLMI ranging from 10.0 g/10 min to 300.0 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 ranging from 11.0 g/10 min to 280.0 g/10 min, preferably an HLMI ranging from 12.0 g/10 min to 270.0 g/10 min, preferably an HLMI ranging from 12.0 g/10 min to 270.0 g/10 min, preferably an HLMI ranging from 13.0 g/10 min to 260.0 g/10 min. The process according to any one of statements 36-42, 44-50, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a melt index MI5 ranging from 0.5 g/10 min to 30.0 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 0.7 g/10 min to 28.0 g/10 min, preferably from 1.0 g/10 min to 25.0 g/10 min. The process according to any one of statements 36-42, 44-51 , wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a melt index ratio HLMI/MI2 of at most 40.0; preferably at most 35.0, preferably at least 15.0, preferably at least 20.0. The process according to any one of statements 36-42, 44-52, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a melt index ratio HLMI/MI5 of at most 20.0; preferably at most 15.0, preferably at least 5.0, preferably at least 7.0. The process according to any one of statements 36-42, 44-53, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a rheology long chain branching index g _r heo of at least 0.90, preferably at least 0.93, preferably at least 0.94. The process according to any one of statements 36-42, 44-54, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a density of at least 0.910 g/cm ³ as measured according to the method of standard ISO 1183- 1 :2012 method A at a temperature of 23 °C. The process according to any one of statements 36-42, 44-55, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a density of at most 0.965 g/cm ³ as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; preferably at most 0.963 g/cm ³ , preferably at least 0.910 g/cm ³ , preferably at least 0.915 g/cm ³ . The process according to any one of statements 36-42, 44-56, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a density ranging from 0.910 g/cm ³ to 0.965 g/cm ³ , preferably ranging from 0.915 g/cm ³ to 0.960 g/cm ³ , as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C. The process according to any one of statements 36-42, 44-57, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having: a density ranging from 0.910 g/cm ³ to 0.965 g/cm ³ , preferably ranging from 0.915 g/cm ³ to 0.960 g/cm ³ , as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; and at least 0.30 % to at most 1.20 % by weight of ethyl branching with regard to the total weight of the ethylene polymer, as determined by ¹³ C NMR analysis, preferably at least 0.31 at most 1.20 % by weight of ethyl branching, preferably at least 0.31 % to at most 1.10 % by weight of ethyl branching, preferably at least 0.32 % to at most 1 .00 % by weight of ethyl branching, preferably at least 0.33 % to at most 0.98 % by weight of ethyl branching, preferably at least 0.34 % to at most 0.98 % by weight of ethyl branching, preferably at least 0.35 % to at most 0.98 % by weight of ethyl branching; preferably wherein the optional comonomer is not 1 -butene. The process according to any one of statements 36-42, 44-58, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having at least one melting temperature T _m determined by DSC below 132 °C, preferably in the range of 100 °C to below 132 °C, more preferably in the range of 110 °C to 132 °C, still more preferably in the range of 120 °C to 132 °C. The process according to any one of statements 36-42, 44-59, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer wherein the Temperature Rising Elution Fractionation (TREF) distribution curve of the ethylene polymer comprises at least one peak appearing at a temperature of at least 96.0 °C to at most 105 °C and having an area under the curve of at least 20.0 % to at most 100.0 %. The process according to statement 60, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer wherein when the density of the polymer is below 0.938 g/cm ³ , the Temperature Rising Elution Fractionation (TREF) distribution curve of the metallocene-catalyzed ethylene polymer comprises at least one second peak appearing at a temperature of at least 65.0 °C to at most 92.0 °C and having an area under the curve of at least 60.0 % to at most 75.0 %. The process according to statement 60, wherein the olefin monomer is ethylene, and comprises the step of contacting ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer wherein when the density of the polymer is below 0.925 g/cm ³ , the Temperature Rising Elution Fractionation (TREF) distribution curve of the metallocene-catalyzed ethylene polymer comprises at least one second peak appearing at a temperature of at least 65.0 °C to at most 73.0 °C and having an area under the curve of at least 60.0 % to at most 75.0 %. An olefin polymer at least partially catalyzed by at least one catalyst composition according to any one of statements 1-35 or produced by the process according to any one of statements 36-62. The olefin polymer according to statement 63, wherein said olefin polymer is an ethylene polymer. A metallocene-catalyzed ethylene polymer having: a melt index MI2 ranging from 0.1 g/10 min to 12.0 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; and a molecular weight distribution M _w /M _n ranging from 4.0 to 12.0, with M _w being the weightaverage molecular weight and M _n being the number-average molecular weight, preferably from 4.0 to 10.0, preferably from 4.0 to 9.0, preferably from 4.0 to 8.5, preferably 4.1 to 8.0, preferably from 4.1 to 7.6, preferably from 4.1 to 7.0. The metallocene-catalyzed ethylene polymer according to statement 65, having at least 0.30 % by weight of ethyl branching with regard to the total weight of the ethylene polymer measured by ¹³ C NMR, wherein said ethyl branching are not generated from using 1- butene as comonomer; preferably wherein said ethylene polymer is a homopolymer or a copolymer obtained by polymerization of ethylene and of at least one comonomer, preferably wherein said comonomer is not 1 -butene. The metallocene-catalyzed ethylene polymer according to statement 65 or 66, having at least 0.30 % by weight of ethyl branching with regard to the total weight of the ethylene polymer measured by ¹³ C NMR, wherein said ethylene polymer is a homopolymer or a copolymer obtained by polymerization of ethylene and of at least one comonomer, preferably wherein said comonomer is not 1 -butene. A metallocene-catalyzed ethylene polymer having: a melt index MI2 ranging from 0.1 g/10 min to 12.0 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; a molecular weight distribution M _w /M _n ranging from 4.0 to 12.0, with M _w being the weightaverage molecular weight and M _n being the number-average molecular weight, preferably from 4.0 to 10.0, preferably from 4.0 to 9.0, preferably from 4.0 to 8.5, preferably 4.1 to 8.0, preferably from 4.1 to 7.6, preferably from 4.1 to 7.0; and at least 0.30 % by weight of ethyl branching with regard to the total weight of the ethylene polymer measured by ¹³ C NMR, wherein said ethyl branching are not generated from using 1 -butene as comonomer; preferably wherein said ethylene polymer is a homopolymer or a copolymer obtained by polymerization of ethylene and of at least one comonomer, preferably wherein said comonomer is not 1 -butene. The metallocene-catalyzed ethylene polymer according to any one of statements 65-68, having a rheology long chain branching index g _r heo of at least 0.90, preferably at least 0.93, preferably at least 0.94. A metallocene-catalyzed ethylene polymer having: a melt index MI2 ranging from 0.1 g/10 min to 12.0 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; a molecular weight distribution M _w /M _n ranging from 4.0 to 12.0, preferably from 4.0 to 8.5, with M _w being the weight-average molecular weight and M _n being the number-average molecular weight; a rheology long chain branching index g _r heo of at least 0.90, preferably at least 0.93, preferably at least 0.95; and at least 0.30 % by weight of ethyl branching with regard to the total weight of the ethylene polymer as determined by ¹³ C NMR; preferably wherein said ethylene polymer is a homopolymer or a copolymer obtained by polymerization of ethylene and of at least one comonomer, preferably wherein said comonomer is not 1 -butene. A metallocene-catalyzed ethylene polymer having: a melt index MI2 ranging from 0.1 g/10 min to 12.0 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; a molecular weight distribution M _w /M _n ranging from 4.0 to 12.0, with M _w being the weightaverage molecular weight and M _n being the number-average molecular weight, preferably from 4.0 to 10.0, preferably from 4.0 to 9.0, preferably from 4.0 to 8.5, preferably 4.1 to 8.0, preferably from 4.1 to 7.6, preferably from 4.1 to 7.0; and having a rheology long chain branching index g _r heo of at least 0.93, preferably at least 0.94, preferably at least 0.95. The metallocene-catalyzed ethylene polymer according to any one of statements 65-71 , having at least 0.31 % by weight of ethyl branching with regard to the total weight of the ethylene polymer, as determined by ¹³ C NMR analysis, preferably at least 0.32 % by weight of ethyl branching, preferably at least 0.33 % by weight of ethyl branching, preferably at least 0.34 % by weight of ethyl branching, preferably at least 0.35 % by weight of ethyl branching, preferably at most 1 .20 % by weight of ethyl branching, preferably at most 1.10 % by weight of ethyl branching, preferably at most 1.00 % by weight of ethyl branching, preferably at most 0.98 % by weight of ethyl branching, with the proviso that said ethyl branching is without addition of 1 -butene as comonomer; and/or preferably wherein said ethylene polymer is a homopolymer or a copolymer obtained by polymerization of ethylene and of at least one comonomer, preferably wherein said comonomer is not 1 -butene. The metallocene-catalyzed ethylene polymer according to any one of statements 65-75, having a molecular weight distribution M _z /M _w of at most 7.0, with M _z being the z average molecular weight, preferably at most 6.0, preferably at most 5.5, preferably at most 4.0, preferably at most 3.5, preferably at least 2.0, preferably at least 2.5.

74. The metallocene-catalyzed ethylene polymer according to any one of statements 65-73, having a molecular weight distribution M _z /M _n of at least 8.0, with M _z being the z average molecular weight and M _n being the number-average molecular weight, preferably at least 9.0, preferably at least 9.5, preferably at least 10.0, preferably at least 10.5, preferably at most 25.0, preferably at most 22.5, preferably at most 20.0.

75. The metallocene-catalyzed ethylene polymer according to any one of statements 65-74, having a melt index MI2 ranging from 0.2 g/10 min to 11.0 g/10 min, preferably from 0.3 g/10 min to 10.0 g/10 min.

76. The metallocene-catalyzed ethylene polymer according to any one of statements 65-75, having a melt index HLMI ranging from 10.0 g/10 min to 300.0 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 ranging from 11.0 g/10 min to 280.0 g/10 min, preferably an HLMI ranging from 12.0 g/10 min to 270.0 g/10 min, preferably an HLMI ranging from 12.0 g/10 min to 270.0 g/10 min, preferably an HLMI ranging from 13.0 g/10 min to 260.0 g/10 min.

77. The metallocene-catalyzed ethylene polymer according to any one of statements 65-76, having a melt index MI5 ranging from 0.5 g/10 min to 30.0 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 0.7 g/10 min to 28.0 g/10 min, preferably from 1.0 g/10 min to 25.0 g/10 min.

78. The metallocene-catalyzed ethylene polymer according to any one of statements 65-77, having a melt index ratio HLMI/MI2 of at most 40.0; preferably at most 35.0, preferably at least 15.0, preferably at least 20.0.

79. The metallocene-catalyzed ethylene polymer according to any one of statements 65-78, having a melt index ratio HLMI/MI5 of at most 20.0; preferably at most 15.0, preferably at least 5.0, preferably at least 7.0.

80. The metallocene-catalyzed ethylene polymer according to any one of statements 65-79, having a density of at least 0.910 g/cm ³ as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C.

81. The metallocene-catalyzed ethylene polymer according to any one of statements 65-80, having a density of at most 0.965 g/cm ³ as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; preferably at most 0.963 g/cm ³ , preferably at least 0.910 g/cm ³ , preferably at least 0.915 g/cm ³ .

82. A metallocene-catalyzed ethylene polymer according to any one of statements 65-81 , having: a density ranging from 0.910 g/cm ³ to 0.965 g/cm ³ , preferably ranging from 0.915 g/cm ³ to 0.960 g/cm ³ , as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; and at least 0.30 % to at most 1.20 % by weight of ethyl branching with regard to the total weight of the ethylene polymer, as determined by ¹³ C NMR analysis, preferably at least 0.31 at most 1.20 % by weight of ethyl branching, preferably at least 0.31 % to at most 1.10 % by weight of ethyl branching, preferably at least 0.32 % to at most 1 .00 % by weight of ethyl branching, preferably at least 0.33 % to at most 0.98 % by weight of ethyl branching, preferably at least 0.34 % to at most 0.98 % by weight of ethyl branching, preferably at least 0.35 % to at most 0.98 % by weight of ethyl branching. The metallocene-catalyzed ethylene polymer according to any one of statements 65-82, having at least one melting temperature T _m determined by DSC below 132 °C, preferably in the range of 100 °C to below 132 °C, more preferably in the range of 110 °C to 132 °C, still more preferably in the range of 120 °C to 132 °C. The metallocene-catalyzed ethylene polymer according to any one of statements 65-83, wherein the Temperature Rising Elution Fractionation (TREF) distribution curve of the metallocene-catalyzed ethylene polymer comprises at least one peak appearing at a temperature of at least 96.0 °C to at most 105 °C and having an area under the curve of at least 20.0 % to at most 100.0 %. The metallocene-catalyzed ethylene polymer according to any one of statements 65-84, wherein said polymer is a homopolymer. The metallocene-catalyzed ethylene polymer according to any one of statements 65-84, wherein said polymer is a copolymer of ethylene and a higher alpha-olefin co-monomer, preferably 1 -hexene. The metallocene-catalyzed ethylene polymer according to any one of statements 65-86, having a total comonomer content, for example 1 -hexene content, relative to the total weight of the ethylene polymer ranging from 0.0 % by weight to 15.0 % by weight, as determined by ¹³ C NMR analysis, preferably at most 10.0 % by weight, preferably from 0.0% by weight to 9.5 % by weight, preferably from 0.0% by weight to 9.0 % by weight. The metallocene-catalyzed ethylene polymer according to any one of statements 65-87, wherein when the density of the polymer is below 0.938 g/cm ³ , the Temperature Rising Elution Fractionation (TREF) distribution curve of the metallocene-catalyzed ethylene polymer comprises at least one second peak appearing at a temperature of at least 65.0 °C to at most 92.0 °C and having an area under the curve of at least 60.0 % to at most 75.0 %.

89. The metallocene-catalyzed ethylene polymer according to any one of statements 65-87, wherein when the density of the polymer is below 0.925 g/cm ³ , the Temperature Rising Elution Fractionation (TREF) distribution curve of the metallocene-catalyzed ethylene polymer comprises at least one second peak appearing at a temperature of at least 65.0 °C to at most 73.0 °C and having an area under the curve of at least 60.0 % to at most 75.0 %.

90. The metallocene-catalyzed ethylene polymer according to any one of statements 65-89, wherein metallocene is a zirconium based metallocene.

91. The metallocene-catalyzed ethylene polymer according to any one of statements 65-90, having below 0.24 ppm of Fe by weight of polymer, preferably below 0.10 ppm of Fe by weight of polymer.

92. The metallocene-catalyzed ethylene polymer according to any one of statements 65-91 , prepared using a continuous process.

93. The metallocene-catalyzed ethylene polymer according to any one of statements 65-92, wherein said metallocene is a metallocene catalyst composition according to any one of statements 1-35.

94. An article comprising the polymer according to any one of statements 63-93, or comprising the polymer obtained using a process according to any one of statements 36-62.

95. The article according to statement 94, wherein the article is for film applications, injections applications, blow moulding applications, rotomoulding applications, extrusion applications, yarn applications.

96. The article according to any one of statements 94-95, wherein the article is selected from the group comprising caps & closures, cereal liners, blown films, yarns, rotomoulded articles, blow moulded articles, pipes, fibers and cast films.

97. The process according to any one of statements 36-62, wherein the ethylene polymer obtained is a metallocene-catalyzed ethylene polymer according to any one of statements 65-93.

98. A process for the preparation of a metallocene-catalyzed ethylene polymer according to any one of statements 65-93, the process comprising: contacting at least one metallocene catalyst composition according to any one of statements 1-35, with ethylene, optionally hydrogen, and optionally one or more alpha-olefin co-monomers; and polymerizing the ethylene, and the optionally one or more alpha-olefin co-monomers, in the presence of the at least one metallocene catalyst composition, and optional hydrogen, thereby obtaining the metallocene-catalyzed ethylene polymer. 99. Use of a polymer according to any one of statements 63-93, or obtained using a process according to any one of statements 36-62, 95-96, in film applications, injections applications, blow moulding applications, rotomoulding applications, extrusion applications, yarn applications, and in polyethylene of raised temperature resistance; preferably in caps & closures applications, in cereal liners applications, in blown film applications, or in cast film applications.

The present invention provides a catalyst composition comprising catalyst component A comprising the meso form of a bridged metallocene compound with two indenyl groups each indenyl being independently substituted with one or more substituents, wherein at least one of the substituents is an aryl or heteroaryl, preferably wherein the meso/rac ratio of the meso form of the bridged metallocene compound of catalyst component A is 95:5 or greater; preferably wherein at least one of the substituents is aryl, preferably phenyl, wherein said aryl and/or phenyl may be unsubstituted or substituted; preferably wherein at least one of the substituents is on position 3 and/or 5 of each indenyl, preferably each indenyl has one substituent on position 3, preferably each indenyl has one substituent on position 5, yet more preferably each indenyl has one substituent on position 3 and one substituent on position 5 of each indenyl, preferably the aryl or heteroaryl substituent is on 3- position of each indenyl; catalyst component B comprising a bridged metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; and an optional activator; an optional support; and an optional co-catalyst.

For nomenclature purposes, the following numbering scheme is used for indenyl. It should be noted that indenyl can be considered a cyclopentadienyl with a fused benzene ring. The structure below is drawn and named as an anion: indenyl.

As used herein, the term “catalyst” refers to a substance that causes a change in the rate of a reaction. In the present invention, it is especially applicable to catalysts suitable for a polymerization, preferably for the polymerization of olefins to polyolefins.

As used herein, the term “meso" or “meso form” means that the bridge metallocene of component A has plane of symmetry containing the metal center, M.

The term "metallocene catalyst" is used herein to describe any transition metal complexes comprising metal atoms bonded to one or more ligands. The 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, tetrahydroindenyl, fluorenyl or their derivatives. Metallocenes 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.

Specifically, for this invention the catalysts need to be comprising the meso form of a bridged metallocene compound with two indenyl groups each indenyl being independently substituted with one or more substituents for catalyst component A, and a bridged metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group for catalyst component B.

In one embodiment, for catalyst A, the bridged metallocene catalyst can be represented by the meso form of compound of formula (III), and for catalyst B by compound of formula (IV): wherein

L ¹ (Ar ¹ ) ₂ M ¹ Q ¹ Q ² (III),

L ² (Ar ² )(Ar ³ )M ² Q ³ Q ⁴ (IV), each Ar ¹ is independently indenyl, optionally substituted with one or more substituents each independently selected from the group comprising alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R ¹⁰ )3, and heteroalkyl; wherein each R ¹⁰ is independently hydrogen, alkyl, or alkenyl. Each indenyl is 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 Ar ¹ is indenyl, each indenyl being independently substituted with one or more substituents, wherein at least one of the substituents is an aryl or heteroaryl; preferably wherein at least one of the substituents is on position 3 and/or 5 of each indenyl, preferably wherein the aryl or heteroaryl is on the 3-position of each indenyl, wherein Ar ¹ can be further substituted with one or more substituents each independently selected from the group comprising alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R ¹⁰ )3, and heteroalkyl; wherein each R ¹⁰ is independently hydrogen, alkyl, or alkenyl;

Ar ² is cyclopentadienyl, optionally substituted with one or more substituents each independently selected from the group comprising alkyl, alkenyl, cycloalkyl, cycloalkenyl, or cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R ¹⁰ )3, and heteroalkyl; wherein each R ¹⁰ is independently hydrogen, alkyl, or alkenyl;

Ar ³ is fluorenyl, optionally substituted with one or more substituents each independently selected from the group comprising alkyl, alkenyl, cycloalkyl, cycloalkenyl, or cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R ¹⁰ )3, and heteroalkyl; wherein each R ¹⁰ is independently hydrogen, alkyl, or alkenyl; each of M ¹ and M ² is a transition metal selected from the group comprising zirconium, hafnium, titanium, and vanadium; and preferably each of M ¹ and M ² is zirconium;

Q ¹ and Q ² are each independently selected from the group comprising halogen, alkyl, -N(R ¹¹ )2, alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R ¹¹ is hydrogen or alkyl;

Q ³ and Q ⁴ are each independently selected from the group comprising halogen, alkyl, -N(R ¹¹ )2, alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein R ¹¹ is hydrogen or alkyl;

L ¹ is a divalent group or moiety bridging the two Ar ¹ groups, preferably selected from SiR ⁸ R ⁹ , -[CR ⁸ R ⁹ ]h-, GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1 , 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl; preferably L ¹ is SiR ⁸ R ⁹ ;

L ² is a divalent group or moiety bridging Ar ² and Ar ³ groups, preferably selected from -[CR ⁸ R ⁹ ]h- , SiR ⁸ R ⁹ , GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1 , 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl.

In some embodiments, each Ar ¹ is indenyl, each indenyl being independently substituted with one or more substituents, wherein at least one of the substituents is an aryl or heteroaryl; preferably wherein at least one of the substituents is on position 3 and/or 5 of each indenyl, preferably wherein the aryl or heteroaryl substituent is on the 3-position of each indenyl; each indenyl being further optionally substituted with one or more substituents each independently selected from the group comprising Ci-2oalkyl, C3-2oalkenyl, C3-2ocycloalkyl, C5-2ocycloalkenyl, C6-2ocycloalkenylalkyl, Ce-2oaryl, Ci-2oalkoxy, C?-2oalkylaryl, C?-2oarylalkyl, halogen, Si(R ¹⁰ )3, and heteroCi. i2alkyl; wherein each R ¹⁰ is independently hydrogen, Ci-2oalkyl, or C3-2oalkenyl. Preferably each Ar ¹ is indenyl, each indenyl being independently substituted with one or more substituents, wherein at least one of the substituents is an Ce-waryl; preferably wherein the Ce- waryl substituent is on the 3-position of each indenyl; each indenyl being further optionally substituted with one or more substituents each independently selected from the group comprising Ci-salkyl, Cs-salkenyl, Cs-scycloalkyl, Cs-scycloalkenyl, Ce-scycloalkenylalkyl, Ce- waryl, Ciwalkoxy, Cy-walkylaryl, Cy-warylalkyl, halogen, Si(R ¹⁰ )3, and heteroCiwalkyl; wherein each R ¹⁰ is independently hydrogen, Ci-salkyl, or Cs-salkenyl. Preferably each Ar ¹ is indenyl, each indenyl being independently substituted with one or more substituents, wherein at least one of the substituents is an C _6-10 aryl; preferably wherein the C _6-10 aryl substituent is on the 3- position of each indenyl; each indenyl being further optionally substituted with one or more substituents each independently selected from the group comprising C _1-8 alkyl, C _3-8 alkenyl, C _{3- 8} cycloalkyl, C _6-10 aryl, and halogen. In some embodiments, Ar ² is cyclopentadienyl, optionally substituted with one or more substituents each independently selected from the group comprising C _1-20 alkyl, C _3-20 alkenyl, C _3-20 cycloalkyl, C _5-20 cycloalkenyl, C _6-20 cycloalkenylalkyl, C _6-20 aryl, C _1-20 alkoxy, C _7-20 alkylaryl, C _7-20 arylalkyl, halogen, Si(R ¹⁰ ) ₃ , and heteroC _1-12 alkyl; wherein each R ¹⁰ is independently hydrogen, C _1-20 alkyl, or C _3-20 alkenyl. Preferably Ar ² is cyclopentadienyl, optionally substituted with one or more substituents each independently selected from the group comprising C1- 8alkyl, C3-8alkenyl, C3-8cycloalkyl, C5-8cycloalkenyl, C6-8cycloalkenylalkyl, C6-10aryl, C1-8alkoxy, C7-12alkylaryl, C7-12arylalkyl, halogen, Si(R ¹⁰ )3, and heteroC1-8alkyl; wherein each R ¹⁰ is independently hydrogen, C1-8alkyl, or C3-8alkenyl. Preferably Ar ² is cyclopentadienyl, optionally substituted with one or more substituents each independently selected from the group comprising C1-8alkyl, C3-8alkenyl, C3-8cycloalkyl, C6-10aryl, and halogen. In some embodiments, Ar ³ is fluorenyl, optionally substituted with one or more substituents each independently selected from the group comprising C1-20alkyl, C3-20alkenyl, C3-20cycloalkyl, C5-20cycloalkenyl, C6-20cycloalkenylalkyl, C6-20aryl, C1-20alkoxy, C7-20alkylaryl, C7-20arylalkyl, halogen, Si(R ¹⁰ )3, and heteroC1-12alkyl; wherein each R ¹⁰ is independently hydrogen, C1-20alkyl, or C3-20alkenyl. Preferably Ar ² is fluorenyl, optionally substituted with one or more substituents each independently selected from the group comprising C1-8alkyl, C3-8alkenyl, C3-8cycloalkyl, C5-8cycloalkenyl, C6-8cycloalkenylalkyl, C6-10aryl, C1-8alkoxy, C7-12alkylaryl, C7-12arylalkyl, halogen, Si(R ¹⁰ )3, and heteroC1-8alkyl; wherein each R ¹⁰ is independently hydrogen, C1-8alkyl, or C3-8alkenyl. Preferably, Ar ³ is fluorenyl, optionally substituted with one or more substituents each independently selected from the group comprising C1-8alkyl, C3-8alkenyl, C3-8cycloalkyl, C6-10aryl, and halogen. In some embodiments, L ¹ is -[CR ⁸ R ⁹ ]h-, SiR ⁸ R ⁹ , GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1, 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C1-20alkyl, C3-20alkenyl, C3-20cycloalkyl, C5-20cycloalkenyl, C6- ₂₀ cycloalkenylalkyl, C _6-10 aryl, and C ₇ -C ₂₀ arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a C _3-20 cycloalkyl, C _5-20 cycloalkenyl or heterocyclyl. Preferably L ¹ is - [CR ⁸ R ⁹ ] _h -, SiR ⁸ R ⁹ , GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1, 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C _1-8 alkyl, C _{3- 8} alkenyl, C ₃ - ₈ cycloalkyl, C _5-8 cycloalkenyl, C _6-8 cycloalkenylalkyl, C _6-10 aryl, and C ₇ -C ₁₂ arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a C _3-8 cycloalkyl, C _{5- 8} cycloalkenyl or heterocyclyl. Preferably, L ¹ is -[CR ⁸ R ⁹ ] _h -, or SiR ⁸ R ⁹ ; wherein h is an integer selected from 1, or 2; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C _1-8 alkyl, C _3-8 alkenyl, C ₃ - ₈ cycloalkyl, C _5-8 cycloalkenyl, C _6-8 cycloalkenylalkyl, and C _{6- 10} aryl. Preferably, L ¹ is SiR ⁸ R ⁹ ; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C _1-8 alkyl, C _3-8 alkenyl, C ₃ - ₈ cycloalkyl, C _5-8 cycloalkenyl, C _{6- 8} cycloalkenylalkyl, and C _6-10 aryl; preferably C _1-8 alkyl. In some embodiments, Q ¹ and Q ² are each independently selected from the group comprising halogen, C _1-20 alkyl, -N(R ¹¹ ) ₂ , C _1-20 alkoxy, C _3-20 cycloalkoxy, C _7-20 aralkoxy, C _3-20 cycloalkyl, C _{6- 20} aryl, C _7-20 alkylaryl, C _7-20 aralkyl, and heteroC _1-20 alkyl; wherein R ¹¹ is hydrogen or C _1-20 alkyl. Preferably Q ¹ and Q ² are each independently selected from the group comprising halogen, C _1- 8alkyl, -N(R ¹¹ )2, C1-8alkoxy, C3-8cycloalkoxy, C7-12aralkoxy, C3-8cycloalkyl, C6-10aryl, C7- 12alkylaryl, C7-12aralkyl, and heteroC1-8alkyl; wherein R ¹¹ is hydrogen or C1-8alkyl. Preferably, Q ¹ and Q ² are each independently selected from the group comprising halogen, C1-8alkyl, - N(R ¹¹ )2, C6-10aryl, and C7-12aralkyl; wherein R ¹¹ is hydrogen or C1-8alkyl, preferably Q ¹ and Q ² are each independently selected from the group comprising Cl, F, Br, I, methyl, benzyl, and phenyl. In some embodiments, L ² is -[CR ⁸ R ⁹ ]h-, SiR ⁸ R ⁹ , GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1, 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C1-20alkyl, C3-20alkenyl, C3-20cycloalkyl, C5-20cycloalkenyl, C6- 20cycloalkenylalkyl, C6-10aryl, and C7-C20arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a C3-20cycloalkyl, C5-20cycloalkenyl or heterocyclyl. Preferably L ² is - [CR ⁸ R ⁹ ]h-, SiR ⁸ R ⁹ , GeR ⁸ R ⁹ , or BR ⁸ ; wherein h is an integer selected from 1, 2, or 3; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C1-8alkyl, C3- 8alkenyl, C3-8cycloalkyl, C5-8cycloalkenyl, C6-8cycloalkenylalkyl, C6-10aryl, and C7-C12arylalkyl; or R ⁸ and R ⁹ together with the atom to which they are attached form a C3-8cycloalkyl, C5- 8cycloalkenyl or heterocyclyl. Preferably, L ² is -[CR ⁸ R ⁹ ]h-, or SiR ⁸ R ⁹ ; wherein h is an integer selected from 1, or 2; each of R ⁸ , and R ⁹ are independently selected from the group comprising hydrogen, C1-8alkyl, C3-8alkenyl, C3-8cycloalkyl, C5-8cycloalkenyl, C6-8cycloalkenylalkyl, and C6- 10aryl. In some embodiments, Q ³ and Q ⁴ are each independently selected from the group comprising halogen, C _1-20 alkyl, -N(R ¹¹ ) ₂ , C _1-20 alkoxy, C _3-20 cycloalkoxy, C _7-20 aralkoxy, C _3-20 cycloalkyl, C _{6- 20} aryl, C _7-20 alkylaryl, C _7-20 aralkyl, and heteroC _1-20 alkyl; wherein R ¹¹ is hydrogen or C _1-20 alkyl. Preferably Q ³ and Q ⁴ are each independently selected from the group comprising halogen, C _{1- 8} alkyl, -N(R ¹¹ ) ₂ , C _1-8 alkoxy, C _3-8 cycloalkoxy, C _7-12 aralkoxy, C _3-8 cycloalkyl, C _6-10 aryl, C _{7- 12} alkylaryl, C _7-12 aralkyl, and heteroC _1-8 alkyl; wherein R ¹¹ is hydrogen or C _1-8 alkyl. Preferably, Q ³ and Q ⁴ are each independently selected from the group comprising halogen, C _1-8 alkyl, - N(R ¹¹ ) ₂ , C _6-10 aryl, and C _7-12 aralkyl; wherein R ¹¹ is hydrogen or C _1-8 alkyl, preferably Q ¹ and Q ² are each independently selected from the group comprising Cl, F, Br, I, methyl, benzyl, and phenyl. In some preferred embodiments, catalyst component A comprises the meso form of a bridged metallocene catalyst of formula (I); wherein wherein each of R ¹ , R ² R ³ and R ⁴ , m, n, p, q, L ¹ , M ¹ , Q ¹ and Q ² have the same meaning as that defined herein above and in the statements. In a preferred embodiment, the meso/rac ratio of the meso form of the bridged metallocene compound of catalyst component A is 95:5 or greater. A non-limiting example of catalyst A is the meso form of the catalyst shown below: . In some preferred embodiments, catalyst component B comprises a bridged metallocene catalyst of formula (II), wherein each of R ⁵ , R ⁶ , R ⁷ , r, s, t, L ² , M ² , Q ³ and Q ⁴ have the same meaning as that defined herein above and in the statements. In some preferred embodiments, catalyst component B comprises a bridged metallocene catalyst of formula (Ila), wherein each of R ⁵ , R ⁶ , R ⁷ , r, L ² , M ² , Q ³ and Q ⁴ have the same meaning as that defined herein.

Non-limiting examples of catalyst B are shown below:

In a preferred embodiment, the weight ratio of catalyst component A to catalyst component B 5 is in a range of from 10/90 to 90/10, preferably in the range of from 15/85 to 80/20, preferably in the range of from 20/80 to 70/30, preferably in the range of from 20/80 to 60/40, preferably in the range of from 20/80 to 50/50, preferably in the range of from 20/80 to 40/60, preferably in the range of from 25/75 to 35/65, preferably 28/72 to 33/67, preferably 29/71 to 32/68, preferably 29/71 to 31/69, preferably 30/70.

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 can be an inert organic or inorganic solid, which is chemically unreactive with any of the components of the conventional bridged 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, or a silica support. The silica may be in granular, agglomerated, fumed or other form.

In some embodiments, the support of catalyst components A and B is a porous support, and preferably a porous titanated silica, or silica support having a surface area comprised between 200 and 900 m ² /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 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, catalyst components A and B 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, or a fluorinated activator. The aluminum-containing activator may comprise an alumoxane, an alkyl aluminum, a Lewis acid and/or a fluorinated catalytic support.

In some embodiments, alumoxane is used as an activator for catalyst components A and B. 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 ^a 2 (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 Tri-Ethyl Aluminum (TEAL), Tri- Iso-Butyl Aluminum (TIBAL), Tri-Methyl Aluminum (TMA), and Methyl-Methyl-Ethyl Aluminum (MMEAL). Especially suitable are trialkylaluminums, the most preferred being triisobutylaluminum (TIBAL) and triethylaluminum (TEAL).

The catalyst composition can be particularly useful in a process for the preparation of a polymer comprising contacting at least one monomer with at least one catalyst composition. Preferably, said polymer is a polyolefin, preferably said monomer is an alpha-olefin.

The catalyst composition of the present invention is therefore particularly suitable for being used in the preparation of a polyolefin. The present invention also relates to the use of a catalyst composition in olefin polymerization.

The present invention also encompasses an olefin polymerization process, the process comprising: contacting a catalyst composition according to the invention, with an olefin monomer, optionally hydrogen, and optionally one or more olefin comonomers; and polymerizing the monomer, and the optionally one or more olefin comonomers, in the presence of the at least one catalyst composition, and optional hydrogen, thereby obtaining a polyolefin.

The term “olefin” refers herein to molecules composed of carbon and hydrogen, containing at least one carbon-carbon double bond. Olefins containing one carbon-carbon double bond are denoted herein as mono-unsaturated hydrocarbons and have the chemical formula C _n H2n, where n equals at least two. “Alpha-olefins”, “a-olefins”, “1 -alkenes” or “terminal olefins” are used as synonyms herein and denote olefins or alkenes having a double bond at the primary or alpha (a) position.

Throughout the present application the terms “olefin polymer”, "polyolefin" and "polyolefin polymer" may be used synonymously.

Suitable polymerization includes but is not limited to homopolymerization of an alpha-olefin, or copolymerization of the alpha-olefin and at least one other alpha-olefin comonomer.

As used herein, the term “comonomer” refers to olefin comonomers which are suitable for being polymerized with alpha-olefin monomer. The comonomer if present is different from the olefin monomer and chosen such that it is suited for copolymerization with the olefin monomer. Comonomers may comprise but are not limited to aliphatic C2-C20 alpha-olefins. Examples of suitable aliphatic C3-C20 alpha-olefins include ethylene, 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. Further examples of suitable comonomers are vinyl acetate (H3C-C(=O)O-CH=CH2) or vinyl alcohol ("HO-CH=CH2"). Examples of olefin copolymers suited which can be prepared can be random copolymers of propylene and ethylene, random copolymers of propylene and 1 -butene, heterophasic copolymers of propylene and ethylene, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and vinyl alcohol (EVOH).

In some embodiments, the olefin monomer is ethylene, and the olefin comonomer comprises propylene, 1 -butene, 2-butene, 3-methyl-1 -butene, isobutylene, 1 -pentene, 2-pentene, 3- methyl-l-pentene, 4-methyl-1 -pentene, 1 -hexene, 2-hexene, 3-ethyl-1 -hexene, 1 -heptene, 2- heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

In some embodiments, the olefin monomer is propylene, and the olefin comonomer comprises ethylene, 1 -butene, 2-butene, 3-methyl-1 -butene, isobutylene, 1 -pentene, 2-pentene, 3- methyl-1 -pentene, 4-methyl-1 -pentene, 1 -hexene, 2-hexene, 3-ethyl-l-hexene, 1 -heptene, 2- heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

The polyolefin 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 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.

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 Cg 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 can also be performed in gas phase, under gas phase conditions. The term "gas phase conditions" as used herein refers to temperatures and pressures suitable for polymerizing one or more gaseous phase olefins to produce polymer therefrom.

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 invention also encompasses a polymer at least partially catalyzed by at least one composition according to the invention or produced by a process according to the invention.

The present invention also encompasses a polymer, preferably an olefin polymer produced by a process as defined herein. In some embodiments, said olefin polymer is polyethylene. In some embodiments, said olefin polymer is polypropylene.

The present invention also encompasses a metallocene-catalyzed ethylene polymer, preferably prepared in the presence of at least one metallocene catalyst composition comprising a dual catalyst which means a catalyst particle with two metallocene active sites on a single support; preferably a catalyst composition as described herein, said polymer having: a melt index MI2 ranging from 0.1 g/10 min to 12.0 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; a molecular weight distribution M _w /M _n ranging from 4.0 to 12.0, with M _w being the weightaverage molecular weight and M _n being the number-average molecular weight, preferably from 4.0 to 10.0, preferably from 4.0 to 9.0, preferably from 4.0 to 8.5, preferably 4.1 to 8.0, preferably from 4.1 to 7.6, preferably from 4.1 to 7.0; preferably a rheology long chain branching index g _r heo of at least 0.90, preferably at least 0.93, preferably at least 0.95; and preferably having at least 0.30 % by weight of ethyl branching with regard to the total weight of the ethylene polymer, as determined by ¹³ C NMR analysis, preferably at least 0.31 % by weight of ethyl branching, preferably at least 0.33 % by weight of ethyl branching, preferably at most 1.20 % by weight of ethyl branching, preferably at most 1.10 % by weight of ethyl branching, preferably ranging from 0.32 % to 1.0 % by weight, preferably from 0.34 to 0.98 % by weight, preferably from 0.35 to 0.98 % by weight, with the proviso that said ethyl branching is not generated from 1 -butene incorporation as comonomer; and/or preferably wherein said ethylene polymer is a homopolymer or a copolymer obtained by polymerization of ethylene and of at least one comonomer, preferably wherein said comonomer is not 1 -butene.

In an embodiment, the invention relates to a metallocene-catalyzed ethylene polymer having: a melt index MI2 ranging from 0.1 g/10 min to 12.0 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 a MI2 ranging from 0.2 g/10 min to 11.0 g/10 min, preferably from 0.3 g/10 min to 10.0 g/10 min; a molecular weight distribution M _w /M _n ranging from 4.0 to 12.0, with M _w being the weightaverage molecular weight and M _n being the number-average molecular weight, preferably from 4.0 to 10.0, preferably from 4.0 to 9.0, preferably from 4.0 to 8.5, preferably 4.1 to 8.0, preferably from 4.1 to 7.6, preferably from 4.1 to 7.0; and preferably at least 0.30 % by weight of ethyl branching with regard to the total weight of the ethylene polymer measured by ¹³ C NMR, preferably ranging from 0.30 % to 1.20 % by weight, preferably from 0.30 to 1.10 % by weight, preferably from 0.35 to 1.00 % by weight, with the proviso that said ethyl branching is not generated from 1 -butene incorporation as comonomer. In an embodiment, the invention relates to a metallocene-catalyzed ethylene polymer having: a melt index MI2 ranging from 0.1 g/10 min to 12.0 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 a MI2 ranging from 0.2 g/10 min to 11.0 g/10 min, preferably from 0.3 g/10 min to 10.0 g/10 min; a molecular weight distribution M _w /M _n ranging from 4.0 to 12.0, with M _w being the weightaverage molecular weight and M _n being the number-average molecular weight, preferably from 4.0 to 10.0, preferably from 4.0 to 9.0, preferably from 4.0 to 8.5, preferably 4.1 to 8.0, preferably from 4.1 to 7.6, preferably from 4.1 to 7.0; a density ranging from 0.910 g/cm ³ to 0.965 g/cm ³ , preferably ranging from 0.915 g/cm ³ to 0.960 g/cm ³ , as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C; and at least 0.30 % to at most 1 .20 % by weight of ethyl branching with regard to the total weight of the ethylene polymer, as determined by ¹³ C NMR analysis, preferably at least 0.31 at most 1.20 % by weight of ethyl branching, preferably at least 0.31 % to at most 1.10 % by weight of ethyl branching, preferably at least 0.32 % to at most 1.00 % by weight of ethyl branching, preferably at least 0.33 % to at most 0.98 % by weight of ethyl branching, preferably at least 0.34 % to at most 0.98 % by weight of ethyl branching, preferably at least 0.35 % to at most 0.98 % by weight of ethyl branching.

The term “ethylene polymer”, “polyethylene resin” 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 polyethylene resin, 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 polyolefin resin 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.

In an embodiment, the ethylene polymer is a homopolymer. The term “ethylene homopolymer” as used herein is intended to encompass polymers which consist essentially of repeat units deriving from ethylene. Homopolymers may, for example, comprise at least 99.8% preferably 99.9% by weight of repeats units derived from ethylene, as determined for example by ¹³ C NMR spectrometry.

In another embodiment, the polyethylene resin is an ethylene copolymer. The term “ethylene copolymer” as used herein is intended to encompass polymers which consist essentially of repeat units deriving from ethylene and at least one other C3-C20 alpha-olefin co-monomer, preferably wherein the co-monomer is 1 -hexene.

As used herein, the term “co-monomer” refers to olefin co-monomers which are suitable for being polymerized with alpha-olefin monomer. Co-monomers may comprise but are not limited to aliphatic C3-C20 alpha-olefins, preferably C3-C12 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. In some preferred embodiments, said co-monomer is 1-hexene.

In some embodiments, said ethylene polymer is a copolymer of ethylene and a higher alphaolefin co-monomer, preferably 1-hexene, wherein the total co-monomer content, preferably 1- hexene (wt % C6) relative to the total weight of the ethylene polymer is at least 0.5 % by weight, preferably at least 1.0 % by weight, preferably at least 1.5 % by weight, preferably at least 2.0 % by weight, preferably at least 2.5 % by weight, preferably at least 3.0 % by weight, as determined by ¹³ C NMR analysis. In some embodiments, said ethylene polymer is a copolymer of ethylene and a higher alpha-olefin co-monomer, preferably 1-hexene, wherein the total comonomer content, preferably 1 -hexene (wt % C6) relative to the total weight of the polyethylene is at most 15.0 % by weight, preferably at most 13.0 % by weight, preferably at most 10.0 % by weight, as determined by ¹³ C NMR analysis.

Ethylene copolymers described herein can, in some embodiments, 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 shown by the ratio of the areas of IR signals (ACHS/ACH2) from IR5-MCT detector as function of log M.

As used herein, the term “monomodal ethylene polymer” or “ethylene polymer 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 “polyethylenes with a multimodal molecular weight distribution” or “multimodal polyethylenes” it is meant polyethylenes 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 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. In some embodiments, the ethylene polymer has a rheology long chain branching index g _r heo of at least 0.90. In some embodiments, the polyethylene resin has a rheology long chain branching index g _r heo of at most 1.10. In some embodiments, the polyethylene resin has a rheology long chain branching index g _r heo of at least 0.90 to at most 1.10, preferably at least 0.93 to at most 1.10, preferably at least 0.94 to at most 1.10, preferably at least 0.95 to at most 1.10.

In some preferred embodiment, the ethylene polymer has: a melt index MI2 ranging from 0.1 g/10 min to 12.0 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; a molecular weight distribution M _w /M _n ranging from 4.0 to 12.0, with M _w being the weightaverage molecular weight and M _n being the number-average molecular weight, preferably from 4.0 to 10.0, preferably from 4.0 to 9.0, preferably from 4.0 to 8.5, preferably 4.1 to 8.0, preferably from 4.1 to 7.6, preferably from 4.1 to 7.0; and preferably at least 0.30 % by weight of ethyl branching with regard to the total weight of the ethylene polymer measured by ¹³ C NMR, preferably at least 0.32 % by weight of ethyl branching, preferably at least 0.35 % by weight of ethyl branching, preferably at most 1.20 % by weight of ethyl branching, preferably at most 1 .10 % by weight of ethyl branching, preferably at most 1.00 % by weight of ethyl branching, preferably at most 0.99 % by weight of ethyl branching, preferably at most 0.98 % by weight of ethyl branching, preferably ranging from 0.30 % to 1.20 % by weight, preferably from 0.30 to 1.10 % by weight, preferably from 0.30 to 1.00 % by weight, with the proviso that said ethyl branching is not generated from 1 -butene incorporation as comonomer; and preferably a rheology long chain branching index g _r heo ranging from 0.90 to 1.10, preferably at least from 0.93 to 1.10, preferably at from 0.95 to 1.10.

In some embodiments, the ethylene polymer has a density of at least 0.910 g/cm ³ as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C, preferably at least O.912 g/cm ³ , preferably at least 0.914 g/cm ³ , preferably at least 0.915 g/cm ³ , preferably at least 0.916 g/cm ³ . In some embodiments, the polyethylene resin has a density of at most 0.964 g/cm ³ , preferably at most 0.962 g/cm ³ . Preferably, the polyethylene resin has a density ranging from 0.910 g/cm ³ to 0.965 g/cm ³ , preferably 0.915 g/cm ³ to 0.963 g/cm ³ , preferably at least 0.916 g/cm ³ to at most 0.963 g/cm ³ . Preferably, the polyethylene resin has a density ranging from 0.910 g/cm ³ to 0.965 g/cm ³ , and from 0.30 % to 1.20 % by weight of ethyl branching with regard to the total weight of the ethylene polymer measured by ¹³ C NMR, with the proviso that said ethyl branching is not generated from 1 -butene incorporation as comonomer, preferably a density ranging from 0.915 g/cm ³ to 0.963 g/cm ³ and from 0.32 % to 1 .10 % by weight of ethyl branching, preferably a density ranging from 0.916 g/cm ³ to at most 0.963 g/cm ³ and from 0.33 % to 1.00 % by weight of ethyl branching, preferably a density ranging from 0.916 g/cm ³ to at most 0.963 g/cm ³ and from 0.33 % to 0.98 % by weight of ethyl branching.

Preferably, the ethylene polymer has a molecular weight distribution M _z /M _w ranging from 2.0 to 7.0, with M _z being the z average molecular weight, preferably ranging from 2.0 to 6.0, preferably from 2.5 to 5.5, preferably from 2.5 to 4.0, preferably from 2.5 to 3.5.

In some preferred embodiment, the ethylene polymer has a molecular weight distribution M _z /M _n ranging from 8.0 to 25.0, preferably from 9.0 to 22.0, preferably from 9.5 to 22.0, preferably from 10.0 to 20.0, preferably from 10.5 to 20.0.

In some preferred embodiment, the ethylene polymer has a melt index ratio HLMI/MI2 ranging from 15.0 to 40.0; preferably ranging from 20.0 to 35.0.

In some preferred embodiment, the ethylene polymer has a melt index ratio HLMI/MI5 ranging from 5.0 to 20.0; preferably from 7.0 to 15.0, preferably 7.0 to 13.0, preferably from 7.5 to 13.0. preferably from 8.0 to 12.0.

In some preferred embodiment, the ethylene polymer has a melt strength of at least 0.010 Newtons, as determined by Gbttfert Rheotens Melt Strength Apparatus, 190 °C, as described in the Experimental section, preferably at least 0.015 Newtons.

In some preferred embodiment, the ethylene polymer has: a melt index MI2 ranging from 0.1 g/10 min to 12.0 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 from 0.2 g/10 min to 11.0 g/10 min, preferably from 0.3 g/10 min to 10.0 g/10 min a molecular weight distribution M _w /M _n ranging from 4.0 to 12.0, with M _w being the weightaverage molecular weight and M _n being the number-average molecular weight, preferably from 4.0 to 10.0, preferably from 4.0 to 9.0, preferably from 4.0 to 8.5, preferably 4.1 to 8.0, preferably from 4.1 to 7.6, preferably from 4.1 to 7.0; and preferably at least 0.30 % by weight of ethyl branching with regard to the total weight of the ethylene polymer measured by ¹³ C NMR, preferably at least 0.32 % by weight of ethyl branching, preferably at least 0.35 % by weight of ethyl branching, preferably at most 1.20 % by weight of ethyl branching, preferably at most 1.10 % by weight of ethyl branching, preferably ranging from 0.30 % to 1 .0 % by weight, preferably from 0.30 to 0.99 % by weight, preferably from 0.35 to 0.98 % by weight, with the proviso that said ethyl branching is not generated from 1 -butene incorporation as comonomer; preferably a rheology long chain branching index g _r heo ranging from 0.91 to 1.10, preferably from 0.93 to 1.10, preferably at from 0.95 to 1.10; preferably a density of at least 0.910 g/cm ³ as measured according to the method of standard ISO 1183-1 :2012 method A at a temperature of 23 °C, preferably at least 0.912 g/cm ³ , preferably at least 0.914 g/cm ³ , preferably at least 0.915 g/cm ³ , preferably at least 0.916 g/cm ³ , preferably at most 0.964 g/cm ³ , preferably at most 0.962 g/cm ³ ; preferably ranging from 0.910 g/cm ³ to 0.965 g/cm ³ , preferably 0.915 g/cm ³ to 0.963 g/cm ³ , preferably at least 0.916 g/cm ³ to at most 0.963 g/cm ³ ; preferably a M _z /M _w ranging from 2.0 to 7.0, preferably ranging from 2.0 to 6.0, preferably from 2.5 to 5.5, preferably from 2.5 to 4.0, preferably from 2.5 to 3.5; preferably a M _z /M _n ranging from 8.0 to 25.0, preferably from 9.0 to 22.0, preferably from 9.5 to 22.0, preferably from 10.0 to 20.0, preferably from 10.5 to 20.0; preferably a melt index ratio HLMI/MI2 ranging from 15.0 to 40.0; preferably ranging from 20.0 to 35.0; and/or preferably a melt index ratio HLMI/MI5 ranging from 5.0 to 20.0; preferably from 7.0 to 15.0, preferably 7.0 to 13.0, preferably from 7.5 to 13.0. preferably from 8.0 to 12.0.

The present invention also encompasses a process, preferably a continuous process, for the preparation of a metallocene-catalyzed ethylene polymer as described herein, the process comprising: contacting a catalyst composition with ethylene, optionally hydrogen, and optionally one or more alpha-olefin co-monomers; and polymerizing the ethylene, and the optionally one or more alpha-olefin co-monomers, in the presence of the at least one catalyst composition, and optional hydrogen, thereby obtaining the metallocene-catalyzed ethylene polymer as described herein.

Preferably the continuous process comprises the step of comprising: contacting a metallocene catalyst composition with ethylene, optionally hydrogen, and optionally one or more alphaolefin co-monomers; and polymerizing the ethylene, and the optionally one or more alphaolefin co-monomers, in the presence of the at least one catalyst composition, and optional hydrogen, thereby obtaining the ethylene polymer as described herein, wherein the catalyst composition comprises: catalyst component A comprising the meso form of a bridged metallocene compound with two indenyl groups, each indenyl being substituted with one or more substituents, wherein at least one of the substituents is an aryl, preferably a phenyl; wherein said aryl may be unsubstituted or substituted; preferably wherein at least one of the substituents is on position 3 and/or 5 of each indenyl, preferably wherein the aryl, preferably the phenyl is on the 3-position of each indenyl; catalyst component B comprising a bridged metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; and an optional activator; an optional support; and an optional co-catalyst; preferably an alumoxane activator; a support; and an optional co-catalyst.

The ethylene polymer can be prepared in a process, preferably in a continuous process, which can be 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. Preferably the process is performed in one or more slurry loop reactor, preferably in a single slurry loop 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 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.

The present invention also encompasses a polyethylene composition comprising the ethylene polymer of the invention and one or more additives.

The additives can be for example antioxidants, UV stabilizers, pigments, processing aids, acid scavengers, lubricants, antistatic agents, fillers, nucleating agents, or clarifying agents, or combination thereof. 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 % by weight based on the weight of the polyethylene composition.

After the ethylene polymer is produced, it may be formed into various articles. The ethylene polymer is particularly suited for articles such as blown or cast film products, caps and closures, cereal liners, grass yarns, rotomoulded articles, blow moulded articles, pipes, fibers, etc.

The present invention therefore also encompasses an article comprising an ethylene polymer as defined herein; or obtained according to a process as defined herein. In some embodiments, said article can be film products, caps and closures, rotomoulded article, fibers, pipes, blow moulded articles, etc. Preferred embodiments for ethylene polymer of the invention are also preferred embodiments for the article of the invention.

The invention also encompasses a process for preparing an article according to the invention. Preferred embodiments as described above are also preferred embodiments for the present process.

The following examples serve to merely illustrate the invention and should not be construed as limiting its scope in any way. While the invention has been shown in only some of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes and modifications without departing from the scope 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) of ethylene polymers 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 measured 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) of ethylene polymers 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 _t h elution fraction and Mj is the molecular weight of species eluting at this increment.

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

Peak crystallization temperature (T _c ), peak melting temperature (T _m ) and heat of fusion (AH) were measured via Differential Scanning using DSC Q2000 instrument by TA Instruments, calibrated with indium and using T zero mode. The polymer analysis was performed with a 2 to 10 mg of polymer sample. The sample was first equilibrated at 30 °C and subsequently heated to 220 °C using a heating rate of 50 °C/min (first heating). The sample was held at 220 °C for 5 min to erase any prior thermal and crystallization history. The sample was subsequently cooled down to 0 °C with a constant cooling rate of 10 °C/min (first cooling). The sample was held isothermal at 0 °C for 5 min before being heated to 220 °C at a constant heating rate of 10 °C/min (second heating). The endothermic peak of melting (second heating) was analyzed using the TA Universal Analysis software and the peak melting temperature (T _m ) corresponding to 10 °C/min heating rate was determined.

Long chain branching index q _r heo

Rheology long chain branching index g _r heo was measured according to the formula, as described in WO 2008/113680: wherein Mw (SEC) is the weight average molecular weight obtained from size exclusion chromatography expressed in kDa; and wherein Mw (q ₀ , MWD, SCB) is determined according to the following, also expressed in kDa:

M^ _o ,MWD,SCB)=e^l21^9+GA99169LnM _n +G2G9G26(LnT] _o )'+G.955{\rip)-

0.007561 (LnM _z \Ln ri _o )+Q.Q2355(\nM _z ) ² ) wherein the zero shear viscosity qO in Pa.s is obtained from a frequency sweep experiment combined with a creep experiment, in order to extend the frequency range to values down to 10' ⁴ s' ¹ or lower, 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 Carreau-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 %. In practice, the creep experiment was carried out at a temperature of 190 °C under nitrogen atmosphere with a stress level such that after 1000 s the total strain was less than 25 %.

Comonomer content

The comonomer content, especially 1 -hexene, (wt.% C6-) relative to the total weight of the ethylene polymer was determined from a ¹³ C{ ¹ H} NMR spectrum. Ethyl branches content, expressed in terms of equivalent wt.% C4-, was also determined from a ¹³ C{ ¹ H} 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 (C6D6, 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 C6D6 and 2 to 3 drops of HMDS.

¹³ C{ ¹ H} 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

¹³ C{ ¹ H} 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 ¹³ C{ ¹ H} NMR spectrum

Small adjustments on integration limits can be applied if necessary.

Chemical shifts are given at ± 0.05 ppm.

The wt.% C6- and wt.% C4- contents are obtained by the following areas (A) combinations:

Meso/ Rac Ratio of metallocene catalyst

The meso I rac ratio of catalyst component A was determined from ¹ H NMR spectrum.

The sample was prepared by dissolving a few dozen mg of solid complex in 0.5 mL of anhydrous methylene chloride (CD2CI2, spectroscopic grade) at room temperature.

¹ H NMR signal was recorded on a Bruker 400 MHz with a 5 mm probe with the following conditions:

Pulse angle: 90°

Pulse repetition time: 60s

Spectral width: 6000 Hz centered at 5.5 ppm

Data points: 32K

Temperature: 25 °C +/- 1 °C

Rotation: 20 Hz

Scan numbers: 8

¹ H NMR spectrum was obtained by Fourier Transform on 32K points after a light exponential multiplication. Spectrum was phased, baseline corrected, and chemical shift scale was referenced to the CH2CL2 peak at 5.33 ppm. Chemical shifts of signals were peak picked, and peaks were integrated as mentioned on Figure 2 and in the following Table B.

Table B: integration regions of ¹ H NMR spectrum

The meso/rac ratio was obtained by the following areas (A) combination:

Meso I Rac = AM eso I AR ac

Comonomer distribution

Co-monomer distribution illustrated by the CH3/CH2 ratio across the molecular weight distribution was also determined using the SEC apparatus described above equipped with an integrated high-sensitivity multiple band IR detector (IR5-MCT) as described by A. Ortin et al. (Macromol. Symp. 330, 63-80 2013 and T. Frijns-Bruls et al. Macromol. Symp. 356, 87-94 2015).

The comonomer distribution can be determined by the ratio of the IR detector intensity corresponding to the CH3 and CH2 channels calibrated with a series of PE homo/copolymer standards whose nominal value were predetermined by NMR.

The detector produced separate and continuous streams of absorbance data, measured through each of their IR selective filters CH3 and CH2 at a fixed acquisition rate of one point per half second. The detector was equipped with a heated flow-through cell of 13 pL internal volume.

The ratio of infra-red absorbance band ratio A CHS to A CH2 (methyl over methylene sensitive channels) can be correlated to the methyl (CH3) per 1000 total carbons (1000TC), denoted as CH3/IOOOTC, as a function of molecular weight.

The IR CH3/CH2 ratio of the polymer was obtained by considering the entire signals of the CH3 and CH2 channels between the integration limits of the concentration chromatogram:

IR ratio= Area of CH3 signal within integration limits/area of CH2 signal within integration limits. In the present invention, an increase of the area ratio CH3/CH2 means an increase in Short Chain Branching content.

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.

Van Gurp-Palmen plot (vGP plot)

Complex modulus, G*, and loss angles, 5, may be obtained from rheological data determined at the test temperature of 190°C and analyzed using the van Gurp-Palmen treatment (reference: van Gurp, M. and Palmen, J., Rheology Bulletin, 1998, 67(1), 5-8). The vGP curve is a plot of phase angle 5 (= tan ^-1 [G'7G']) versus magnitude of the complex modulus, |G*| . In linear polymers, for a decrease of the modulus value, 5 will initially drop, it will then pass a minimum, rises again, moves through an inflection point, and finally approaches its limiting value of 90°. LCB shifts the vGP curve down. The higher the LCB density, the lower the 5 values. The area included under the vGP curve can be used as a parameter to evaluate the degree of LCB. In addition, the magnitude of the drop at the apparent plateau caused by LCB is related to the relative length of long chain branches on the polymer backbone. Low levels of long chain branching can be detected and quantified on a relative basis, using this methodology.

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/s ² , 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/s ² 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.

TREF

Temperature Rising Elution Fractionation analysis (TREF analysis) was performed using the method similar to as described in Soares and Hamielec, Polymer, 36 (10), 1995 1639-1654, incorporated herein in its entirety by reference. The TREF analysis was performed on a TREF model 200 TF series instrument equipped with Infrared detector from Polymer Char, (Valencia, Spain). The samples were dissolved in 1 ,2-dichlorobenzene at 150 °C for 1 h. The following parameters as shown in Table C were used.

Table C

Determination of Al and Zr contents

The Al and Zr contents were determined using inductively coupled plasma atomic emission spectroscopy (ICP-AES) after mineralization of the sample and recovery of the residues in an acid medium. The spectrometer used was ICP-AES ARCOS, by Spectro. The determination of the elements was carried out by nebulization of the solution in an argon plasma, measurement of the intensities of the most sensitive and interference-free emission lines and comparison of these intensities with those of calibration solutions (external calibration method).

Preparation of the solution to be analyzed (test solution): Under an inert atmosphere (in a glove box), about 0.3 g of catalyst were added into a platinum crucible and 3 to 5 mL of isopropyl alcohol were added to "deactivate" the catalyst. The mixture was heated to dryness in a sand bath (30 minutes). The platinum crucible was placed in an oven at 600 °C for 10 minutes. After cooling, Milli-Q® deionized water was added to impregnate all the ashes, and 1 mL of concentrated HCI (Merck HCI 32% v/v) and concentrated HF (Merck HF 48% v/v) were added. The crucible was placed in a sand bath, and Milli-Q® deionized water was added to mix the content of the crucible. After 24 h, 1 mL of concentrated HCI, 0.5 mL of concentrated HF and Milli-Q® deionized water were added while agitating the mixture under heat to achieve full dissolution. After cooling the mixture was transferred to a 50 mL polypropylene tube and the volume made up to 50 mL with Milli-Q® deionized water. The test solutions were then diluted 25 times ensuring that 2% HCI/HF1 % medium was maintained.

Preparation of calibration standards and control solutions: Standard solutions were prepared by dilution of commercial single-element solutions of certified concentrations. The standard solutions were prepared by transferring the required volume of the certified solution to a 50 mL polypropylene tube, then rinsing the sides of the tube with Milli-Q® deionized water, and adding 1 mL of concentrated HCI and 0.5 mL of concentrated HF per 50 mL to obtain the same acid content in solution as in the sample solutions, and finalizing the dilution with Milli-Q® deionized water. Control solutions were prepared by dilution of commercial multi-element solutions of certified concentrations. The presence of other elements in solution allowed verification of the presence/absence of possible interferences.

Determination of Fe content

The Fe content was determined using inductively coupled plasma atomic emission spectroscopy (ICP-AES) after mineralization of the sample and recovery of the residues in an acid medium. The spectrometer used was ICP-AES ARCOS, by Spectro.

Determination of the contents of Fe was carried out by ICP-AES, after calcination of the sample and recovery of the ashes in an acidic medium.

The determination of the elements was carried out by nebulization of the solution in an argon plasma, measurement of the intensities of the most sensitive and interference-free emission lines and comparison of these intensities with those of calibration solutions (external calibration method).

Preparation of the solution to be analyzed (test solution): About 10 g of sample were added into a platinum crucible. Using a Bunsen burner, the sample was burned on a low flame until complete combustion of the sample. The calcination was finished by placing the platinum crucible in an oven at 600 °C for minimum 30 minutes. After cooling, Milli-Q® deionized water was added to impregnate all the ashes, and 1mL of concentrated HCI (Merck HCI 32% v/v) and concentrated HF (Merck HF 48% v/v) were added. The crucible was placed in a sand bath, and Milli-Q® deionized water was added to mix the content of the crucible. After 24 h, 1 mL of concentrated HCI, and Milli-Q® deionized water were added while agitating the mixture under heat to achieve full dissolution. After cooling the mixture was transferred to a 50 mL polypropylene tube and the volume made up to 50 mL with Milli-Q® deionized water.

Preparation of calibration standards and control solutions: Standard solutions were prepared by dilution of commercial single-element solutions of certified concentrations. The standard solutions were prepared by transferring the required volume of the certified solution to a 50 mL polypropylene tube, then rinsing the sides of the tube with Milli-Q® deionized water, and adding 1 mL of concentrated HCI per 50 mL to obtain the same acid content in solution as in the sample solutions, and finalizing the dilution with Milli-Q® deionized water. Control solutions were prepared by dilution of commercial multi-element solutions of certified concentrations. The preparation protocol is the same as for the standards solutions. The presence of other elements in solution allowed verification of the presence/absence of possible interferences.

Expression of results for Zr, Al and Fe contents:

The content (in ppm) of the element measured in the sample was calculated as follows:

Concentration in mg/1 of the element in solution x Volume (50 mL) x Dilution factor Mass (g)

The Limit of Quantification (LOQ) was calculated for each element from 10 blank measurements:

LOQ in solution (mg/l) = standard deviation of 10 replicates of the blank x 10

LQ in solution x Volume (50 mL) x Dilution factor

LOQ in sample (ppm) = - — -

^{H J} Mass (g)

CATALYSTS

Metallocene 1 : meso-Metallocene 1 (mMetl) mMetl

/Weso-Metallocene 1 (mMetl) was prepared as described below and as shown under Scheme 1. Unless otherwise mentioned, all procedures take place in a glovebox under a nitrogen atmosphere using dry solvents.

Scheme 1

Step 1:

To a solution of 3.52 g (0.022 mol) of diethyl malonate in 25 mL of THF, 0.88 g (60% in oil, 0.022 mol) of sodium hydride was added at 0 °C. This mixture was refluxed for 1 h and then cooled to room temperature. Next, 5 g (0.022 mol) of 4-tBu-benzylbromide was added, and the resulting mixture was refluxed for 3 h. A precipitate formed (NaBr). This mixture was cooled to room temperature and filtered through a glass frit (G2). The precipitate (NaBr) was additionally washed with 3x5 mL of THF. The combined filtrates were evaporated to dryness.

The residue was dissolved in 20 mL of ethanol and 2.5 mL of water were added then 8 g of potassium hydroxide at 0 °C. The resulting mixture was refluxed for 2 h, and then 10 mL of water was added. Ethanol was distilled off under reduced pressure and controlled T°C (max 30 °C). The resulting aqueous solution was acidified with HCI to pH 1 and the product was extracted with ether (3 x 100 mL). The combined organic fractions were washed with HCI 1 M (1 x 25 mL) and brine (1 x 25 mL) then dried over MgSCU and concentrated under reduced pressure.

The dibasic acid was decarboxylated by heating for 2 h at 160 °C (a gas evolution is noticed). The product obtained was dissolved in 30 mL of dichloromethane, and 30 mL of SOCh was added. The mixture was refluxed for 3 h and then evaporated to dryness.

The residue was dissolved in 12 mL of dry dichloromethane, and the solution obtained was added dropwise to a suspension of 6.5 g (0.05 mol) of AlCh in 68 mL of dichloromethane for 1 h at 0 °C, while vigorously stirring. Next, the reaction mixture was refluxed for 3h, cooled to room temperature, poured on 250 cm ³ of ice, and extracted with DCM (3 x 50 mL).

The organic layer was washed with HCI 1 M and brine (1 x 25 mL each). The combined organic fractions were dried over MgSCUand then evaporated to dryness. The product was isolated by filtration over silica (1 to 10 % AcOEt in isopentane). The desired product was a yellow oil (Yield = 35%).

Step 2:

6-tBu-1 -indanone (1 eq., 5.078 g) was dissolved in 80 mL of Et20. PhMgBr (1.1 eq., 10 mL, 3M) was added at 0 °C dropwise and the solution was heated at reflux during 2h and then stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with 50 mL of 1 M HCI and stirred during 1 h. The mixture was neutralized with saturated solution of NaHCCh and extracted with diethyl ether (x2). The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The product was isolated as a slightly yellow oil (6.54 g, 95%) and used directly in the next step without further purification (or in some cases a filtration over silica with n-pentane was performed).

Step 3:

2 g (8 mmol) of 6-tBu-(phenyl)-1 -indene were introduced into 50 mL of diethyl ether, and 5.3 mL of n-butyllithium (1.6 M in hexane) were added dropwise at 0°C. After this addition was complete, the mixture was stirred at room temperature overnight. A catalytic amount of CuCN was added and the resulting solution was stirred for 30 minutes then 0.49 mL of (dimethyl)dichlorosilane (4 mmol) were added in one portion. After this addition, the reaction solution was stirred overnight at room temperature. The reaction mixture was filtered through alumina and the solvent was removed in vacuo. The product was purified by silica gel flash column chromatography with hexane/DCM (9/1) as eluent to obtain an orange powder. Yield = 52%.

Step 4:

To a solution of ligand bis(5-tert-butyl-3-phenyl-1 H-inden-1-yl)-dimethyl-silane (9.7 g, 552.8 g/mol, 0.0176 mol) in 130 mL of toluene (500 mL round-bottom flask) was added n-BuLi (1.6 M in hexanes, 22.0 mL, 0.0351 mol) over the course of 15 min. The mixture was left to stir at room temperature for 24 h. In a second 500 mL round-bottom flask, ZrCL (4.1 g, 233.04 g/mol, 0.0176 mol) was suspended in 50 mL toluene. With stirring, THF (tetrahydrofuran, 2.7 g, 72.11 g/mol, 0.0370 mol) was added dropwise over ca. 5 minutes. This reaction mixture was left to stir at room temperature for 2 h. The ligand/n-BuLi mixture was then added via pipette over the course of 15 minutes to the ZrCL/THF mixture. An extra ca. 2 mL of THF was used to wash the white solid off the walls of the ligand/n-BuLi flask, and ensure complete transfer. The resulting mixture was left to stir at room temperature for 18 h and then filtered over a 75 mL POR3 glass frit packed with Celite (dried in the oven for 3 days prior to use). The reaction flask and Celite was washed with an extra 40 mL toluene. The filtrate was concentrated under vacuum to ca. 200 mL. The flask was well sealed using silicone grease and a glass stopper, shipped out of the glovebox, and stored at -35 °C for 20 h. The flask was then left at room temperature to de-frost prior to returning to the glovebox. The mixture was filtered over a 75 mL POR4 glass frit, collecting a bright orange solid and a red-orange filtrate. The solid was washed with 2 x 3 mL of pentane, then dried on the frit for ca. 1.5 h. The solid was then transferred to a vial for storage: fraction 1 , 2.58 g (21% yield). The filtrate was concentrated under vacuum in a 500 mL round-bottom flask until an orange precipitate began to form. The flask was sealed with a greased stopper, shipped out of the glovebox, and stored at -35 °C for 20 h. The flask was de-frosted at room temperature, returned to the glovebox, and the mixture was filtered over a POR4 glass frit, collecting a second fraction of bright orange solid and an orange filtrate. The solid was washed with 2 x 3 mL pentane and was left to dry under vacuum on the frit for 2 h. The solid was then transferred to a vial for storage: fraction 2, 446 mg (4% yield). The same procedure as indicated above was repeated for the filtrate at this point, allowing a third (942 mg, 8% yield) fraction of orange solid to be isolated.

The meso purity of each fraction was determined by 1 H NMR. Based on these results, it was concluded that fractions 1 and 2 had similar meso purities and could be combined, resulting in an overall yield of 25% Met1 with 96% meso purity (i.e. , meso/rac ratio of the meso form of Met1 is 96:4) ( ¹ H NMR of the catalyst is shown in Figure 2). This metallocene is referred as mMetl and is used without further purification for supporting and polymerization described herein.

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 Et2<D (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 0 °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. Reaction was quenched with water and extracted with Et20 (3 x 50 mL). Combined organic fractions were dried over MgSCU 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%).

¹ H NMR (500 MHz, CD ₂ CI ₂ ) 6 1.34 (s, 9 H, CH ₃ tBu); 1.36 (s, 9 H, CH ₃ tBu); 2.30 (m, CH ₂ alk); 2.43 (s, 3 H, CH ₃ ); 2.55 (m, 1 H, CH ₂ alk.); 2.65 (m, 1 H, CH ₂ alk.); 3.25 (m, 1 H, CH ₂ 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)

Metallocene 3: Dichlorofrac-ethvlenebis(4,5,6-tetrahvdro-1-indenyl)1zirconi um (Met3)

Dichloro[rac-ethylenebis(4,5,6-tetrahydro-1-indenyl)]zirc onium was purchased from KOEI CHEMICAL Co., Ltd. (CAS 100163-29-9).

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. Titanated silica from PQ (PD12052) was used as catalyst support (D50: 25 pm).

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 h. 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 components A and B (total A+B: 200 mg) were introduced and the mixture was stirred 2 h 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 (3 times). The powder was dried under reduced pressure overnight to obtain a free-flowing grey powder.

The samples were analyzed for zirconium and aluminum content (wt.%) using ICP-AES spectroscopy (Inductively Coupled Plasma - Atomic Emission Spectroscopy). The results are shown in Table 1. Table 1

EXAMPLE A:

Polymerization reactions were performed in a 132 mL autoclave with an agitator, a temperature controller, and inlets for feeding of ethylene and hydrogen. The reactor was dried at 110 °C with nitrogen for 1 h and then cooled to 40 °C.

All polymerizations were performed under the heterogenous conditions depicted in table 2 (unless otherwise stated). The reactor was loaded with 75 mL of isobutane, 1.6 mL of 1-hexene (C6-) and pressurized with 23.8 bar of ethylene (C2-) with 800 ppm of hydrogen. Catalyst (3.5 mg) was added. Polymerization started upon catalyst composition suspension injection, was performed at 85 °C and was stopped after 60 minutes by reactor depressurization. Reactor was flushed with nitrogen prior opening.

Table 2

*ln comparison to iC4 ** in ethylene feed The results of the co-polymerization of ethylene with 1-hexene as comonomer in the presence of dual catalyst compositions are shown in Tables 3. The polymerization conditions were the same as listed in Table 2.

Table 3

Figure 3 shows the GPC trace of the polymers obtained with dual catalyst composition mMet1/Met2 having increasing mMetl content (from 20/80 to 50/50 mMet1/Met2 weight ratio).

Table 4 below shows the results of the co-polymerization of ethylene with 1 -hexene as comonomer in the presence of mMet1/Met2 compositions with varying weight ratio of each catalyst. The polymerization conditions were the same as listed in Table 2. Table 4

The polymers were further examined by melt rheology (RDA). For this purpose, the trend of the log of the complex viscosity (| q*|) as a function of the log of the angular frequency (co) was investigated (Figure 4). The van Gurp-Palmen (vGP) plots were investigated (Figure 5).

The 1 -hexene response was also studied for catalyst composition mMet1/Met2 (30/70 weight ratio). The polymerization conditions were the same as listed in Table 2 (800 ppm H2), except for the 1 -hexene concentration. The results are shown in Table 5.

Table 5

The results of the NMR investigation of the polymers obtained with catalyst composition mMet1/Met2 (30/70 weight ratio) as a function of 1 -hexene concentration are shown in Table 6. Table 6

Further polyethylenes were prepared with different dual catalyst compositions. All polymerizations were performed under the conditions depicted in Table 2. The results are shown in Table 7. Table 7

EXAMPLE B:

Further ethylene polymers were prepared with mMet1/Met2 catalyst composition (30/70 weight ratio). Polymerization reactions were performed in a single slurry loop reactor with isobutane as diluent. All polymerizations were performed under the conditions depicted in Table 8. Analytical results on pellets are also shown in Table 8. Productivity for the produced resins is shown in Figure 6.

Table 8: operating conditions and analytical results for each of the resins

*The iron content of the resins was below 0.1 ppm by weight, as measured by using ICP-AES spectroscopy. Comparative resins were also prepared using the operating conditions depicted in Table 9.

Table 9

Figure 7 shows the hydrogen response. 1 -Hexene content for the produced resins is shown in Table 10 and in Figure 8. Table 10

GPC, DSC, RDA and melt strength results for resins A to I are shown in Figures 9, 10, 11 , 12, and 13 and in Table 11. Table 11

The van Gurp-Palmen (vGP) plots were investigated (Figures 14 and 15). Melt strength results are shown in Figures 16 and 17.

TREF analysis: Resins H, I, F and E were fractionated by a Temperature Rising Elution Fractionation (TREF) process. The results are shown in Figure 18. For each of the resin tested, the temperature of each of the peaks observed in the TREF distribution curves, and the percentage of the area under said peaks are displayed in Table 12.

Table 12