Binary catalyst composition

Abstract

The present invention relates to a catalyst composition comprising: catalyst component A, which comprises a meso isomer of a bridged metallocene compound having two indenyl groups, each indenyl substituted with one or more substituents, at least one of the substituents being aryl or heteroaryl; a meso / rac ratio of the meso isomers of the bridged metallocene compound of catalyst component A being 95:5 or greater; catalyst component B, which comprises a bridged metallocene compound having substituted or unsubstituted cyclopentadienyl groups and substituted or unsubstituted fluorenyl groups; and an optional activator; an optional support; and an optional cocatalyst. The present invention also relates to a polymerization process using said composition. The present invention further relates to an olefin polymer at least partially catalyzed by said catalyst composition and to an article comprising said olefin polymer. The present invention also relates to a melt index MI2 in the range of 0.1 g / 10 min to 12.0 g / 10 min, where MI2 is determined according to ISO 1133:2005 Method B, Condition D, at a temperature of 190° C. and a 2.096 mm die at a load of 2.16 kg; w is the weight average molecular weight, M n The number average molecular weight is 4.0 to 12.0, and the molecular weight distribution M w / M n a rheological long chain branching index grheo of at least 0.90, preferably at least 0.93, preferably at least 0.95; and preferably 13 The present invention also relates to metallocene catalyzed ethylene polymers having at least 0.30 wt. % ethyl branches, based on the total weight of the ethylene polymer, as measured by C NMR, with the proviso that said ethyl branches do not result from the incorporation of 1-butene as a comonomer.

Description

[Technical field]

[0001] FIELD OF THEINVENTION The present invention relates to new dual-site catalyst compositions, particularly dual-site catalyst compositions for polymerization reactions. The invention also relates to new ethylene polymers and articles comprising said ethylene polymers. [Background technology]

[0002] 2. Background of the Invention In the field of polymers, continuous improvement of mechanical properties is essential. In the last few years, metallocene catalysts in combination with cascade reactors have been used to produce tailor-made bimodal resins. However, the need for multiple reactors increases both construction and operation costs, which can be overcome by using dual-site catalyst compositions in a single reactor.

[0003] In the prior art, the first obvious solution was multiple separate catalyst injections. Although this method showed high flexibility, some drawbacks could be highlighted: multiple catalyst injections led to increased costs and polymer uniformity was difficult to achieve.

[0004] Therefore, the strategy of using dual-site catalysts in a single reactor seemed to be a good alternative. However, this technique is fraught with difficulties in properly controlling the heterogenization and, more importantly, the activation. This may be related to the different behavior of the metallocenes during the heterogenization process, which usually results in a favored structure while others appear inactive. Also, in several examples in the literature, certain combinations lack reactivity or only work under certain conditions or in certain processes. The challenge is to find the right combination of metallocenes to avoid these drawbacks. Summary of the Invention [Problem to be solved by the invention]

[0005] SUMMARY OF THE PRESENT APPLICATION It is therefore an object of the present invention to provide a new dual catalyst which avoids the above mentioned drawbacks. [Means for solving the problem]

[0006] The present invention provides a dual catalyst composition containing a bridged bis-indenyl metallocene having meso stereoisomeric geometry, where each indenyl is independently substituted with one or more substituents, preferably at least one of the substituents being at the 3- and / or 5-position of each indenyl, preferably at the 3-position of each indenyl, and a second metallocene having a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group. The novel composition of the present invention provides polyethylene products with unique molecular architecture and high density split in a single reactor configuration.

[0007] In a first aspect, the present invention provides a method for producing a composition comprising the steps of: a catalyst component A comprising a meso isomer of a bridged metallocene compound having two indenyl groups, each indenyl being independently substituted with one or more substituents, at least one of the substituents being aryl or heteroaryl; a meso / rac ratio of the meso isomer of the bridged metallocene compound of the catalyst component A being 1 Catalyst component A, which has a molecular weight of 95:5 or greater as determined using H NMR; preferably with at least one of the substituents at the 3 and / or 5 positions of each indenyl, preferably with an aryl or heteroaryl substituent at the 3 position of each indenyl; a catalyst component B comprising a bridged metallocene compound having a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; an optional activator; an optional support; and an optional cocatalyst. A catalyst composition comprising:

[0008] In a second aspect, the present invention provides a process for the polymerization of olefins 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 optionally one or more olefin comonomers in the presence of the at least one catalyst composition, and optionally hydrogen, to obtain a polyolefin.

[0009] 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 a process according to the second aspect of the invention.

[0010] In a fourth aspect, the present invention provides a metallocene catalyzed ethylene polymer, preferably such an ethylene polymer prepared using a continuous process, and at least one metallocene catalyst composition, said metallocene catalyzed ethylene polymer comprising: a melt index MI2 in the range of 0.1 g / 10 min to 12.0 g / 10 min, where MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature of 190° C. and using a 2.096 mm die with a 2.16 kg load; M w is the weight average molecular weight, M n The number average molecular weight is 4.0 to 12.0, and the molecular weight distribution M w / M n ; A rheology long chain branching index g of at least 0.90, preferably at least 0.93, preferably at least 0.95 rheo and 13 Preferably at least 0.30 wt. % ethyl branches, based on the total weight of the ethylene polymer, as measured by C NMR, with the proviso that said ethyl branch content does not result from the incorporation of 1-butene as a comonomer. has.

[0011] The invention also includes articles comprising an olefin polymer according to the third aspect, and / or a metallocene-catalyzed ethylene polymer according to the fourth aspect.

[0012] The present invention overcomes the drawbacks of the above-mentioned approaches by providing compositions comprising dual catalyst compositions, meaning catalyst particles with two metallocene active sites on a single support.

[0013] Such catalyst compositions can be used, for example, to produce ethylene-copolymers with broad molecular weight distribution, ideal comonomer incorporation to improve mechanical properties, and higher activity compared to other systems. The catalysts used in the compositions provide control over targeted molecular architecture and allow inverse comonomer distribution (comonomer concentrated in higher molecular weight chains). In the case of copolymerization of ethylene and α-olefins, the dual catalyst composition provides a higher density split between lower and higher molecular weight fractions (very low comonomer incorporation in shorter vs. longer chains) in addition to extremely high catalytic activity. The lower molecular weight component can improve product processability, while the higher molecular weight component can enhance mechanical properties.

[0014] Catalyst component A has very low comonomer incorporation and provides a low molecular weight, high density product, while catalyst component B produces a low density, high molecular weight product with a low number of long chain branches.

[0015] The dual catalyst compositions can provide polyethylene products with novel broad / bimodal molecular weight distributions, desirable reverse comonomer incorporation, and improved processing / mechanical properties.

[0016] The catalyst composition can be used in a single reactor process (slurry loop and / or gas phase) or even in a multi-reactor process.

[0017] The present invention also provides ethylene polymers with broad molecular weight distribution, ideal comonomer incorporation and improved processing and mechanical properties.

[0018] Once produced, the polymers may be formed into a variety of articles including, but not limited to, film products, caps and closures, liners, rotomolded articles, glass yarns, and the like.

[0019] 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.

[0020] The present invention will be further described below. In the following description, various aspects of the present invention are defined in more detail. Each aspect so defined may be combined with any one or more of the other aspects unless clearly indicated to the contrary. In particular, any feature or term indicated as being preferred or advantageous may be combined with any other feature or term indicated as being preferred or advantageous. [Brief description of the drawings]

[0021] [Figure 1] FIG. 1 represents a graph plotting the 13C{1H} NMR spectra of metallocene ethylene polymers. [Diagram 2] FIG. 2 represents a graph plotting the 1H NMR spectrum of meso-Met1 (mMet1). [Diagram 3] FIG. 3 shows a plot of the GPC traces (ie, molecular weight distributions (logarithm of molecular weight)) of polymers obtained with various mMet1 / Met2 weight ratio compositions of each catalyst. [Figure 4] Figure 4 represents a graph plotting the logarithm of the complex viscosity (|η*|Pa.s) as a function of the logarithm of the angular frequency (ω, rad / s) for polymers obtained with mMet1 / Met2 compositions of various weight ratios of each catalyst, at a shear strain (γ) of 10%, and at angular frequencies (ω) from −1 to 2.477 (i.e., 0.1 to 300 s−1) expressed on a logarithmic scale. [Diagram 5] FIG. 5 shows the van Gurp-Palmen plots of the polymers obtained with various mMet1 / Met2 weight ratio compositions of each catalyst. [Figure 6] FIG. 6 shows a graph plotting the productivity of Resins A to I. [Figure 7] FIG. 7 depicts a graph plotting the melt index of Resins A through I as a function of hydrogen / ethylene feed concentration. [Figure 8] FIG. 8 depicts a graph plotting the densities of Resins A through I as a function of 1-hexene / ethylene feed concentration. [Figure 9] FIG. 9 depicts a graph plotting the GPC traces of Resins A-D. [Figure 10] FIG. 10 depicts a graph plotting the GPC traces of Resins E through I. [Figure 11] FIG. 11 represents a graph plotting the ratio CH3 / CH2 (GPC-IR) as a function of the logarithm of the molecular weight of resins E through I. [Figure 12] Figure 12 shows a graph plotting the logarithm of the complex viscosity (|η*|Pa.s) as a function of the logarithm of the angular frequency (ω, rad / s) for resins A to D. Shear strain (γ) is 10%, and angular frequency (ω) is −1 to 2.477 (i.e., 0.1 to 300 s−1) on a logarithmic scale. [Figure 13] Figure 13 shows a graph plotting the logarithm of the complex viscosity (|η*| Pa.s) as a function of the logarithm of the angular frequency (ω, rad / s) for resins E to I. Shear strain (γ) 10%, angular frequency (ω) -1 to 2.477 (i.e., 0.1 to 300 s-1) expressed on a logarithmic scale. [Figure 14] FIG. 14 shows the van Gurp-Palmen plots for Resins A-D. [Figure 15] FIG. 15 shows the van Gurp-Palmen plots of resins E through I. [Figure 16] FIG. 16 depicts a graph plotting the measured melt strengths for Resins A-D. [Figure 17] FIG. 17 depicts a graph plotting the melt strengths measured for resins E through I. [Figure 18] FIG. 18 depicts a graph plotting the TREF (Temperature Rising Elution Fractionation) profiles of Resins E, F, H, and I. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Detailed Description of the Invention Before describing the present compositions, compounds, polymers, methods, articles, and uses encompassed by the present invention, it is to be understood that the invention is not limited to the particular compositions, compounds, polymers, methods, articles, and uses described, as such compositions, compounds, polymers, methods, 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 invention will be limited only by the appended claims.

[0023] Unless otherwise defined, all terms used in disclosing the present invention, including technical and scientific terms, have the meanings commonly understood by those skilled in the art to which this invention belongs.With further guidance, the definitions of the terms used in this description are included to better understand the teachings of the present invention.When describing the compounds, methods, articles, and uses of the present invention, the terms used should be interpreted according to the following definitions, unless the context dictates otherwise.

[0024] 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.

[0025] 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, unrecited members, elements, or method steps. The terms "comprising," "comprises," and "comprised of" also include the term "consisting of."

[0026] The recitation of numerical ranges by endpoints includes all integers and, where appropriate, fractions subsumed within that range (e.g., 1 to 5 can include 1, 2, 3, 4, e.g., when referring to the number of elements, and can also include 1.5, 2, 2.75, and 3.80, e.g., when referring to measurements). The recitation of endpoints also includes the endpoint values ​​themselves (e.g., 1.0 to 5.0 includes both 1.0 and 5.0). Every numerical range recited herein is intended to include all subranges subsumed therein.

[0027] References throughout this specification to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various parts throughout this specification do not necessarily all refer to the same embodiment, but may. Furthermore, particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments, as would be apparent to one of ordinary skill in the art from this disclosure. Furthermore, as would be understood by one of ordinary skill in the art, although some embodiments described herein include some features included in other embodiments and others do not, combinations of features of different embodiments are intended to be within the scope of the invention and form different embodiments. For example, any embodiment may be used in any combination in the following claims and clauses.

[0028] The term "substituted," as used herein, is meant to indicate that one or more hydrogen atoms on the atom designated with "substituted" have been replaced with a selection from the designated group, provided that the normal valence of the designated atom is not exceeded and that the substitution results in a chemically stable compound, i.e., a compound that is robust enough to survive isolation from a reaction mixture. Preferred substituents for the indenyl, cyclopentadienyl and fluorenyl groups are alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 ) 3, heteroalkyl; 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, an aryl or heteroaryl substituent is at the 3-position of each indenyl; and the indenyl may further be substituted with alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 103, optionally substituted with one or more substituents selected from the group including heteroalkyl; each R 10 is independently hydrogen, alkyl, or alkenyl.

[0029] The terms "halo" or "halogen" as a group or part of a group are generic to fluoro, chloro, bromo and iodo.

[0030] The term “alkyl” as a group or part of a group refers to a group of formula C n H 2n+1 where n is a number equal to or greater than 1. The alkyl groups may be linear or branched and may be substituted as provided herein. Generally, the alkyl groups of this invention contain from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, and more preferably from 1 to 4 carbon atoms. When a subscript number is used herein following a carbon atom, the subscript number refers to the number of carbon atoms that the named group may contain. For example, the term "C" as a group or part of a group 1~20 "Alkyl" refers to a group of the formula -C, where n is a number ranging from 1 to 20. n H 2n+1 Thus, for example, "C 1~8 "Alkyl" includes all straight or branched alkyl groups having 1 to 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, and the like. "Substituted alkyl" refers to an alkyl group substituted with one or more substituents (e.g., 1 to 3 substituents, e.g., 1, 2, or 3 substituents) at any available point of attachment.

[0031] When the suffix "ene" is used in connection with an alkyl group, i.e., "alkylene," it is intended to mean an alkyl group, as defined herein, having two single bonds as points of attachment to other groups. The term "alkylene," also referred to as "alkanediyl," as used herein by itself or as part of another substituent, refers to an alkyl group that is divalent, i.e., has 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-), ethylene (-CH-CH-), methylmethylene (-CH(CH)-), 1-methyl-ethylene (-CH(CH)-CH-), n-propylene (-CH-CH-CH-), 2-methylpropylene (-CH-CH(CH)-CH-), 3-methylpropylene (-CH-CH-CH(CH)-), n-butylene (-CH-CH-CH-CH-CH-), 2-methylbutylene (-CH-CH(CH)-CH-CH-), 4-methylbutylene (-CH-CH-CH-CH(CH)-), pentylene and its linkage isomers, and hexylene and its linkage isomers.

[0032] The term "alkenyl" as a group or part of a group refers to an unsaturated hydrocarbyl group, which may be linear or branched, containing one or more carbon-carbon double bonds. Generally, alkenyl groups of this invention contain from 3 to 20 carbon atoms, preferably from 3 to 10 carbon atoms, and preferably from 3 to 8 carbon atoms. When a subscript number is used herein following a carbon atom, the subscript number refers to the number of carbon atoms that the named group may contain. C 3~20 Examples of alkenyl 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.

[0033] The term “alkoxy” or “alkyloxy” as a group or part of a group refers to R b is alkyl as defined herein above; bNon-limiting examples of suitable alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy and hexyloxy.

[0034] 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 one or more ring structures and containing 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms. Cycloalkyl includes all saturated hydrocarbon groups containing one or more rings, including monocyclic, bicyclic or tricyclic groups. The additional rings of polycyclic cycloalkyls may be fused, bridged and / or linked through one or more spiro atoms. When a subscript number is used herein following a carbon atom, the subscript number refers to the number of carbon atoms that the named group may contain. For example, the term "C 3~20 "Cycloalkyl" is a cyclic alkyl group containing 3 to 20 carbon atoms. For example, the term "C 3~10 "Cycloalkyl" is a cyclic alkyl group containing 3 to 10 carbon atoms. For example, the term "C 3~8 "Cycloalkyl" is a cyclic alkyl group containing 3 to 8 carbon atoms. For example, the term "C 3~6 "Cycloalkyl" is a cyclic alkyl group containing 3 to 6 carbon atoms. 3~12 Examples of cycloalkyl groups include, but are not limited to, adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptan-2-yl, (1S,4R)-norbornan-2-yl, (1R,4R)-norbornan-2-yl, (1S,4S)-norbornan-2-yl, (1R,4S)-norbornan-2-yl.

[0035] When the suffix "ene" is used in connection with a cycloalkyl group, i.e., cycloalkylene, it is intended to mean a 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.

[0036] When an alkylene or cycloalkylene group is present, the connections to the molecular structure of which it forms a part may be through a common carbon atom or through different carbon atoms. Illustrated by applying the asterisk nomenclature of this invention, a C3 alkylene group may be, for example, *-CH2CH2CH2-*, *-CH(-CH2CH3)-* or *-CH2CH(-CH3)-*. Similarly, a C3 cycloalkylene group may be

[0037] [ka]

[0038] It could be. The term "cycloalkenyl" as a group or part of a group refers to a non-aromatic cyclic alkenyl group having at least one site (usually 1 to 3, preferably 1) of unsaturation, i.e., a carbon-carbon sp2 double bond; preferably having 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, more preferably 5 to 6 carbon atoms. Cycloalkenyl encompasses all unsaturated hydrocarbon groups containing one or more rings, including monocyclic, bicyclic or tricyclic groups. The further rings may be fused, bridged and / or linked through one or more spiro atoms. When a subscript number is used herein following a carbon atom, the subscript number refers to the number of carbon atoms that the named group may contain. For example, the term "C 5~20"Cycloalkenyl" refers to a cyclic alkenyl group containing 5 to 20 carbon atoms. For example, the term "C 5~10 "Cycloalkenyl" refers to a cyclic alkenyl group containing 5 to 10 carbon atoms. For example, the term "C 5~8 "Cycloalkenyl" refers to a cyclic alkenyl group containing 5 to 8 carbon atoms. For example, the term "C 5~6 "Cycloalkyl" is a cyclic alkenyl group containing 5 to 6 carbon atoms. Examples include, but are not limited to, cyclopentenyl (-C5H7), cyclopentenylpropylene, methylcyclohexenylene, and cyclohexenyl (-C6H9). The double bond may be in either the cis or trans configuration.

[0039] The term "cycloalkenylalkyl" as a group or part of a group means an alkyl, as defined herein, in which at least one hydrogen atom is replaced by at least one cycloalkenyl, as defined herein.

[0040] The term “cycloalkoxy” as a group or part of a group means R h is cycloalkyl as defined herein above; h The formula is:

[0041] 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 covalently linked together, typically containing 6 to 20 atoms; preferably 6 to 10, in which at least one ring is aromatic. The aromatic ring may optionally have 1 to 2 additional rings (either cycloalkyl, heterocyclyl or heteroaryl) fused thereto. Examples of suitable aryls include C 6~20 Aryl, preferably C 6~10 Aryl, more preferably C 6~8Aryl. Non-limiting examples of aryl include phenyl, biphenylyl, biphenylenyl, or 1- or 2-naphthanelyl; 1-, 2-, 3-, 4-, 5-, or 6-tetralinyl (also referred to as "1,2,3,4-tetrahydronaphthalene"); 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. "Substituted aryl" refers to an aryl group having one or more substituents (e.g., 1, 2, or 3 substituents, or 1-2 substituents) at any available point of attachment.

[0042] The term “aryloxy” as a group or part of a group refers to R g is aryl as defined herein above; g The formula is:

[0043] The term "arylalkyl" as a group or part of a group means an alkyl group, as defined herein, in which at least one hydrogen atom is replaced by at least one aryl group, as defined herein. Non-limiting examples of arylalkyl groups include benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl, 3-(2-naphthyl)-butyl, and the like.

[0044] The term "alkylaryl" as a group or part of a group means aryl, as defined herein, in which at least one hydrogen atom is replaced by at least one alkyl, as defined herein. Non-limiting examples of alkylaryl groups include R g p-CH3-R is aryl as defined herein above g -There is.

[0045] The term “arylalkyloxy” or “aralkoxy” as a group or part of a group refers to R gis aryl, and R a is alkylene as defined herein above; a -R g The formula is:

[0046] The term "heteroalkyl" as a group or part of a group refers to an acyclic alkyl in which one or more carbon atoms are replaced by at least one heteroatom selected from the group including O, Si, S, B, and P, with the proviso that the chain cannot contain two adjacent heteroatoms. This means that one or more -CH3 of said acyclic alkyl may be replaced by, for example, -OH, and / or one or more -CR2- of said acyclic alkyl may be replaced by O, Si, S, B, and P.

[0047] The term “aminoalkyl” as a group or part of a group refers to R j is alkylene, and R k is hydrogen or alkyl as defined herein; R l is a group -R j -NR k R l This refers to.

[0048] The term "heterocyclyl" as a group or part of a group refers to a non-aromatic fully saturated or partially unsaturated cyclic group (e.g., 3-7 membered monocyclic group, 7-10 membered bicyclic group) containing at least one heteroatom in at least one ring containing carbon atoms, preferably containing a total of 3-10 ring atoms. Each ring of a heteroatom-containing heterocyclic group may have 1, 2, 3 or 4 heteroatoms selected from N, S, Si, Ge, the nitrogen and sulfur heteroatoms may be optionally oxidized, and the nitrogen heteroatom may be optionally quaternized. Heterocyclic groups may be attached at any heteroatom or carbon atom of the ring or ring system, if valences permit. The rings of polycyclic heterocycles may be fused, bridged, and / or attached through one or more spiro atoms.

[0049] Non-limiting representative 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-quinolidinyl, 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 inyl), 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-yl sulfoxide, thiomorpholin-4-yl sulfone, 1,3-dioxolanyl, 1,4-oxathianyl, 1,4-dithianyl, 1,3,5-trioxanyl, 1H-pyrrolidinyl, tetrahydro-1,1-dioxothiophenyl, N-formylpiperazinyl, and morpholin-4-yl.

[0050] The term "compound" or similar term as used herein is meant to include the compounds of general formula (I) and / or (II) as defined below and any subgroup thereof, including all polymorphs and crystal habits thereof, and their isomers (including optical, geometric and tautomeric isomers).

[0051] The compounds of formula (I) and / or (II) or any subgroups thereof may contain alkenyl groups, and geometric cis / trans (or Z / E) isomers are encompassed by the present invention. Where structural isomers are interconvertible via a low energy barrier, tautomeric isomerism ("tautomerism") may occur. This can take the form of, for example, proton tautomerism in compounds of formula (I) that contain a keto group, or so-called valence tautomerism in compounds that contain an aromatic moiety. As a result, a single compound may exhibit more than one type of isomerism.

[0052] Cis / trans isomers may be separated by conventional techniques well known to those skilled in the art, such as chromatography and fractional crystallization.

[0053] Preferred clauses (features) and embodiments of the compositions, methods, polymers, articles, and uses of the invention are described below. Each clause and embodiment of the invention so defined may be combined with any other clause 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 feature or clause indicated as being preferred or advantageous. In this regard, the invention is particularly encompassed by any one of the clauses and embodiments numbered below, or any combination of one or more of them with any other aspect and / or embodiment.

[0054] 1. A catalyst component A comprising a meso isomer of a bridged metallocene compound having two indenyl groups, each indenyl being independently substituted with one or more substituents, at least one of the substituents being aryl or heteroaryl, preferably the meso / rac ratio of the meso isomer of the bridged metallocene compound of catalyst component A is preferably 1a catalyst component A having a ratio of 95:5 or greater as determined using H NMR; preferably at least one of the substituents is aryl; preferably at least one of the substituents is at the 3 and / or 5 position of each indenyl, preferably each indenyl has one substituent at the 3 position, preferably each indenyl has one substituent at the 5 position, even more preferably each indenyl has one substituent at the 3 position and one substituent at the 5 position of each indenyl, preferably an aryl or heteroaryl substituent is at the 3 position of each indenyl; Catalyst component B containing a bridged metallocene compound having a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group. an optional activator; an optional support; and an optional cocatalyst. A catalyst composition comprising:

[0055] 2. A catalyst component A comprising a meso isomer of a bridged metallocene compound having two indenyl groups, each indenyl being independently substituted with one or more substituents, at least one of the substituents being aryl or heteroaryl, preferably the meso / rac ratio of the meso isomer of the bridged metallocene compound of catalyst component A is preferably 1 a catalyst component A having a ratio of 95:5 or greater as determined using H NMR; preferably at least one of the substituents is aryl; preferably at least one of the substituents is at the 3 and / or 5 position of each indenyl, preferably each indenyl has one substituent at the 3 position, preferably each indenyl has one substituent at the 5 position, even more preferably each indenyl has one substituent at the 3 position and one substituent at the 5 position of each indenyl, preferably an aryl or heteroaryl substituent is at the 3 position of each indenyl; a catalyst component B comprising a bridged metallocene compound having a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; Activators; supports; and optional cocatalysts A catalyst composition comprising:

[0056] 3. The meso / rac ratio of the meso form of the bridged metallocene compound of catalyst component A is preferably 1 3. The catalyst composition according to any one of items 1 to 2, wherein the ratio is 95:5 or greater as determined using H NMR.

[0057] 4. The composition according to any one of items 1 to 3, wherein the weight ratio of the catalyst component A to the catalyst component B is in the range of 10 / 90 to 90 / 10, preferably in the range of 15 / 85 to 80 / 20, preferably in the range of 20 / 80 to 70 / 30, preferably in the range of 20 / 80 to 60 / 40, preferably in the range of 20 / 80 to 50 / 50, preferably in the range of 20 / 80 to 40 / 60, more preferably in the range of 25 / 75 to 35 / 65, preferably in the range of 28 / 72 to 33 / 67, preferably in the range of 29 / 71 to 32 / 68, preferably in the range of 29 / 71 to 31 / 69, preferably in the range of 30 / 70.

[0058] 5. The bridged metallocene compound of catalyst component B has at least one alkenyl, cycloalkenyl, or cycloalkenylalkyl substituent, preferably at least one C 3~20 Alkenyl, C 5~20 Cycloalkenyl, or C 6~20 Cycloalkenylalkyl substituents, more preferably at least one C 3~8 Alkenyl, C 5~8 Cycloalkenyl, or C 6~8 5. The composition according to any one of items 1 to 4, comprising a cycloalkenylalkyl substituent.

[0059] 6. The bridged metallocene compound of catalyst component B has at least one alkenyl, cycloalkenyl, or cycloalkenylalkyl substituent on the bridge; preferably at least one C 3~20 Alkenyl, C 5~20 Cycloalkenyl, or C 6~20 The cycloalkenylalkyl substituent is preferably selected from the group consisting of at least one C 3~8 Alkenyl, C 5~8 Cycloalkenyl, or C 6~8 6. The composition according to any one of items 1 to 5, comprising a cycloalkenylalkyl substituent.

[0060] 7. The composition according to any one of items 1 to 6, wherein catalyst component A contains a Si or C bridging atom, which may be optionally substituted with one or two substituents, each independently selected from alkyl, alkenyl, cycloalkyl, or cycloalkenyl.

[0061] 8. The composition according to any one of items 1 to 7, wherein catalyst component B contains a C, Si, B or Ge bridging atom.

[0062] 9. The composition according to any one of items 1 to 8, wherein the activator comprises an aluminoxane compound, an organoborate compound, an ionizing ionic compound, or any combination thereof, preferably, the activator comprises an alumoxane compound.

[0063] 10. The activator is represented by the formula (V) or (VI) R for oligomeric linear alumoxanes a -(Al(R a )-O) x -AlR a 2(V); or For oligomeric cyclic alumoxanes, (-Al(R a )-O-) y (VI) [In the formula, x is 1 to 40, preferably 10 to 20; y is 3 to 40, preferably 3 to 20; Each R a is independently C 1~8 alkyl, preferably methyl. 10. The composition according to any one of items 1 to 9, comprising at least one alumoxane compound.

[0064] 11. The composition according to any one of items 1 to 10, wherein the activator is methylalumoxane.

[0065] 12. The composition according to any one of items 1 to 11, wherein the catalyst composition comprises a cocatalyst. 13. The composition according to any one of items 1 to 12, wherein the catalyst composition comprises an organoaluminum cocatalyst.

[0066] 14. The composition according to any one of items 1 to 13, wherein the catalyst composition comprises an organoaluminum cocatalyst selected from the group consisting of 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.

[0067] 15. The composition according to any one of paragraphs 1 to 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, mixed oxides thereof, or any mixture thereof; preferably silica, titanated silica, fluoride-treated silica, silica-alumina, fluoride-treated alumina, sulfated alumina, fluoride-treated silica-alumina, sulfated silica-alumina, silica-coated alumina, fluoride-treated silica, sulfated silica-coated alumina, or any combination thereof.

[0068] 16. The composition according to any one of paragraphs 1 to 15, wherein the support has a D50 of at most 50 μm, preferably at most 40 μm, preferably at most 30 μm, where D50 is defined as the particle size at which 50 weight percent of the particles have a size smaller than D50, and the particle size can be measured by laser diffraction analysis on a Malvern type analyzer.

[0069] 17. The composition according to any one of paragraphs 1 to 16, comprising an alumoxane activator; and a titanated silica or silica solid support; and an optional cocatalyst.

[0070] 18. Catalyst component A is a compound represented by the formula (I)

[0071] [ka]

[0072] [In the formula, R 1 and R 3 each independently represents an alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 ) 3, and heteroalkyl; R 1 or R 3 At least one of R is aryl, and each R 10 are independently hydrogen, alkyl, or alkenyl; m, p are each independently an integer selected from 0, 1, 2, 3, or 4, where at least one of m or p is at least 1; R 2 and R 4 each independently represents an alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 ) 3, and heteroalkyl; R 2 or R 4 At least one of R is aryl, and each R 10 are independently hydrogen, alkyl, or alkenyl; n, q are each independently an integer selected from 0, 1, 2, 3, or 4, where at least one of n or q is at least 1; L 1 is SiR 8 R 9 , -[CR 8 R 9 ] h -, GeR8 R 9 , or B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9 each is independently selected from the group consisting of 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 consisting of zirconium, titanium, hafnium, and vanadium; preferably M is zirconium; Q 1 and Q 2 are each independently a halogen, an alkyl, or -N(R 11 )2, selected from the group consisting of alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; R 11 is hydrogen or alkyl. Item 18. The composition according to any one of items 1 to 17, comprising a meso isomer of the bridged metallocene catalyst.

[0073] 19. Catalyst component A is SiR 8 R 9 Or - [CR 8 R 9 ] h -Bridge group; preferably SiR 8 R 9 contains a bridging group; h is an integer selected from 1, 2, or 3; R 8 and R 9 each is independently selected from the group including hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl, preferably alkyl; or R 8 and R 9together with the atom to which they are attached form a cycloalkyl, cycloalkenyl, or heterocyclyl.

[0074] 20. Catalyst component A is a compound represented by the formula (I)

[0075] [ka]

[0076] [In the formula, R 1 , R 3 Each of the 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 Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1~12 alkyl; R 1 or R 3 At least one of the following is C 6~20 aryl, preferably phenyl; 10 are independently hydrogen, C 1~20 Alkyl, or C 3~20 alkenyl; m, p are each independently an integer selected from 0, 1, 2, 3, or 4, and at least one of m or p is at least 1; R 2 , R 4 Each of the 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 7~20Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1~12 alkyl; R 2 or R 4 At least one of the following is C 6~20 aryl, preferably phenyl; 10 are independently hydrogen, C 1~20 Alkyl, or C 3~20 alkenyl; n, q are each independently an integer selected from 0, 1, 2, 3, or 4, and 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 B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9 each independently represents 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, Amino C 1~6 Alkyl, and C 7~ C 20 arylalkyl; or R 8 and R 9 C along with the atoms to which they are attached 3~20 Cycloalkyl, C 5~20 forms a cycloalkenyl or heterocyclyl; preferably L 1 is SiR 8 R 9 ;R 8 and R 9 each independently represents hydrogen, C 1~20 Alkyl, C 3~20 Alkenyl, C 3~20 Cycloalkyl, C 5~20 Cycloalkenyl, C 6~20Cycloalkenylalkyl, C 6~10 Aryl, Amino C 1~6 Alkyl, and C 7~ C 20 arylalkyl; or R 8 and R 9 C along with the atoms to which they are attached 3~20 Cycloalkyl, C 5~20 forms a cycloalkenyl or heterocyclyl; preferably R 8 and R 9 Each of the above is independently C 1~6 is alkyl; M 1 is a transition metal selected from the group consisting of zirconium, titanium, hafnium, and vanadium; preferably M is zirconium; Q 1 and Q 2 are each independently a halogen, C 1~20 Alkyl, -N(R 11 )2, C 1~20 Alkoxy, C 3~20 Cycloalkoxy, C 7~20 Aralkoxi, C 3~20 Cycloalkyl, C 6~20 Aryl, C 7~20 Alkylaryl, C 7~20 Aralkyl, and Hetero C 1~20 alkyl; R 11 is hydrogen or C 1~20 is alkyl] 20. The composition according to any one of items 1 to 19, comprising a meso isomer of a bridged metallocene.

[0077] 21.R 1 and R 3 Each of the above is independently 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, C7~12 Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1~8 alkyl; R 1 or R 3 At least one of the following is C 6~10 aryl, preferably phenyl; 10 are independently hydrogen, C 1~8 Alkyl, or C 3~8 alkenyl; m, p are each independently an integer selected from 0, 1, 2, 3, or 4, and at least one of m or p is at least 1; R 2 and R 4 Each of the above is independently 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 Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1~8 alkyl; R 2 or R 4 At least one of the following is C 6~10 aryl, preferably phenyl; 10 are independently hydrogen, C 1~8 Alkyl, or C 3~8 alkenyl; n, q are each independently an integer selected from 0, 1, 2, 3, or 4, and at least one of n or q is at least 1; L 1 SiR 8 R 9 , -[CR 8 R 9 ] h -, GeR 8 R 9 , or B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9each independently represents 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, Amino C 1~6 Alkyl, and C 7~ C 12 arylalkyl; or R 8 and R 9 C along with the atoms to which they are attached 3~8 Cycloalkyl, C 5~8 forming a cycloalkenyl or heterocyclyl; preferably L 1 SiR 8 R 9 and preferably R 8 and R 9 each independently represents hydrogen, or C 1~8 alkyl; M 1 is a transition metal selected from the group consisting of zirconium, titanium, hafnium, and vanadium; preferably M is zirconium; Q 1 and Q 2 are each independently a halogen, C 1~8 Alkyl, -N(R 11 )2, C 1~8 Alkoxy, C 3~8 Cycloalkoxy, C 7~12 Aralkoxi, C 3~8 Cycloalkyl, C 6~10 Aryl, C 7~12 Alkylaryl, C 7~12 Aralkyl, and Hetero C 1~8 alkyl; R 11 is hydrogen or C 1~8 21. The composition according to any one of items 18 to 20, wherein the alkyl is alkyl.

[0078] 22.R 1 and R 3 Each of the above is independently C 1~8 Alkyl, C 3~8Alkenyl, C 3~8 Cycloalkyl, C 6~10 aryl, and halogen; R 1 or R 3 At least one of the following is C 6~10 aryl, preferably phenyl; 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, and at least one of m or p is at least 1; R 2 and R 4 Each of the above is independently C 1~8 Alkyl, C 3~8 Alkenyl, C 3~8 Cycloalkyl, C 6~10 aryl, and halogen; R 2 or R 4 At least one of the following is C 6~10 aryl, preferably phenyl; 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, and at least one of n or q is at least 1; L 1 SiR 8 R 9 , or -[CR 8 R 9 ] h h is an integer selected from 1 or 2; R 8 and R 9 each independently represents 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 SiR 8 R 9 and preferably R 8 and R 9 each independently represents hydrogen, or C 1~8alkyl; M 1 is a transition metal selected from zirconium, or hafnium; preferably M is zirconium; Q 1 and Q 2 are each independently a halogen, C 1~8 Alkyl, -N(R 11 )2, C 6~10 Aryl, and C 7~12 aralkyl; R 11 is hydrogen or C 1~8 is alkyl, preferably Q 1 and Q 2 22. The composition according to any one of items 18 to 21, wherein each is independently selected from the group consisting of Cl, F, Br, I, methyl, benzyl, and phenyl.

[0079] 23. Catalyst component A is represented by the formula (Ia)

[0080] [ka]

[0081] [In the formula, R 1 , R 2 , R 3 , R 4 , L 1 , M 1 , Q 1 , Q 2 , p and q have the same meaning as defined in any one of items 18 to 22, preferably R 1 and R 2 are each independently C 6~10 is aryl] 23. The composition according to any one of items 1 to 22, comprising a meso isomer of a bridged metallocene.

[0082] 24. Catalyst component A is represented by the formula (Ib)

[0083] [ka]

[0084] [In the formula, R 1 , R 2 , R 3 , R 4 , L 1 , M 1 , Q 1 , and Q 2 has the same meaning as defined in any one of paragraphs 18 to 22, preferably R 1 and R 2 are each independently C 6~10 is aryl] 24. The composition according to any one of items 1 to 23, comprising a meso isomer of a bridged metallocene.

[0085] 25. Catalyst component A is represented by the formula (Ic)

[0086] [ka]

[0087] 25. The composition according to any one of items 1 to 24, comprising a meso-bridged metallocene. 26. Catalyst component B is a compound represented by the formula (II)

[0088] [ka]

[0089] [In the formula, R 5 , R 6 , and R 7 each independently represents an alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 ) 3, and heteroalkyl; each R 10 are independently hydrogen, alkyl, or alkenyl; r, s, and t are each independently an integer selected from 0, 1, 2, 3, or 4; L 2 - [CR 8 R9 ] h -,SiR 8 R 9 , G.E.R. 8 R 9 , or B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9 each is independently selected from the group consisting of 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 consisting of zirconium, titanium, hafnium, and vanadium; preferably zirconium; Q 3 and Q 4 are each independently a halogen, an alkyl, or -N(R 11 )2, selected from the group consisting of alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; R 11 is hydrogen or alkyl. 26. The composition according to any one of items 1 to 25, comprising a bridged metallocene.

[0090] 27. Catalyst component B is a compound represented by the formula (II)

[0091] [ka]

[0092] [In the formula, R 5 , R 6 , and R 7 Each of the C 1~20 Alkyl, C 3~20 Alkenyl, C 3~20 Cycloalkyl, C 5~20 Cycloalkenyl, C6~20 Cycloalkenylalkyl, C 6~20 Aryl, C 1~20 Alkoxy, C 7~20 Alkylaryl, C 7~20 Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1~20 alkyl; each R 10 are independently hydrogen, C 1~20 Alkyl, or C 3~20 alkenyl; r, s, and t are each independently an integer selected from 0, 1, 2, 3, or 4; L 2 - [CR 8 R 9 ] h -,SiR 8 R 9 , G.E.R. 8 R 9 , or B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9 each independently represents 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, Amino C 1~6 Alkyl, and C 7~ C 20 arylalkyl; or R 8 and R 9 C along with the atoms to which they are attached 3~20 Cycloalkyl, C 5~20 forming a cycloalkenyl or heterocyclyl; M 2 is a transition metal selected from the group consisting of zirconium, titanium, hafnium, and vanadium; preferably zirconium; Q 3 and Q 4 are each independently a halogen, C 1~20 Alkyl, -N(R 11 )2, C1~20 Alkoxy, C 3~20 Cycloalkoxy, C 7~20 Aralkoxi, C 3~20 Cycloalkyl, C 6~20 Aryl, C 7~20 Alkylaryl, C 7~20 Aralkyl, and Hetero C 1~20 alkyl; R 11 is hydrogen or C 1~20 is alkyl] 27. The composition according to any one of items 1 to 26, comprising a bridged metallocene.

[0093] 28.R 5 , R 6 , and R 7 Each of the above is independently 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 Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1~8 alkyl; each R 10 are independently hydrogen, C 1~8 Alkyl, or C 3~8 alkenyl; r, s, and t are each independently an integer selected from 0, 1, 2, 3, or 4; L 2 - [CR 8 R 9 ] h -,SiR 8 R 9 , G.E.R. 8 R 9 , or B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9 each independently represents hydrogen, C 1~8 Alkyl, C 3~8 Alkenyl, C 3~8Cycloalkyl, C 5~8 Cycloalkenyl, C 6~8 Cycloalkenylalkyl, C 6~10 Aryl, Amino C 1~6 Alkyl, and C 7~ C 12 arylalkyl; or R 8 and R 9 C along with the atoms to which they are attached 3~8 Cycloalkyl, C 5~8 forming a cycloalkenyl or heterocyclyl; M 2 is a transition metal selected from the group consisting of zirconium, titanium, hafnium, and vanadium; preferably zirconium; Q 3 and Q 4 are each independently a halogen, C 1~8 Alkyl, -N(R 11 )2, C 1~8 Alkoxy, C 3~8 Cycloalkoxy, C 7~12 Aralkoxi, C 3~8 Cycloalkyl, C 6~10 Aryl, C 7~12 Alkylaryl, C 7~12 Aralkyl, and Hetero C 1~8 alkyl; R 11 is hydrogen or C 1~8 28. The composition according to any one of items 26 to 27, wherein the alkyl is alkyl.

[0094] 29.R 5 , R 6 , and R 7 Each of the above is independently C 1~8 Alkyl, C 3~8 Alkenyl, C 3~8 Cycloalkyl, C 6~10 aryl, and halogen; 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 - [CR8 R 9 ] h - or SiR 8 R 9 h is an integer selected from 1 or 2; R 8 and R 9 each independently represents 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; M 2 is a transition metal selected from zirconium, or hafnium; preferably zirconium; Q 3 and Q 4 are each independently a halogen, C 1~8 Alkyl, -N(R 11 )2, C 6~10 Aryl, and C 7~12 aralkyl; R 11 is hydrogen or C 1~8 is alkyl, preferably Q 1 and Q 2 29. The composition according to any one of items 26 to 28, wherein each independently is selected from the group consisting of Cl, F, Br, I, methyl, benzyl, and phenyl.

[0095] 30. Catalyst component A is represented by the formula (IIa)

[0096] [ka]

[0097] [In the formula, R 5 , R 6 , R 7 , L 2 , M 2 , Q 3 , Q 4 and r have the same meaning as defined in any one of paragraphs 26 to 29, preferably each R 6 and R7 is C 1~8 is alkyl] 30. The composition according to any one of items 1 to 29, comprising a bridged metallocene.

[0098] 31. Catalyst component B is represented by the formula (IIb)

[0099] [ka]

[0100] [In the formula, R 6 , R 7 , L 2 , M 2 , Q 3 , Q 4 has the same meaning as defined in any one of paragraphs 26 to 29, preferably each R 6 and R 7 is C 1~8 is alkyl] Item 31. The composition according to any one of items 1 to 30, comprising a bridged metallocene.

[0101] 32. Catalyst component B is represented by the formula (IIc)

[0102] [ka]

[0103] [In the formula, R 6 , R 7 , R 8 , R 9 , M 2 , Q 3 , Q 4 has the same meaning as defined in any one of paragraphs 26 to 29, preferably each R 6 and R 7 is C 1~8 is alkyl] Item 32. The composition according to any one of items 1 to 31, comprising a bridged metallocene.

[0104] 33. The catalyst component B is represented by the formula (IId)

[0105] [ka]

[0106] Item 33. The composition according to any one of items 1 to 32, comprising a bridged metallocene. 34. The composition according to any one of items 1 to 33, wherein the meso / rac ratio of the meso isomer of the bridged metallocene compound of catalyst component A is 95:5 or more, and the weight ratio of catalyst component A to catalyst component B is in the range of 20 / 80 to 50 / 50, preferably in the range of 20 / 80 to 40 / 60, preferably in the range of 25 / 75 to 35 / 65, preferably in the range of 28 / 72 to 33 / 67, preferably in the range of 29 / 71 to 32 / 68, preferably in the range of 29 / 71 to 31 / 69, preferably in the range of 30 / 70.

[0107] 35. The composition according to any one of paragraphs 1 to 34, wherein the meso / rac ratio of the meso isomer of the bridged metallocene compound of catalyst component A is 90:10 or more, preferably 95:5 or more, and the weight ratio of catalyst component A to catalyst component B is preferably in the range of 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.

[0108] 36. A process for polymerizing olefins, comprising contacting the catalyst composition according to any one of paragraphs 1 to 35 with an olefin monomer, optionally hydrogen, and optionally one or more olefin comonomers; and polymerizing the monomer and optionally one or more olefin comonomers in the presence of at least one catalyst composition, and optionally hydrogen, to obtain a polyolefin.

[0109] 37. The process according to item 36, wherein the process is carried out in the slurry phase or the gas phase or the liquid phase, preferably in the slurry phase.

[0110] 38. The method according to any one of paragraphs 36 to 37, wherein the method is carried out in one or more batch reactors, slurry reactors, gas phase reactors, solution reactors, high pressure reactors, tubular reactors, autoclave reactors, or combinations thereof.

[0111] 39. The method according to any one of paragraphs 36 to 38, wherein the method is carried out in a single reaction zone.

[0112] 40. The method according to any one of paragraphs 36 to 39, wherein the polymerization can be carried out in a batch or continuous manner.

[0113] 41. The method according to any one of paragraphs 36 to 40, wherein the polymerization is carried out in a continuous manner. 42. The process according to any one of paragraphs 36 to 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-1-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.

[0114] 43. The process according to any one of paragraphs 36 to 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-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

[0115] 44. The olefin monomer is ethylene, and the ethylene and optionally the olefin comonomer are contacted with a catalyst composition; M w is the weight average molecular weight, M nis the number average molecular weight, and the molecular weight distribution M is in the range of 4.0 to 12.0, preferably 4.0 to 10.0, preferably 4.0 to 9.0, preferably 4.0 to 8.5, preferably 4.1 to 8.0, preferably 4.1 to 7.6, preferably 4.1 to 7.0, preferably 4.0 to 6.5, preferably 4.0 to 6.0, preferably 4.0 to 5.8. w / M n Item 36. The method according to any one of items 36 to 42, comprising obtaining an ethylene polymer having the formula:

[0116] 45. The olefin monomer is ethylene, and the ethylene and optionally the olefin comonomer are contacted with a catalyst composition; M z is the z-average molecular weight, and the molecular weight distribution M z / M w Item 36. The method according to any one of items 36 to 42 and 44, comprising obtaining an ethylene polymer having the formula:

[0117] 46. ​​The olefin monomer is ethylene, and the ethylene and optionally the olefin comonomer are contacted with a catalyst composition; z is the z-average molecular weight, M n is the number average molecular weight, and the molecular weight distribution M is at least 8.0, 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. z / M n The method according to any one of items 36 to 42 and 44 to 45, comprising obtaining an ethylene polymer having the formula:

[0118] 47. The olefin monomer is ethylene, contacting the ethylene and optionally the olefin comonomer with a catalyst composition; 1347. The process according to any one of paragraphs 36 to 42, 44 to 46, comprising the step of obtaining an ethylene polymer having at least 0.30 wt.% ethyl branches, preferably at least 0.31 wt.% ethyl branches, preferably at least 0.32 wt.% ethyl branches, preferably at least 0.33 wt.% ethyl branches, preferably at least 0.34 wt.% ethyl branches, preferably at least 0.35 wt.% ethyl branches, preferably at most 1.20 wt.% ethyl branches, preferably at most 1.10 wt.% ethyl branches, preferably at most 1.00 wt.% ethyl branches, preferably at most 0.98 wt.% ethyl branches, based on the total weight of the ethylene polymer, as determined by C NMR analysis, with the proviso that said ethyl branches do not result from 1-butene comonomer incorporation; and / or with the proviso that the optional comonomer used in the process is not 1-butene.

[0119] 48. The olefin monomer is ethylene, contacting the ethylene and optionally the olefin comonomer with a catalyst composition; 13 48. The process according to any one of paragraphs 36 to 42, 44 to 47, comprising obtaining an ethylene polymer having a total comonomer content, such as a 1-hexene content, in the range of 0.0 wt.% to 15.0 wt.%, preferably 0.0 wt.% to 10.0 wt.%, preferably 0.0 wt.% to 9.0 wt.%, based on the total weight of the ethylene polymer, as determined by C NMR analysis.

[0120] 49. The method according to any one of paragraphs 36 to 42, 44 to 48, wherein the olefin monomer is ethylene, the method comprising the steps of contacting the ethylene and optionally the olefin comonomer with a catalyst composition; obtaining an ethylene polymer having a melt index MI2 in the range of 0.1 g / 10 min to 12.0 g / 10 min, preferably 0.2 g / 10 min to 11.0 g / 10 min, preferably 0.3 g / 10 min to 10.0 g / 10 min, wherein MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature of 190° C. and a load of 2.16 kg, using a 2.096 mm die.

[0121] 50. The method according to any one of paragraphs 36 to 42, 44 to 49, wherein the olefin monomer is ethylene, the method comprising the steps of contacting the ethylene and optionally the olefin comonomer with a catalyst composition; obtaining an ethylene polymer having a melt index HLMI in the range of 10.0 g / 10 min to 300.0 g / 10 min, preferably in the range of 11.0 g / 10 min to 280.0 g / 10 min, preferably in the range of 12.0 g / 10 min to 270.0 g / 10 min, preferably in the range of 12.0 g / 10 min to 270.0 g / 10 min, preferably in the range of 13.0 g / 10 min to 260.0 g / 10 min, wherein the melt index HLMI is determined according to ISO 1133:2005 Method B, condition G, at a temperature of 190° C., using a 2.096 mm die with a load of 21.6 kg.

[0122] 51. The method according to any one of paragraphs 36 to 42, 44 to 50, wherein the olefin monomer is ethylene, comprising the steps of contacting the ethylene and optionally the olefin comonomer with a catalyst composition; obtaining an ethylene polymer having a melt index MI5 in the range of 0.5 g / 10 min to 30.0 g / 10 min, preferably 0.7 g / 10 min to 28.0 g / 10 min, preferably 1.0 g / 10 min to 25.0 g / 10 min, wherein MI5 is determined according to ISO 1133:2005 Method B, Condition T, at a temperature of 190° C., using a 2.096 mm die with a load of 5 kg.

[0123] 52. The process according to any one of paragraphs 36 to 42, 44 to 51, wherein the olefin monomer is ethylene, comprising the step of contacting ethylene and optionally an olefin comonomer with a catalytic composition; obtaining an ethylene polymer having a melt index ratio HLMI / MI2 of up to 40.0; preferably up to 35.0, preferably at least 15.0, preferably at least 20.0.

[0124] 53. The process according to any one of paragraphs 36 to 42, 44 to 52, wherein the olefin monomer is ethylene, comprising the step of contacting ethylene and optionally an olefin comonomer with a catalytic composition; 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.

[0125] 54. The olefin monomer is ethylene, and contacting the ethylene and optionally the olefin comonomer with a catalyst composition; a rheological long chain branching index g of at least 0.90, preferably at least 0.93, preferably at least 0.94. rheo The method according to any one of items 36 to 42 and 44 to 53, comprising obtaining an ethylene polymer having the formula:

[0126] 55. The olefin monomer is ethylene, and the ethylene and optionally the olefin comonomer are contacted with the catalyst composition; the olefin monomer has a viscosity of at least 0.910 g / cm3 measured at a temperature of 23°C according to standard ISO 1183-1:2012, method A. 3 The method according to any one of items 36 to 42, 44 to 54, comprising obtaining an ethylene polymer having a density of

[0127] 56. The olefin monomer is ethylene, and the ethylene and optionally the olefin comonomer are contacted with the catalyst composition; a maximum of 0.965 g / cm3 is obtained according to standard ISO 1183-1:2012, method A, at a temperature of 23°C. 3 ; preferably up to 0.963 g / cm 3 , preferably at least 0.910 g / cm 3 , preferably at least 0.915 g / cm 3 Item 36. The method according to any one of items 36 to 42 and 44 to 55, comprising obtaining an ethylene polymer having a density of

[0128] 57. The olefin monomer is ethylene, and the ethylene and optionally the olefin comonomer are contacted with the catalyst composition; the olefin monomer has a viscosity of 0.910 g / cm3 measured at a temperature of 23°C according to standard ISO 1183-1:2012, method A. 3 ~0.965g / cm 3 in the range of 0.915 g / cm 3 ~0.960g / cm 3 Item 36. The method according to any one of items 36 to 42, 44 to 56, comprising obtaining an ethylene polymer having a density in the range of

[0129] 58. The olefin monomer is ethylene, and the ethylene and optionally the olefin comonomer are contacted with the catalyst composition; the ethylene / olefin copolymer has a viscosity of 0.910 g / cm3 measured at 23°C according to standard ISO 1183-1:2012, method A. 3 ~0.965g / cm 3 in the range of 0.915 g / cm 3 ~0.960g / cm 3 Density in the range of; and 13 at least 0.30% to at most 1.20% by weight of ethyl branches, preferably at least 0.31 and at most 1.20% by weight of ethyl branches, preferably at least 0.31% to at most 1.10% by weight of ethyl branches, preferably at least 0.32% to at most 1.00% by weight of ethyl branches, preferably at least 0.33% to at most 0.98% by weight of ethyl branches, preferably at least 0.34% to at most 0.98% by weight of ethyl branches, preferably at least 0.35% to at most 0.98% by weight of ethyl branches, based on the total weight of the ethylene polymer, as determined by C NMR analysis; 58. The process according to any one of paragraphs 36 to 42, 44 to 57, comprising obtaining an ethylene polymer having the formula:

[0130] 59. The olefin monomer is ethylene, and the ethylene and optionally the olefin comonomer are contacted with a catalyst composition; and at least one melting temperature T determined by DSC is less than 132 ° C, preferably in the range of 100 ° C to less than 132 ° C, more preferably in the range of 110 ° C to 132 ° C, and even more preferably in the range of 120 ° C to 132 ° C. m The method according to any one of items 36 to 42 and 44 to 58, comprising obtaining an ethylene polymer having the formula:

[0131] 60. The method according to any one of paragraphs 36 to 42 and 44 to 59, wherein the olefin monomer is ethylene, and the method comprises contacting ethylene and optionally an olefin comonomer with a catalyst composition; obtaining an ethylene polymer in which a temperature rising elution fractionation (TREF) distribution curve of the ethylene polymer includes at least one peak that appears at a temperature of at least 96.0 ° C. to a maximum of 105 ° C. and has an area under the curve of at least 20.0% to a maximum of 100.0%.

[0132] 61. The olefin monomer is ethylene, and the ethylene and optionally the olefin comonomer are contacted with a catalyst composition; the density of the polymer is 0.938 g / cm 3 Item 60. The method according to item 60, comprising obtaining an ethylene polymer in which a temperature rising elution fractionation (TREF) distribution curve of the metallocene catalyzed ethylene polymer includes at least one second peak that appears at a temperature of at least 65.0°C to a maximum of 92.0°C and has an area under the curve of at least 60.0% to a maximum of 75.0% when the temperature rising elution fractionation (TREF) distribution curve of the metallocene catalyzed ethylene polymer is less than 65.0°C to a maximum of 92.0°C.

[0133] 62. The olefin monomer is ethylene, and the ethylene and optionally the olefin comonomer are contacted with a catalyst composition; the density of the polymer is 0.925 g / cm 3 Item 60. The method according to item 60, comprising obtaining an ethylene polymer in which a temperature rising elution fractionation (TREF) distribution curve of the metallocene catalyzed ethylene polymer includes at least one second peak that appears at a temperature of at least 65.0° C. and at most 73.0° C. and has an area under the curve of at least 60.0% and at most 75.0%.

[0134] 63. An olefin polymer at least partially catalyzed by at least one catalyst composition according to any one of paragraphs 1 to 35 or produced by a process according to any one of paragraphs 36 to 62.

[0135] 64. The olefin polymer according to item 63, wherein the olefin polymer is an ethylene polymer.

[0136] 65. A melt index MI2 in the range of 0.1 g / 10 min to 12.0 g / 10 min, where MI2 is determined according to ISO 1133:2005 Method B, Condition D, at a temperature of 190° C. and using a 2.096 mm die with a 2.16 kg load; and M w is the weight average molecular weight, M n The number average molecular weight is 4.0 to 12.0, preferably 4.0 to 10.0, preferably 4.0 to 9.0, preferably 4.0 to 8.5, preferably 4.1 to 8.0, preferably 4.1 to 7.6, preferably 4.1 to 7.0. w / M n A metallocene catalyzed ethylene polymer having the formula:

[0137] 66. 13 66. The metallocene catalyzed ethylene polymer according to claim 65, having at least 0.30% by weight of ethyl branches based on the total weight of the ethylene polymer as measured by C NMR, said ethyl branches not arising from the use of 1-butene as a comonomer; preferably said ethylene polymer is a homopolymer or a copolymer obtained by polymerization of ethylene and at least one comonomer, preferably said comonomer is not 1-butene.

[0138] 67. 1367. The metallocene catalyzed ethylene polymer according to paragraph 65 or 66, having at least 0.30% by weight of ethyl branches based on the total weight of the ethylene polymer as measured by C NMR, said ethylene polymer being a homopolymer or a copolymer obtained by polymerization of ethylene and at least one comonomer, preferably said comonomer being not 1-butene.

[0139] 68. A melt index MI2 in the range of 0.1 g / 10 min to 12.0 g / 10 min, where MI2 is determined according to ISO 1133:2005 Method B, Condition D, at a temperature of 190°C and using a 2.096 mm die with a 2.16 kg load; M w is the weight average molecular weight, M n The number average molecular weight is 4.0 to 12.0, preferably 4.0 to 10.0, preferably 4.0 to 9.0, preferably 4.0 to 8.5, preferably 4.1 to 8.0, preferably 4.1 to 7.6, preferably 4.1 to 7.0. w / M n and 13 at least 0.30% by weight of ethyl branches based on the total weight of the ethylene polymer as measured by C NMR, said ethyl branches not arising from the use of 1-butene as a comonomer; preferably said ethylene polymer is a homopolymer or a copolymer obtained by polymerization of ethylene and at least one comonomer, preferably said comonomer is not 1-butene, A metallocene catalyzed ethylene polymer having the formula:

[0140] 69. A rheological long chain branching index g of at least 0.90, preferably at least 0.93, preferably at least 0.94 rheo Item 69. The metallocene-catalyzed ethylene polymer according to any one of items 65 to 68, wherein

[0141] 70. A melt index MI2 in the range of 0.1 g / 10 min to 12.0 g / 10 min, where MI2 is determined according to ISO 1133:2005 Method B, Condition D, at a temperature of 190°C and using a 2.096 mm die with a 2.16 kg load; M w is the weight average molecular weight, M n The number average molecular weight is 4.0 to 12.0, preferably 4.0 to 8.5. w / M n ; A rheological long chain branching index g of at least 0.90, preferably at least 0.93, preferably at least 0.95 rheo and 13 at least 0.30% by weight of ethyl branches based on the total weight of the ethylene polymer as determined by C NMR; preferably said ethylene polymer is a homopolymer or a copolymer obtained by polymerization of ethylene and at least one comonomer, preferably said comonomer is not 1-butene, A metallocene catalyzed ethylene polymer having the formula:

[0142] 71. A melt index MI2 in the range of 0.1 g / 10 min to 12.0 g / 10 min, where MI2 is determined according to ISO 1133:2005 Method B, Condition D, at a temperature of 190°C and using a 2.096 mm die with a 2.16 kg load; M w is the weight average molecular weight, M n The number average molecular weight is 4.0 to 12.0, preferably 4.0 to 10.0, preferably 4.0 to 9.0, preferably 4.0 to 8.5, preferably 4.1 to 8.0, preferably 4.1 to 7.6, preferably 4.1 to 7.0. w / M n and A rheological long chain branching index g of at least 0.93, preferably at least 0.94, preferably at least 0.95 rheo A metallocene catalyzed ethylene polymer having the formula:

[0143] 72. 13 72. The metallocene catalyzed ethylene polymer according to any one of paragraphs 65 to 71, having at least 0.31 wt.% ethyl branches, preferably at least 0.32 wt.% ethyl branches, preferably at least 0.33 wt.% ethyl branches, preferably at least 0.34 wt.% ethyl branches, preferably at least 0.35 wt.% ethyl branches, preferably at most 1.20 wt.% ethyl branches, preferably at most 1.10 wt.% ethyl branches, preferably at most 1.00 wt.% ethyl branches, preferably at most 0.98 wt.% ethyl branches based on the total weight of the ethylene polymer as determined by C NMR analysis, with the proviso that said ethyl branches are without the addition of 1-butene as comonomer; and / or preferably said ethylene polymer is a homopolymer or a copolymer obtained by polymerization of ethylene and at least one comonomer, preferably said comonomer is not 1-butene.

[0144] 73.M z a molecular weight distribution M of at most 7.0, 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, z / M w Item 65 to 75. A metallocene-catalyzed ethylene polymer according to any one of items 65 to 75.

[0145] 74.M z is the z-average molecular weight, M n a molecular weight distribution M of at least 8.0, 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; z / M n Item 65 to 73. A metallocene-catalyzed ethylene polymer according to any one of items 65 to 73, comprising:

[0146] 75. A metallocene-catalyzed ethylene polymer according to any one of paragraphs 65 to 74, having a melt index MI2 in the range of 0.2 g / 10 min to 11.0 g / 10 min, preferably 0.3 g / 10 min to 10.0 g / 10 min.

[0147] 76. The metallocene catalyzed ethylene polymer according to any one of paragraphs 65 to 75, having a melt index HLMI in the range of 10.0 g / 10 min to 300.0 g / 10 min, the melt index HLMI being determined according to ISO 1133:2005 Method B, condition G at a temperature of 190° C. and a 2.096 mm die at a load of 21.6 kg, preferably a HLMI in the range of 11.0 g / 10 min to 280.0 g / 10 min, preferably a HLMI in the range of 12.0 g / 10 min to 270.0 g / 10 min, preferably a HLMI in the range of 12.0 g / 10 min to 270.0 g / 10 min, preferably a HLMI in the range of 13.0 g / 10 min to 260.0 g / 10 min.

[0148] 77. The metallocene catalyzed ethylene polymer according to any one of paragraphs 65 to 76, having a melt index MI5 in the range of 0.5 g / 10 min to 30.0 g / 10 min, preferably 0.7 g / 10 min to 28.0 g / 10 min, preferably 1.0 g / 10 min to 25.0 g / 10 min, wherein MI5 is determined according to ISO 1133:2005 Method B, Condition T, at a temperature of 190° C., using a 2.096 mm die with a 5 kg load.

[0149] 78. A metallocene-catalyzed ethylene polymer according to any one of paragraphs 65 to 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.

[0150] 79. A metallocene-catalyzed ethylene polymer according to any one of paragraphs 65 to 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.

[0151] 80. At least 0.910 g / cm3 measured at 23°C according to standard ISO 1183-1:2012 Method A 3 80. The metallocene-catalyzed ethylene polymer of any one of claims 65 to 79, having a density of

[0152] 81. Maximum 0.965 g / cm3 measured at 23°C according to standard ISO 1183-1:2012 method A 3 ; preferably up to 0.963 g / cm 3 , preferably at least 0.910 g / cm 3 , preferably at least 0.915 g / cm 3 Item 65 to 80. A metallocene-catalyzed ethylene polymer according to any one of items 65 to 80, having a density of

[0153] 82. 0.910 g / cm3 measured according to standard ISO 1183-1:2012 method A at 23°C 3 ~0.965g / cm 3 in the range of 0.915 g / cm 3 ~0.960g / cm 3 Density in the range of; and 13 at least 0.30% to at most 1.20% by weight of ethyl branches, preferably at least 0.31 and at most 1.20% by weight of ethyl branches, preferably at least 0.31% to at most 1.10% by weight of ethyl branches, preferably at least 0.32% to at most 1.00% by weight of ethyl branches, preferably at least 0.33% to at most 0.98% by weight of ethyl branches, preferably at least 0.34% to at most 0.98% by weight of ethyl branches, preferably at least 0.35% to at most 0.98% by weight of ethyl branches, based on the total weight of the ethylene polymer as determined by C NMR analysis; Item 65 to 81. A metallocene-catalyzed ethylene polymer according to any one of items 65 to 81.

[0154] At least one melting temperature T determined by DSC is less than 83.132 ° C, preferably in the range of 100 ° C to less than 132 ° C, more preferably in the range of 110 ° C to 132 ° C, even more preferably in the range of 120 ° C to 132 ° C. m Item 65 to 82. A metallocene-catalyzed ethylene polymer according to any one of items 65 to 82, comprising:

[0155] 84. A metallocene-catalyzed ethylene polymer according to any one of paragraphs 65 to 83, wherein the temperature rising elution fractionation (TREF) distribution curve of the metallocene-catalyzed ethylene polymer includes at least one peak that appears at a temperature of at least 96.0°C and at most 105°C and has an area under the curve of at least 20.0% and at most 100.0%.

[0156] 85. The metallocene-catalyzed ethylene polymer of any one of paragraphs 65 to 84, wherein the polymer is a homopolymer.

[0157] 86. The metallocene-catalyzed ethylene polymer according to any one of paragraphs 65 to 84, wherein the polymer is a copolymer of ethylene and a higher alpha-olefin comonomer, preferably 1-hexene.

[0158] 87. 13 87. The metallocene catalyzed ethylene polymer according to any one of paragraphs 65 to 86, having a total comonomer content, such as a 1-hexene content, in the range of 0.0 wt.% to 15.0 wt.%, preferably up to 10.0 wt.%, preferably 0.0 wt.% to 9.5 wt.%, preferably 0.0 wt.% to 9.0 wt.%, based on the total weight of the ethylene polymer, as determined by C NMR analysis.

[0159] 88. The density of a polymer is 0.938 g / cm 3Item 65-87, wherein the temperature rising elution fractionation (TREF) distribution curve of the metallocene catalyzed ethylene polymer comprises at least one second peak that appears at a temperature of at least 65.0 ° C. to a maximum of 92.0 ° C. and has an area under the curve of at least 60.0% to a maximum of 75.0%.

[0160] 89. The density of a polymer is 0.925 g / cm 3 Item 65-87, wherein the temperature rising elution fractionation (TREF) distribution curve of the metallocene catalyzed ethylene polymer comprises at least one second peak that appears at a temperature of at least 65.0 ° C. to a maximum of 73.0 ° C. and has an area under the curve of at least 60.0% to a maximum of 75.0%.

[0161] 90. A metallocene-catalyzed ethylene polymer according to any one of paragraphs 65 to 89, wherein the metallocene is a zirconium-based metallocene.

[0162] 91. A metallocene-catalyzed ethylene polymer according to any one of paragraphs 65 to 90, having less than 0.24 ppm Fe by weight of the polymer, preferably less than 0.10 ppm Fe by weight of the polymer.

[0163] 92. A metallocene-catalyzed ethylene polymer according to any one of paragraphs 65 to 91, prepared using a continuous process.

[0164] 93. A metallocene-catalyzed ethylene polymer according to any one of paragraphs 65 to 92, wherein the metallocene is a metallocene catalyst composition according to any one of paragraphs 1 to 35.

[0165] 94. An article comprising a polymer according to any one of items 63 to 93 or obtained by the method according to any one of items 36 to 62.

[0166] 95. The article according to paragraph 94, wherein the article is intended for film applications, injection applications, blow molding applications, rotational molding applications, extrusion applications, or yarn applications.

[0167] 96. The article according to any one of paragraphs 94 to 95, wherein the article is selected from the group comprising caps and closures, cereal liners, blown films, yarns, rotationally molded articles, blown molded articles, pipes, fibers and cast films.

[0168] 97. The process according to any one of paragraphs 36 to 62, wherein the ethylene polymer obtained is a metallocene-catalyzed ethylene polymer according to any one of paragraphs 65 to 93.

[0169] 98. A process for the preparation of a metallocene-catalyzed ethylene polymer according to any one of paragraphs 65 to 93, the process comprising: contacting at least one metallocene catalyst composition according to any one of paragraphs 1 to 35 with ethylene, optionally hydrogen, and optionally one or more alpha-olefin comonomers; and polymerizing the ethylene, and optionally one or more alpha-olefin comonomers, in the presence of the at least one metallocene catalyst composition, and optionally hydrogen, to obtain a metallocene-catalyzed ethylene polymer.

[0170] 99. Use of a polymer according to any one of paragraphs 63 to 93 or a polymer obtained by the process according to any one of paragraphs 36 to 62, 95 to 96 in film applications, injection applications, blow molding applications, rotational molding applications, extrusion applications, yarn applications, and raised temperature resistance polyethylene; preferably in caps and closures, serial liners, blown films, or cast films.

[0171] The present invention relates to a catalyst component A comprising the meso form of a bridged metallocene compound having two indenyl groups, each indenyl being independently substituted with one or more substituents, at least one of the substituents being aryl or heteroaryl, preferably the meso / rac ratio of the meso form of the bridged metallocene compound of catalyst component A is 95:5 or greater; preferably at least one of the substituents is aryl, preferably phenyl, said aryl and / or phenyl being unsubstituted or substituted; preferably at least one of the substituents is at the 3 and / or 5 position of each indenyl, preferably each indenyl has one substituent at the 3 position, preferably each indenyl has one substituent at the 5 position, even more preferably each indenyl has one substituent at the 3 position and one substituent at the 5 position of each indenyl, preferably an aryl or heteroaryl substituent at the 3 position of each indenyl; a catalyst component B comprising a bridged metallocene compound having a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; and an optional activator; an optional support; and an optional cocatalyst. A catalyst composition comprising:

[0172] For purposes of nomenclature, the following numbering convention is used for indenyl. It should be noted that indenyl can be thought of as a cyclopentadienyl with a fused benzene ring. The structure below is drawn and named as the anion:

[0173] [ka]

[0174] As used herein, the term "catalyst" refers to a substance that produces a change in the rate of a reaction, and in the present invention, particularly applies to catalysts suitable for polymerization, preferably the polymerization of olefins to polyolefins.

[0175] As used herein, the term "meso" or "meso form" means that the bridged metallocene of component A has a plane of symmetry containing the metal center M.

[0176] The term "metallocene catalyst" is used herein to describe a transition metal complex containing a metal atom bound to one or more ligands. Metallocene catalysts are compounds of Group IV transition metals of the periodic table, such as titanium, zirconium, hafnium, etc., with a coordination structure of the metal compound and a ligand consisting of one or two groups of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, or derivatives thereof. Metallocenes contain a single metal site, which allows for better control of polymer branching and molecular weight distribution. Monomers are inserted between the metal and the growing chain of the polymer.

[0177] In particular, for the present invention, the catalyst must comprise, as catalyst component A, the meso form of a bridged metallocene compound having two indenyl groups, each indenyl being independently substituted with one or more substituents, and, as catalyst component B, a bridged metallocene compound having a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group.

[0178] In one embodiment, for catalyst A, the bridged metallocene catalyst can be represented by the meso form of a compound of formula (III) and for catalyst B, by a compound of formula (IV): L 1 (Ar 1 )2M 1 Q 1 Q 2 (III), L 2 (Ar 2 )(Ar 3 )M 2 Q 3 Q 4 (IV) During the ceremony, Each Ar 1are independently indenyl, and optionally each independently represent alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 ) 3, and heteroalkyl; each R 10 is independently hydrogen, alkyl, or alkenyl. Each indenyl is substituted the same or differently at one or more positions on any of the fused rings. Each substituent can be independently selected. Preferably, each Ar 1 is indenyl, each indenyl is independently substituted with one or more substituents, at least one of the substituents being aryl or heteroaryl; preferably at least one of the substituents is at the 3- and / or 5-position of each indenyl, preferably an aryl or heteroaryl is at the 3-position of each indenyl, and Ar 1 each independently represents an alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 ) 3, and heteroalkyl; each R 10 is independently hydrogen, alkyl, or alkenyl; Ar 2 is cyclopentadienyl, optionally each independently being alkyl, alkenyl, cycloalkyl, cycloalkenyl, or cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 ) 3, and heteroalkyl; each R 10 is independently hydrogen, alkyl, or alkenyl; Ar 3 is fluorenyl, optionally each independently being alkyl, alkenyl, cycloalkyl, cycloalkenyl, or cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10) 3, and heteroalkyl; each R 10 is independently hydrogen, alkyl, or alkenyl; M 1 and M. 2 Each of M is a transition metal selected from the group including zirconium, hafnium, titanium, and vanadium; preferably M 1 and M. 2 each of which is zirconium; Q 1 and Q 2 are each independently a halogen, an alkyl, or -N(R 11 )2, selected from the group consisting of alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; R 11 is hydrogen or alkyl; Q 3 and Q 4 are each independently a halogen, an alkyl, or -N(R 11 )2, selected from the group consisting of alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; R 11 is hydrogen or alkyl; L 1 is 2 Ar 1 is a divalent group or moiety that bridges groups, preferably SiR 8 R 9 , -[CR 8 R 9 ] h -, GeR 8 R 9 , or B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9 each is independently selected from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R 8 and R 9together with the atom to which they are attached form a cycloalkyl, cycloalkenyl, or heterocyclyl; preferably L 1 is SiR 8 R 9 and; L 2 Ar 2 and Ar 3 is a divalent group or moiety that bridges groups, preferably -[CR 8 R 9 ] h -,SiR 8 R 9 , G.E.R. 8 R 9 , or B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9 each is independently selected from the group consisting of 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.

[0179] In some embodiments, each Ar 1 is indenyl, each indenyl independently substituted with one or more substituents, at least one of which is aryl or heteroaryl; preferably at least one of the substituents is at the 3- and / or 5-position of each indenyl, preferably an aryl or heteroaryl substituent is at the 3-position of each indenyl; each indenyl is further optionally, each independently, 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 Aryl alkyl, halogen, Si(R 10)3, and hetero C 1~12 each R 10 are independently hydrogen, C 1~20 Alkyl, or C 3~20 alkenyl. Preferably, each Ar 1 is indenyl, each indenyl independently substituted with one or more substituents, at least one of the substituents being C 6~10 aryl; preferably C 6~10 An aryl substituent is at the 3-position of each indenyl; each indenyl may further optionally be independently selected from 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 Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1~8 each R 10 are independently hydrogen, C 1~8 Alkyl, or C 3~8 alkenyl. Preferably, each Ar 1 is indenyl, each indenyl independently substituted with one or more substituents, at least one of the substituents being C 6~10 aryl; preferably C 6~10 An aryl substituent is at the 3-position of each indenyl; each indenyl may further optionally be independently selected from C 1~8 Alkyl, C 3~8 Alkenyl, C 3~8 Cycloalkyl, C 6~10 It may be substituted with one or more substituents selected from the group including aryl, and halogen.

[0180] In some embodiments, Ar 2 is cyclopentadienyl, optionally each independently C1~20 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 Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1~12 each R 10 are independently hydrogen, C 1~20 Alkyl, or C 3~20 Alkenyl. Preferably, Ar 2 is cyclopentadienyl, optionally each independently 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 Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1~8 each R 10 are independently hydrogen, C 1~8 Alkyl, or C 3~8 Alkenyl. Preferably, Ar 2 is cyclopentadienyl, optionally each independently C 1~8 Alkyl, C 3~8 Alkenyl, C 3~8 Cycloalkyl, C 6~10 It may be substituted with one or more substituents selected from the group including aryl, and halogen.

[0181] In some embodiments, Ar 3 is fluorenyl, optionally each independently C 1~20Alkyl, 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 Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1-12 each R 10 are independently hydrogen, C 1~20 Alkyl, or C 3~20 Alkenyl. Preferably, Ar 2 is fluorenyl, optionally each independently 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 Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1~8 each R 10 are independently hydrogen, C 1~8 Alkyl, or C 3~8 Alkenyl. Preferably, Ar 3 is fluorenyl, optionally each independently C 1~8 Alkyl, C 3~8 Alkenyl, C 3~8 Cycloalkyl, C 6~10 It may be substituted with one or more substituents selected from the group including aryl, and halogen.

[0182] In some embodiments, L 1 - [CR 8 R 9 ] h -,SiR8 R 9 , G.E.R. 8 R 9 , or B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9 each independently represents 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, and C7-C 20 arylalkyl; or R 8 and R 9 C along with the atoms to which they are attached 3~20 Cycloalkyl, C 5~20 It forms a cycloalkenyl or heterocyclyl. Preferably, L 1 - [CR 8 R 9 ] h -,SiR 8 R 9 , G.E.R. 8 R 9 , or B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9 each independently represents 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 C7-C 12 arylalkyl; or R 8 and R 9 C along with the atoms to which they are attached 3~8 Cycloalkyl, C 5~8 Forms a cycloalkenyl or heterocyclyl. Preferably, L 1 - [CR 8 R 9 ] h - or SiR8 R 9 h is an integer selected from 1, or 2; R 8 and R 9 each independently represents 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 ;R 8 and R 9 each independently represents 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-containing group; preferably C 1~8 is selected from alkyl.

[0183] In some embodiments, Q 1 and Q 2 are each independently a halogen, C 1~20 Alkyl, -N(R 11 )2, C 1~20 Alkoxy, C 3~20 Cycloalkoxy, C 7~20 Aralkoxi, C 3~20 Cycloalkyl, C 6~20 Aryl, C 7~20 Alkylaryl, C 7~20 Aralkyl, and Hetero C 1~20 alkyl; R 11 is hydrogen or C 1~20 Alkyl. Preferably, Q 1 and Q 2 are each independently a halogen, C 1~8 Alkyl, -N(R 11 )2, C 1~8 Alkoxy, C 3~8 Cycloalkoxy, C7~12 Aralkoxi, C 3~8 Cycloalkyl, C 6~10 Aryl, C 7~12 Alkylaryl, C 7~12 Aralkyl, and Hetero C 1~8 alkyl; R 11 is hydrogen or C 1~8 Preferably, Q is an alkyl group. 1 and Q 2 are each independently a halogen, C 1~8 Alkyl, -N(R 11 )2, C 6~10 Aryl, and C 7~12 aralkyl; R 11 is hydrogen or C 1~8 is alkyl, preferably Q 1 and Q 2 are each independently selected from the group consisting of Cl, F, Br, I, methyl, benzyl, and phenyl.

[0184] In some embodiments, L 2 - [CR 8 R 9 ] h -,SiR 8 R 9 , G.E.R. 8 R 9 , or B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9 each independently represents 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, and C7-C 20 arylalkyl; or R 8 and R 9 C along with the atoms to which they are attached 3~20 Cycloalkyl, C 5~20 It forms a cycloalkenyl or heterocyclyl. Preferably, L2 - [CR 8 R 9 ] h -,SiR 8 R 9 , G.E.R. 8 R 9 , or B.R. 8 h is an integer selected from 1, 2, or 3; R 8 and R 9 each independently represents 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 C7-C 12 arylalkyl; or R 8 and R 9 C along with the atoms to which they are attached 3~8 Cycloalkyl, C 5~8 Forms a cycloalkenyl or heterocyclyl. Preferably, L 2 - [CR 8 R 9 ] h - or SiR 8 R 9 h is an integer selected from 1, or 2; R 8 and R 9 each independently represents 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 is selected from the group consisting of

[0185] In some embodiments, Q 3 and Q 4 are each independently a halogen, C 1~20 Alkyl, -N(R 11 )2, C 1~20 Alkoxy, C 3~20 Cycloalkoxy, C 7~20 Aralkoxi, C3~20 Cycloalkyl, C 6~20 Aryl, C 7~20 Alkylaryl, C 7~20 Aralkyl, and Hetero C 1~20 alkyl; R 11 is hydrogen or C 1~20 Alkyl. Preferably, Q 3 and Q 4 are each independently a halogen, C 1~8 Alkyl, -N(R 11 )2, C 1~8 Alkoxy, C 3~8 Cycloalkoxy, C 7~12 Aralkoxi, C 3~8 Cycloalkyl, C 6~10 Aryl, C 7~12 Alkylaryl, C 7~12 Aralkyl, and Hetero C 1~8 alkyl; R 11 is hydrogen or C 1~8 Preferably, Q is an alkyl group. 3 and Q 4 are each independently a halogen, C 1~8 Alkyl, -N(R 11 )2, C 6~10 Aryl, and C 7~12 aralkyl; R 11 is hydrogen or C 1~8 is alkyl, preferably Q 1 and Q 2 are each independently selected from the group consisting of Cl, F, Br, I, methyl, benzyl, and phenyl.

[0186] In some preferred embodiments, catalyst component A has formula (I);

[0187] [ka]

[0188] [In the formula, R 1 , R 2 , R 3 and R 4, m, n, p, q, L 1 , M 1 , Q 1 and Q 2 Each of has the same meaning as defined above and in the paragraphs herein. This includes the meso form of a bridged metallocene catalyst.

[0189] In a preferred embodiment, the meso / rac ratio of the meso isomer of the bridged metallocene compound of catalyst component A is 95:5 or greater.

[0190] A non-limiting example of catalyst A is the meso form of the catalyst shown below:

[0191] [ka]

[0192] In some preferred embodiments, catalyst component B has formula (II)

[0193] [ka]

[0194] [In the formula, R 5 , R 6 , R 7 , r, s, t, L 2 , M 2 , Q 3 and Q 4 Each of has the same meaning as defined above and in the paragraphs herein. The present invention includes a bridged metallocene catalyst.

[0195] In some preferred embodiments, catalyst component B has formula (IIa)

[0196] [ka]

[0197] [In the formula, R 5 , R6 , R 7 , r, L 2 , M 2 , Q 3 and Q 4 each of which has the same meaning as defined hereinabove. The present invention includes a bridged metallocene catalyst.

[0198] Non-limiting examples of Catalyst B are shown below:

[0199] [ka]

[0200] [ka]

[0201] In a preferred embodiment, the weight ratio of catalyst component A to catalyst component B is in the range of 10 / 90 to 90 / 10, preferably in the range of 15 / 85 to 80 / 20, preferably in the range of 20 / 80 to 70 / 30, preferably in the range of 20 / 80 to 60 / 40, preferably in the range of 20 / 80 to 50 / 50, preferably in the range of 20 / 80 to 40 / 60, preferably in the range of 25 / 75 to 35 / 65, preferably in the range of 28 / 72 to 33 / 67, preferably in the range of 29 / 71 to 32 / 68, preferably in the range of 29 / 71 to 31 / 69, preferably in the range of 30 / 70.

[0202] In the present invention, catalyst components A and B are preferably provided on a solid support, preferably both catalysts being provided on a single solid support, thereby forming a dual catalyst system.

[0203] The support may be an inert organic or inorganic solid, and is chemically unreactive with any of the components of conventional bridged metallocene catalysts. Suitable support materials for supported catalysts include solid inorganic oxides such as silica, alumina, magnesium oxide, titanium oxide, thorium oxide, and 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. A preferred example of such a mixed oxide is silica-alumina. For example, the solid oxide may include titanated silica, silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any mixture thereof, preferably silica, titanated silica, fluoride-treated silica, silica-alumina, fluoride-treated alumina, sulfated alumina, fluoride-treated silica-alumina, sulfated silica-alumina, silica-coated alumina, fluoride-treated silica, sulfated silica-coated alumina, or any combination thereof. Most preferred are titanated silica, or silica compounds. In a preferred embodiment, the bridged metallocene catalyst is provided on a solid support, preferably a titanated silica, or silica support. The silica may be in granular, agglomerated, fumed, or other form.

[0204] In some embodiments, the support for catalyst components A and B is a porous support, preferably a porous titanated silica, or a 200 to 900 mm 2 / g。 In another embodiment, the support of the polymerization catalyst is a porous support, preferably a porous titanated silica, or a silica support with 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, preferably a porous titanated silica, or a silica support with an average pore size comprised between 50 and 300 Å, preferably between 75 and 220 Å.

[0205] In some embodiments, the support has a D50 of at most 150 μm, preferably at most 100 μm, preferably at most 75 μm, preferably at most 50 μm, preferably at most 40 μm, preferably at most 30 μm. D50 is defined as the particle size at which 50 weight percent of the particles have a size smaller than D50. The particle size can be measured according to International Standard ISO 13320:2009 ("Particle size analysis - Laser diffraction methods"). For example, D50 can be measured by sieving, BET surface measurements, or laser diffraction analysis. For example, laser diffraction systems from Malvern Instruments can be advantageously used. The particle size can be measured by laser diffraction analysis on a Malvern type analyzer. The particle size can be measured by laser diffraction analysis on a Malvern type analyzer after suspending the supported catalyst in cyclohexane. Suitable Malvern systems include the Malvern 2000, Malvern MasterSizer (e.g. Mastersizer S), Malvern 2600 and Malvern 3600 series. Such instruments together with their operating manuals meet or even exceed the requirements within the ISO 13320 standard. The Malvern MasterSizer (e.g. Mastersizer S) may also be useful as by applying Mie's theory, D50 can be measured more accurately, for example towards the lower end of the range below 8 μm for mean particle size, using appropriate optical means.

[0206] Preferably, catalyst components A and B are activated by an activator. The activator may 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 include alumoxanes, alkyl aluminums, Lewis acids, and / or fluorinated catalyst supports.

[0207] In some embodiments, alumoxanes are used as activators for catalyst components A and B. Alumoxanes can be used with the catalyst to improve the activity of the catalyst during the polymerization reaction.

[0208] As used herein, the terms "alumoxane" and "aluminoxane" are used interchangeably and refer to a material capable of activating a bridged metallocene catalyst. In some embodiments, the alumoxane comprises an oligomeric linear and / or cyclic alkylalumoxane. In further embodiments, the alumoxane has the formula (V) or (VI): R for oligomeric linear alumoxanes a -(Al(R a )-O) x -AlR a 2(V); or For oligomeric cyclic alumoxanes, (-Al(R a )-O-) y (VI) (In the formula, x is 1 to 40, preferably 10 to 20; y is 3 to 40, preferably 3 to 20; Each R a is independently C 1~8 alkyl, preferably methyl. In a preferred embodiment, the alumoxane is methylalumoxane (MAO).

[0209] The catalyst composition may include a cocatalyst. b x One or more additional aluminum alkyls represented by the formula: bare the same or different and are selected from halogen or an alkoxy or alkyl group having 1 to 12 carbon atoms, and x is 1 to 3. Non-limiting examples are triethylaluminum (TEAL), tri-iso-butylaluminum (TIBAL), tri-methylaluminum (TMA) and methyl-methyl-ethylaluminum (MMEAL). Particularly suitable are the trialkylaluminums, most preferably triisobutylaluminum (TIBAL) and triethylaluminum (TEAL).

[0210] The catalyst composition may be particularly useful in a process for preparing a polymer comprising contacting at least one monomer with at least one catalyst composition. Preferably, the polymer is a polyolefin, and preferably, the monomer is an alpha-olefin.

[0211] The catalyst composition of the present invention is therefore particularly suitable for use in the preparation of polyolefins.The present invention also relates to the use of the catalyst composition in the polymerization of olefins.

[0212] The present invention also encompasses a process for the polymerization of olefins, comprising contacting the catalytic composition according to the present invention with an olefin monomer, optionally hydrogen, and optionally one or more olefin comonomers; and polymerizing the monomer and optionally one or more olefin comonomers in the presence of at least one catalytic composition, and optionally hydrogen, to obtain a polyolefin.

[0213] The term "olefin" as used herein refers to a molecule composed of carbon and hydrogen and containing at least one carbon-carbon double bond. An olefin containing one carbon-carbon double bond is referred to herein as a monounsaturated hydrocarbon and has the chemical formula C n H 2n where n is at least equal to 2. "Alpha-olefin", "α-olefin", "1-alkene" or "terminal olefin" are used synonymously herein and refer to an olefin or alkene having a double bond in the primary or alpha (α) position.

[0214] Throughout this application the terms "olefin polymer," "polyolefin," and "polyolefin polymer" may be used interchangeably.

[0215] Suitable polymerizations include, but are not limited to, the homopolymerization of an alpha-olefin or the copolymerization of an alpha-olefin and at least one other alpha-olefin comonomer.

[0216] As used herein, the term "comonomer" refers to an olefin comonomer suitable for polymerization with an alpha-olefin monomer. The comonomer, when present, is different from the olefin monomer and is selected so as to be suitable for copolymerization with the olefin monomer. Comonomers include, but are not limited to, aliphatic C2-C 20 Alpha-olefins may be included. Suitable aliphatic C3-C 20 Examples of 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 (HC-C(=O)O-CH=CH2) or vinyl alcohol ("HO-CH=CH2"). Examples of suitable olefin copolymers that 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).

[0217] 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-1-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.

[0218] 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-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

[0219] The polyolefins can be prepared in bulk, gas, solution and / or slurry phase. The process can be carried out in one or more batch reactors, slurry reactors, gas phase reactors, solution reactors, high pressure reactors, tubular reactors, autoclave reactors, or combinations thereof.

[0220] The polymerization can be carried out in a batch or continuous manner. In a preferred embodiment of the invention, the polymerization is carried out in a continuous manner.

[0221] The term "continuous" refers to a system that operates without interruption or cessation. For example, a continuous process for producing a polymer would be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn. By this, it is meant herein that when a reactor is operated, it is operating in a continuous mode, i.e., at least one feed stream is primarily continuously fed to the reactor, while at least one stream is primarily continuously withdrawn.

[0222] The terms "slurry" or "polymerization slurry" or "polymer slurry" as used herein refer to a substantially multiphase composition comprising at least a polymer solid and a liquid phase, the liquid phase being the continuous phase. The solids may include catalyst and polymerized monomers.

[0223] In some embodiments, the liquid phase comprises a diluent. As used herein, the term "diluent" refers to any organic diluent that does not dissolve the synthesized polyolefin. As used herein, the term "diluent" refers to a diluent in the liquid state that is liquid at room temperature in the loop reactor, preferably liquid under pressure conditions. Suitable diluents include, but are not limited to, hydrocarbon diluents, such as aliphatic, cycloaliphatic and aromatic hydrocarbon solvents, or halogenated versions of such solvents. Preferred solvents are C 12 or lower linear or branched saturated hydrocarbons, C5-C9 saturated alicyclic or aromatic hydrocarbons, or C2-C6 halogenated hydrocarbons. Non-limiting examples of solvents are butane, isobutane, pentane, hexane, heptane, cyclopentane, cyclohexane, cycloheptane, methylcyclopentane, methylcyclohexane, isooctane, benzene, toluene, xylene, chloroform, chlorobenzene, tetrachloroethylene, dichloroethane and trichloroethane, preferably isobutane or hexane.

[0224] The polymerization can also be carried out in the 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 gas phase olefins to produce a polymer.

[0225] The polymerization step can be carried out in a wide range of temperatures. In certain embodiments, the polymerization step can be carried out at a temperature of 20° C. to 125° C., preferably 60° C. to 110° C., more preferably 75° C. to 100° C., and most preferably 78° C. to 98° C. Preferably, the temperature range can be within the range of 75° C. to 100° C., and most preferably 78° C. to 98° C. The temperatures mentioned above can be within the more general term of polymerization conditions.

[0226] In certain embodiments, under slurry conditions, the polymerization process may be carried out at a pressure of about 20 bar to about 100 bar, preferably about 30 bar to about 50 bar, and more preferably about 37 bar to about 45 bar, which pressures may fall within the more general term for polymerization conditions.

[0227] The present invention also includes polymers at least partially catalyzed by at least one composition according to the present invention or produced by a process according to the present invention.

[0228] The present invention also encompasses a polymer, preferably an olefin polymer, produced by the process defined herein. In some embodiments, the olefin polymer is polyethylene. In some embodiments, the olefin polymer is polypropylene.

[0229] The present invention also encompasses metallocene catalyzed ethylene polymers, preferably at least one metallocene catalyst composition comprising a dual catalyst, meaning a catalyst particle having two metallocene active sites on a single support; said ethylene polymers preferably prepared in the presence of a catalyst composition as described herein, said polymers comprising: A melt index MI2 in the range of 0.1 g / 10 min to 12.0 g / 10 min, where MI2 is determined according to ISO 1133:2005 Method B, Condition D, at a temperature of 190° C. and using a 2.096 mm die with a 2.16 kg load; M w is the weight average molecular weight, M n The number average molecular weight is 4.0 to 12.0, preferably 4.0 to 10.0, preferably 4.0 to 9.0, preferably 4.0 to 8.5, preferably 4.1 to 8.0, preferably 4.1 to 7.6, preferably 4.1 to 7.0. w / M n ; A rheological long chain branching index g of preferably at least 0.90, preferably at least 0.93, preferably at least 0.95 rheo ; and Preferably, 13 having at least 0.30 wt.% ethyl branches, preferably at least 0.31 wt.% ethyl branches, preferably at least 0.33 wt.% ethyl branches, preferably at most 1.20 wt.% ethyl branches, preferably at most 1.10 wt.% ethyl branches, preferably in the range of 0.32% to 1.0 wt.%, preferably 0.34 to 0.98 wt.%, preferably 0.35 to 0.98 wt.%, based on the total weight of the ethylene polymer, as determined by C NMR analysis, with the proviso that said ethyl branches do not result from the incorporation of 1-butene as a comonomer; and / or preferably said ethylene polymer is a homopolymer or a copolymer obtained by polymerization of ethylene and at least one comonomer, preferably said comonomer is not 1-butene.

[0230] In one embodiment, the present invention provides a method for the preparation of a a melt index MI2 in the range of 0.1 g / 10 min to 12.0 g / 10 min, MI2 being determined according to ISO 1133:2005 Method B, Condition D at a temperature of 190° C. and using a 2.096 mm die with a load of 2.16 kg, preferably in the range of 0.2 g / 10 min to 11.0 g / 10 min, preferably 0.3 g / 10 min to 10.0 g / 10 min; M w is the weight average molecular weight, M n The number average molecular weight is 4.0 to 12.0, preferably 4.0 to 10.0, preferably 4.0 to 9.0, preferably 4.0 to 8.5, preferably 4.1 to 8.0, preferably 4.1 to 7.6, preferably 4.1 to 7.0. w / M n and Preferably 13ethyl cracking, based on the total weight of the ethylene polymer, as measured by C NMR, of at least 0.30% by weight, preferably in the range of 0.30% to 1.20% by weight, preferably 0.30 to 1.10% by weight, preferably 0.35 to 1.00% by weight, with the proviso that said ethyl branches do not result from the incorporation of 1-butene as a comonomer; The present invention relates to a metallocene catalyzed ethylene polymer having the formula:

[0231] In one embodiment, the present invention provides a method for the preparation of a a melt index MI2 in the range of 0.1 g / 10 min to 12.0 g / 10 min; MI2 is determined according to ISO 1133:2005 Method B, Condition D, at a temperature of 190° C. and using a 2.096 mm die with a load of 2.16 kg, preferably in the range of 0.2 g / 10 min to 11.0 g / 10 min, preferably in the range of 0.3 g / 10 min to 10.0 g / 10 min; M w is the weight average molecular weight, M n The number average molecular weight is 4.0 to 12.0, preferably 4.0 to 10.0, preferably 4.0 to 9.0, preferably 4.0 to 8.5, preferably 4.1 to 8.0, preferably 4.1 to 7.6, preferably 4.1 to 7.0. w / M n ; 0.910 g / cm3 measured at 23°C according to standard ISO 1183-1:2012 method A 3 ~0.965g / cm 3 in the range of 0.915 g / cm 3 ~0.960g / cm 3 Density in the range of; 13at least 0.30% to at most 1.20% by weight of ethyl branches, preferably at least 0.31 and at most 1.20% by weight of ethyl branches, preferably at least 0.31% to at most 1.10% by weight of ethyl branches, preferably at least 0.32% to at most 1.00% by weight of ethyl branches, preferably at least 0.33% to at most 0.98% by weight of ethyl branches, preferably at least 0.34% to at most 0.98% by weight of ethyl branches, preferably at least 0.35% to at most 0.98% by weight of ethyl branches, based on the total weight of the ethylene polymer as determined by C NMR analysis; The present invention relates to a metallocene catalyzed ethylene polymer having the formula:

[0232] The terms "ethylene polymer," "polyethylene resin," or "polyethylene," as used herein, refer to extruded and / or melted and / or pelletized ethylene polymer fluff or powder, which may be prepared by compounding and homogenizing ethylene polymers as taught herein, e.g., in a mixer and / or extruder. Unless otherwise specified, all parameters used to define the polyethylene resin are measured on the ethylene polymer pellets.

[0233] The term "fluff" or "powder", as used herein, refers to an ethylene polymer material having a solid catalyst particle at the core of each grain, and is defined as the polymer material after it leaves the polymerization reactor (or the last polymerization reactor in the case of multiple reactors connected in series). The term "pellets" refers to an ethylene polymer that has been pelletized, for example, by melt extrusion. As used herein, the terms "extrusion" or "extrusion process", "pelletization" or "pelletizing" are used synonymously herein and refer to the process of converting a polyolefin resin into a "polyolefin product" or "pellets" after pelletization. The pelletization process preferably involves several devices connected in series, including one or more rotating screws in an extruder, a die, and a means for cutting the extruded filaments into pellets.

[0234] In certain embodiments, the ethylene polymer is a homopolymer. The term "ethylene homopolymer," as used herein, is intended to encompass polymers that consist essentially of repeat units derived from ethylene. A homopolymer may be, for example, 13 It may contain at least 99.8%, preferably 99.9%, by weight, of repeat units derived from ethylene as determined by C NMR spectroscopy.

[0235] In another embodiment, the polyethylene resin is an ethylene copolymer. The term "ethylene copolymer" as used herein refers to a copolymer of ethylene and at least one other C-C 20 It is intended to encompass polymers consisting essentially of repeat units derived from an alpha olefin comonomer, preferably the comonomer is 1-hexene.

[0236] As used herein, the term "comonomer" refers to an olefin comonomer suitable for polymerization with an alpha-olefin monomer. Comonomers include, but are not limited to, aliphatic C3-C 20 Alpha olefins, preferably C3-C 12Alpha olefins may be included. Suitable aliphatic C3-C 20 Examples of 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, the comonomer is 1-hexene.

[0237] In some embodiments, the ethylene polymer is a copolymer of ethylene and a higher alpha olefin comonomer, preferably 1-hexene, where the total comonomer content, preferably 1-hexene (wt% C6), relative to the total weight of the ethylene polymer is 13 %, preferably at least 0.5 wt%, preferably at least 1.0 wt%, preferably at least 1.5 wt%, preferably at least 2.0 wt%, preferably at least 2.5 wt%, preferably at least 3.0 wt% as determined by C NMR analysis. In some embodiments, the ethylene polymer is a copolymer of ethylene and a higher alpha-olefin comonomer, preferably 1-hexene, where the total comonomer content relative to the total weight of the polyethylene, preferably 1-hexene (wt% C6), is 13 At most 15.0 wt.%, preferably at most 13.0 wt.%, preferably at most 10.0 wt.%, as determined by C NMR analysis.

[0238] The ethylene copolymers described herein can, in some embodiments, have a non-conventional (inverse or reverse) comonomer distribution, i.e., the high molecular weight portions of the polymer have higher comonomer incorporation than the low molecular weight portions. Preferably, the area ratio of the IR signal from the IR5-MCT detector as a function of logM (A CH3 / A CH2 ) comonomer incorporation increases with increasing molecular weight.

[0239] As used herein, the term "unimodal ethylene polymer" or "ethylene polymer with unimodal molecular weight distribution" refers to a polyethylene having one maximum in its molecular weight distribution curve, also defined as a unimodal distribution curve. As used herein, the term "polyethylene with bimodal molecular weight distribution" or "bimodal polyethylene" refers to a polyethylene having a distribution curve that is 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 a different weight average molecular weight. The term "polyethylene with multimodal molecular weight distribution" or "multimodal polyethylene" refers to a polyethylene having a distribution curve that is the sum of at least two, and 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 a different weight average molecular weight. Multimodal polyethylene can have an "apparent unimodal" molecular weight distribution, which is a molecular weight distribution curve with a single peak without a shoulder. Nonetheless, a polyethylene is also multimodal if it comprises two distinct populations of polyethylene macromolecules, each having a different weight average molecular weight, as defined above, for example when the two distinct populations were prepared in different reactors, and / or under different conditions, and / or using different catalysts.

[0240] In some embodiments, the ethylene polymer has a rheological long chain branching index g of at least 0.90. rheo In some embodiments, the polyethylene resin has a rheological long chain branching index g of at most 1.10. rheo In some embodiments, the polyethylene resin has a rheological long chain branching index g of at least 0.90 and up to 1.10, preferably at least 0.93 and up to 1.10, preferably at least 0.94 and up to 1.10, preferably at least 0.95 and up to 1.10. rheo has.

[0241] In one preferred embodiment, the ethylene polymer is: a melt index MI2 in the range of 0.1 g / 10 min to 12.0 g / 10 min, where MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature of 190° C. and using a 2.096 mm die with a 2.16 kg load; M w is the weight average molecular weight, M n The number average molecular weight is 4.0 to 12.0, preferably 4.0 to 10.0, preferably 4.0 to 9.0, preferably 4.0 to 8.5, preferably 4.1 to 8.0, preferably 4.1 to 7.6, preferably 4.1 to 7.0. w / M n and Preferably, 13 at least 0.30 wt% ethyl branches, preferably at least 0.32 wt% ethyl branches, preferably at least 0.35 wt% ethyl branches, preferably at most 1.20 wt% ethyl branches, preferably at most 1.10 wt% ethyl branches, preferably at most 1.00 wt% ethyl branches, preferably at most 0.99 wt% ethyl branches, preferably at most 0.98 wt% ethyl branches, preferably in the range of 0.30% to 1.20 wt%, preferably 0.30 to 1.10 wt%, preferably 0.30 to 1.00 wt%, based on the total weight of the ethylene polymer, as measured by C NMR, with the proviso that said ethyl branches do not result from the incorporation of 1-butene as a comonomer; and Preferably, the rheological long chain branching index g in the range of 0.90 to 1.10, preferably at least 0.93 to 1.10, preferably 0.95 to 1.10. rheo has.

[0242] In some embodiments, the ethylene polymer has a viscosity of at least 0.910 g / cm as measured according to standard ISO 1183-1:2012, Method A, at a temperature of 23° C. 3 , preferably at least 0.912 g / cm 3 , preferably at least 0.914 g / cm 3 , preferably at least 0.915 g / cm3 , 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 of 0.910 g / cm 3 ~0.965g / cm 3 , preferably 0.915 g / cm 3 ~0.963g / cm 3 , preferably at least 0.916 g / cm 3 ~ Maximum 0.963g / cm 3 Preferably, the polyethylene resin has a density in the range of 0.910 g / cm 3 ~0.965g / cm 3 Density in the range of, and 13 0.30% to 1.20% by weight of ethyl branches based on the total weight of the ethylene polymer, preferably 0.915 g / cm 3 ~0.963g / cm 3 and 0.32% to 1.10% by weight of ethyl branching, preferably 0.916 g / cm 3 ~ Maximum 0.963g / cm 3 and 0.33% to 1.00% by weight ethyl branching, preferably 0.916 g / cm 3 ~ Maximum 0.963g / cm 3 and 0.33% to 0.98% by weight of ethyl branches, provided that said ethyl branches do not result from the incorporation of 1-butene as a comonomer.

[0243] Preferably, the ethylene polymer is M w is the weight average molecular weight, M n is in the range of 2.0 to 7.0, preferably 2.0 to 6.0, preferably 2.5 to 5.5, preferably 2.5 to 4.0, and preferably 2.5 to 3.5, as a number average molecular weight. z / M w has.

[0244] In some preferred embodiments, the ethylene polymer has a molecular weight distribution M in the range of 8.0 to 25.0, preferably 9.0 to 22.0, preferably 9.5 to 22.0, preferably 10.0 to 20.0, preferably 10.5 to 20.0. z / M n has.

[0245] In some preferred embodiments, the ethylene polymer has a melt index ratio HLMI / MI2 in the range of 15.0 to 40.0; preferably in the range of 20.0 to 35.0.

[0246] In some preferred embodiments, the ethylene polymer has a melt index ratio HLMI / MI5 in the range of 5.0 to 20.0; preferably 7.0 to 15.0, preferably 7.0 to 13.0, preferably 7.5 to 13.0, preferably 8.0 to 12.0.

[0247] In some preferred embodiments, the ethylene polymer has a melt strength of at least 0.010 Newtons, preferably at least 0.015 Newtons, as determined at 190° C. by a Goettfert Rheotens Melt Strength Apparatus as described in the Experimental Section.

[0248] In some preferred embodiments, the ethylene polymer is: a melt index MI2 ranging from 0.1 g / 10 min to 12.0 g / 10 min; 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, where MI2 is determined according to ISO 1133:2005 Method B, Condition D, at a temperature of 190° C. and using a 2.096 mm die with a load of 2.16 kg; M w is the weight average molecular weight, M nThe number average molecular weight is 4.0 to 12.0, preferably 4.0 to 10.0, preferably 4.0 to 9.0, preferably 4.0 to 8.5, preferably 4.1 to 8.0, preferably 4.1 to 7.6, preferably 4.1 to 7.0. w / M n and Preferably, 13 at least 0.30 wt% ethyl branches, preferably at least 0.32 wt% ethyl branches, preferably at least 0.35 wt% ethyl branches, preferably at most 1.20 wt% ethyl branches, preferably at most 1.10 wt% ethyl branches, preferably in the range of 0.30% to 1.0 wt%, preferably 0.30 to 0.99 wt%, preferably 0.35 to 0.98 wt%, based on the total weight of the ethylene polymer as measured by C NMR, with the proviso that said ethyl branches do not result from the incorporation of 1-butene as a comonomer; Rheological long chain branching index g preferably in the range of 0.91 to 1.10, preferably 0.93 to 1.10, preferably 0.95 to 1.10 rheo ; Preferably at least 0.910 g / cm3 measured according to standard ISO 1183-1:2012 Method A at a temperature of 23°C. 3 , 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 up to 0.962 g / cm 3 ;preferably 0.910 g / cm 3 ~0.965g / cm 3 , preferably 0.915 g / cm 3 ~0.963g / cm 3 , preferably at least 0.916 g / cm 3 ~ Maximum 0.963g / cm 3 Density in the range of; M is preferably in the range of 2.0 to 7.0, preferably 2.0 to 6.0, preferably 2.5 to 5.5, preferably 2.5 to 4.0, preferably 2.5 to 3.5. z / M w ; M in the range of preferably 8.0 to 25.0, preferably 9.0 to 22.0, preferably 9.5 to 22.0, preferably 10.0 to 20.0, preferably 10.5 to 20.0 z / M n ; a melt index ratio HLMI / MI2 preferably ranging from 15.0 to 40.0; preferably ranging from 20.0 to 35.0; and / or Preferably, the melt index ratio HLMI / MI5 is in the range of 5.0 to 20.0; preferably, 7.0 to 15.0, preferably, 7.0 to 13.0, preferably, 7.5 to 13.0, preferably, 8.0 to 12.0. has.

[0249] The present invention also encompasses a process, preferably a continuous process, for the preparation of the metallocene-catalyzed ethylene polymers described herein, which process comprises: contacting a catalyst composition with ethylene, optionally hydrogen, and optionally one or more alpha-olefin comonomers; and polymerizing the ethylene, and optionally one or more alpha-olefin comonomers, in the presence of at least one catalyst composition, and optionally hydrogen, to obtain the metallocene-catalyzed ethylene polymers described herein.

[0250] Preferably, the continuous process comprises the steps of: contacting a metallocene catalyst composition with ethylene, optionally hydrogen, and optionally one or more alpha-olefin comonomers; polymerizing the ethylene, and optionally one or more alpha-olefin comonomers, in the presence of at least one catalyst composition, and optionally hydrogen, to obtain an ethylene polymer as described herein; wherein the catalyst composition a catalyst component A comprising the meso form of a bridged metallocene compound having two indenyl groups, each indenyl being substituted with one or more substituents, at least one of which is aryl, preferably phenyl; said aryl may be unsubstituted or substituted; preferably at least one of the substituents is at the 3 and / or 5 position of each indenyl, preferably an aryl, preferably a phenyl, is at the 3 position of each indenyl; a catalyst component B comprising a bridged metallocene compound having a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; and an optional activator; an optional support; and an optional cocatalyst; preferably an alumoxane activator; a support; and an optional cocatalyst. Includes.

[0251] The ethylene polymers can be prepared in a process which can be in gas, solution and / or slurry phase, preferably a continuous process. The process can be carried out in one or more slurry loop reactors, gas phase reactors, continuous stirred tank reactors or combinations thereof. Preferably the process is carried out in one or more slurry loop reactors, preferably in a single slurry loop reactor.

[0252] As used herein, the terms "loop reactor" and "slurry loop reactor" may be used interchangeably herein. In certain embodiments, each loop reactor may include interconnected pipes that define a reactor path. In certain embodiments, each loop reactor may include 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, and may further include one or more feed lines, one or more outlets, one or more cooling jackets per pipe, and a pump, thus defining a continuous flow path for the polymer slurry. The vertical sections of the pipe segments are preferably equipped with cooling jackets. Polymerization heat may be extracted by cooling water circulating through these jackets of the reactor. The loop reactor is preferably operated in an all-liquid mode.

[0253] The polymerization step can be carried out over a wide temperature range. In certain embodiments, the polymerization step can be carried out at a temperature of 20° C. to 125° C., preferably 60° C. to 110° C., more preferably 75° C. to 100° C., and most preferably 78° C. to 98° C. Preferably, the temperature range can be within the range of 75° C. to 100° C., and most preferably 78° C. to 98° C. Said temperatures can be within the more common polymerization conditions.

[0254] The present invention also includes polyethylene compositions comprising the ethylene polymer of the present invention and one or more additives.

[0255] The additives can be, for example, antioxidants, UV stabilizers, pigments, processing aids, acid scavengers, lubricants, antistatic agents, fillers, nucleating agents, or clarifiers, or combinations thereof. An overview of useful additives can be found in Plastics Additives Handbook, edited by H. Zweifel, 5th Edition, Hanser Publishers. These additives may generally be present in an amount of 0.01 to 10% by weight, based on the weight of the polyethylene composition.

[0256] Once produced, the ethylene polymers can be formed into a variety of articles. Ethylene polymers are particularly suited for articles such as blown or cast film products, caps and closures, serial liners, glass yarns, rotational molded articles, blow molded articles, pipes, fibers, and the like.

[0257] The present invention therefore also encompasses articles comprising the ethylene polymers defined herein; or obtained according to the processes defined herein. In some embodiments, the articles can be film products, caps and closures, rotationally molded articles, fibers, pipes, blow molded articles, etc. The preferred embodiments for the ethylene polymers of the present invention are also preferred embodiments for the articles of the present invention.

[0258] The present invention also includes a method for preparing an article according to the present invention. The preferred embodiments described above are also preferred embodiments for this method.

[0259] The following examples are merely useful for illustrating the present invention and should not be construed as limiting its scope in any way. Although the present invention has been illustrated in only some of its forms, it will be apparent to those skilled in the art that the present invention is not limited thereto and that various changes and modifications can be made without departing from the scope of the present invention. EXAMPLES

[0260] Test Method The properties mentioned herein and hereinafter have been determined in accordance with the following test procedures. Any of these properties, when referred to in the appended claims, will be measured in accordance with the specified test procedures.

[0261] density The density of the polyolefins was measured according to standard ISO 1183-1:2012 method A at a temperature of 23° C. (weight of the fluid displaced in isopropanol at 23° C. (buoyancy)).

[0262] 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 2.096 mm die.

[0263] Melt flow rate (MI5) was measured according to ISO 1133:2005, Method B, Condition T, at 190° C. and a 5 kg load using a 2.096 mm die.

[0264] 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 load of 21.6 kg using a 2.096 mm die.

[0265] Molecular weight, molecular distribution Molecular weight (M n (number average molecular weight), M w (weight average molecular weight) and molecular weight distribution D(M w / M n ), and D'(M z / M w ) was determined by size exclusion chromatography (SEC), specifically IR-detected gel permeation chromatography (GPC) at high temperature (145 °C). Briefly, GPC-IR5MCT from Polymer Char was used: 8 mg of polymer sample was dissolved in 8 mL of trichlorobenzene stabilized with 1000 ppm by weight of butylhydroxytoluene (BHT) at 160 °C for 1 hour (h). Injection volume: about 400 μl, 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 at a flow rate of 1 mL / min. Detector: infrared detector (2800–3000 cm) collecting all C–H bonds. -1) and two narrow band filters tuned to the absorption regions assigned to CH3 and CH2 groups. Calibration: narrow polystyrene (PS) standards (commercially available). The molecular weight M of each fraction i of the eluted polymer i The calculation is based on the Mark-Houwink relation (log 10 (M PE )=0.965909×log10(M PS )-0.28264)(M PE Based on the cutoff for the low molecular weight end at 1000.

[0266] The molecular weight averages used in establishing molecular weight / property relationships are number averages (M n ), weighted average (M w ) and z-mean (M z ) molecular weight. These averages are defined and calculated as follows: i Determined from:

[0267]

number

[0268] In the formula, N i and W i are the molecular weights M i are the number and weight of molecules with i, i = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, i is the molecular weight of the species eluting at this increment.

[0269] 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 (ΔH) were measured by differential scanning using a DSC Q2000 instrument from TA Instruments calibrated with indium and using T-zero mode. Polymer analysis was performed on 2-10 mg polymer samples. The samples were first equilibrated at 30°C and then heated to 220°C using a heating rate of 50°C / min (first heat). The samples were held at 220°C for 5 min to erase the previous thermal and crystallization history. The samples were then cooled to 0°C at a constant cooling rate of 10°C / min (first cool). The samples were held isothermally at 0°C for 5 min and then heated to 220°C at a constant heating rate of 10°C / min (second heat). The endothermic peak of melting (second heat) was analyzed using TA Universal Analysis software and the peak melting temperature (T m ) was decided.

[0270] Long chain branching index g rheo Rheological long chain branching index g rheo was measured according to the formula described in WO 2008 / 113680:

[0271]

number

[0272] where Mw(SEC) is the weight average molecular weight in kDa obtained from size exclusion chromatography; Mw(η0,MWD,SCB) is determined according to the following formula, also expressed in kDa: M w (η0,MWD,SCB)=exp(1.7789+0.199769LnM n +0.209026(Lnη0)+0.955(lnρ)-0.00756(LnM z )(Lnη0)+0.02355(lnM z ) 2 ) In the formula, the zero shear viscosity η0 (Pa.s) is the frequency range of 10 -4 s -1or lower, in frequency sweep experiments combined with creep experiments, obtained with the usual assumption of equivalence of angular frequency (rad / s) and shear rate; where the zero shear viscosity η0 was estimated by fitting the Carreau-Yasuda flow curve (η-W) at a temperature of 190 °C obtained by oscillatory shear rheology on an ARES-G2 instrument (manufactured by TA Instruments) in the linear viscoelastic region; the circular frequency (W, rad / s) varied from 0.1 rad / s to 300 rad / s, and the shear strain was typically 10%. In practice, creep experiments were performed at a stress level such that the total strain was less than 25% after 1000 s in nitrogen atmosphere at a temperature of 190 °C.

[0273] Comonomer Content The comonomer content, especially 1-hexene (wt.% C6-), based on the total weight of the ethylene polymer is 13 C{ 1 The ethyl branch content, expressed as equivalent wt.% C4-, was also determined from the H NMR spectrum. 13 C{ 1 H NMR spectra.

[0274] Samples were prepared by dissolving a sufficient amount of polymer in 1,2,4-trichlorobenzene (TCB 99% spectroscopic grade) at 130°C, swirling occasionally to homogenize the sample, and then adding hexadeuterobenzene (C6D6, spectroscopic grade) and a small amount of hexamethyldisiloxane (HMDS, 99.5+%). HMDS serves as an internal standard. As an example, approximately 220 mg of polymer was dissolved in 2.0 mL of TCB, followed by the addition of 0.5 mL of C6D6 and 2-3 drops of HMDS.

[0275] 13 C{ 1 H}NMR signals were recorded on a Bruker 500 MHz with a 10 mm probe (or a 10 mm cryoprobe) under the following conditions: Pulse angle: 90° Pulse repetition time: 30s Spectral width: 25000Hz centered on 95ppm Data points: 64K Temperature: 130℃+ / -2℃ Rotation: 15Hz Number of scans: 2000-4000 (240 scans, 10 mm cryoprobe) Decoupling sequence: reverse gated decoupling sequence, to avoid NOE effects 13 C{ 1 H} NMR spectra were obtained by light Gaussian multiplication followed by Fourier transform to 131 K. Spectra were phased and baseline corrected, and the chemical shift scale was compared to the internal standard HMDS at 2.03 ppm.

[0276] The chemical shifts of the signals were peak picked and the peaks were integrated as described in FIG.

[0277] [Table 1]

[0278] Small adjustments can be made to the integral limits if necessary. Chemical shifts are given in ±0.05 ppm. The wt.% C6- and wt.% C4- contents are obtained by combining the following areas (A): A C3 =0.5×A CH2(a)B1 A C4 =A CH3B2 A C6 =A CH2(2)B4 A C2 =0.5×(A Tv1 +A Tv2 +A Tv3 +A ビニリデン1+ A ビニリデン2 +0.5×A CH2(a)B1 +A Ts3 +2×A Ts2 +A CH2n -A C6 +A CH2(b) ) wt.%C6-=(84 * A C6 ) / (28 * A C2 +42 * A C3 +56 * A C4 +84 * A C6 ) x 100 wt.%C4-=(56 * A C6 ) / (28 * A C2 +42 * A C3 +56 * A C4 +84 * A C6 ) x 100 Meso / Rac ratio of metallocene catalysts The meso / rac ratio of catalyst component A is 1 Determined from 1 H NMR spectrum.

[0279] The samples were prepared by dissolving several tens of milligrams of the solid complex in 0.5 mL of anhydrous methylene chloride (CD2Cl2, spectroscopic grade) at room temperature.

[0280] 1 H NMR signals were recorded on a Bruker 400 MHz with a 5 mm probe under the following conditions: Pulse angle: 90° Pulse repetition time: 60s Spectral width: 6000Hz centered on 5.5ppm Data points: 32K Temperature: 25℃+ / -1℃ Rotation: 20Hz Number of scans: 8 1 H NMR spectra were obtained by light exponential multiplication followed by Fourier transformation to 32 K. Spectra were phased and baseline corrected, and the chemical shift scale was referenced to the CH2CL2 peak at 5.33 ppm.

[0281] The chemical shifts of the signals were peak picked and the peaks were integrated as described in FIG.

[0282] [Table 2]

[0283] The meso / rac ratio was obtained by combining the following areas (A): meso / Rac=A meso / A Rac Comonomer Distribution The comonomer distribution, as indicated by the CH3 / CH2 ratio across the molecular weight distribution, was also determined using the above SEC instrument equipped with an integral high-sensitivity multiband IR detector (IR5-MCT) as described by A. Ortin et al. (Macromol. Symp. Vol. 330, pp. 63-80 2013 and T. Frijns-Bruls et al. Macromol. Symp. Vol. 356, pp. 87-94 2015).

[0284] The comonomer distribution can be determined by the ratio of the IR detector intensities corresponding to the CH3 and CH2 channels calibrated with a series of PE homo / copolymer standards whose nominal values ​​have previously been determined by NMR.

[0285] The detector generated separate continuous streams of absorbance data measured through each of its IR selective filters CH3 and CH2 at a fixed acquisition rate of one point per second. The detector was equipped with a heated flow-through cell with an internal volume of 13 μL.

[0286] Infrared absorbance band ratio A CH3 Against A CH2 The ratio of (methyl / methylene sensitive channels) can be related to the methyl (CH3) per 1000 total carbons (1000TC) as a function of molecular weight, denoted as CH3 / 1000TC.

[0287] The IR CH3 / CH2 ratio of the polymer was obtained by considering the total signal in the CH3 and CH2 channels between the integration limits of the concentration chromatogram: IR ratio = area of ​​CH3 signal within integral limits / area of ​​CH2 signal within integral limits.

[0288] In the present invention, an increase in the area ratio CH3 / CH2 means an increase in the short chain branch content. Dynamic Rheometric Analysis (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 the angular frequency range of 0.1 to 300 rad / s using the small amplitude oscillatory shear (SAOS) test, as described below.

[0289] From the data generated by such tests, it is possible to determine the phase or loss angle δ, which is the arctangent of the ratio of G″ (loss modulus) to G′ (storage modulus). For a typical linear polymer, the loss angle at low frequencies (or long times) approaches 90°, and the loss modulus becomes much larger than the storage modulus. As the frequency increases, more and more chains relax very slowly and are unable to absorb the energy in the vibrations, and the storage modulus becomes large relative to the loss modulus. Eventually, the storage and loss moduli become equal and the loss angle reaches 45°. In contrast, branched polymers relax very slowly. Such branched polymers never reach a state where all their chains are able to relax in vibration, and the loss angle never reaches 90° even at the lowest frequency ω of the experiment. The loss angle is also relatively independent of the frequency of vibration in SAOS experiments; this is another indication that the chains are not able to relax on these timescales.

[0290] In a plot of phase angle δ versus measurement frequency ω, polymers with long chain branching exhibit a plateau in function of δ(ω), whereas linear polymers have no such plateau. According to Garcia-Franco et al. (34(10) Macromolecules pp. 3115-3117 (2001)), the plateau in the aforementioned plot shifts to smaller phase angles δ with increasing amounts of long chain branching in the polymer sample.

[0291] Van Gurp-Palmen plot (vGP plot) Complex modulus of elasticity G * and loss angle δ are determined at a test temperature of 190°C and can be obtained from rheological data analyzed using the van Gurp-Palmen procedure (see van Gurp, M. and Palmen, J., Rheology Bulletin, 1998, Vol. 67(1), pp. 5-8). The vGP curves are plotted against the phase angle δ (=tan -1 [G'' / G'] vs. the magnitude of the complex modulus |G * | plot. In linear polymers, δ first decreases with decreasing modulus value, then passes through a minimum, increases again, passes through an inflection point, and finally approaches its 90° limit value. LCBs lower the vGP curve. The higher the LCB density, the lower the δ value. The area contained under the vGP curve can be used as a parameter to evaluate the degree of LCB. In addition, the magnitude of the apparent plateau decrease caused by LCBs is related to the relative length of the long chain branches on the polymer backbone. Low levels of long chain branching can be detected and relatively quantified using this methodology.

[0292] Melt Strength Melt strength (also called breaking strength) was measured using a Goettfert Rheotens melt strength instrument, model 71-97, in combination with a Rheograph Goettfert RG50 (both from Goettfert) under the following test conditions: Rheograph Goettfert (RG50) = Die geometry (L / D): 30mm / 2mm, 180° entrance angle; Barrel + die temperature: 190°C; Piston diameter 12mm, Piston speed: 0.25mm / s; Rheotens (model 71-97) Wheels: standard (ribbed wheels); Wheel gap: 0.4mm; Wheel acceleration: 2mm / s 2 , strand length: 100.0 mm, wheel initial speed Vo: 9.0 mm / s. In the Rheotens test, the tension required to stretch / draw the extruded molten filament exiting the capillary die was measured as a function of the wheel winding speed, which increased continuously at a constant accelerated speed. The tension typically increased with increasing wheel (roller) speed, and above a certain winding speed, the force remained constant until the filament (strand) broke.

[0293] For each material, a Rheotens curve was generated to verify data reproducibility. The polymer was loaded into the barrel and melted at 190 °C for 360 seconds before starting the test. Virtually the entire amount of material present in the barrel of the Rheograph was extruded through the die and picked up by the wheel of the Rheotens device. The strand was left to stabilize between the wheels rotating at 9 mm / s, and once the strand was stabilized, the force was adjusted to 0 N and the wheel acceleration was started. Once the test was started, the wheel speed was increased to 2.0 mm / s. 2 The tension was measured for each given speed, increasing with an acceleration of 100 rpm. After each strand broke or slipped 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. Measurements were continued until all material in the barrel was consumed. In this invention, the average tension vs. draw ratio for each material was reported.

[0294] TREF Temperature rising elution fractionation analysis (TREF analysis) was performed using a method similar to that described by Soares and Hamielec, Polymer, Vol. 36(No. 10), 1995, pp. 1639-1654, which is incorporated herein by reference in its entirety. TREF analysis was performed on a Polymer Char (Valencia, Spain) TREF model 200 TF series instrument equipped with an infrared detector. Samples were dissolved in 1,2-dichlorobenzene at 150° C. for 1 h. The following parameters, shown in Table C, were used:

[0295] [Table 3]

[0296] Determination of Al and Zr contents The Al and Zr contents were determined using inductively coupled plasma atomic emission spectrometry (ICP-AES) after mineralization of the samples and recovery of the residues in an acid medium. The spectrometer used was a Spectro ICP-AES ARCOS.

[0297] The elemental determination was performed by nebulization of the solutions 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).

[0298] Preparation of the solution to be analyzed (test solution): Under an inert atmosphere (in a glove box), approximately 0.3 g of catalyst was placed in a platinum crucible and 3-5 ml of isopropyl alcohol was added to "deactivate" the catalyst. The mixture was heated to dryness in a sand bath (30 min). The platinum crucible was placed in a 600 °C oven for 10 min. After cooling, Milli-Q® deionized water was added to impregnate all the ash, and 1 mL of concentrated HCl (Merck HCl 32% v / v) and concentrated HF (Merck HF 48% v / v) were added. The crucible was placed in a sand bath, Milli-Q® deionized water was added, and the contents of the crucible were mixed. After 24 h, 1 ml of concentrated HCl, 0.5 ml of concentrated HF and Milli-Q® deionized water were added and the mixture was stirred under heat to achieve complete dissolution. After cooling, the mixture was transferred to a 50 ml polypropylene tube and the volume was made up to 50 ml with Milli-Q® deionized water. The test solution was then diluted 25-fold to ensure that a 2% HCl / HF 1% medium was maintained.

[0299] Preparation of calibration standards and control solutions: Standard solutions were prepared by dilution of commercial single element solutions of guaranteed concentration. Standard solutions were prepared by transferring the required volume of the certified solution into a 50 ml polypropylene tube, then rinsing the sides of the tube with Milli-Q® deionized water, adding 1 ml of concentrated HCl and 0.5 ml of concentrated HF per 50 ml to obtain the same acid content in the solution as the sample solution, and finally finishing the dilution with Milli-Q® deionized water. Control solutions were prepared by dilution of commercial multi-element solutions of guaranteed concentration. The presence of other elements in the solution allowed verification of the presence / absence of possible interferences.

[0300] Determination of Fe content The Fe content was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES) after mineralization of the samples and recovery of the residue in acid medium. The spectrometer used was an ICP-AES ARCOS from Spectro.

[0301] The Fe content was determined by ICP-AES after calcination of the samples and recovery of the ash in acid medium.

[0302] The elemental determination was performed by nebulization of the solutions 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).

[0303] Preparation of the solution to be analyzed (test solution): Approximately 10 g of sample was placed in a platinum crucible. Using a Bunsen burner, the sample was fired with a small flame until it was completely combusted. Firing was completed by placing the platinum crucible in a 600°C oven for a minimum of 30 minutes. After cooling, Milli-Q® deionized water was added to impregnate all ash, and 1 mL of concentrated HCl (Merck HCl 32% v / v) and concentrated HF (Merck HF 48% v / v) were added. The crucible was placed in a sand bath, Milli-Q® deionized water was added, and the contents of the crucible were mixed. After 24 h, 1 mL of concentrated HCl, and Milli-Q® deionized water were added while stirring the mixture under heat to achieve complete dissolution. After cooling, the mixture was transferred to a 50 mL polypropylene tube and the volume was made up to 50 mL with Milli-Q® deionized water.

[0304] Preparation of calibration standards and control solutions: Standard solutions were prepared by dilution of commercial single element solutions of guaranteed concentration. Standard solutions were prepared by transferring the required volume of the certified solution into a 50 mL polypropylene tube, then rinsing the sides of the tube with Milli-Q® deionized water, adding 1 mL of concentrated HCl per 50 mL to obtain the same acid content in the solution as the sample solution, and finishing the dilution with Milli-Q® deionized water. Control solutions were prepared by dilution of commercial multi-element solutions of guaranteed concentration. The preparation protocol is the same as for the standard solutions. The presence of other elements in the solution allowed verification of the presence / absence of possible interferences.

[0305] Expression of results for Zr, Al and Fe contents: The contents (ppm) of the measured elements in the samples were calculated as follows:

[0306]

number

[0307] Limits of Quantification (LOQ) were calculated from 10 blank measurements for each element: LOQ in solution (mg / l) = standard deviation of 10 replicates of blank x 10

[0308]

number

[0309] catalyst Metallocene 1: meso-metallocene 1 (mMet1)

[0310] [ka]

[0311] The meso-metallocene 1 (mMet1) was prepared as described below and shown in Scheme 1. Unless otherwise stated, all procedures are carried out in a glove box under nitrogen atmosphere with dry solvents.

[0312] [ka]

[0313] Step 1: To a solution of 3.52 g (0.022 mol) of diethyl malonate in 25 mL of THF was added 0.88 g (60% in oil, 0.022 mol) of sodium hydride at 0° C. The mixture was refluxed for 1 h and then cooled to room temperature. Then, 5 g (0.022 mol) of 4-tBu-benzyl bromide was added and the resulting mixture was refluxed for 3 h. A precipitate formed (NaBr). The mixture was cooled to room temperature and filtered through a glass frit (G2). The precipitate (NaBr) was further washed with 3×5 mL of THF. The combined filtrates were evaporated to dryness.

[0314] The residue was dissolved in 20 mL of ethanol and 2.5 mL of water, and then 8 g of potassium hydroxide was added at 0°C. The resulting mixture was refluxed for 2 h, and then 10 mL of water was added. Ethanol was distilled under reduced pressure at a controlled T°C (maximum 30°C). The resulting aqueous solution was acidified to pH 1 with HCl, and the product was extracted with ether (3 x 100 mL). The combined organic fractions were washed with HCl 1M (1 x 25 mL) and brine (1 x 25 mL), then dried over MgSO4 and concentrated under reduced pressure.

[0315] The diacid was decarboxylated by heating at 160° C. for 2 h (gas evolution was observed). The resulting product was dissolved in 30 mL of dichloromethane and 30 mL of SOCl2 was added. The mixture was refluxed for 3 h and then evaporated to dryness.

[0316] The residue was dissolved in 12 mL of dry dichloromethane, and the resulting solution was added dropwise to a suspension of 6.5 g (0.05 mol) of AlCl in 68 mL of dichloromethane at 0 °C for 1 h while vigorously stirring. The reaction mixture was then refluxed for 3 h, cooled to room temperature, and stirred at 250 cm 3 The mixture was poured onto ice and extracted with DCM (3×50 mL).

[0317] The organic layer was washed with HCl 1M and brine (1×25 mL each). The combined organic fractions were dried over MgSO4 and then evaporated to dryness. The product was isolated by filtration over silica (1-10% AcOEt in isopentane). The desired product was a yellow oil (yield=35%).

[0318] Step 2: 6-tBu-1-indanone (1 eq., 5.078 g) was dissolved in 80 mL of Et2O. PhMgBr (1.1 eq., 10 mL, 3 M) was added dropwise at 0° C. and the solution was heated to reflux for 2 h and then stirred at room temperature overnight. After stirring overnight, the reaction was slowly quenched with 50 mL of 1 M HCl and stirred for 1 h. The mixture was neutralized with saturated NaHCO3 solution and extracted with diethyl ether (x2). The organic layer was dried over 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 optionally after filtration over silica with n-pentane).

[0319] 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 the addition was complete, the mixture was stirred overnight at room temperature. A catalytic amount of CuCN was added, the resulting solution was stirred for 30 min, and then 0.49 mL of (dimethyl)dichlorosilane (4 mmol) was added in one portion. After the addition, the reaction solution was stirred overnight at room temperature. The reaction mixture was filtered through alumina and the solvent was removed in vacuum. The product was purified by silica gel flash column chromatography eluting with hexane / DCM (9 / 1) to give an orange powder. Yield=52%.

[0320] Step 4: To a solution of the ligand bis(5-tert-butyl-3-phenyl-1H-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 hexane, 22.0 mL, 0.0351 mol) over 15 min. The mixture was left stirring at room temperature for 24 h. In a second 500 mL round bottom flask, ZrCl4 (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 about 5 min. The reaction mixture was left stirring at room temperature for 2 h. The ligand / n-BuLi mixture was then added by pipette over 15 min to the ZrCl4 / THF mixture. An additional 2 mL of THF was used to wash the white solid off the walls of the Ligand / n-BuLi flask to ensure complete transfer. The resulting mixture was allowed to stir at room temperature for 18 h before being filtered through a POR3 glass frit (oven dried for 3 days prior to use) packed with 75 mL of Celite. The reaction flask and Celite were washed with an additional 40 mL of toluene. The filtrate was concentrated under vacuum to approximately 200 mL. The flask was tightly sealed with 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 defrost before being returned to the glovebox. The mixture was filtered through a 75 mL POR4 glass frit to collect a bright orange solid and a red-orange filtrate. The solid was washed with 2 x 3 mL of pentane and then dried on the frit for approximately 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 glove box, and stored at -35 °C for 20 h. The flask was defrosted at room temperature and returned to the glove box, and the mixture was filtered through a POR4 glass frit, collecting a bright orange solid and a second fraction of orange filtrate. The solid was washed with 2 × 3 mL of pentane and dried on the frit under vacuum for 2 h.The solid was then transferred to a vial for storage: fraction 2, 446 mg (4% yield). At this point the same procedure as shown above was repeated on the filtrate allowing a third (942 mg, 8% yield) fraction of an orange solid to be isolated.

[0321] Meso purity of each fraction 1 Based on these results, it was concluded that fractions 1 and 2 had similar meso purity and could be combined to give an overall yield of 25% Met1 with a meso purity of 96% (i.e., the meso / rac ratio of the meso form of Met1 was 96:4) (catalyst 1 1 H NMR is shown in Figure 2. This metallocene is called mMet1 and is used without further purification to support the polymerizations described herein.

[0322] Metallocene 2: (Butenyl)MeC(Cp)(2,7-tBu2-Flu)ZrCl2(Met2) Metallocene 2 was prepared according to the synthesis described in Journal of Organometallic Chemistry, Vol. 553, 1998, pp. 205-220, as described below:

[0323] [ka]

[0324] Step 1:

[0325] [ka]

[0326] A 200 mL three-neck flask equipped with a gas inlet tube and a magnetic stir bar was charged under nitrogen with 2.5 eq of freshly cracked cyclopentadiene and 1 eq of 5-hexen-2-one in 60 mL of methanol. Then 2 eq of pyrrolidine were added dropwise at 0° C. and the mixture was stirred overnight at room temperature. The reaction was quenched with 50 mL of HCl 1M and extracted with Et2O (3×50 mL). The organic fraction was dried over MgSO4 and the solvent was removed under reduced pressure. The fulvene was obtained as a yellow oil and used without further purification (yield=65%).

[0327] Step 2:

[0328] [ka]

[0329] In a three-neck flask, 1 eq of di-tert-butylfluorene was added under nitrogen flow and dissolved in 70 mL of Et2O. To this solution, 1.1 eq of n-BuLi (1.6 M in hexane) was added dropwise at 0°C 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 Et2O was added dropwise. The reaction mixture was left stirring overnight. The reaction was quenched with water and extracted with Et2O (3 x 50 mL). The combined organic fractions were dried over MgSO4 and the solvent was removed under reduced pressure. The product was crystallized in pentane / MeOH at 0°C to give a white solid (yield = 85%).

[0330] Step 3:

[0331] [ka]

[0332] In a round bottom flask, 1 g of the ligand was introduced and dissolved in 40 mL of Et2O. 2.1 eq. of nBuLi was added dropwise and the mixture was stirred overnight at room temperature. The solvent was removed in vacuum and 40 mL of dry pentane was added. Then 1 eq. of ZrCl4 was added in portions at room temperature. The reaction was stirred for 2 days and filtered. The resulting precipitate was diluted with DCM and centrifuged to remove the lithium chloride. The solvent was removed in vacuum to give a deep pink powder (yield=70%). 1 1.36 (s, 9 H, CH3tBu); 2.30 (m, CH2alk); 2.43 (s, 3 H, CH3); 2.55 (m, 1 H, CH2alk.); 2.65 (m, 1 H, CH2alk.); 3.25 (m, 1 H, CH2alk.); 5.13 (m; 1 H, CH vinyl); 5.18 (m; 1 H, CH vinyl); 5.70 (m, 2 H, CHcp); 6.10 (m; 1 H, CH vinyl); 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: Dichloro[rac-ethylenebis(4,5,6-tetrahydro-1-indenyl)]zirconium (Met3)

[0333] [ka]

[0334] Dichloro[rac-ethylenebis(4,5,6-tetrahydro-1-indenyl)]zirconium was purchased from KOEI CHEMICAL Co., Ltd. (CAS 100163-29-9).

[0335] Synthesis of supported catalysts All catalytic and cocatalytic experiments were carried out under nitrogen atmosphere in a glove box. Methylaluminoxane (30 wt.%) in toluene (MAO) from Albemarle was used as the activator. Titanated silica (PD12052) from PQ was used as the catalyst support (D50: 25 μm).

[0336] The supported metallocene catalyst was prepared in two steps using the following method: 1. Impregnation of silica with MAO: 10 grams of dried silica (dried at 450°C under nitrogen for 6 h) was introduced into a round bottom flask equipped with a mechanical stirrer and a slurry was formed by adding 100 mL of toluene. MAO (21 mL) was added dropwise via an addition 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 dry pentane (3 x 20 mL). The powder was dried under reduced pressure overnight to give a free-flowing grey powder.

[0337] 2. Deposition of metallocenes onto silica / MAO supports: 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 at room temperature for 2 h. The reaction mixture was filtered through a glass frit and the powder was washed with dry toluene (3×20 mL) and dry pentane (3 times). The powder was dried under reduced pressure overnight to give a free-flowing grey powder.

[0338] The samples were analyzed for zirconium and aluminum content (wt.%) using ICP-AES spectroscopy (Inductively Coupled Plasma Atomic Emission Spectroscopy), and the results are shown in Table 1.

[0339] [Table 4]

[0340] Example A: The polymerization reaction was carried out in a 132 ml autoclave equipped with stirrer, temperature controller and inlets for feeding ethylene and hydrogen. The reactor was dried with nitrogen at 110° C. for 1 h and then cooled to 40° C.

[0341] All polymerizations were carried out under the heterogeneous conditions listed in Table 2 (unless otherwise stated). The reactor was charged with 75 ml of isobutane, 1.6 ml of 1-hexene (C6-) and pressurized to 23.8 bar with ethylene (C2-) containing 800 ppm of hydrogen. Catalyst (3.5 mg) was added. Polymerizations were initiated upon injection of the catalyst composition suspension, carried out at 85° C. and stopped after 60 minutes by depressurizing the reactor. The reactor was flushed with nitrogen before being opened.

[0342] [Table 5]

[0343] The results of copolymerization of ethylene and 1-hexene comonomer in the presence of the dual catalyst composition are shown in Table 3. The polymerization conditions were the same as those listed in Table 2.

[0344] [Table 6]

[0345] FIG. 3 shows the GPC traces of polymers obtained with the binary catalyst composition mMet1 / Met2 with increasing mMet1 content (mMet1 / Met2 weight ratio from 20 / 80 to 50 / 50).

[0346] Table 4 below shows the results of copolymerization of ethylene and 1-hexene comonomer in the presence of various mMet1 / Met2 weight ratio compositions of each catalyst. The polymerization conditions were the same as those listed in Table 2.

[0347] [Table 7]

[0348] The polymers were further tested by melt rheology (RDA). For this, the complex viscosity (|η * The logarithmic trends of the mean mean and mean mean (|) were examined (Figure 4). The van Gurp-Palmen (vGP) plot was examined (Figure 5).

[0349] The 1-hexene response was also studied for the catalyst composition mMet1 / Met2 (30 / 70 weight ratio). The polymerization conditions were the same as those listed in Table 2, except for the 1-hexene concentration (800 ppm H2). The results are shown in Table 5.

[0350] [Table 8]

[0351] The results of the NMR study of the polymers obtained with the catalyst composition mMet1 / Met2 (30 / 70 weight ratio) as a function of the 1-hexene concentration are given in Table 6.

[0352] [Table 9]

[0353] Additional polyethylene was prepared with various binary catalyst compositions. All polymerizations were carried out under the conditions shown in Table 2. The results are shown in Table 7.

[0354] [Table 10]

[0355] Example B: Further ethylene polymers were prepared with mMet1 / Met2 catalyst composition (30 / 70 weight ratio). The polymerization reactions were carried out in a single slurry loop reactor using isobutane as diluent. All polymerizations were carried out under the conditions shown in Table 8. The analytical results for the pellets are also shown in Table 8. The productivity for the resins produced is shown in Figure 6.

[0356] [Table 11-1]

[0357] [Table 11-2]

[0358] Comparative resins were also prepared using the operating conditions shown in Table 9.

[0359] [Table 12]

[0360] The hydrogen response is shown in Figure 7. The 1-hexene content for the resins produced is shown in Table 10 and Figure 8.

[0361] [Table 13]

[0362] The GPC, DSC, RDA and melt strength results for Resins A through I are shown in Figures 9, 10, 11, 12, and 13 and Table 11.

[0363] [Table 14]

[0364] The van Gurp-Palmen (vGP) plots were examined (Figures 14 and 15). The melt strength results are shown in Figures 16 and 17.

[0365] 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 resins tested, the temperature of each peak observed in the TREF distribution curve, and the percentage of area under said peak are shown in Table 12.

[0366] [Table 15]

Claims

1. Catalyst component A comprising a meso form of a bridged metallocene compound having two indenyl groups, each indenyl being independently substituted with one or more substituents, wherein at least one of said substituents is aryl or heteroaryl, preferably aryl; preferably at least one of said substituents is at the 3 and / or 5 position of each indenyl, preferably each indenyl has one substituent at the 3 position, preferably each indenyl has one substituent at the 5 position, even more preferably each indenyl has one substituent at the 3 position and one substituent at the 5 position of each indenyl, preferably said aryl or heteroaryl substituent is at the 3 position of each indenyl; the meso / rac ratio of said meso form of the bridged metallocene compound of catalyst component A is １ Catalyst component A having a ratio of 95:5 or greater as determined using H NMR; a catalyst component B comprising a bridged metallocene compound having a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; and an optional activator; an optional support; and an optional cocatalyst. A catalyst composition comprising:

2. Catalyst composition according to claim 1, wherein the weight ratio of catalyst component A to catalyst component B is in the range of from 25 / 75 to 35 / 65, preferably from 28 / 72 to 33 / 67, preferably from 29 / 71 to 32 / 68, preferably from 29 / 71 to 31 / 69, preferably 30 / 70.

3. The catalyst component A is represented by the formula (I) 【Chemistry 1】 [In the formula, R １ and R ３ each independently represents an alkyl, an alkenyl, a cycloalkyl, a cycloalkenyl, a cycloalkenylalkyl, an aryl, an alkoxy, an alkylaryl, an arylalkyl, a halogen, Si(R １０ ) ３ and heteroalkyl; R １ Or R ３ At least one of R is aryl; １０ are independently hydrogen, alkyl, or alkenyl; m, p are each independently an integer selected from 0, 1, 2, 3, or 4, where at least one of m or p is at least 1; R ２ and R ４ each independently represents an alkyl, an alkenyl, a cycloalkyl, a cycloalkenyl, a cycloalkenylalkyl, a phenyl, an alkoxy, an alkylaryl, an arylalkyl, a halogen, Si(R １０ ) ３ and heteroalkyl; R ２ Or R ４ At least one of R is aryl; １０ are independently hydrogen, alkyl, or alkenyl; n, q are each independently an integer selected from 0, 1, 2, 3, or 4, where 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 B.R. ８ h is an integer selected from 1, 2, or 3; R ８ and R ９ each is independently selected from the group consisting of 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 consisting of zirconium, titanium, hafnium, and vanadium; preferably M is zirconium; Q １ and Q. ２ are each independently a halogen, an alkyl, or -N(R １１ ) ２ , alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; R １１ is hydrogen or alkyl.

3. The catalyst composition according to claim 1, comprising a meso isomer of a bridged metallocene of the formula:

4. The catalyst component B is represented by the formula (II) 【Chemistry 2】 [In the formula, R ５ , R ６ , and R ７ each independently represents an alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R １０ ) ３ and heteroalkyl; each R １０ are independently hydrogen, alkyl, or alkenyl; r, s, and 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 B.R. ８ h is an integer selected from 1, 2, or 3; R ８ and R ９ each is independently selected from the group consisting of 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 consisting of zirconium, titanium, hafnium, and vanadium; preferably zirconium; Q ３ and Q. ４ are each independently a halogen, an alkyl, or -N(R １１ ) ２ , alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; R １１ is hydrogen or alkyl.

4. The catalyst composition according to claim 1, comprising a bridged metallocene of the formula:

5. A process for the polymerization of olefins comprising contacting the catalyst composition according to any one of claims 1 to 4 with an olefin monomer, optionally hydrogen, and optionally one or more olefin comonomers; and polymerizing said monomer and said optionally one or more olefin comonomers in the presence of said at least one catalyst composition, and optionally hydrogen, to obtain a polyolefin.

6. Melt index MI in the range of 0.1g / 10min to 12.0g / 10min ２ Wherein, M.I. ２ is determined according to ISO 1133:2005 Method B, Condition D, using a 2.096 mm die at a temperature of 190° C. and a load of 2.16 kg; ２ ; M ｗ is the weight average molecular weight, M ｎ The number average molecular weight is 4.0 to 12.0, preferably 4.0 to 8.

5. ｗ / M ｎ ; A rheological long chain branching index g of at least 0.90, preferably at least 0.93, preferably at least 0.95 ｒｈｅｏ and １３ At least 0.30 wt. % ethyl branches based on the total weight of the ethylene polymer as determined by C NMR, provided that said ethyl branch content does not result from the incorporation of 1-butene as a comonomer. A metallocene catalyzed ethylene polymer having the formula:

7. M ｚ a molecular weight distribution M of at most 7.0, preferably at most 6.0, preferably at most 5.0, preferably at most 4.0, preferably at most 3.5, preferably at least 2.0, preferably at least 2.5, ｚ / M ｗ 7. The metallocene catalyzed ethylene polymer of claim 6, having the formula:

8. Molecular weight distribution M in the range of 8.0 to 25.0, preferably 10.0 to 20.0, preferably 10.5 to 20.0 ｚ / M ｎ The metallocene catalyzed ethylene polymer of any one of claims 6 to 7, having

9. At least 0.910 g / cm3 measured at a temperature of 23°C according to standard ISO 1183-1:2012 Method A ３ The metallocene catalyzed ethylene polymer of any one of claims 6 to 8, having a density of

10. Maximum 0.965 g / cm3 measured at 23°C according to standard ISO 1183-1:2012 method A ３ The metallocene catalyzed ethylene polymer of any one of claims 6 to 9, having a density of

11. The metallocene catalyzed ethylene polymer according to any one of claims 6 to 10, 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 and at most 105°C and having an area under the curve of at least 20.0% and at most 100.0%.

12. The density of the polymer is 0.938 g / cm ３ 12. The metallocene catalyzed ethylene polymer of claim 11, wherein a 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. and up to 92.0° C. and having an area under the curve of at least 60.0% and up to 75.0%, when the temperature rising elution fractionation (TREF) distribution curve of the metallocene catalyzed ethylene polymer is less than 65.0° C. and up to 92.0° C.

13. The density of the polymer is 0.925 g / cm ３ 12. The metallocene catalyzed ethylene polymer of claim 11, wherein a temperature rising elution fractionation (TREF) distribution curve of the metallocene catalyzed ethylene polymer comprises at least one second peak that appears at a temperature of at least 65.0°C and at most 73.0°C and has an area under the curve of at least 60.0% and at most 75.0% when the temperature rising elution fractionation (TREF) distribution curve of the metallocene catalyzed ethylene polymer is less than 65.0°C and at most 73.0°C.

14. The metallocene catalyzed ethylene polymer of any one of claims 6 to 13, wherein the metallocene is the metallocene catalyst composition of any one of claims 1 to 5.

15. An article comprising the metallocene catalyzed ethylene polymer of any one of claims 6-14.

16. 16. The article of claim 15, wherein the article is for film applications, injection applications, blow molding applications, rotational molding applications, extrusion applications, yarn applications.

Images