Binary catalyst composition

Abstract

The present invention relates to a 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, at least one of the substituents being at the 3- and / or 5-position of each indenyl, at least one of the substituents being aryl or heteroaryl; the meso / rac ratio of the meso form of the bridged metallocene compound of catalyst component A is 1 The present invention relates to a catalyst composition comprising: a catalyst component A having a molecular weight ratio of 95:5 or greater as determined using H NMR; preferably an aryl or heteroaryl substituent at the 3-position of each indenyl; a catalyst component B comprising a bridged metallocene compound having two indenyl groups, each indenyl being independently substituted with one or more substituents, at least one of which is an unsubstituted or substituted aryl or heteroaryl; and the unsubstituted or substituted aryl or heteroaryl is not at the 3- and / or 5-position of the indenyl; 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.

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. [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 comprising a bridged bis-indenyl metallocene having meso stereoisomeric geometry, wherein each indenyl is independently substituted with one or more substituents, preferably at least one of the substituents is at the 3- and / or 5-position of each indenyl, preferably at the 3-position of each indenyl, and a second catalyst which is a bridged bis-indenyl metallocene, wherein each indenyl of said second catalyst is independently substituted with one or more substituents, wherein one or more substituents are not at the 3- and / or 5-position of each indenyl, preferably at least one of the substituents is at the 2- and / or 4-position of each indenyl. Each indenyl of the second metallocene is independently substituted with one or more substituents, wherein at least one of the substituents is an unsubstituted or substituted aryl or heteroaryl; preferably the unsubstituted or substituted aryl or heteroaryl is not at the 3- and / or 5-position of the indenyl. The novel compositions of the present invention provide polyethylene products with unique molecular architecture and high density splits 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 at the 3- and / or 5-position of each indenyl, at least one of the substituents being aryl or heteroaryl; a meso / rac ratio of the meso isomer of the bridged metallocene compound of catalyst component A being 1 Catalyst component A, which has a molecular weight of 95:5 or greater as determined using H NMR; preferably an aryl or heteroaryl substituent at the 3-position of each indenyl; a catalyst component B comprising a bridged metallocene compound having two indenyl groups, each indenyl being independently substituted with one or more substituents, at least one of which is an unsubstituted or substituted aryl or heteroaryl; no unsubstituted or substituted aryl or heteroaryl substituent is at the 3- and / or 5-position of each indenyl, preferably each indenyl has one or more substituents at the 2- and / or 4-position of each indenyl, preferably each indenyl has one substituent at the 2-position and one substituent at the 4-position of each indenyl, preferably an unsubstituted or substituted aryl or heteroaryl is at the 4-position of each indenyl; and 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] The invention also includes an article comprising an olefin polymer according to the third aspect.

[0011] 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.

[0012] Using the present composition, blending occurs on a microscale, resulting in improved uniformity of the resulting product. This has a significant effect on processability when very broad bimodal molecular weight distributions are required. The placement and substitution pattern of both catalyst components can be used as a means to control the desired properties of the resulting bimodal polymer. The catalyst components of the present composition allow for the production of polymers with broad molecular weight distributions and reverse comonomer incorporation.

[0013] Once the polymers are produced, they may be formed into a variety of articles including, but not limited to, film products, caps and closures, rotational molded articles, glass yarns, pressure / heat resistant pipes, and the like.

[0014] 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.

[0015] 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]

[0016] [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 GPC traces of polymers obtained with various mMet1 / Met2 weight ratio compositions of each catalyst. [Figure 4]FIG. 4 represents a graph plotting the GPC traces of polymers obtained with a catalyst composition having a mMet1 / Met2 weight ratio of 20 / 80 as a function of hydrogen concentration. [Diagram 5] FIG. 5 represents a graph plotting the GPC traces of polymers obtained with a catalyst composition having a mMet1 / Met3 weight ratio of 20 / 80. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] Detailed Description of the Invention Before describing the present compounds, methods, articles, and uses encompassed by the present invention, it is to be understood that this invention is not limited to the particular compositions, compounds, methods, articles, and uses described, as such compositions, compounds, 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.

[0018] 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.

[0019] As used herein, the singular forms "a," "an," and "the" include both singular and plural referents unless the context clearly dictates otherwise. By way of example, "a resin" means one resin or more than one resin.

[0020] 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."

[0021] 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.

[0022] 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.

[0023] 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.

[0024] The terms "halo" or "halogen" as a group or part of a group are generic to fluoro, chloro, bromo and iodo.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy and hexyloxy.

[0029] The term "cycloalkyl" as a group or part of a group refers to a cyclic alkyl group having one or more ring structures and being a monovalent saturated hydrocarbyl group 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 further 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.

[0030] 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.

[0031] 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

[0032] [ka]

[0033] It could be.

[0034] 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.

[0035] 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.

[0036] The term “cycloalkoxy” as a group or part of a group means R h is cycloalkyl as defined herein above; h The formula is:

[0037] 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.

[0038] The term “aryloxy” as a group or part of a group means R g is aryl as defined herein above; g The formula is:

[0039] 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.

[0040] 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.

[0041] 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:

[0042] 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.

[0043] 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.

[0044] 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, 7-11 membered bicyclic, or containing a total of 3-10 ring atoms) having at least one heteroatom in at least one ring containing carbon 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.

[0045] 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.

[0046] 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).

[0047] 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.

[0048] Cis / trans isomers may be separated by conventional techniques well known to those skilled in the art, such as chromatography and fractional crystallization.

[0049] 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.

[0050] 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 at the 3 and / or 5 position of each indenyl, 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 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 two indenyl groups, each indenyl being independently substituted with one or more substituents, at least one of which is an unsubstituted or substituted aryl or heteroaryl; the unsubstituted or substituted aryl or heteroaryl is not at the 3- and / or 5-position of each indenyl, preferably the unsubstituted or substituted aryl or heteroaryl is not at the 3- and 5-position of each indenyl; preferably each indenyl has one or more substituents at the 2- and / or 4-position of each indenyl, preferably each indenyl has one substituent at the 2-position, preferably each indenyl has one substituent at the 4-position, even more preferably each indenyl has one substituent at the 2-position and one substituent at the 4-position of each indenyl, preferably the unsubstituted or substituted aryl or heteroaryl is at the 4-position of each indenyl; and an optional activator; an optional support; and an optional cocatalyst. A catalyst composition comprising:

[0051] 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 at the 3 and / or 5 position of each indenyl, 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 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 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 two indenyl groups, each indenyl being independently substituted with one or more substituents, at least one of which is an unsubstituted or substituted aryl or heteroaryl; each indenyl having at least one substituent at the 2- and / or 4-position of each indenyl, preferably each indenyl having one substituent at the 2-position, preferably each indenyl having one substituent at the 4-position, even more preferably each indenyl having one substituent at the 2-position and one substituent at the 4-position of each indenyl, preferably said unsubstituted or substituted aryl substituent at the 4-position of each indenyl; and an optional activator; an optional support; and an optional cocatalyst. A catalyst composition comprising:

[0052] 3. 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 at the 3 and / or 5 position of each indenyl, 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 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 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 two indenyl groups, each indenyl being independently substituted with two or more substituents, one substituent at the 2-position of each indenyl and one other at the 4-position of each indenyl, preferably at least one of the substituents being an unsubstituted or substituted aryl or heteroaryl; preferably the unsubstituted or substituted aryl or heteroaryl is at the 4-position of each indenyl; and preferably the other substituent is not at the 3- and / or 5-position of the indenyl; and an optional activator; an optional support; and an optional cocatalyst. A catalyst composition comprising:

[0053] 4. 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 at the 3 and / or 5 position of each indenyl, 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 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 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 two indenyl groups, each indenyl being independently substituted with one or more substituents, at least one of the substituents being an unsubstituted or substituted aryl or heteroaryl; an unsubstituted or substituted aryl or heteroaryl being at the 4-position of each indenyl; and an optional activator; an optional support; and an optional cocatalyst. A catalyst composition comprising:

[0054] 5. The catalyst composition according to any one of items 1 to 4, wherein the meso / rac ratio of the meso isomer of the bridged metallocene compound of the catalyst component A is preferably 95:5 or more.

[0055] 6. The composition according to any one of items 1 to 5, 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 10 / 90 to 80 / 20, preferably in the range of 10 / 90 to 70 / 30, preferably in the range of 10 / 90 to 50 / 50, preferably in the range of 10 / 90 to 40 / 60.

[0056] 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.

[0057] 8. The composition according to any one of items 1 to 7, wherein the catalyst component B contains a Si or C bridging atom, each of which may be optionally substituted with one or two substituents independently selected from alkyl, alkenyl, cycloalkyl, or cycloalkenyl.

[0058] 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.

[0059] 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.

[0060] 11. The composition according to any one of items 1 to 10, wherein the activator is methylalumoxane.

[0061] 12. The composition according to any one of items 1 to 11, wherein the catalyst composition comprises a cocatalyst.

[0062] 13. The composition according to any one of items 1 to 12, wherein the catalyst composition comprises an organoaluminum cocatalyst.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 18. Catalyst component A is a compound represented by the formula (I)

[0068] [ka]

[0069] [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; R1 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 -, 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(R11 )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 form of the bridged metallocene catalyst.

[0070] 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 9 together with the atom to which they are attached form a cycloalkyl, cycloalkenyl, or heterocyclyl.

[0071] 20. Catalyst component A is a compound represented by the formula (I)

[0072] [ka]

[0073] [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 7~20Alkylaryl, 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 7~20 Aryl 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 R9 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 6~20 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 R 8 and R 9 Each of the 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, 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] 20. The composition according to any one of items 1 to 19, comprising a meso isomer of a bridged metallocene.

[0074] 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, C 7~12 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, C1~8 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 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, 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; M1 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.

[0075] 22.R 1 and R 3 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 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 6~10aryl, 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 1~8 alkyl; 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.

[0076] 23. Catalyst component A is represented by the formula (Ia)

[0077] [ka]

[0078] [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.

[0079] 24. Catalyst component A is represented by the formula (Ib)

[0080] [ka]

[0081] [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.

[0082] 25. Catalyst component A is represented by the formula (Ic)

[0083] [ka]

[0084] 25. The composition according to any one of items 1 to 24, comprising a meso-bridged metallocene.

[0085] 26. Catalyst component B is a compound represented by the formula (II)

[0086] [ka]

[0087] [In the formula, R 1* and R 3* each independently represents an alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 each of said groups may be unsubstituted or substituted with one or more substituents each independently selected from the group including alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, alkoxy, halogen, haloalkyl; R 1* or R 3* at least one of R is unsubstituted or substituted aryl; 1* is not in third place and / or R 3* is not in the 5th position of each indenyl, 10 is independently hydrogen, alkyl, aryl, or alkenyl; m * , p * are each independently an integer selected from 0, 1, 2, 3, or 4; m * or p * at least one of is at least 1; R 2* and R 4* each independently represents an alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10each of said groups may be unsubstituted or substituted with one or more substituents each independently selected from the group including alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, alkoxy, halogen, haloalkyl; R 2* or R 4* at least one of R is unsubstituted or substituted aryl; 2* is not in third place and / or R 4* is not in the 5th position of each indenyl, 10 are independently hydrogen, alkyl, aryl, or alkenyl; * , q * are each independently an integer selected from 0, 1, 2, 3, or 4; * or q * at least one of 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 1* is zirconium; Q 1* and Q 2* are each independently hydrogen, halogen, hydroxyl, alkyl, alkenyl, -N(R 11 )2, -SR 11, alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, aryloxy, alkylaryl, aralkyl, and heteroalkyl; R 11 is hydrogen or alkyl or aryl. 26. The composition according to any one of items 1 to 25, comprising a bridged metallocene.

[0088] 27. Catalyst component B 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 9 27. The composition according to any one of items 1 to 26, wherein together with the atom to which they are attached, form a cycloalkyl, cycloalkenyl, or heterocyclyl.

[0089] 28. Catalyst component B is represented by the formula (IIa)

[0090] [ka]

[0091] [In the formula, R 1* , R 2* , R 3* , R 4* , L 1* , M 1* , Q 1* , Q 2* , m * and n * has the same meaning as defined in any one of paragraphs 26 to 27, preferably R 3* and R 4*are each independently C 6~10 aryl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 and optionally substituted with one or more substituents selected from the group consisting of alkyl. 28. The composition according to any one of items 1 to 27, comprising a bridged metallocene.

[0092] 29.R 1* 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; each of said groups is unsubstituted or each independently selected from the group consisting of C 1~6 Alkyl, C 3~6 Alkenyl, C 3~6 Cycloalkyl, C 3~6 Cycloalkyl C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 Each R may be substituted with one or more substituents selected from the group consisting of alkyl; 10 are independently hydrogen, C 1~20 Alkyl, or C 3~20 alkenyl; m * is an integer selected from 0 or 1, and preferably m * is 1; R 3* C 6~20 aryl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 3~6 Alkenyl, C 3~6 Cycloalkyl, C 3~6 Cycloalkyl C1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 may be substituted with one or more substituents selected from the group including alkyl, preferably R 3* are phenyl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 3~6 Alkenyl, C 3~6 Cycloalkyl, C 3~6 Cycloalkyl C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 may be substituted with one or more substituents selected from the group including alkyl; R 2* 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; each of said groups is unsubstituted or each independently selected from the group consisting of C 1~6 Alkyl, C 3~6 Alkenyl, C 3~6 Cycloalkyl, C 3~6 Cycloalkyl C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 Each R may be substituted with one or more substituents selected from the group consisting of alkyl; 10 are independently hydrogen, C 1~20 Alkyl, or C 3~20 alkenyl; n * is an integer selected from 0 or 1, preferably n * is 1; R 4* C 6~20aryl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 3~6 Alkenyl, C 3~6 Cycloalkyl, C 3~6 Cycloalkyl C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 may be substituted with one or more substituents selected from the group including alkyl, preferably R 4* are phenyl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 3~6 Alkenyl, C 3~6 Cycloalkyl, C 3~6 Cycloalkyl C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 may be substituted with one or more substituents selected from the group including alkyl; L 1* SiR 8 R 9 , or -[CR 8 R 9 ] h - 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 heterocycle; preferably L 1* SiR 8 R 9 ;R 8and 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 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 hydrogen, halogen, or 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 29. The composition according to any one of items 26 to 28, wherein the alkyl is alkyl.

[0093] 30.R 1* C 1~10 Alkyl, C 3~10 Alkenyl, C 6~10 Aryl, C 1~10 Alkoxy, halogen, and hetero C 1~10alkyl; preferably R 1* C 1~8 is alkyl; R 3* C 6~10 aryl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 3~6 Alkenyl, C 3~6 Cycloalkyl, C 3~6 Cycloalkyl C 1~6 Alkyl, C 1-6 Alkoxy, halogen, haloC 1~6 may be substituted with one or more substituents selected from the group including alkyl, preferably R 3* are phenyl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 3~6 Alkenyl, C 3~6 Cycloalkyl, C 3~6 Cycloalkyl C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 may be substituted with one or more substituents selected from the group including alkyl; m * is an integer selected from 0 or 1, and preferably m * is 1; R 2* C 1~10 Alkyl, C 2~10 Alkenyl, C 6~10 Aryl, C 1~10 Alkoxy, halogen, and hetero C 1~10 alkyl; preferably R 2* C 1~8 is alkyl; R 4* C 6~10 aryl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 3~6 Alkenyl, C 3~6 Cycloalkyl, C 3~6 Cycloalkyl C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC1~6 may be substituted with one or more substituents selected from the group including alkyl, preferably R 4* are phenyl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 3~6 Alkenyl, C 3~6 Cycloalkyl, C 3~6 Cycloalkyl C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 may be substituted with one or more substituents selected from the group including alkyl; n * is an integer selected from 0 or 1, preferably n * is 1; L 1* SiR 8 R 9 , -[CR 8 R 9 ] h 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, Amino C 1~6 Alkyl, 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* 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 hydrogen, halogen, or 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 30. The composition according to any one of items 26 to 29, wherein the alkyl is alkyl.

[0094] 31.R 1* C 1~8 Alkyl, C 3~8 Alkenyl, C 3~8 Cycloalkyl, C 6~10 aryl, and halogen; preferably R 1* C 1~8 is alkyl; R 3* C 6~10 aryl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 3~6 Alkenyl, C 1~6 Alkoxy, halogen, haloC 1~6 may be substituted with one or more substituents selected from the group including alkyl, preferably R 3* are phenyl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 may be substituted with one or more substituents selected from the group including alkyl; m * is an integer selected from 0 or 1, and preferably m* is 1; R 2* C 1~8 Alkyl, C 3~8 Alkenyl, C 3~8 Cycloalkyl, C 6~10 aryl, and halogen; preferably R 2* C 1~8 is alkyl; R 4* C 6~10 aryl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 3~6 Alkenyl, C 1~6 Alkoxy, halogen, haloC 1~6 may be substituted with one or more substituents selected from the group including alkyl, preferably R 4* are phenyl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 may be substituted with one or more substituents selected from the group including alkyl; n * is an integer selected from 0 or 1, preferably n * is 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 9each independently represents hydrogen, or C 1~8 alkyl; M 1* is a transition metal selected from zirconium, or hafnium; preferably M is zirconium; Q 1* and Q 2* are each independently hydrogen, halogen, or 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.

[0095] 32. Catalyst component B is represented by the formula (IIb)

[0096] [ka]

[0097] [In the formula, R 1* , R 2* , R 3* , R 4* , L 1* , M 1* , Q 1* , Q 2* has the same meaning as defined in any one of paragraphs 26 to 31, preferably R 3* and R 4* are each independently C 6~10 aryl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 and optionally substituted with one or more substituents selected from the group including alkyl. Item 32. The composition according to any one of items 1 to 31, comprising a bridged metallocene.

[0098] 33. Catalyst component B is represented by the formula (IIc)

[0099] [ka]

[0100] [In the formula, R 1* , R 2* , R 3* , R 4* , L 1* , M 1* , Q 1* , Q 2* has the same meaning as defined in any one of paragraphs 26 to 31, preferably R 3* and R 4* are each independently C 6~10 aryl, which are unsubstituted or each independently represent C 1~6 Alkyl, C 1~6 Alkoxy, halogen, haloC 1~6 and optionally substituted with one or more substituents selected from the group consisting of alkyl. Item 33. The composition according to any one of items 1 to 32, comprising a bridged metallocene.

[0101] 34. Catalyst component B is a compound represented by the formula (IId) or (IIe)

[0102] [ka]

[0103] Item 34. The composition according to any one of items 1 to 33, comprising a bridged metallocene.

[0104] 35. The composition according to any one of paragraphs 1 to 34, wherein catalyst component B comprises a rac form of a bridged metallocene of formula (II), (IIa), (IIb), (IIc), (IId) or (IIe).

[0105] 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.

[0106] 37. The process according to item 36, wherein the process is carried out in the slurry phase or gas phase or liquid phase, preferably in the slurry phase.

[0107] 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.

[0108] 39. The method according to any one of paragraphs 36 to 38, wherein the method is carried out in a single reaction zone.

[0109] 40. The process according to any one of paragraphs 36 to 39, 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.

[0110] 41. The process according to any one of paragraphs 36 to 39, 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.

[0111] 42. 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 n is the number average molecular weight, and the molecular weight distribution M is in the range of 4.5 to 16.0, preferably 5.0 to 15.0, and preferably 5.5 to 14.0. w / M n Item 36 to 40. The method according to any one of items 36 to 40, comprising obtaining an ethylene polymer having the formula:

[0112] 43. 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, and the molecular weight distribution M z / M w Item 36. The method according to any one of items 36 to 40 and 42, comprising obtaining an ethylene polymer having the formula:

[0113] 44. The olefin monomer is ethylene, contacting the ethylene and optionally the olefin comonomer with a catalyst composition; 13 44. The process according to any one of items 36 to 40, 42 to 43, comprising obtaining an ethylene polymer having a total comonomer content, such as a 1-hexene content, in the range of 0.0 wt.% to 12.0 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.

[0114] 45. The process according to any one of paragraphs 36 to 40, 42 to 44, wherein the olefin monomer is ethylene, comprising contacting the ethylene and optionally the olefin comonomer with the catalyst composition; and obtaining an ethylene polymer having a melt index in the range of HL275 of 0.10 g / 10 min to a melt index MI2 of 15.0 g / 10 min, where MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature of 190° C. and with a 2.096 mm die load of 2.16 kg, and HL275 is determined according to ISO 1133:2005 Method B, condition G, at a temperature of 190° C. and with a load of 21.6 kg, except that a 2.75 mm die is used.

[0115] 46. ​​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 45.

[0116] 47. The olefin polymer according to item 46, wherein the olefin polymer is an ethylene polymer.

[0117] 48. An olefin polymer according to paragraph 47 having a melt index in the range of HL275 of 0.10 g / 10 min to a melt index MI2 of 15.0 g / 10 min, where MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature of 190°C and a load of 2.16 kg using a 2.096 mm die, and HL275 is determined according to ISO 1133:2005 Method B, condition G, at a temperature of 190°C and a load of 21.6 kg, except that a 2.75 mm die is used.

[0118] 49.M w is the weight average molecular weight, M n is the number average molecular weight, and the molecular weight distribution M is in the range of 4.5 to 16.0, preferably 5.0 to 15.0, and preferably 5.5 to 14.0. w / M nItem 49. The olefin polymer according to any one of items 47 to 48, having the following structure:

[0119] 50.M z is the z-average molecular weight, and the molecular weight distribution M z / M w Item 47 to 49. The olefin polymer according to any one of items 47 to 49,

[0120] 51. The olefin polymer according to any one of items 47 to 50, wherein the polymer is a homopolymer.

[0121] 52. The olefin polymer according to any one of paragraphs 47 to 51, wherein the polymer is a copolymer of ethylene and a higher alpha-olefin comonomer, preferably 1-hexene.

[0122] 53. 13 53. The olefin polymer according to any one of paragraphs 47 to 52, having a total comonomer content, e.g., 1-hexene content, in the range of 0.0 wt.% to 12.0 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.

[0123] 54. A melt index in the range of HL275 of 0.10 g / 10 min to a melt index MI2 of 15.0 g / 10 min, where MI2 is determined according to ISO 1133:2005 Method B, condition D, at a temperature of 190 °C and a 2.16 kg load using a 2.096 mm die, and HL275 is determined according to ISO 1133:2005 Method B, condition G, but using a 2.75 mm die, at a temperature of 190 °C and a load of 21.6 kg; M w is the weight average molecular weight, and M n is the number average molecular weight, and the molecular weight distribution M is in the range of 4.5 to 16.0, preferably 5.0 to 15.0, and preferably 5.5 to 14.0.w / M n ; M z is the z-average molecular weight, and the molecular weight distribution M z / M w and 13 A total comonomer content, e.g., 1-hexene content, in the range of 0.0 wt.% to 12.0 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. 54. The olefin polymer according to any one of items 47 to 53, having the following structure:

[0124] 55. An olefin polymer according to any one of paragraphs 46 to 54, catalyzed with a composition according to any one of paragraphs 1 to 35.

[0125] 56. An article comprising a polymer according to any one of items 45 to 55 or obtained by the method according to any one of items 36 to 45.

[0126] 57. The article according to paragraph 56, wherein the article is selected from the group including film products, caps and closures, rotational moldings, glass yarns, pressure / heat resistant pipes, etc.

[0127] 58. Use of a polymer according to any one of items 46 to 55, or a polymer obtained by using a method according to any one of items 36 to 45, in a film application, a cap and closure application, a rotational molding application, a glass yarn application, a pressure-resistant / heat-resistant pipe application, or the like.

[0128] The present invention relates to Catalyst component A comprises 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 at the 3- and / or 5-position of each indenyl, at least one of the substituents being an unsubstituted or substituted aryl or heteroaryl, preferably the meso / rac ratio of the meso isomer of the bridged metallocene compound of catalyst component A is 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 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 two indenyl groups, each indenyl being independently substituted with one or more substituents, at least one of the substituents being an unsubstituted or substituted aryl or heteroaryl; no unsubstituted or substituted aryl or heteroaryl substituent is at the 3- and / or 5-position of the indenyl, preferably no unsubstituted or substituted aryl or heteroaryl substituent is at the 3- and 5-position of each indenyl; preferably each indenyl has one or more substituents at the 2- and / or 4-position of each indenyl, preferably each indenyl has one substituent at the 2-position, preferably each indenyl has one substituent at the 4-position, even more preferably each indenyl has one substituent at the 2-position and one substituent at the 4-position of each indenyl, preferably the unsubstituted or substituted aryl or heteroaryl is at the 4-position of each indenyl; and an optional activator; an optional support; and an optional cocatalyst. A catalyst composition comprising:

[0129] 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:

[0130] [ka]

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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 1* (Ar 1* )2M 1* Q 1* Q 2* (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; Each Ar 1* are independently indenyl, each indenyl independently substituted with one or more substituents, at least one of which is unsubstituted or substituted aryl or heteroaryl; preferably no unsubstituted or substituted aryl or heteroaryl substituent is at the 3- and / or 5-position of the indenyl, and preferably an unsubstituted or substituted aryl or heteroaryl is at the 4-position of each indenyl; preferably, the one or more substituents on the indenyl are independently alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10each of said groups may be unsubstituted or substituted with one or more substituents each independently selected from the group including alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, alkoxy, halogen, haloalkyl; each R 10 is independently hydrogen, alkyl, or alkenyl. Each indenyl is substituted the same or differently from each other at one or more positions on any of the fused rings. Each substituent may be independently selected. Preferably, each Ar 1* is indenyl, each indenyl independently substituted with one or more substituents, at least one of the substituents being aryl or heteroaryl; at least one of the substituents being unsubstituted or substituted aryl or heteroaryl; preferably an unsubstituted or substituted aryl or heteroaryl substituent is at the 4-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; M 1 and M. 1* 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 1* and Q 2* are each independently hydrogen, halogen, alkyl, -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 9 together with the atom to which they are attached form a cycloalkyl, cycloalkenyl, or heterocyclyl; preferably L 1 is SiR 8 R 9 and; 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 It is.

[0135] 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 7~12Alkylaryl, 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.

[0136] 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 the aryl or heteroaryl substituent is at the 4-position of each indenyl; each indenyl may further optionally be each independently selected from the group consisting of C 1~20 Alkyl, C 3~20 Alkenyl, C 3~20 Cycloalkyl, C 5~20 Cycloalkenyl, C 6~20 Cycloalkenylalkyl, C 6~20 Aryl, C 1~20 Alkoxy, C 7~20 Alkylaryl, C 7~20 Aryl alkyl, halogen, Si(R 10 )3, and hetero C 1~12 each R 10 are independently hydrogen, C 1~20Alkyl, or C 3~20 It is alkenyl.

[0137] Preferably, each Ar 1* is indenyl, each indenyl independently substituted with one or more substituents, at least one of the substituents being unsubstituted or substituted C 6~10 Aryl; unsubstituted or substituted C 6~10 An aryl is at the 4-position of each indenyl; and each indenyl further has at the 2-position, each independently, 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 and each R is substituted with one or more substituents selected from the group consisting of alkyl, 10 are independently hydrogen, C 1~8 Alkyl, or C 3~8 It is alkenyl.

[0138] Preferably, each Ar 1* is indenyl, each indenyl independently substituted with one or more substituents, at least one of the substituents being unsubstituted or substituted C 6~10 aryl; preferably unsubstituted or substituted C 6~10 An aryl is at the 4-position of each indenyl; each indenyl further optionally has at the 2-position independently a C 1~8 Alkyl, C 3~8 Alkenyl, C 3~8 Cycloalkyl, C 6~10 It may be substituted with a substituent selected from the group including aryl, and halogen.

[0139] In some embodiments, L 1 - [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 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 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 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 8R 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. 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.

[0140] 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 1~8Alkoxy, 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. 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.

[0141] In some embodiments, 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 1~20 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 5~20It 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 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. 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, C5~8 Cycloalkenyl, C 6~8 Cycloalkenylalkyl, and C 6~10 Aryl; preferably C 1~8 The alkyl group is selected from the group consisting of alkyl.

[0142] In some embodiments, Q 1* and Q 2* are each independently hydrogen, halogen, or 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, 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. 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.

[0143] In some preferred embodiments, catalyst component A has formula (I);

[0144] [ka]

[0145] [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.

[0146] 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.

[0147] A non-limiting example of catalyst A is the meso form of the catalyst shown below.

[0148] [ka]

[0149] In some preferred embodiments, catalyst component B has formula (II)

[0150] [ka]

[0151] [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. The present invention includes a bridged metallocene catalyst.

[0152] In some preferred embodiments, catalyst component B has formula (IIb) or (IIc)

[0153] [ka]

[0154] [In the formula, R 1* , R 2* , R 3* , R 4* , L 1* , M 1* , Q 1* , Q 2* have the same meaning as defined above and in paragraphs herein. The present invention includes a bridged metallocene catalyst.

[0155] Non-limiting examples of Catalyst B are shown below.

[0156] [ka]

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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).

[0164] 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).

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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 that has a double bond in the primary or alpha (α) position.

[0169] Throughout this application the terms "olefin polymer," "polyolefin," and "polyolefin polymer" may be used interchangeably.

[0170] 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.

[0171] 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).

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] The terms "polyolefin resin" or "polyolefin" as used herein refer to extruded and / or melted and / or pelletized polyolefin fluff or powder, which may be prepared by compounding and homogenizing polyolefin resins as taught herein, e.g., in a mixer and / or extruder.

[0181] The term "fluff" or "powder" as used herein refers to polyolefin material having a solid catalyst particle at the core of each grain and is defined as the polymeric material after exiting the polymerization reactor (or the last polymerization reactor in the case of multiple reactors connected in series). The term "pellets" refers to polyolefin fluff 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 polyolefin resin into "polyolefin product" or "pellets" after pelletization. The pelletization process preferably includes 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.

[0182] In certain embodiments, the olefin polymer is a homopolymer. The term "homopolymer," as used herein, is intended to encompass a polymer that consists essentially of repeat units derived from a monomer. A homopolymer can be, for example, 13 It may contain at least 99.8%, preferably 99.9%, by weight of repeat units derived from the monomer as determined by C NMR spectroscopy.

[0183] In another embodiment, the polyethylene resin is a copolymer. The term "copolymer" as used herein means a copolymer of a monomer and at least one other C-C 20It is intended to encompass polymers consisting essentially of repeat units derived from an alpha olefin comonomer, preferably the comonomer is 1-hexene.

[0184] 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 12 Alpha 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.

[0185] In some embodiments, the olefin polymer is an ethylene polymer. 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 %. In some embodiments, the ethylene polymer is a copolymer of ethylene and a higher alpha-olefin comonomer, preferably 1-hexene, wherein the total comonomer content, preferably 1-hexene (wt.% C6), relative to the total weight of the polyethylene is 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, wherein the total comonomer content, preferably 1-hexene (wt.% C6), relative to the total weight of the polyethylene is 13 At most 12.0 wt.%, preferably at most 10.0 wt.%, preferably at most 9.0 wt.%, as determined by C NMR analysis.

[0186] 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.

[0187] 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.

[0188] The present invention also includes polyethylene compositions comprising the ethylene polymer of the present invention and one or more additives.

[0189] 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.

[0190] Once produced, the ethylene polymers can be formed into a variety of articles. Ethylene polymers are particularly suited for articles such as film products, caps and closures, rotational molded articles, glass yarns, pressure / heat resistant pipes, and the like.

[0191] 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, rotational molded articles, glass yarns, pressure / heat resistant pipes, etc.

[0192] The preferred embodiments for the ethylene polymers of the present invention are also preferred embodiments for the articles of the present invention.

[0193] The present invention also encompasses a method for preparing an article according to the present invention. The preferred embodiments described above are also preferred embodiments for this method.

[0194] 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

[0195] 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.

[0196] 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.

[0197] 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.

[0198] The melt flow index (HL275) of ethylene polymers was determined according to ISO 1133:2005 Method B, Condition G, except that a 2.75 mm die was used at a temperature of 190° C. and a load of 21.6 kg.

[0199] 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 done using the Mark-Houwink relation (log 10 (M PE )=0.965909×log 10 (M PS )-0.28264)(M PE Based on the cutoff for the low molecular weight end at 1000.

[0200] 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:

[0201]

number

[0202] In the formula, N i and W i are the molecular weights M iare 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, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, i is the molecular weight of the species eluting at this increment.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] The chemical shifts of the signals were peak picked and the peaks were integrated as described in FIG.

[0207] [Table 1]

[0208] Small adjustments can be made to the integral limits if necessary.

[0209] Chemical shifts are given to ±0.05 ppm.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] The chemical shifts of the signals were peak picked and the peaks were integrated as described in FIG.

[0214] [Table 2]

[0215] 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).

[0216] 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.

[0217] 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.

[0218] 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.

[0219] 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.

[0220] In the present invention, an increase in the area ratio CH3 / CH2 means an increase in the short chain branch content.

[0221] 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.

[0222] 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).

[0223] 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.

[0224] 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.

[0225] Result expression: The contents (ppm) of the measured elements in the samples were calculated as follows:

[0226]

number

[0227] 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

[0228]

number

[0229] catalyst Metallocene 1: meso-metallocene 1 (mMet1)

[0230] [ka]

[0231] 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.

[0232] [ka]

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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).

[0237] 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%).

[0238] 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).

[0239] 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%.

[0240] 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.

[0241] The meso purity of each fraction was determined by 1H NMR. 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.

[0242] Metallocene 2: rac-Cyclohexyl(methyl)silanediylbis[2-methyl-4-(4′-tert-butylphenyl)indenyl]zirconium dichloride (Met2) was purchased from South Pacific Chemical Industries (CAS 888227-55-2).

[0243] [ka]

[0244] Metallocene 3:

[0245] [ka]

[0246] rac-Dimethylsilanediyl-bis[(2-methyl-4-phenyl)-indenyl]2zirconium dichloride (Met3) was purchased from Grace (CAS 153882-67-8).

[0247] Synthesis of supported catalyst: 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).

[0248] 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.

[0249] 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.

[0250] 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.

[0251] [Table 3]

[0252] Polymerization 1 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.

[0253] 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. Polymerization was started upon injection of the catalyst composition suspension, carried out at 85° C. and stopped after 60 min by depressurizing the reactor. The reactor was flushed with nitrogen before opening. Finally, the obtained polymer fluff was then analyzed.

[0254] [Table 4]

[0255] The results of copolymerization of ethylene and 1-hexene comonomer in the presence of mMet1 / Met2 binary catalyst compositions with various weight ratios of each catalyst are shown in Table 4. The polymerization conditions were the same as those listed in Table 2.

[0256] [Table 5]

[0257] FIG. 3 shows the GPC traces of polymers obtained with the binary catalyst composition mMet1 / Met2 with different catalyst ratios (mMet1 / Met2 weight ratios from 50 / 50 to 10 / 90).

[0258] The hydrogen response was also studied for a catalyst composition with a mMet1 / Met2 weight ratio of 20 / 80. The polymerization conditions were the same as those listed in Table 2, except for the hydrogen concentration. The results are shown in Table 5 and Figure 4.

[0259] [Table 6]

[0260] Polymerization 2 Further polymerization reactions were carried out using catalyst composition mMet1 / Met3 (20 / 80 weight ratio) (2.12 mg) under the conditions in Table 2. The results are detailed in Table 6 and the GPC results are plotted in FIG.

[0261] [Table 7]

Claims

1. 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 said substituents being at the 3 and / or 5 position of each indenyl, at least one of said substituents being aryl or heteroaryl; the meso / rac ratio of said meso isomer of said 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 two indenyl groups, each indenyl being independently substituted with one or more substituents, at least one of said substituents being an unsubstituted or substituted aryl or heteroaryl; said unsubstituted or substituted aryl or heteroaryl substituent is not at the 3- and / or 5-position of said indenyl, and preferably each indenyl has one or more substituents at the 2- and / or 4-position of each indenyl; and an optional activator; an optional support; and an optional cocatalyst. A catalyst composition comprising:

2. Catalyst component A is a compound represented by the formula (I) [Formula 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, １ is in the third position and / or one R ３ is in the 5-position of each indenyl, and each R １０are 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, ２ is in the third position and / or one R ４ is in the 5-position of each indenyl, 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 -, 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. ２are 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.

2. The catalyst composition of claim 1, comprising the meso form of a bridged metallocene of formula:

3. Catalyst component A is of formula (Ia) [chemical 2] [In the formula, R １ , R ２ , R ３ , R ４ , L １ , M. １ , Q １ , Q ２ , p, q have the same meanings as defined in claim 2. The composition according to any one of claims 1 to 2, comprising a meso isomer of a bridged metallocene of the formula:

4. The catalyst component A is represented by the formula (Ib) [C3] [In the formula, R １ , R ２ , R ３ , R ４ , L １ , M. １ , Q １ , Q ２ have the same meaning as defined in claim 2. The composition according to any one of claims 1 to 3, comprising a meso isomer of a bridged metallocene of the formula:

5. The catalyst component B is represented by the formula (II) [C4] [In the formula, R １＊ and R ３＊each independently represents an alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R １０ ) ３ and heteroalkyl; each of said groups may be unsubstituted or substituted with one or more substituents each independently selected from the group including alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, alkoxy, halogen, haloalkyl; R １＊ Or R ３＊ At least one of R is unsubstituted or substituted aryl; １＊ is not in the third position, and / or R ３＊ is not at the 5th position of each indenyl, １０ is independently hydrogen, alkyl, aryl, or alkenyl; ＊ , p ＊ are each independently an integer selected from 0, 1, 2, 3, or 4; ＊ Or p ＊ at least one of is at least 1; R ２＊ and R ４＊ each independently represents an alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R １０ ) ３ and heteroalkyl; each of said groups may be unsubstituted or substituted with one or more substituents each independently selected from the group including alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, alkoxy, halogen, haloalkyl; R ２＊ Or R ４＊ At least one of R is unsubstituted or substituted aryl; ２＊ is not in the third position, and / or R ４＊ is not at the 5th position of each indenyl, １０ is independently hydrogen, alkyl, aryl, or alkenyl; ＊ , q ＊ are each independently an integer selected from 0, 1, 2, 3, or 4; ＊ or q ＊ at least one of 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 １＊ is zirconium; Q １＊ and Q. ２＊ are each independently hydrogen, halogen, hydroxyl, alkyl, alkenyl, -N(R １１ ) ２ , -SR １１ , alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, aryloxy, alkylaryl, aralkyl, and heteroalkyl; R １１ is hydrogen, alkyl or aryl. The composition of any one of claims 1 to 4, comprising a bridged metallocene of the formula:

6. The catalyst component B is represented by the formula (IIa) [C5] [In the formula, R １＊ , R ２＊ , R ３＊ , R ４＊ , L １＊ , M. １＊ , Q １＊ , Q ２＊ , m ＊ and n ＊ have the same meaning as defined in claim 5.

6. The composition according to any one of claims 1 to 5, comprising a bridged metallocene of formula:

7. The catalyst component B is represented by the formula (IIb) [C6] [In the formula, R １＊ , R ２＊ , R ３＊ , R ４＊ , L １＊ , M. １＊ , Q １＊ , Q ２＊ have the same meaning as defined in claim 5. The composition of any one of claims 1 to 6, comprising a bridged metallocene of the formula:

8. The composition of any one of claims 1 to 7, wherein catalyst component B comprises a rac form of a bridged metallocene of formula (II), (IIa), or (IIb).

9. 9. The composition according to any one of claims 1 to 8, wherein 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 10 / 90 to 80 / 20, preferably in the range of 10 / 90 to 70 / 30, preferably in the range of 10 / 90 to 50 / 50, preferably in the range of 10 / 90 to 40 / 60.

10. 10. The composition of any one of claims 1 to 9, wherein the catalyst composition comprises an activator, preferably the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof; preferably the activator is methylalumoxane.

11. 11. The composition of any one of claims 1 to 10, wherein the catalyst composition comprises a co-catalyst, preferably an organoaluminum co-catalyst, preferably selected from the group comprising trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and any combination thereof.

12. 12. The composition of any one of claims 1 to 11, wherein the support comprises a solid 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.

13. A process for the polymerization of olefins comprising contacting the catalyst composition according to any one of claims 1 to 12 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.

14. An olefin polymer at least partially catalyzed by at least one catalyst composition according to any one of claims 1 to 12 or produced by the process according to claim 13.

15. 15. An article comprising the olefin polymer of claim 14.

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