Novel metallocene catalysts and uses thereof

Abstract

The present invention relates to catalysts of formula (I) wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , L 1 , M 1 , Q 1 and Q 2 have the meanings as defined in the description and claims. The present invention also relates to catalyst compositions comprising at least one catalyst according to the present invention, optionally an activator; optionally a support; and optionally a co-catalyst. The present invention also relates to the use of a catalyst or catalyst composition according to the present invention for the preparation of an olefin polymer. The present invention also relates to an olefin polymerization process comprising: contacting a catalyst or catalyst composition according to the present invention with olefin monomers, optionally hydrogen and optionally one or more olefin comonomers; polymerizing said monomers and optionally one or more olefin comonomers in the presence of at least one catalyst composition and optionally hydrogen, thereby obtaining an olefin polymer. The present invention also relates to an olefin polymer and to an article comprising said olefin polymer.

Description

Technical Field

[0001] This invention relates to novel metallocene catalysts. It also relates to the use of these novel metallocene catalysts in polymerization reactions. Furthermore, it relates to polyolefins obtained using these novel metallocene catalysts and articles made therefrom. Background Technology

[0002] Metallocene catalysts have been used in the production of polyolefins for many years. Numerous academic and patent publications describe the applications of these catalysts in olefin polymerization. Despite the significant work done in the field of metallocene catalysts, several questions remain, primarily concerning the productivity or activity of the catalysts.

[0003] Metallocene catalysts possess several advantages, such as excellent sensory and optical properties, and unique characteristics like narrow distribution. However, using these catalysts does not always readily facilitate the production of polypropylene with high melting temperatures or low melt flow rates.

[0004] Many metallocene structures have been synthesized, some of which enable the production of polypropylene with low melt flow rates or high melting temperatures, but compromise other parameters such as low activity.

[0005] Therefore, there is room for improvement in catalyst behavior. Thus, it is desirable to find catalyst systems that provide high and stable activity, and, in addition to the properties mentioned above, also offer a wide molecular weight range or higher crystallinity of the final product. Summary of the Invention

[0006] Therefore, one object of the present invention is to provide a novel catalyst that avoids the above-mentioned disadvantages.

[0007] In a first aspect, the present invention provides a metallocene catalyst of formula (I), wherein

[0008]

[0009] R 2 R 3 R 4 R 5 R 6 R 7 Each is independently selected from hydrogen or alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, -OR 15 Alkyl aryl, arylalkyl, halogen, Si(R) 12 )3 and heteroalkyl; wherein each of the said groups may be unsubstituted or substituted by one or more substituents Z 1 Replace; where Z 1 Selected from -OR 16 alkyl and alkenyl groups; wherein R15 R 16 Each is independently selected from alkyl, arylalkyl, alkylaryl, and aryl; preferably R 15 R 16 Each is independently an alkyl group;

[0010] And R 3 R 4 R 5 R 6 R 7 At least one of them is -OR 15 ;

[0011] R 8 R 9 R 10 R 11 Each is independently selected from hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R) 12 )3 and heteroalkyl;

[0012] L 1 For SiR 13 R 14 -[CR 13 R 14 ] h -、GeR 13 R 14 or BR 13 Where h is an integer selected from 1, 2, or 3; R 13 and R 14 Each is independently selected from hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R 13 and R 14 The atoms attached to them together form cycloalkyl, cycloalkenyl, or heterocyclic groups;

[0013] M 1 M is a transition metal selected from zirconium, titanium, hafnium, and vanadium; and preferably zirconium.

[0014] Q 1 and Q 2 Each is independently selected from halogens, alkyl groups, and -N(R) groups. 17 2. Alkoxy, cycloalkoxy, aryloxy, arylalkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein each R 17 Independently selected from hydrogen, alkyl, Si(R) 12 3. Cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; and

[0015] Each R 12 It can be hydrogen, alkyl, or alkenyl on its own.

[0016] In a second aspect, the present invention provides a catalyst composition comprising the catalyst according to the first aspect of the invention, an optional activator, an optional support, and an optional co-catalyst.

[0017] In a third aspect, the present invention provides an olefin polymerization process comprising: contacting at least one catalyst according to a first aspect or a catalyst composition according to a second aspect with an olefin monomer, optional hydrogen, and optional one or more olefin comonomers; and polymerizing the monomer and the optional one or more olefin comonomers in the presence of the at least one catalyst or catalyst composition and optional hydrogen, thereby obtaining an olefin polymer.

[0018] In a fourth aspect, the present invention provides an olefin polymer that is at least partially catalyzed by at least one catalyst according to the first aspect or at least one catalyst composition according to the second aspect, or an olefin polymer produced by a process according to the third aspect of the present invention.

[0019] The present invention also covers articles comprising the olefin polymers according to the fourth aspect.

[0020] The independent and dependent claims state the specific and preferred features of the invention. Features from the dependent claims may be appropriately combined with features from the independent or other dependent claims.

[0021] The invention will now be described further. Different aspects of the invention are defined in more detail in the following paragraphs. Each aspect so defined may be combined with any other aspect or plural aspects unless expressly indicated to the contrary. In particular, any feature or statement indicated as preferred or advantageous may be combined with any other feature or statement indicated as preferred or advantageous. Detailed Implementation

[0022] Before describing the compositions, catalysts, compounds, processes, articles, and uses covered by this invention, it should be understood that the invention is not limited to the specific compositions, catalysts, compounds, processes, articles, and uses described, as such compositions, catalysts, compounds, processes, articles, and uses can certainly vary. It should also be understood that the terminology used herein is not intended to be limiting, as the scope of the invention will be limited only by the appended claims.

[0023] Unless otherwise defined, all terms used in disclosing this invention, including technical and scientific terms, shall have the meanings commonly understood by one of ordinary skill in the art to which this invention pertains. Further guidance, including definitions of terms used in the specification, is provided to better understand the teachings of this invention. When describing the compounds, processes, articles, and uses of this invention, the terms used shall be interpreted according to the following definitions unless the context otherwise requires.

[0024] As used herein, unless the context clearly indicates otherwise, the singular forms “a” and “the” include both singular and plural indicators. For example, “resin” means one or more kinds of resin.

[0025] As used herein, the terms “comprising” and “comprised of” are synonymous with “including” or “containing” and are inclusive or open-ended, and do not exclude additional, unlisted members, elements, or method steps. The terms “comprising” and “comprised of” also include the term “consisting of”.

[0026] Numerical ranges stated (enumerated) by endpoints include all integers and, where appropriate, fractions falling into that range (e.g., when multiple factors are involved, 1 to 5 may include 1, 2, 3, 4, and when measurements are involved, 1.5, 2, 2.75, and 3.80 may also be included). Endpoint statements also include the endpoint values ​​themselves (e.g., 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range stated herein is intended to include all subranges falling into it.

[0027] Throughout this specification, references to "one embodiment" or "implementation" mean that a specific feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the invention. Therefore, the phrases "in one embodiment" or "in an embodiment" appearing in different places throughout this specification do not necessarily refer to the same embodiment, but may all refer to the same embodiment. Furthermore, as will be apparent to those skilled in the art from this disclosure, specific features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. Moreover, as will be understood by those skilled in the art, although some embodiments described herein include features included in other embodiments but are not other features, combinations of features from different embodiments are intended to be within the scope of the invention and form different embodiments. For example, in the following statements and representations, any embodiments may be used in any combination.

[0028] Whenever the term “substituted” is used herein, it is intended to indicate that one or more hydrogen atoms on the atom indicated in the use of “substituted” are replaced by an option from the indicated group, provided that the substitution does not exceed the normal valence state of the indicated atom, and that the substitution results in a chemically stable compound, i.e., a compound sufficiently robust to withstand separation from the reaction mixture. Preferred substituents for the indenyl, cyclopentadienyl, and fluorenyl groups may be selected from alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R) 10 3. Heteroalkyl groups; wherein each R 10 Independently hydrogen, alkyl, or alkenyl. Preferably, each indenyl group is substituted with at least one aryl or heteroaryl, more preferably aryl; preferably, the aryl or heteroaryl substituent is at the 3-position of each indenyl group; the indenyl group may further be selected from alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R) 10 3. Substitution of one or more substituents in a heteroalkyl group; wherein each R 10 It can be hydrogen, alkyl, or alkenyl on its own.

[0029] The terms “halogenated” or “halogen” as a group or part of a group are generally used for fluorine, chlorine, bromine, and iodine.

[0030] The term "alkyl" as a group or part of a group refers to the formula C n H 2n+1 The alkyl group is a hydrocarbon group, where n is a number greater than or equal to 1. The alkyl group may be linear or branched and may be substituted as shown herein. Generally, the alkyl group of the present invention comprises 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. When a subscript is used after a carbon atom herein, the subscript indicates the number of carbon atoms that the named group may contain. For example, the term "C1-20 "alkyl", as a group or part of a group, refers to the formula -C n H 2n+1 The hydrocarbon group, where n is a number ranging from 1 to 20. Therefore, for example, "C 1-8 "Alkyl" includes all linear or branched alkyl groups having between 1 and 8 carbon atoms, and therefore includes methyl, ethyl, n-propyl, isopropyl, butyl and their isomers (e.g., n-butyl, isobutyl and tert-butyl); pentyl and its isomers, hexyl and its isomers, etc. "Substituted alkyl" refers to an alkyl group that is substituted by one or more substituents (e.g., 1 to 3 substituents, such as 1, 2 or 3 substituents) at any available connection point.

[0031] When the suffix "ene" is used with an alkyl group (i.e., "alkylene"), it is intended to indicate that the alkyl group, as defined herein, has two single bonds as connection points to other groups. As used herein, the term "alkylene," also known as "alkyl dieryl," refers, either alone or as part of another substituent, to a divalent alkyl group, i.e., having two single bonds for connection to two other groups. Alkylene groups can be linear or branched and can be substituted as shown herein. Non-limiting examples of alkene groups include: methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH(CH3)-), 1-methyl-ethylene (-CH(CH3)-CH2-), n-propylene (-CH2-CH2-CH2-), 2-methylpropylene (-CH2-CH(CH3)-CH2-), 3-methylpropylene (-CH2-CH2-CH(CH3)-), n-butylene (-CH2-CH2-CH2-CH2-), 2-methylbutylene (-CH2-CH(CH3)-CH2-CH2-), 4-methylbutylene (-CH2-CH2-CH2-CH(CH3)-), pentylene and its chain isomers, and hexylene and its chain isomers.

[0032] The term "alkenyl," as a group or part of a group, refers to an unsaturated hydrocarbon group, which may be linear or branched, containing one or more carbon-carbon double bonds. Generally, the alkenyl groups of the present invention contain 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms. When a subscript is used after a carbon atom herein, the subscript indicates the number of carbon atoms that the named group may contain. 3-20 Examples of alkenyl groups include vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl and its isomers, 2-hexenyl and its isomers, 2,4-pentadienyl, etc.

[0033] The term "alkoxy" (or "alkyloxy"), as a group or part of a group, refers to a group having the formula -OR b The group, wherein R b Alkyl groups as defined above. Non-limiting examples of suitable alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, and hexoxy.

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

[0035] When the suffix "ene" is used with a cycloalkyl group (i.e., cycloalkylene), it is intended to indicate that the cycloalkyl group, as defined herein, has two single bonds as connection points to other groups. Non-limiting examples of "cycloalkylene" include 1,2-cyclopropylene, 1,1-cyclopropylene, 1,1-cyclobutylene, 1,2-cyclobutylene, 1,3-cyclopentylene, 1,1-cyclopentylene, and 1,4-cyclohexylene.

[0036] In the presence of alkylene or cycloalkylene groups, the molecular structure of the formed portion can be linked by a common carbon atom or by different carbon atoms. To illustrate this using the asterisk nomenclature of this invention, the C3 alkylene group can be, for example, *-CH2CH2CH2-*, *-CH(-CH2CH3)-*, or *-CH2CH(-CH3)-*. Similarly, the C3 cycloalkylene group can be...

[0037]

[0038] The term "cycloalkenyl," as a group or part of a group, refers to a non-aromatic cyclic alkenyl group having at least one (often 1 to 3, preferably 1) unsaturated site (i.e., a carbon-carbon sp2 double bond); it preferably has 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, and even more preferably 5 to 6 carbon atoms. Cycloalkenyl includes all unsaturated hydrocarbon groups containing one or more rings, including monocyclic, bicyclic, or tricyclic groups. Further rings may be fused, bridged, and / or linked by one or more spiro atoms. When a subscript is used after a carbon atom herein, the subscript indicates the number of carbon atoms that the named group may contain. For example, the term "C 5-20 "Cycloalkenyl": A cyclic alkenyl group containing 5 to 20 carbon atoms. For example, the term "C 5-10 "Cycloalkenyl": A cyclic alkenyl group containing 5 to 10 carbon atoms. For example, the term "C 5-8 "Cycloalkenyl": A cyclic alkenyl group containing 5 to 8 carbon atoms. For example, the term "C..." 5-6 "Cycloalkenyl": A cyclic alkenyl group containing 5 to 6 carbon atoms. Examples include, but are not limited to: cyclopentenyl (-C5H7), cyclopentenylpropylidene, methylcyclohexeneyl, and cyclohexenyl (-C6H9). The double bond may be in cis or trans configuration.

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

[0040] The term "cycloalkoxy", as a group or part of a group, refers to a group having the formula -OR h The group, wherein R h It is a cycloalkyl group as defined above.

[0041] The term "aryl," as a group or part of a group, refers to a polyunsaturated aromatic hydrocarbon group having a single ring (i.e., phenyl), or multiple aromatic rings fused together (e.g., naphthyl) or covalently linked, typically containing 6 to 20 atoms; preferably 6 to 10 atoms, wherein at least one ring is aromatic. The aromatic ring may optionally include one or two additional rings (cycloalkyl, heterocyclic, or heteroaryl) fused thereto. Examples of suitable aryl groups include C 6-20 Aryl, preferred C 6-10 Aryl, more preferably C 6-8 Aryl. Non-limiting examples of aryl groups include phenyl, biphenylyl, biphenylenyl, or 1- or 2-naphthyl; 1-, 2-, 3-, 4-, 5-, or 6-tetrahydronaphthyl (also known as "1,2,3,4-tetrahydronaphthyl"); 1-, 2-, 3-, 4-, 5-, 6-, 7-, or 8-azulenyl; 4-, 5-, 6-, or 7-indanyl; 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" means an aryl group having one or more substituents (e.g., 1, 2, or 3 substituents, or 1 to 2 substituents) at any available junction.

[0042] The term "aryloxy group," as a group or part of a group, refers to a group having the formula -OR g The group, wherein R g It is an aryl group as defined above.

[0043] The term "arylalkyl", as a group or part of a group, means an alkyl group as defined herein, wherein 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, etc.

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

[0045] The term "aralkoxy" or "aralkoxy" as a group or part of a group refers to a group having the formula -OR a -R g The group, wherein R g It is aryl, and Ra It is an alkylene group as defined above.

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

[0047] The term "aminoalkyl" as a group or part of a group refers to the group -R j -NR k R l , where R j It is an alkylene group, R k It is hydrogen or an alkyl group as defined herein, and R l It is hydrogen or an alkyl group as defined herein.

[0048] The term "heterocyclic group," as a group or part of a group, refers to a non-aromatic, fully saturated, or partially unsaturated cyclic group (e.g., a 3- to 7-membered monocyclic, 7- to 11-membered bicyclic, or containing a total of 3 to 10 ring atoms) having at least one heteroatom in at least one carbon-containing ring. Each ring of the heterocyclic group containing heteroatoms may have 1, 2, 3, or 4 heteroatoms selected from N, S, Si, and Ge, wherein the nitrogen and sulfur heteroatoms may optionally be oxidized, and the nitrogen heteroatom may optionally be quaternized. Where valence state permits, the heterocyclic group may be linked at any heteroatom or carbon atom in the ring or ring system. The rings of polycyclic heterocycles may be fused, bridged, and / or linked by one or more spiro atoms.

[0049] Non-limiting exemplary heterocyclic groups include aziridinyl, oxiranyl, thiiranyl, piperidinyl, azetidinyl, 2-imidazolinyl, pyrazolyl, imidazolinyl, isoxazolinyl, oxazolidinyl, isoxazolidinyl, thiazolidinyl, isothiazolinyl, succinyl Succinimidyl, 3H-indolinyl, indolinyl, isoindolinyl, 2H-pyrroleyl, 1-pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, pyrrolizinyl, 4H-quinolizinyl, 2-oxopiperazinyl, piperazinyl, homopiperazinyl, 2-pyrazolinyl, 3-pyrazolinyl, tetrahydro-2H-pyranyl, 2H-pyranyl, 4 H-pyranyl, 3,4-dihydro-2H-pyranyl, 3,4-dihydro-2H-pyranyl, oxetanyl, thietanyl, 3-dioxolanyl, 1,4-dioxanyl, 2,5-dioxoimidazolyl, 2-oxopyrrolodinyl, 2-oxopyrrolodinyl, indololinyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydroquinone Linoyl, tetrahydroisoquinoline-1-yl, tetrahydroisoquinoline-2-yl, tetrahydroisoquinoline-3-yl, tetrahydroisoquinoline-4-yl, thiomorpholine-4-yl, thiomorpholine-4-yl sulfoxide, thiomorpholine-4-yl sulfone, 1,3-dioxacyclopentyl, 1,4-oxathianyl, 1,4-dithionyl, 1,3,5-trioxacyclohexyl, 1H-pyrrolizinyl, tetrahydro-1,1-dioxothiopheneyl, N-formylpiperazinyl, and morpholine-4-yl.

[0050] Preferred descriptions (features) and embodiments of the compositions, catalysts, compounds, processes, polymers, articles, and uses of the present invention are set forth below. Each description and embodiment so defined in the present invention may be combined with any other description and / or embodiment unless expressly indicated to the contrary. In particular, any feature indicated as preferred or advantageous may be combined with any other feature or description indicated as preferred or advantageous. Herein, the present invention is particularly understood as any one or any combination of one or more of the numbered descriptions and embodiments below with any other aspects and / or embodiments.

[0051] 1. The metallocene catalyst of formula (I), wherein

[0052]

[0053] R 2 R 3 R 4 R 5 R 6 R 7 Each is independently selected from hydrogen or alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, -OR 15 Alkyl aryl, arylalkyl, halogen, Si(R) 12 )3 and heteroalkyl; wherein each of the said groups may be unsubstituted or substituted by one or more substituents Z 1 Replace; where Z 1 Selected from -OR 16 alkyl and alkenyl groups; wherein R 15 R 16 Each is independently selected from alkyl, arylalkyl, alkylaryl, and aryl; preferably R 15 R 16 Each is independently an alkyl group;

[0054] And R 3 R 4 R 5 R 6 R 7 At least one of them is -OR 15 ;

[0055] R 8 R 9 R 10 R 11 Each is independently selected from hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R) 12 )3 and heteroalkyl;

[0056] L 1 For SiR 13 R 14 -[CR 13 R 14 ] h -、GeR 13 R 14 or BR 13 Where h is an integer selected from 1, 2, or 3; R 13 and R 14 Each is independently selected from hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R 13 and R 14The atoms attached to them together form cycloalkyl, cycloalkenyl, or heterocyclic groups;

[0057] M 1 M is a transition metal selected from zirconium, titanium, hafnium, and vanadium; and preferably zirconium.

[0058] Q 1 and Q 2 Each is independently selected from halogens, alkyl groups, and -N(R) groups. 17 2. Alkoxy, cycloalkoxy, aryloxy, arylalkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein each R 17 Independently selected from hydrogen, alkyl, Si(R) 12 3. Cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; and

[0059] Each R 12 It can be hydrogen, alkyl, or alkenyl on its own.

[0060] 2. The catalyst according to statement 1, wherein

[0061] R 2 R 3 R 4 R 5 R 6 R 7 Each is independently selected from hydrogen or C. 1-20 Alkyl, C 2-20 alkenyl, C 3-20 cycloalkyl, C 5-20 Cycloalkenyl, C 5-20 Cycloalkenyl C 1-20 Alkyl, C 6-20 Aryl, -OR 15 C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, halogen, Si(R) 12 )3 and miscellaneous C 1-12 Alkyl groups; wherein each of the said groups may be unsubstituted or substituted with one or more substituents. 1 Replace; where Z 1 Selected from -OR 16 C 1-20 Alkyl and C 2-20 alkenyl; wherein R 15 R 16 Each is independently selected from C 1-20 Alkyl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkyl C 6-20 Aryl and C 6-20 Aryl; preferred R15 R 16 Each independently is C 1-20 alkyl;

[0062] And R 3 R 4 R 5 R 6 R 7 At least one of them is -OR 15 ,

[0063] R 8 R 9 R 10 R 11 Each is independently selected from hydrogen and C. 1-20 Alkyl, C 2-20 alkenyl, C 3-20 cycloalkyl, C 5-20 Cycloalkenyl, C 5-20 Cycloalkenyl C 1-20 Alkyl, C 6-20 Aryl, C 1-20 Alkoxy, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, halogen, Si(R) 12 )3 and miscellaneous C 1-12 alkyl;

[0064] L 1 For SiR 13 R 14 -[CR 13 R 14 ] h -、GeR 13 R 14 or BR 13 Where h is an integer selected from 1, 2, or 3; R 13 and R 14 Each is independently selected from hydrogen and C. 1-20 Alkyl, C 2-20 alkenyl, C 3-20 cycloalkyl, C 5-20 Cycloalkenyl, C 5-20 Cycloalkenyl C 1-20 Alkyl, C 6-20 Aryl, amino C 1-20 Alkyl and C 6-20 Aryl C 1-20 Alkyl; or R 13 and R 14 Together with the atoms they are attached to, they form C 3-20 cycloalkyl, C 5-20 Cycloalkenyl or 3-14 membered heterocyclic groups;

[0065] M 1 M is a transition metal selected from zirconium, titanium, hafnium, and vanadium; and preferably zirconium.

[0066] Q 1 and Q 2 Each is independently selected from halogens, C 1-20 Alkyl, -N(R) 17 2. C 1-20 Alkoxy, C 3-20 Cycloalkoxy, C 6-20 Aryl C 1-20 Alkoxy, C 3-20 cycloalkyl, C 6-20 Aryl, C 6-20 aryloxy group, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl and hetero C 1-20 Alkyl; wherein each R 17 Independently selected from hydrogen and C 1-20 Alkyl, Si(R) 12 3. C 3-20 cycloalkyl, C 6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl and hetero C 1-20 Alkyl; preferably Q 1 and Q 2 Each is independently selected from halogen or C 1-20 Alkyl; and

[0067] Each R 12 Independently hydrogen, C 1-20 Alkyl or C 2-20 Alkenyl group.

[0068] 3. The catalyst according to any one of statements 1-2, wherein

[0069] R 2 R 3 R 4 R 5 R 6 R 7 Each is independently selected from hydrogen or C. 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, -OR15 C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, halogen, Si(R) 12 )3 and miscellaneous C 1-8 Alkyl groups; wherein each of the said groups may be unsubstituted or substituted with one or more substituents. 1 Replace; where Z 1 Selected from -OR 16 C 1-8 Alkyl and C 2-8 alkenyl; each R 12 Independently hydrogen, C 1-8 Alkyl or C 2-8 alkenyl; wherein R 15 R 16 Each is independently selected from C 1-8 Alkyl, C 6-10 Aryl C 1-8 Alkyl, C 7-8 Alkyl C 6-10 Aryl and C 6-10 Aryl; preferred R 15 R 16 Each independently is C 1-8 Alkyl; and wherein R 3 R 4 R 5 R 6 R 7 At least one of them is -OR 15 Preferred R 4 R 5 R 6 R 7 At least one of them is -OR 15 Preferred R 4 R 5 R 6 At least one of them is -OR 15 Preferred R 4 R 5 R 6 At least one of them is -OR 15 Preferred R 5 R 6 At least one of them is -OR 15 ;

[0070] Preferred R 2 R 3 R 4 R 6 R 7 Each is independently selected from hydrogen or C. 1-8 Alkyl, C 2-8 alkenyl, C3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, -OR 15 C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, halogen, Si(R) 12 )3 and miscellaneous C 1-8 Alkyl groups; wherein each of the said groups may be unsubstituted or substituted with one or more substituents. 1 Replace; where Z 1 Selected from -OR 16 C 1-8 Alkyl and C 2-8 alkenyl; each R 12 Independently hydrogen, C 1-8 Alkyl or C 2-8 alkenyl; wherein R 15 R 16 Each is independently selected from C 1-8 Alkyl, C 6-10 Aryl C 1-8 Alkyl, C 7-8 Alkyl C 6-10 Aryl and C 6-10 Aryl; preferred R 15 R 16 Each independently is C 1-8 Alkyl; and R 5 For -OR 15 ;

[0071] Preferred R 2 R 3 R 6 R 7 Each is independently selected from hydrogen or C. 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, -OR 15 C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, halogen, Si(R) 12 )3 and miscellaneous C 1-8 Alkyl; wherein each of the said groups may be unsubstituted or substituted with one or more Z groups. 1 Replace; where Z 1 Selected from -OR16 C 1-8 Alkyl and C 2-8 alkenyl; each R 12 Independently hydrogen, C 1-8 Alkyl or C 2-8 alkenyl; wherein R 15 R 16 Each is independently selected from C 1-8 Alkyl, C 6-10 Aryl C 1-8 Alkyl, C 7-8 Alkyl C 6-10 Aryl and C 6-10 Aryl; preferred R 15 R 16 Each independently is C 1-8 Alkyl; R 4 C 6-10 Aryl, wherein the C 6-10 The aryl group can be unsubstituted or substituented by one or more substituents. 1 Replace; and R 5 For -OR 15 ;

[0072] Preferably R 2 R 3 R 6 R 7 Each is independently selected from hydrogen or C. 1-8 Alkyl, C 2-8 alkenyl, C 6-10 Aryl, -OR 15 halogens and miscellaneous C 1-8 Alkyl; wherein each of the said groups may be unsubstituted or substituted with one or more Z groups. 1 Replace; where Z 1 Selected from -OR 16 and C 1-8 Alkyl; wherein R 15 R 16 Each is independently selected from C 1-8 Alkyl and C 6-10 Aryl; preferred R 15 R 16 Each independently is C 1-8 Alkyl; R 4 C 6-10 Aryl, wherein the C 6-10 The aryl group can be unsubstituted or substituented by one or more substituents. 1 Replace; and R 5 For -OR 15 ;

[0073] Preferred R 3 R 7Each is independently selected from hydrogen or C. 1-8 Alkyl, C 2-8 alkenyl, C 6-10 Aryl, -OR 15 halogens and miscellaneous C 1-8 Alkyl; wherein each of the said groups may be unsubstituted or substituted with one or more Z groups. 1 Replace; where Z 1 Selected from -OR 16 and C 1-8 Alkyl; wherein R 15 R 16 Each is independently selected from C 1-8 Alkyl and C 6-10 Aryl; preferred R 15 R 16 Each independently is C 1-8 Alkyl; R 2 and R 6 Each is independently selected from C 1-8 Alkyl, C 6-10 Aryl, -OR 15 halogens and miscellaneous C 1-8 Alkyl; R 4 C 6-10 Aryl, wherein the C 6-10 The aryl group can be unsubstituted or substituented by one or more substituents. 1 Replace; and R 5 For -OR 15 ;

[0074] Preferably R 3 R 7 Each is independently selected from hydrogen or C. 1-8 Alkyl, preferably hydrogen; R 2 and R 6 Each is independently selected from C 1-8 Alkyl, C 6-10 Aryl, -OR 15 halogens and miscellaneous C 1-8 Alkyl, preferably C 1-8 Alkyl; R 4 C 6-10 Aryl, wherein the C 6-10 The aryl group can be unsubstituted or substituented by one or more substituents. 1 Replace; and R 5 For -OR 15 .

[0075] 4. The catalyst according to any one of statements 1-3, wherein

[0076] R 8 R 9 R 10 R11 Each is independently selected from hydrogen and C. 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, C 1-8 Alkoxy, C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, halogen, Si(R) 12 )3 and miscellaneous C 1-8 Alkyl; each R 12 Independently hydrogen, C 1-8 Alkyl or C 2-8 Alkenyl; preferably R 8 R 9 R 10 R 11 Each is independently selected from hydrogen and C. 1-8 Alkyl, C 2-8 alkenyl, C 6-10 Aryl, C 1-8 Alkoxy, halogen and Si(R) 12 )3; Each R 12 Independently hydrogen or C 1-6 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently selected from hydrogen and C. 1-6 Alkyl or halogen; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-4 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-2 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or methyl; R is preferred. 8 R 9 R 10 R 11 Each is independently a methyl group.

[0077] 5. The catalyst according to any one of statements 1-4, wherein

[0078] L1 For SiR 13 R 14 -[CR 13 R 14 ] h -、GeR 13 R 14 or BR 13 Where h is an integer selected from 1, 2, or 3; R 13 and R 14 Each of them is independently selected from hydrogen, C 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, amino C 1-8 Alkyl and C 6-10 Aryl C 1-8 Alkyl; or R 13 and R 14 Together with the atoms they are attached to, they form C 3-8 cycloalkyl, C 5-8 Cycloalkenyl or 3-8 membered heterocyclic group; preferably L 1 For SiR 13 R 14 or -[CR 13 R 14 ] h -; where h is an integer selected from 1 or 2; R 13 and R 14 Each is independently selected from hydrogen and C. 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl and C 6-10 Aryl; or R 13 and R 14 Together with the atoms they are attached to, they form C 3-8 cycloalkyl, C 5-8 Cycloalkenyl; preferably L 1 For SiR 13 R 14 or -[CR 13 R 14 ]-;R 13 and R 14 Each is independently selected from hydrogen and C. 1-8 Alkyl and C 3-8 cycloalkyl; or R 13 and R 14 Together with the atoms they are attached to, they form C 3-8 cycloalkyl; preferably L 1For SiR 13 R 14 or -[CR 13 R 14 ]-;R 13 and R 14 Each is independently selected from hydrogen or C. 1-6 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-4 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-2 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or methyl; preferably L 1 It is SiMe2.

[0079] 6. The catalyst according to any one of statements 1-5, wherein

[0080] M 1 M is a transition metal selected from zirconium, titanium, hafnium, and vanadium; and preferably zirconium; and

[0081] Q 1 and Q 2 Each is independently selected from halogens, C 1-8 Alkyl, -N(R) 17 2. C 1-8 Alkoxy, C 3-8 Cycloalkoxy, C 6-10 Aryl C 1-8 Alkoxy, C 3-8 cycloalkyl, C 6-10 Aryl, C 6-10 aryloxy group, C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl and hetero C 1-8 Alkyl; wherein each R 17 Independently selected from hydrogen and C 1-8 Alkyl, Si(R) 12 3. C 3-8 cycloalkyl, C 6-10 Aryl, C 1-8 Alkyl C 6-10 Aryl, C6-10 Aryl C 1-8 Alkyl and hetero C 1-8 Alkyl; preferably each R 17 Independently selected from hydrogen and C 1-20 Alkyl, Si(R) 12 3. C 3-20 cycloalkyl, C 6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl and hetero C 1-20 Alkyl groups, preferably each R 17 Independently selected from hydrogen or C 1-8 Alkyl; each R 12 Independently hydrogen or C 1-8 Alkyl; preferably Q 1 and Q 2 Each is independently selected from halogens, C 1-8 Alkyl, C 1-8 Alkoxy and heterocarbon 1-8 Alkyl; preferably Q 1 and Q 2 Each is independently selected from halogen or C 1-8 Alkyl; preferably Q 1 and Q 2 Each is independently selected from halogen or C 1-8 Alkyl; preferably Q 1 and Q 2 Each is independently a halogen, preferably chlorine.

[0082] 7. The catalyst according to any one of statements 1-6, wherein

[0083] R 2 R 3 R 4 R 5 R 6 R 7 Each is independently selected from hydrogen or C. 1-8 Alkyl, C 2-8 alkenyl, C 6-10 Aryl, -OR 15 Each of the stated groups may be unsubstituted or substituted with one or more substituents. 1 Replace; where Z 1 Selected from -OR 16 C 1-6 Alkyl and C 2-6 alkenyl; wherein R 15 R 16 Each is independently selected from C 1-6 Alkyl, C 6-10 Aryl C 1-8Alkyl, C 7-8 Alkyl C 6-10 Aryl and C 6-10 Aryl; preferred R 15 R 16 Each independently is C 1-6 alkyl;

[0084] And R 3 R 4 R 5 R 6 R 7 At least one of them is -OR 15 ,

[0085] R 8 R 9 R 10 R 11 Each is independently selected from hydrogen and C. 1-8 Alkyl, C 2-8 alkenyl, C 6-10 Aryl and C 1-8 Alkoxy;

[0086] L 1 For SiR 13 R 14 or -[CR 13 R 14 ] h -; where h is an integer selected from 1 or 2; R 13 and R 14 Each is independently selected from hydrogen and C. 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl; or R 13 and R 14 Together with the atoms they are attached to, they form C 3-8 cycloalkyl or C 5-8 Cycloalkenyl;

[0087] M 1 It is zirconium or titanium; preferably, M is zirconium; and

[0088] Q 1 and Q 2 Each is independently selected from halogens, C 1-8 Alkyl and C 1-8 Alkoxy; preferably Q 1 and Q 2 Each is independently selected from halogen or C 1-8 alkyl.

[0089] 8. The catalyst according to any one of statements 1-7, wherein

[0090] R 2 R 3 R 4 R 5 R 6 R 7 Each is independently selected from hydrogen or C. 1-6 Alkyl, C 6-10 aryl or -OR 15 Each of the stated groups may be unsubstituted or substituted with one or more substituents. 1 Replace; where Z 1 Selected from -OR 16 Or C 1-6 Alkyl; wherein R 15 R 16 Each independently is C 1-6 alkyl;

[0091] And R 3 R 4 R 5 R 6 R 7 At least one of them is -OR 15 ,

[0092] R 8 R 9 R 10 R 11 Each is independently selected from hydrogen and C. 1-6 Alkyl and C 2-6 Alkenyl; preferably R 8 R 9 R 10 R 11 Each is independently selected from hydrogen or C. 1-6 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently selected from hydrogen or C. 1-4 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently selected from hydrogen or C. 1-2 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently selected from hydrogen or methyl; preferably R 8 R 9 R 10 R 11 Each is independently a methyl group;

[0093] L 1 For SiR13 R 14 or -[CR 13 R 14 ] h -; where h is an integer selected from 1 or 2; R 13 and R 14 Each is independently selected from hydrogen and C. 1-6 Alkyl, C 3-6 cycloalkyl; or R 13 and R 14 Together with the atoms they are attached to, they form C 3-6 cycloalkyl; preferably L 1 For SiR 13 R 14 or -[CR 13 R 14 ] h -; where h is 1; R 13 and R 14 Each is independently selected from hydrogen or C. 1-6 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-6 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-4 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or methyl; preferably L 1 It is SiMe2;

[0094] M represents zirconium; and

[0095] Q 1 and Q 2 Each is independently selected from halogen or C 1-6 Alkyl; preferably Q 1 and Q 2 Each is independently selected from chlorine, fluorine, or C. 1-4 Alkyl group. Preferably Q. 1 and Q 2 Each is chlorine independently.

[0096] 9. The catalyst according to any one of statements 1-8, wherein R 5 For -OR 15 .

[0097] 10. The catalyst according to any one of statements 1-9, having formula (II)

[0098]

[0099] Where R 2 R 3 R 4 R 15 R 6 R 7 R 8 R 9 R 10 R 11 L 1 M 1 Q 1 Q 2 It has the same meaning as any of statements 1-9.

[0100] 11. The catalyst according to any one of statements 1-10, wherein R 4 For not replaced or by one or more Z 1 Substituted aryl groups.

[0101] 12. The catalyst according to any one of statements 1-11, having formula (III) or (IV),

[0102]

[0103] Where n is an integer selected from 0, 1, 2, 3, or 4; m is an integer selected from 0, 1, 2, or 3; and R 2 R 3 R 15 R 16 R 6 R 7 R 8 R 9 R 10 R 11 L 1 Z 1 M 1 Q 1 Q 2 It has the same meaning as any of statements 1-11.

[0104] 13. The catalyst according to any one of statements 1-12, wherein

[0105] R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-8 Alkyl; preferably R8 R 9 R 10 R 11 Each independently is hydrogen, C 1-6 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-4 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-2 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or methyl; R is preferred. 8 R 9 R 10 R 11 Each is independently a methyl group.

[0106] 14. The catalyst according to any one of statements 1-13, having formula (V) or (VI),

[0107]

[0108] Where n is an integer selected from 0, 1, 2, 3, or 4, and m is an integer selected from 0, 1, 2, or 3; and where R 2 R 3 R 15 R 16 R 6 R 7 L 1 Z 1 M 1 Q 1 Q 2 It has the same meaning as any of statements 1-13.

[0109] 15. The catalyst according to any one of statements 1-14, wherein L 1 For SiR 13 R 14 or -[CR 13 R 14 ]-, and R 13 R 14 Having the same meaning as defined in any one of statements 1-14, preferably L 1 For SiR 13 R 14 R is preferred 13 R14 Each is independently selected from hydrogen or alkyl groups, preferably R. 13 R 14 Each is independently an alkyl group, preferably C10. 1-6 Alkyl, preferably C 1-4 Alkyl, preferably C 1-2 Alkyl, preferably methyl.

[0110] 16. The catalyst according to any one of statements 1-15, having formula (VII) or (VIII),

[0111]

[0112] Where n is an integer selected from 0, 1, 2, 3, or 4, and m is an integer selected from 0, 1, 2, or 3; and where R 2 R 3 R 15 R 16 R 6 R 7 Z 1 M 1 Q 1 Q 2 It has the same meaning as any of statements 1-15.

[0113] 17. The catalyst according to any one of statements 1-16, having formula (IX) or (X),

[0114]

[0115] Where n is an integer selected from 0, 1, 2, 3, or 4, and m is an integer selected from 0, 1, 2, or 3; and where R 2 R 3 R 15 R 16 R 6 R 7 Z 1 Q 1 Q 2 It has the same meaning as any of statements 1-16.

[0116] 18. The catalyst according to any one of statements 1-17, having formula (XI) or (XII),

[0117]

[0118] Where n is an integer selected from 0, 1, 2, 3, or 4, and m is an integer selected from 0, 1, 2, or 3; and where R 2 R 3 R 15 R 16R 6 R 7 Z 1 It has the same meaning as any of statements 1-17.

[0119] 19. The catalyst according to any one of statements 1-18, having formula (XIII) or (XIV),

[0120]

[0121] Where n is an integer selected from 0, 1, 2, 3, or 4, and m is an integer selected from 0, 1, 2, or 3; and where R 2 R 6 R 15 R 16 Z 1 It has the same meaning as any of statements 1-18.

[0122] 20. The catalyst according to any one of statements 1-18, wherein R 2 R 3 Each is independently selected from hydrogen or C. 1-6 alkyl.

[0123] 21. The catalyst according to any one of statements 1-20, having formula (XV) or (XVI),

[0124]

[0125] Where n is an integer selected from 0, 1, 2, 3, or 4, and m is an integer selected from 0, 1, 2, or 3; and where R 6 Z 1 It has the same meaning as any of statements 1-20.

[0126] 22. The catalyst according to any one of statements 1-21, having formula (XVII) or (XVIII),

[0127]

[0128] Where n is an integer selected from 0, 1, 2, 3, or 4; m is an integer selected from 0, 1, 2, or 3; and Z 1 It has the same meaning as any of statements 1-21.

[0129] 23. The catalyst according to any one of statements 1-22, having the formula (XIX) or (XX),

[0130]

[0131] 24. A supported catalyst comprising a catalyst and a support according to any one of statements 1-23, preferably an inorganic porous support.

[0132] 25. A catalyst composition comprising:

[0133] At least one catalyst according to any one of statements 1-24;

[0134] Optional activator; optional support; and optional co-catalyst.

[0135] 26. The catalyst composition according to statement 25, wherein the catalyst composition comprises an activator, preferably wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionized ionic compound or any combination thereof; preferably wherein the activator is methylaluminoxane.

[0136] 27. The catalyst composition according to any one of statements 25-26, wherein the activator comprises at least one aluminoxane compound of formula (A1) or (A2).

[0137] For oligomeric linear aluminum oxanes, R a -(Al(R a )-O) x -AlR a 2(A1); or

[0138] For oligocyclic aluminum oxanes, (-Al(R) a )-O-) y (A2),

[0139] Where x is 1-40, and preferably 10-20;

[0140] Where y is 3-40, and preferably 3-20; and

[0141] Each R a Selected independently from C 1-8 Alkyl groups, and preferably methyl groups.

[0142] 28. The catalyst composition according to any one of statements 25-27, wherein the activator is methylaluminoxane.

[0143] 29. The catalyst composition according to any one of statements 25-28, wherein the catalyst composition comprises a co-catalyst.

[0144] 30. The catalyst composition according to any one of statements 25-29, wherein the catalyst composition comprises an organoaluminum co-catalyst.

[0145] 31. The catalyst composition according to any one of statements 25-30, wherein the catalyst composition comprises a co-catalyst, preferably an organoaluminum co-catalyst, preferably selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethanolate, diethylaluminum chloride, and any combination thereof.

[0146] 32. The catalyst composition according to any one of statements 25-31, or the supported catalyst according to statement 24, wherein the support comprises a solid oxide, preferably a solid inorganic oxide, preferably, the solid oxide comprising titanated silica, silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titanium dioxide, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, mixed oxides thereof, or any mixture thereof; preferably silica, titanated silica, fluorinated silica, silica-alumina, fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, silica-coated alumina, fluorinated silica, sulfated silica-coated alumina, or any combination thereof.

[0147] 33. The catalyst composition according to any one of statements 25-32, wherein the support comprises a solid oxide, the solid oxide comprising titanated silicon oxide, silicon oxide, aluminum oxide, silicon oxide-alumina, silicon oxide-coated aluminum oxide, aluminum phosphate, phosphoaluminate, heteropolytungstate, titanium oxide, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, mixed oxides thereof, or any mixture thereof.

[0148] 34. The catalyst composition according to any one of statements 25-33, comprising an aluminoxane activator; a titanated silica or silica solid support; and optionally a co-catalyst.

[0149] 35. Use of the catalyst according to any one of statements 1 to 24, or use of the catalyst composition according to any one of statements 25 to 34, for the preparation of olefin polymers.

[0150] 36. Use of the catalyst according to any one of statements 1 to 24 above, or use of the catalyst composition according to any one of statements 25 to 34, said use being for the preparation of polypropylene, preferably propylene homopolymers, propylene random copolymers and heterophylasic propylene copolymers.

[0151] 37. An olefin polymerization process comprising: contacting a catalyst according to any one of statements 1-24 or a catalyst composition according to any one of statements 25-34 with an olefin monomer, optional hydrogen, and optional one or more olefin comonomers; and polymerizing the monomer and the optional one or more olefin comonomers in the presence of the at least one catalyst composition and optional hydrogen to obtain an olefin polymer.

[0152] 38. The process according to statement 37, wherein the process is carried out in a slurry phase, a gas phase, or a liquid phase.

[0153] 39. The process according to any one of statements 37-38, wherein the process 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.

[0154] 40. The process according to any one of statements 37-39, wherein the process is carried out in a single reaction zone.

[0155] 41. The process according to any one of statements 37-40, wherein the olefin monomer is propylene, and the olefin comonomer comprises ethylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutene, 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 mixtures thereof.

[0156] 42. The process according to any one of statements 37-41, wherein the olefin monomer is ethylene, and the olefin comonomer comprises propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutene, 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 mixtures thereof.

[0157] 43. A process for preparing polypropylene, comprising polymerizing propylene to form polypropylene in the presence of a catalyst according to any one of statements 1-24 or in the presence of a catalyst composition according to any one of statements 25-34.

[0158] 44. An olefin polymer, which is at least partially catalyzed by at least one catalyst according to any one of statements 1-24 or at least one catalyst composition according to any one of statements 24-34, or prepared by a process according to any one of statements 37-43.

[0159] 45. The olefin polymer according to statement 44, wherein the olefin polymer is polypropylene.

[0160] 46. ​​An article comprising an olefin polymer according to any one of statements 44-45.

[0161] As used herein, the term "catalyst" refers to a substance that causes a change in the reaction rate. In this invention, it is particularly applicable to catalysts suitable for polymerization, preferably for the polymerization of olefins into olefin polymers.

[0162] The term "metallocene catalyst" is used herein to describe any transition metal complex containing metal atoms bonded to one or more ligands. Metallocene catalysts are compounds of Group IV transition metals of the periodic table, such as titanium, zirconium, hafnium, etc., and have coordination structures with the metal compound and ligands. Metallocenes include a single metal site, which allows for greater control over the branching and molecular weight distribution of the polymer. Monomers are inserted between the metal and the growing polymer chains.

[0163] In some embodiments, the present invention provides a metallocene catalyst of any one of formulas (I) to (XVIII), wherein

[0164] R 2 R 3 R 4 R 5 R 6 R 7 Each is independently selected from: hydrogen or C 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, -OR 15 C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, halogen, Si(R) 12 )3 and miscellaneous C 1-8 Alkyl groups; wherein each of the said groups may be unsubstituted or substituted with one or more substituents. 1 Replace; where Z 1 Selected from -OR 16 C 1-8 Alkyl and C 2-8 alkenyl; each R 12 Independently hydrogen, C 1-8 Alkyl or C 2-8 alkenyl; wherein R 15 R 16 Each is independently selected from C1-8 Alkyl, C 6-10 Aryl C 1-8 Alkyl, C 7-8 Alkyl C 6-10 Aryl and C 6-10 Aryl; preferred R 15 R 16 Each independently is C 1-8 Alkyl; and wherein R 3 R 4 R 5 R 6 R 7 At least one of them is -OR 15 Preferred R 4 R 5 R 6 R 7 At least one of them is -OR 15 Preferred R 4 R 5 R 6 At least one of them is -OR 15 Preferred R 5 R 6 At least one of them is -OR 15 ;

[0165] R 8 R 9 R 10 R 11 Each is independently selected from hydrogen and C. 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, C 1-8 Alkoxy, C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, halogen, Si(R) 12 )3 and miscellaneous C 1-8 Alkyl; each R 12 Independently hydrogen, C 1-8 Alkyl, or C 2-8 alkenyl;

[0166] L 1 For SiR 13 R 14 or -[CR 13 R 14 ] h -; where h is an integer selected from 1 or 2; R 13and R 14 Each is independently selected from hydrogen and C. 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl and C 6-10 Aryl; or R 13 and R 14 Together with the atoms they are attached to, they form C 3-8 cycloalkyl, C 5-8 Cycloalkenyl; preferably L 1 For SiR 13 R 14 or -[CR 13 R 14 ]-;R 13 and R 14 Each is independently selected from hydrogen and C. 1-8 Alkyl and C 3-8 cycloalkyl; or R 13 and R 14 Together with the atoms they are attached to, they form C 3-8 cycloalkyl; preferably L 1 For SiR 13 R 14 or -[CR 13 R 14 ]-;R 13 and R 14 Each is independently selected from hydrogen or C. 1-6 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-4 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-2 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or methyl; preferably L 1 It is SiMe2.

[0167] In some embodiments, the present invention provides a metallocene catalyst of any one of formulas (I) to (XVI), wherein

[0168] R 2 R 3 R 4 R6 R 7 Each is independently selected from hydrogen or C. 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, -OR 15 C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, halogen, Si(R) 12 3. Mixed C 1-8 Alkyl groups; wherein each of the said groups may be unsubstituted or substituted with one or more substituents. 1 Replace; where Z 1 Selected from -OR 16 C 1-8 Alkyl and C 2-8 alkenyl; each R 12 Independently hydrogen, C 1-8 Alkyl or C 2-8 alkenyl; wherein R 15 R 16 Each is independently selected from C 1-8 Alkyl, C 6-10 Aryl C 1-8 Alkyl, C 7-8 Alkyl C 6-10 Aryl and C 6-10 Aryl; preferred R 15 R 16 Each independently is C 1-8 Alkyl; and R 5 For -OR 15 ;

[0169] R 8 R 9 R 10 R 11 Each is independently selected from hydrogen and C. 1-8 Alkyl, C 2-8 alkenyl, C 6-10 Aryl, C 1-8 Alkoxy, halogen and Si(R) 12 )3; Each R 12 Independently hydrogen or C 1-6 alkyl;

[0170] L 1 For SiR 13 R 14 or -[CR 13 R 14]-;R 13 and R 14 Each is independently selected from hydrogen and C. 1-8 Alkyl and C 3-8 cycloalkyl; or R 13 and R 14 Together with the atoms they are attached to, they form C 3-8 cycloalkyl; preferably L 1 For SiR 13 R 14 or -[CR 13 R 14 ]-;R 13 and R 14 Each is independently selected from hydrogen or C. 1-6 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-4 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-2 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or methyl; preferably L 1 It is SiMe2.

[0171] In some embodiments, the present invention provides a metallocene catalyst of any one of formulas (I) to (XVIII), wherein

[0172] R 2 R 3 R 6 R 7 Each is independently selected from hydrogen or C. 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, -OR 15 C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, halogen, Si(R) 12 )3 and miscellaneous C 1-8Alkyl; wherein each of the said groups may be unsubstituted or substituted with one or more Z groups. 1 Replace; where Z 1 Selected from -OR 16 C 1-8 Alkyl and C 2-8 alkenyl; each R 12 Independently hydrogen, C 1-8 Alkyl or C 2-8 alkenyl; wherein R 15 R 16 Each is independently selected from C 1-8 Alkyl, C 6-10 Aryl C 1-8 Alkyl, C 7-8 Alkyl C 6-10 Aryl and C 6-10 Aryl; preferred R 15 R 16 Each independently is C 1-8 Alkyl; R 4 C 6-10 Aryl, wherein the C 6-10 The aryl group can be unsubstituted or substituented by one or more substituents. 1 Replace; and R 5 For -OR 15 ;

[0173] R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-4 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-2 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or methyl; R is preferred. 8 R 9 R 10 R 11 Each is independently a methyl group.

[0174] L 1 For SiR 13 R 14 or -[CR 13 R 14 ]-;R 13 and R 14 Each is independently selected from hydrogen or C. 1-6 Alkyl; preferably L 1 For SiR13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-4 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-2 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or methyl; preferably L 1 It is SiMe2.

[0175] In some embodiments, the present invention provides a metallocene catalyst of any one of formulas (I) to (XVIII), wherein

[0176] R 2 R 3 R 6 R 7 Each is independently selected from hydrogen or C. 1-8 Alkyl, C 2-8 alkenyl, C 6-10 Aryl, -OR 15 halogens and miscellaneous C 1-8 Alkyl; wherein each of the said groups may be unsubstituted or substituted with one or more Z groups. 1 Replace; where Z 1 Selected from -OR 16 and C 1-8 Alkyl; wherein R 15 R 16 Each is independently selected from C 1-8 Alkyl and C 6-10 Aryl; preferred R 15 R 16 Each independently is C 1-8 Alkyl; R 4 C 6-10 Aryl, wherein the C 6-10 The aryl group can be unsubstituted or substituented by one or more substituents. 1 Replace; and R 5 For -OR 15 ;

[0177] R 8 R 9 R 10 R 11 Each is independently selected from hydrogen and C. 1-6 Alkyl or halogen; preferably R8 R 9 R 10 R 11 Each is independently hydrogen or C 1-4 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-2 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or methyl; R is preferred. 8 R 9 R 10 R 11 Each is independently a methyl group.

[0178] L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-2 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or methyl; preferably L 1 It is SiMe2.

[0179] In some embodiments, the present invention provides a metallocene catalyst of any one of formulas (I) to (XVIII), wherein

[0180] R 3 R 7 Each is independently selected from hydrogen or C. 1-8 Alkyl, C 2-8 alkenyl, C 6-10 Aryl, -OR 15 halogens and miscellaneous C 1-8 Alkyl; wherein each of the said groups may be unsubstituted or substituted with one or more Z groups. 1 Replace; where Z 1 Selected from -OR 16 and C 1-8 Alkyl; wherein R 15 R 16 Each is independently selected from C 1-8 Alkyl and C 6-10 Aryl; preferred R 15 R 16 Each independently is C 1-8 Alkyl; R 2 and R6 Each is independently selected from C 1-8 Alkyl, C 6-10 Aryl, -OR 15 halogens and miscellaneous C 1-8 Alkyl; R 4 C 6-10 Aryl, wherein the C 6-10 The aryl group can be unsubstituted or substituented by one or more substituents. 1 Replace; and R 5 For -OR 15 ;

[0181] R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-6 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-2 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or methyl; R is preferred. 8 R 9 R 10 R 11 Each is independently a methyl group.

[0182] L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-4 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-2 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or methyl; preferably L 1 It is SiMe2.

[0183] In some embodiments, the present invention provides a metallocene catalyst of any one of formulas (I) to (XVIII), wherein

[0184] R 3 R7 Each is independently selected from hydrogen or C. 1-8 Alkyl, preferably hydrogen; R 2 and R 6 Each is independently selected from C 1-8 Alkyl, C 6-10 Aryl, -OR 15 halogens and miscellaneous C 1-8 Alkyl, preferably C 1-8 Alkyl; R 4 C 6-10 Aryl, wherein the C 6-10 The aryl group can be unsubstituted or substituented by one or more substituents. 1 Replace; and R 5 For -OR 15 .

[0185] R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-6 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or C 1-2 Alkyl; preferably R 8 R 9 R 10 R 11 Each is independently hydrogen or methyl; R is preferred. 8 R 9 R 10 R 11 Each is independently a methyl group.

[0186] L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-4 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or C. 1-2 Alkyl; preferably L 1 For SiR 13 R 14 ;R 13 and R 14 Each is independently selected from hydrogen or methyl; preferably L 1 It is SiMe2.

[0187] In some embodiments, the present invention provides a metallocene catalyst of any one of formulas (I) to (X), wherein M 1 It is zirconium or titanium; preferably M is zirconium; and Q 1 and Q 2 Each is independently selected from halogens, C 1-8 Alkyl and C 1-8 Alkoxy; preferably Q 1 and Q 2 Each is independently selected from halogens such as chlorine or C. 1-8 alkyl.

[0188] The catalysts used in this paper are preferably provided on a solid support.

[0189] The support can be an inert organic or inorganic solid that is chemically unreactive with any component of a conventionally bridged metallocene catalyst. Suitable support materials for supported catalysts include solid inorganic oxides, such as silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, thorium oxide, and mixed oxides of silicon oxide and one or more Group 2 or 13 metal oxides, such as silicon oxide-magnesium oxide and silicon oxide-alumina oxide mixed oxides. Silicon oxide, aluminum oxide, and mixed oxides of silicon oxide and one or more Group 2 or 13 metal oxides are preferred support materials. A preferred example of such mixed oxides is silicon oxide-alumina oxide. For example, solid oxides include titanated silicon oxide, silicon oxide, aluminum oxide, silicon oxide-alumina, silicon oxide-coated aluminum oxide, aluminum phosphate, phosphoaluminate, heteropolytungstate, titanium oxide, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, mixed oxides thereof, or any mixture thereof, preferably silicon oxide, titanated silicon oxide, fluoride-treated silicon oxide, silicon oxide-alumina, fluoride-treated aluminum oxide, sulfated aluminum oxide, fluoride-treated silicon oxide-alumina, sulfated silicon oxide-alumina, silicon oxide-coated aluminum oxide, fluoride-treated silicon oxide, sulfated silicon oxide-coated aluminum oxide, or any combination thereof. Most preferably, it is titanated silicon oxide or a silicon oxide compound. In a preferred embodiment, the bridging metallocene catalyst is provided on a solid support, preferably titanated silicon oxide or a silicon oxide support. Silica may be particulate, agglomerated, pyrolytic (fumed) or other forms.

[0190] In some embodiments, the catalyst component is supported by a porous support, and preferably porous titanium-treated silica, or has a density of 200 to 900 μm. 2A silica support with a surface area between 0.5 and 4 ml / g. In another embodiment, the support for the polymerization catalyst is a porous support, preferably porous titanized silica, or a silica support with an average pore volume between 50 and 4 ml / g. In yet another embodiment, the support for the polymerization catalyst is a porous support, preferably porous titanized silica, or a silica support with an average pore volume between 50 and 4 ml / g. Between, and preferably at 75 and The average pore size of the silica carrier.

[0191] In some embodiments, the support has a D50 of up to 150 μm, preferably up to 100 μm, preferably up to 75 μm, preferably up to 50 μm, preferably up to 40 μm, and preferably up to 30 μm. D50 is defined as the particle size at which 50% by weight of the particles have a size smaller than this D50. Particle size can be measured according to the international standard ISO 13320:2009 (“Particle size analysis – Laser diffraction methods”). For example, D50 can be measured by sieving, by BET surface measurement, or by laser diffraction analysis. For example, a laser diffraction system from Malvern Instruments can be advantageously used. Particle size can be measured by laser diffraction analysis on a Malvern-type analyzer. After the supported catalyst is placed in suspension in cyclohexane, the particle size can be measured by laser diffraction analysis on a Malvern-type analyzer. Suitable Malvern systems include the Malvern 2000, Malvern MasterSizer (e.g., MasterSizer S), Malvern 2600, and Malvern 3600 series. These instruments, along with their operating manuals, meet or even exceed the requirements specified in ISO 13320. The Malvern MasterSizer (e.g., MasterSizer S) may also be useful because it can measure D50 more accurately near the lower end of the range, for example, for average particle sizes less than 8 μm, by applying the theory of Mie using appropriate optical methods.

[0192] Preferably, the catalyst is activated by an activator. The activator can be any activator known for this purpose, such as an aluminum-containing activator, a boron-containing activator, or a fluorinated activator. The aluminum-containing activator may include aluminum oxanes, alkyl aluminum, Lewis acids, and / or fluorinated catalyst supports.

[0193] In some embodiments, aluminoxanes are used as activators for the catalyst. Aluminoxanes can be used with the catalyst to enhance its activity during the polymerization reaction.

[0194] As used herein, the terms "alumoxane" and "aluminoxane" are used interchangeably and refer to substances capable of activating bridging metallocene catalysts. In some embodiments, the aluminoxane comprises oligomeric linear and / or cyclic alkylaluminoxanes. In further embodiments, the aluminoxane has formula (A1) or (A2).

[0195] For oligomeric linear aluminum oxanes, R a -(Al(R a )-O) x -AlR a 2(A1); or

[0196] For oligocyclic aluminum oxanes, (-Al(R) a )-O-) y (A2)

[0197] Where x is 1-40, and preferably 10-20;

[0198] Where y is 3-40, and preferably 3-20; and

[0199] Each R a Selected independently from C 1-8 Alkyl groups, and preferably methyl groups. In a preferred embodiment, the aluminum oxane is methylaluminoxane (MAO).

[0200] The catalyst composition may include a co-catalyst, preferably an organoaluminum co-catalyst. Preferably, it is composed of AIR... b x One or more alkylaluminum molecules can be used as additional co-catalysts, wherein each R... b The same or different, and selected from halogens or alkoxy or alkyl groups having 1 to 12 carbon atoms, and x is 1 to 3. Non-limiting examples are triethylaluminum (TEAL), triisobutylaluminum (TIBAL), trimethylaluminum (TMA), tri-n-propylaluminum, tri-n-butylaluminum, methyl-methyl-ethylaluminum (MMEAL), tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and any combination thereof. Trialkylaluminum is particularly suitable, and triisobutylaluminum (TIBAL) and triethylaluminum (TEAL) are most preferred.

[0201] Catalyst compositions can be particularly useful in processes for preparing polymers, which involve contacting at least one monomer with at least one catalyst composition. Preferably, the polymer is an olefin polymer, and more preferably, the monomer is an α-olefin.

[0202] Therefore, the catalyst compositions of the present invention are particularly suitable for use in the preparation of olefin polymers. The present invention also relates to the use of the catalyst compositions in olefin polymerization.

[0203] The present invention also covers an olefin polymerization process comprising: contacting a catalyst composition according to the invention with an olefin monomer, optionally hydrogen, and optionally one or more olefin comonomers; and polymerizing the monomer and optionally one or more olefin comonomers in the presence of said at least one catalyst composition and optionally hydrogen, thereby obtaining an olefin polymer.

[0204] The term "alkene" in this document refers to a molecule containing carbon and hydrogen and having at least one carbon-carbon double bond. An alkene containing one carbon-carbon double bond is represented herein as a monounsaturated hydrocarbon and has the chemical formula C0. n H 2n , where n equals at least 2. “Alpha-olefin”, “α-olefin (alkene)”, “1-chain olefin” or “terminal olefin” are used as synonyms in this document and refer to olefins or chain olefins having a double bond at the primary or alpha (α) position.

[0205] Throughout this application, the terms "olefin polymer," "polyolefin," and "polyolefin polymer" are used synonymously.

[0206] Suitable polymerization includes, but is not limited to, homopolymerization of α-olefins, or copolymerization of α-olefins with at least one other α-olefin comonomer.

[0207] As used herein, the term "comonomer" refers to an olefin comonomer suitable for polymerization with an α-olefin monomer. The comonomer (if present) differs from the olefin monomer, and the comonomer is selected such that it is suitable for copolymerization with the olefin monomer. The comonomer may include, but is not limited to, aliphatic C2-C... 20 α-Alkenes. Suitable aliphatic C3-C 20 Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Further examples of suitable comonomers are vinyl acetate (H3C-C(=O)O-CH=CH2) or vinyl alcohol ("HO-CH=CH2"). Examples of suitable olefin copolymers that can be prepared include random copolymers of propylene and ethylene, random copolymers of propylene and 1-butene, multiphase copolymers of propylene and ethylene, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, copolymers of ethylene and vinyl acetate (EVA), and copolymers of ethylene and vinyl alcohol (EVOH).

[0208] In some embodiments, the olefin monomer is ethylene, and the olefin comonomer comprises propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutene, 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 mixtures thereof.

[0209] In some embodiments, the olefin monomer is propylene, and the olefin comonomer comprises ethylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutene, 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 mixtures thereof.

[0210] Olefin polymers can be prepared in bulk, gas, solution, and / or slurry phases. The process can be carried out in one or more batch reactors, slurry reactors, gas-phase reactors, solution reactors, high-pressure reactors, tubular reactors, batch reactors, or combinations thereof.

[0211] As used herein, the terms "slurry" or "polymer slurry" essentially refer to a multiphase composition comprising at least a polymer solid and a liquid phase, wherein the liquid phase is a continuous phase. The solid may include a catalyst and monomers to be polymerized.

[0212] In some embodiments, the liquid phase includes 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 liquid form, which is liquid at room temperature and preferably liquid under pressure conditions in a circulating reactor. Suitable diluents include, but are not limited to, hydrocarbon diluents, such as aliphatic, alicyclic, and aromatic hydrocarbon solvents, or halogenated forms of these solvents. Preferred solvents are C 12 Or lower straight-chain or branched saturated hydrocarbons, C5 to C9 saturated alicyclic or aromatic hydrocarbons, or C2 to C6 halogenated hydrocarbons. Non-limiting illustrative examples of solvents include butane, isobutane, pentane, hexane, heptane, cyclopentane, cyclohexane, cycloheptane, methylcyclopentane, methylcyclohexane, isooctane, benzene, toluene, xylene, chloroform, chlorobenzene, tetrachloroethylene, dichloroethane, and trichloroethane, preferably isobutane or hexane.

[0213] Polymerization reactions can also be carried out in the gas phase under gas-phase conditions. As used herein, the term "gas-phase conditions" refers to the temperature and pressure suitable for polymerizing one or more gas-phase olefins to thereby produce a polymer.

[0214] The polymerization step can be carried out over a wide temperature range. In some embodiments, the polymerization step can be carried out at temperatures ranging from 20°C to 125°C, preferably from 60°C to 110°C, more preferably from 75°C to 100°C, and most preferably from 78°C to 98°C. Preferably, the temperature range is from 75°C to 100°C, and most preferably from 78°C to 98°C. These temperatures may fall under the more general polymerization conditions.

[0215] In some embodiments, under slurry conditions, the polymerization step can 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. The pressure may fall under the more general polymerization conditions.

[0216] The present invention also covers polymers at least partially catalyzed by at least one catalyst composition according to the invention or polymers produced by the process of the present invention.

[0217] This invention also covers polymers, preferably olefin polymers produced by processes as defined herein. In some embodiments, the olefin polymer is polyethylene. In some embodiments, the olefin polymer is polypropylene.

[0218] After the polymer is produced, it can be molded into various articles. Such articles can be, for example, various polyethylene articles used in extrusion and injection molding applications, including but not limited to film products, caps and closures, rotational molding parts, grass yarn, tubes, etc. Such articles can also be, for example, various polypropylene articles used in extrusion and injection applications, including but not limited to injection molding, blow molding, injection stretch blow molding (ISBM), cast or blown film extrusion, sheet extrusion, thermoforming, fibers, etc.

[0219] Therefore, the present invention also covers articles comprising polymers as defined herein; preferably olefin polymers as defined herein, or olefin polymers obtained according to processes as defined herein.

[0220] The following embodiments are for illustrative purposes only and should not be construed as limiting the scope of the invention in any way. Although the invention has only been shown in some forms, it should be apparent to those skilled in the art that the invention is not limited thereto, but is readily adaptable to various changes and modifications without departing from its scope.

[0221] Example

[0222] Test methods

[0223] The properties cited herein and those cited below shall be determined according to the following test procedure. Where any of these properties is cited in the appended claims, the measurement shall be performed according to the prescribed test procedure.

[0224] Melt Flow Index

[0225] 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 load of 2.16 kg using a 2.096 mm mold.

[0226] The 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 mold.

[0227] The melt flow index (MI2) of polypropylene was determined according to ISO 1133:2005, Method B, Condition M, at a temperature of 230°C and a load of 2.16 kg using a 2.096 mm mold.

[0228] Molecular weight, molecular distribution

[0229] Molecular weight (M) was determined by size exclusion chromatography (SEC) and, in particular, by gel permeation chromatography (GPC). 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 In short, using a GPC-IR5 from Polymer Char: 10 mg of polymer sample was dissolved in 10 ml of trichlorobenzene (industrial grade) at 160 °C for 1 hour. Injection volume: approximately 400 μl, automated sample preparation, and injection temperature: 160 °C. Column temperature: 145 °C. Detector temperature: 160 °C. Two Shodex AT-806MS (Showa Denko) columns and one Styragel HT6E (Waters) column were used at a flow rate of 1 ml / min. Mobile phase: trichlorobenzene, stabilized with 1000 ppm by weight of butylated hydroxytoluene (BHT) filtered through a 0.45 μm PTFE filter. Detector: Infrared detector (2800-3000 cm⁻¹). -1 Used for concentration measurement, a narrow filter centered at 2928 cm⁻¹ -1 And a narrow filter centered at 2959cm -1 Calibration: Narrow standard of polystyrene (PS) (commercially available).

[0230] For polyethylene, the molecular weight M of each fraction i of the eluted polymer is... i The calculation is based on the Mark-Houwink relation (log 10 (M PE )=0.965909x log 10 (M PS -0.28264)(in M PE =1000 low molecular weight end truncation).

[0231] For polypropylene, the molecular weight M of each fraction i of the eluted polymer is... i The calculation is based on the Mark-Houwink relation (log 10 (M PP ) = log 10 (M PS -0.25323 (in M) PP =1000 low molecular weight end truncation).

[0232] The average molecular weight used to establish molecular weight / property relationships is the number mean (M). n ), weight average (M) w ) and z (M) z Molecular weight. These average values ​​are defined by the following expression and are calculated from M. i Sure:

[0233]

[0234]

[0235]

[0236] Here, N i and W i They are respectively those with molecular weight M i The number and weight of molecules. The third representation in each case (far right) defines how these averages were obtained from the SEC chromatogram. hi is the height of the SEC curve at the i-th elution fraction (from the baseline), and M... i This represents the molecular weight of the substance eluted at this increment.

[0237] Xylene soluble content

[0238] The xylene-soluble content is determined as follows: A propylene polymer is dissolved in refluxed xylene, the solution is cooled to 25°C, the solution is filtered, and the solvent is subsequently evaporated. The residue, which is the xylene-soluble portion of the propylene polymer, is then dried and weighed. The procedure is as follows: Approximately 2.5 g of the propylene polymer is weighed into a flask, and 250 ml of xylene is added. The xylene is heated with stirring, then refluxed for 15 minutes until dissolved. Heating and stirring are stopped, and the solution is allowed to stand for exactly 15 minutes. The flask is then placed in a thermostat set to 25°C ± 1°C for 1 hour. The solution is filtered through Whatman n°4 filter paper, and exactly 50 ml of the solution is collected. The solution is then evaporated, and the residue is dried and weighed. The percentage of xylene-soluble content (“XS”) is then calculated according to XS (in weight %) = (weight of residue / initial total weight of PP) * 500, where all weights are expressed in the same units.

[0239] Differential scanning calorimetry (DSC) is used to determine crystallization and melting temperatures.

[0240] Peak crystallization temperature (T0) was measured via differential scanning using a TA Instruments DQ 2000 instrument. c Peak melting temperature (T) m The heat of fusion (ΔH) was calibrated with indium and used in T-zero mode. Polymer analysis was performed using polymer samples ranging from 2 to 10 mg. The samples were first equilibrated at 20 °C and then heated to 220 °C at a heating rate of 20 °C / min (first heating). The samples were held at 220 °C for 5 minutes to eliminate any prior thermal and crystallization history. The samples were then cooled to 20 °C at a constant cooling rate of 20 °C / min (first cooling). The samples were held isothermally at 20 °C for 5 minutes and then heated to 220 °C at a constant heating rate of 20 °C / min (second heating). The exothermic peak of crystallization (first cooling) was analyzed using TA Universal Analysis software, and the peak crystallization temperature (Tc) corresponding to a cooling rate of 20 °C / min was determined. c The endothermic peak of the melting (second heating) was also analyzed using TA Universal Analysis software, and the peak melting temperature (T) corresponding to a heating rate of 20 °C / min was determined. m Unless otherwise stated, T in this invention c T m The reported values ​​refer to cooling and heating rates of 20°C / minute, respectively.

[0241] 13 C NMR / Stage regularity

[0242] pass 13C-NMR spectroscopy determined stereoregularity. The spectroscopy was performed at 125 MHz using a 500 MHz Bruker NMR spectrometer with a high-temperature 10 mm cryogenic probe, under conditions where the signal intensity in the spectrum was proportional to the total number of contributing carbon atoms in the sample. 13 C-NMR spectroscopy analysis. Such conditions are well known to those skilled in the art and include, for example, appropriate relaxation times. In practice, the signal intensity is obtained from its integral, i.e., the corresponding area. Data were acquired at 130 °C using proton decoupling, 240 scans per spectrum, an 11-second pulse repetition delay, and a spectral width of 26000 Hz. Samples were prepared by dissolving a sufficient amount of polymer in 1,2,4-trichlorobenzene (TCB, 99%, spectral grade) at 130 °C, with occasional stirring to homogenize the sample, followed by the addition of hexadeuterated benzene (C6D6, spectral grade) and a small amount of hexamethyldisiloxane (HMDS, 99.5+%), with HMDS acting as an internal standard. For example, approximately 600 mg of polymer was dissolved in 2.0 mL of TCB, followed by the addition of 0.5 mL of C6D6 and 2 to 3 drops of HMDS.

[0243] After acquiring the data, the chemical shift reference internal standard HMDS signal was used, with a assigned (specified) value of 2.03 ppm.

[0244] According to procedures well-known in the art, by analyzing the total polymer... 13 C-NMR spectroscopy was used to determine isotactic regularity. In the spectral region of the methyl group, signals corresponding to the pentads mmmm, mmmr, mmrr, and mrrm were assigned using published data, such as A. Razavi, Macromol. Symp., vol. 89, pp. 345-367. Only the pentads mmmm, mmmr, mmrr, and mrrm were considered. Other remaining pentads were ignored due to their weak signal intensity. For the signal associated with the mmrr pentad, the overlap with the methyl signal associated with the 2,1-insertion was corrected. The percentage of the mmmm pentad was then calculated as follows: %mmmm = AREAmmmm / (AREAmmmm + AREAAmmmr + AREAmmrr + AREAAmrrm) * 100.

[0245] The regio-defect content in polypropylene is the percentage of 2,1-intercalation in polypropylene.

[0246] For propylene homopolymers, signals corresponding to 2,1-insertions are determined by means of published data, such as HNCheng, J. Ewen, Makromol. Chem., vol. 190 (1989), pp. 1931-1940.

[0247] For propylene copolymers, the determination of the percentage of 2,1-insertion is detailed below relative to ethylene as a comonomer, but it can also be applied with other comonomers.

[0248] For copolymers with propylene and ethylene as comonomers, the percentage of 2,1-insertion is determined by two contributions:

[0249] (i) the percentage of propylene homopolymers as defined above for 2,1-interpolation, and

[0250] (ii) 2,1-percentage of insertions, where the 2,1-inserted propylene is adjacent to ethylene.

[0251] Therefore, the total percentage of 2,1-insertion corresponds to the sum of these two contributions. The first area AREA1 is defined as the average area corresponding to the signal with 2,1-insertion. The second area AREA2 is defined as the average area corresponding to the signal with 1,2-insertion. The distribution of signals related to 1,2-insertion is well known to those skilled in the art. The percentage of 2,1-insertion is calculated as follows:

[0252] 2,1-Insertion (in percentage) = AREA1 / (AREA1+AREA2) * 100

[0253] The percentage of 2,1-insertion is given as the molar percentage of 2,1-inserted propylene relative to total propylene.

[0254] Signal assignment for case (ii) can be performed by using a reference spectrum or by referring to published literature.

[0255] Comonomer content

[0256] Comonomer content of polypropylene: The total copolymer content (particularly ethylene (C2), i.e., C2 wt%) relative to the total weight of the polypropylene composition. 13 C NMR determination.

[0257] The samples were prepared as follows: a sufficient amount of polymer was dissolved in 1,2,4-trichlorobenzene (TCB 99% spectral grade) at 130 °C, with occasional stirring to homogenize the sample. Hexadeuterated benzene (C6D6, spectral grade) and a small amount of hexamethyldisiloxane (HMDS, 99.5+%) were then added, with HMDS acting as an internal standard. For example, approximately 600 mg of polymer was dissolved in 2.0 ml of TCB, followed by the addition of 0.5 ml of C6D6 and 2 to 3 drops of HMDS.

[0258] Record data using a 10mm probe at a Bruker 500MHz using the conditions listed in Table 1. 13 C NMR signal.

[0259] Table 1

[0260] Pulse angle: 90° Pulse repetition time: 20 seconds Spectral width: 25000Hz concentrated at 95ppm Data points: 64K Temperature: 130℃ + / - 2℃ Rotation: 15Hz Number of scans: 2000-4000 Decoupling sequences: Inverse-gated decoupling sequences to avoid NOE effects.

[0261] 13 C{ 1 H NMR spectra were obtained by Fourier transform at 131 K following light Gaussian multiplication. The spectra were phased, baseline corrected, and chemical shifts scaled to an internal standard HMDS of 2.03 ppm.

[0262] As shown in Figure 2 and Table 2 below, peak picking and integration are performed on the chemical shifts of the signal.

[0263] Table 2

[0264] area Displacement (ppm) area Displacement (ppm) area Displacement (ppm) A 22.80-19.6 I 27.74-27.54 W 30.12-29.84 B 42.37-42.18 P 34.92-34.73 X 27.55-27.10 C 38.64-38.43 Q 34.67-34.50 Y 24.94-24.26 D 36.04-35.81 R 34.06-33.9 E 31.6-31.49 S 31.4-31.21 F 30.63-30.51 T 38.34-37.7 G 17.71-17.49 U 37.7-37.37 H 17.31-17.10 V 30.46-30.31

[0265] Chemical shifts are given in ±0.05 ppm.

[0266] The main peak A represents 1.2 PP units.

[0267] Peak I represents 1.3 PP units.

[0268] Peaks B, C, D, E, F, G, and H represent 2,1 PP units.

[0269] Peaks T, U, V, W, X, and Y indicate that ethylene is included in 1 or 2 PP units.

[0270] Peaks P, Q, R, and S indicate that ethylene is included with 2.1 PP units.

[0271] The weight percentage of C2 content is obtained by combining the following areas (A).

[0272] A C3 1,2 =AA

[0273] A C3 2,1 =(A B +A C +A D +A E+ A F +A G +A H ) / 7+(0.5*A P +0.5*A Q +0.5*A S ) / 3

[0274] A C3 1,3 =A I / 2

[0275] A C2 E1 1,2 =(0.5*A T +A Y ) / 2

[0276] A C2 E2 1,2 =(A U -A I +A X ) / 2-A V

[0277] A C2 E3 1,2 =((A U -A I +A T )*0.5+(A X -A V )*0.5+A V +A W +A X +A Y ) / 2-A C2 E1 1,2 -A C2 E2 1,2

[0278] A C2 2,1 =(0.5*A P +0.5*A Q +0.5*A S+ A R ) / 4

[0279] A C2 =(A C2 E11,2 +A C2 E2 1,2 +A C2 E3 1,2 +A C2 2,1 )

[0280] A C3 =(A C3 1,2 +A C3 2,1 +A C3 1,3 )

[0281] % (weight) C2 = (28 * A) C2 ) / (28*A C2 +42*A C3 )x 100

[0282] Randomness (%) = A C2 E1 1,2 / A C2

[0283] Determination of Al and Zr content

[0284] After mineralizing the sample in an acidic medium and collecting the residue, the Al and Zr contents were determined using inductively coupled plasma atomic emission spectrometry (ICP-AES). The spectrometer used was a Spectro ICP-AES ARCOS.

[0285] The elemental determination is performed by nebulizing the solution in argon plasma, measuring the intensity of the most sensitive and interference-free emission line, and comparing these intensities with the intensity of the calibration solution (external calibration method).

[0286] Preparation of test solution Under an inert atmosphere (in a glove box), add approximately 0.3 g of catalyst to a platinum crucible and add 3 to 5 ml of isopropanol to deactivate the catalyst. Heat the mixture in a sand bath until dry (30 minutes). Place the platinum crucible in an oven at 600°C for 10 minutes. After cooling, add... Deionized water was used to impregnate all ash, and 1 ml of concentrated HCl and concentrated HF were added. The crucible was placed in a sand bath and then... Add deionized water to mix the contents of the crucible. After 24 hours, add 1 ml of concentrated HCl, 0.5 ml of concentrated HF, and... Add deionized water while stirring the mixture under heating to achieve complete dissolution. After cooling, transfer the mixture to a 50 ml polypropylene tube and use... Make up the volume to 50 ml with deionized water. Then dilute the test solution 25 times, ensuring to maintain a 2% HCl / HF 1% medium.

[0287] Preparation of calibration standards and control solutions The standard solution is prepared by diluting a commercially available single-element solution of certified concentration. The standard solution is prepared by transferring the required volume of the certified solution into a 50 ml polypropylene tube, and then... Rinse the sides of the tube with deionized water, and add 1 ml of HCl and 0.5 ml of concentrated HF per 50 ml to obtain the same acid content as the sample solution, and finally use... The solution was diluted with deionized water. The control solution was prepared by diluting a commercially available multi-element solution of certified concentration. The presence of other elements in the solution allowed for verification of the presence / absence of potential interferences.

[0288] Result presentation:

[0289] The elemental content (in ppm) measured in the sample is calculated as follows:

[0290] Concentration of element in solution (mg / L) x Volume (50 ml) x Dilution factor / mass (g)

[0291] Calculate the limit of quantitation (LOQ) for each element from 10 blank measurements:

[0292] LOQ (mg / L) in solution = Standard deviation of 10 replicates of blank sample x 10

[0293] LOQ (ppm) in the sample = LQ in the solution x volume (50 ml) x dilution factor / mass (g).

[0294] A. Catalyst

[0295] Catalyst 1:

[0296] Metallocene catalyst 1 (Cata 1) was prepared as described below and is shown in Scheme 1.

[0297]

[0298] 2-tert-Butylanisole: A solution of 2-butylphenol (20.0 g, 0.13 mol) in THF (8.3 mL) was slowly added to a suspension of freshly powdered KOH (26.15 g, 0.47 mol) in THF (17 mL) while maintaining the temperature below 10 °C; the resulting mixture was then stirred at room temperature for 3 hours. Subsequently, CH3I (56.7 g, 0.40 mol) was added dropwise at 0 °C, and the reaction mixture was stirred overnight at room temperature. It was then filtered and concentrated to obtain a pale yellow liquid, which was dried under vacuum (20.2 g, 93%). 1 H NMR (400MHz, CDCl3, 25℃): δ7.40(dd,J=7.7,1.5,1H,o-(OMe)Ph),7.29(td,J=8.0,1.6 ,1H,o-(tBu)Ph),7.00(td,J=8.3,3.2,2H,m-Ph),3.93(s,3H,OCH3),1.50(s,9H,CH3).

[0299]

[0300] 6-tert-Butyl-5-methoxy-2-methyl-1-indanone: A mixture of 2-tert-butyl anisole (17.8 g, 0.11 mol) and methacrylic acid (11.7 g, 0.14 mol) was added dropwise at 60 °C to a well-stirred Eaton reagent prepared by mixing P₂O₅ (31.0 g, 0.22 mol) in methanesulfonic acid (156.0 mL, 2.4 mol). The resulting mixture was stirred at 60 °C for 1 hour, followed by stirring overnight at room temperature. It was then poured into ice water (400 mL) and extracted with toluene (2 × 200 mL). The combined organic layers were washed with an aqueous solution of water and NaHCO₃ (1.0 M, 200 mL), dried over MgSO₄, evaporated, and distilled at 145–150 °C at 0.7 Torr (93.3257 Pa) (11.6 g, 46%). 1 H NMR (400MHz, CDCl3, 25℃): δ7.70(s,1H,t-Bu-Ph),6.92-6.87(m,1H,OMe-Ph),3.94(d,J=2.8,3H,CH3-O),3. 38-3.29(m,1H,2-ind),2.75-2.62(m,2H,3-ind),1.39(s,9H,t-Bu),1.31(dd,J=7.4,2.5,3H,2-CH3-ind).

[0301]

[0302] 4-Bromo-6-tert-butyl-5-methoxy-2-methyl-1-indanone: Bromine (5.95 mL, 0.12 mol) was added dropwise to a mixture of 6-tert-butyl-5-methoxy-2-methyl-1-indanone (27.0 g, 0.12 mol), NaOAc (28.6 g, 0.35 mol), tetrabutylammonium bromide in CH2Cl2 (30 mL) (0.75 g, 2% mol), and water (90 mL). The mixture was then stirred overnight at room temperature. After 16 hours, bromine (3.4 mL, 0.066 mol) and NaOAc (16.2 g, 0.2 mol) were added, and the mixture was stirred at room temperature for 6 hours. The organic phase was separated and washed with an aqueous solution of Na2S2O3 (1.0 M, 300 mL), a 5% saturated aqueous solution of NaHCO3, and water. After drying and evaporation on MgSO4, the compound was obtained in the desired viscous orange oil form (35.3 g, 98%). 1H NMR (400MHz, CDCl3, 25℃): δ7.69(s,1H,Ph),4.02(s,3H,OMe),3.34-3.25(m,1H,2H-ind) ,2.77-2.57(m,2H,3H-ind),1.39(s,9H,t-Bu-Ph),1.31(dd,J=7.5,1.6,3H,2-CH3-ind).

[0303]

[0304] 6-(tert-butyl)-5-methoxy-2-methyl-4-phenyl-1-indanone: Pd(OAc)2 (0.11 g, 3% mol) and [(tBu)3PH]BF4 (0.29 g, 6% mol) were added to a mixture of 4-bromo6-(tert-butyl)-5-methoxy-2-methyl-1-indanone (5.1 g, 0.017 mol), phenylboronic acid (2.82 g, 0.023 mol), 1,2-dimethoxyethane (60 mL), K2CO3 (6.39 g, 0.046 mol), and water (20 mL) under argon purging. The reaction mixture was refluxed overnight. The reaction mixture was then poured into water (200 mL) and extracted with CH2Cl2 (3 × 100 mL). The combined organic phases were washed with an aqueous solution of water and Na2CO3 (2.0 M, 100 mL), dried with MgSO4, and evaporated under reduced pressure to give an orange liquid (5.3 g, 83%). 1 H NMR (400MHz, CDCl3, 25℃): δ7.76(s,1H,o-(t-Bu)-Ph),7.51-7.39(m,5H,4-Ph-ind),3.29(s,3H,OMe),3.14(ddd,J=17.4,7.9,5.5,1H,2-Me-in d), 2.64 (dd, J = 11.4, 7.5, 3.8, 1H, 3H-ind), 2.48 (ddd, J = 17.4, 11.6, 4.0, 1H, 2H-ind), 1.43 (s, 9H, t-Bu), 1.25 (dd, J = 7.4, 1.7, CH3, 2-Me-ind).

[0305]

[0306] 6-tert-Butyl-5-methoxy-4-phenyl-2-phenyl-1H-indene: 6-(tert-Butyl)-5-methoxy-2-methyl-4-phenyl-1-indene (6.3 g, 0.0204 mol) was dissolved in Et₂O (40 mL) and added dropwise at 0 °C to a mixture of LiAlH₄ (0.39 g, 0.010 mmol) in Et₂O (50 mL). After stirring for 1 hour, water (50 mL) and 5% w / v HCl aqueous solution (10 mL) were added, and the organic phase was separated, washed with an aqueous solution of Na₂CO₃ (2.0 M, 200 mL), dried over MgSO₄, and evaporated. The residue was dissolved in toluene (60 mL), p-TSA (0.28 g, 9% mol) was added, and the resulting mixture was refluxed for 30 min, cooled, washed with water, dried over MgSO₄, and evaporated. The brown oil was obtained and purified by rapid column chromatography (Al2O3-petroleum ether) to give the desired product (2.8 g, 48%) as a colorless viscous oil. 1 H NMR (400MHz, CDCl3, 25℃): δ7.51-7.41(m,4H,4-Ph-ind),7.38-7.31(m,1H,o-(t-Bu)Ph),7.22(s,1H,4-Ph-ind),6. 46-6.31(m,1H,1H-ind),3.22(s,3H,OMe),3.13(s,2H,2H-ind),2.10-2.04(m,3H,2(CH3)-ind),1.44(s,9H,t-Bu).

[0307]

[0308] (1,2,3,4-Tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)-dimethylsilane (proligand C) OMe，tBu6-tert-butyl-5-methoxy-4-phenyl-2-methyl-1H-indene (0.62 g, 0.0021 mol) was dissolved in anhydrous Et₂O (20 mL) and cooled at -78 °C. n-BuLi (0.93 mL of 2.26 M solution in hexane, 0.0021 mol) was added to this solution via syringe, and the temperature was raised to room temperature. The solution changed color from colorless to orange, and the product precipitated as a yellow solid. The resulting mixture was stirred overnight. CuCN (0.076 g, 0.00084 mol) was added at -25 °C. After stirring for 10 minutes, 5-(chlorodimethylsilyl)-1,2,3,4-tetramethyl-1,3-cyclopentadiene (0.45 g, 0.0021 mol, 1 equivalent) was added dropwise at the same temperature, and the resulting mixture was allowed to warm at room temperature and stirred overnight. The mixture was poured into water (30 mL), the organic layer was separated, and the aqueous layer was extracted with Et2O (2 x 30 mL). The combined organic phases were dried with Na2SO4 and then evaporated to dryness to give a yellow viscous oil (0.90 g, 91%), which was used without further purification. 1 H NMR (300MHz, CDCl3, 25℃): δ7.53-7.30(m,5H,4-Ph-ind),6.41(t,J=1.5,1H,3H-ind),3.58(s,1H,1H-ind),3.23(s ,3H),2.16(d,J=1.3,3H),1.99(d,J=7.7,9H),1.87-1.77(m,10H),1.44(s,11H,tBu),-0.24(d,J=3.2,6H,Si-CH3).

[0309]

[0310] Catalyst 1: C OMe,tBu -ZrCl2(1,2,3,4-tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)-dimethylsilane-zirconium dichloride-(IV): n-BuLi (2.30 mL of 2.26 M solution in hexane, 0.0052 mol) was added dropwise to the preligand C at -78 °C. OMe，tBuA solution of 1.00 g (0.0026 mol) in Et₂O (30 mL) was prepared and stirred overnight. ZrCl₄ (0.61 g, 0.0026 mol, 1 equivalent) was added to this solution at -78 °C, and the resulting mixture was allowed to heat and stir overnight at room temperature. The mixture was evaporated to dryness, and dichloromethane / heptane (40 mL, 1:1 volume / volume) was added. The precipitated LiCl was filtered through a cannula to give an orange solution. The latter was concentrated to approximately 1 / 3 volume, and the resulting yellow microcrystalline powder was separated from the solution by cannula filtration and then dried under vacuum (0.60 g, 50%). 1 H NMR (400MHz, CD2Cl2, 25℃): δ7.64(s,2H), 7.46(q,J=7.4,6.3,4H), 7.41-7.32(m,1H), 6.59(s,1H,H of Cp ring), 3.34(s,3H,OMe-ind),2. 20(s,3H,C-CH3),2.05(s,3H,Cp-CH3),1.99(s,3H,Cp-CH3),1.90(d,J=5.5,6H,Cp-CH3),1.20(s,3H,Si-CH3),1.09(s,3H,Si-CH3). 13 C10 NMR (400MHz, CD2Cl2, 25℃): δ 159.24, 143.04, 137.26, 135.22, 135.06, 134.56, 129.77, 128.40, 127.44, 127.20, 126.28, 121.86, 121.41, 119.70, 93.88, 82.60, 62.29, 35.60, 30.09, 17.89, 15.83, 15.33, 12.26, 11.91, 2.77. For C10 NMR... 32 H 40 The calculated piASAP of Cl2OSiZr is 628.1273, and the m / z is found to be 630.1266.

[0311]

[0312] Comparative Example 1C:

[0313] Comparative catalyst 1C (Comp 1C) was prepared as described below and is shown in Scheme 2.

[0314]

[0315] 2-Bromo-4-tert-butyltoluene: Bromine (8.3 mL, 0.16 mol) was slowly added to a solution of 4-tert-butyltoluene (20.0 g, 0.14 mol) in glacial acetic acid (62 mL) at room temperature, and the solution was then stirred at 50 °C for 4 days. The reaction mixture was allowed to cool at room temperature, and then water (200 mL) and an aqueous solution of Na₂S₂O₃ (1.0 M, 200 mL) were added. The aqueous phase was extracted with Et₂O (2 × 250 mL). The combined organic phases were washed with water, dried over Na₂SO₄, evaporated and distilled (90 °C / 0.05 mbar) to obtain the desired compound (24.4 g, 77%) in the form of a yellow liquid. 1 H NMR (300MHz, CDCl3, 25℃): δ7.26(s,1H,o-PhBr),6.94(dd,J=7.9,2.0,1H,o-Ph (t-Bu)), 6.87 (d, J = 8.0, 1H, m-Ph (t-Bu)), 2.08 (s, 3H, CH3), 1.02 (s, 9H, t-Bu).

[0316]

[0317] 2-Bromo-4-tert-butylbenzene bromide: A magnetically stirred mixture of 2-bromo-4-tert-butyltoluene (14.0 g, 0.062 mol), N-bromosuccinimide (11.0 g, 0.062 mol), and benzoyl peroxide (45.0 mg, 0.0002 mol) in α,α,α-trifluorotoluene (90 mL) was refluxed overnight. The mixture was cooled, and the succinimide formed was removed by filtration. The filtrate was rotary evaporated and distilled (0.06 mbar, 75–84 °C) to give a yellow liquid (13.1 g, 70%). 1 H NMR (300MHz, CDCl3, 25℃): δ7.58(d,J=1.9,1H,o-PhBr),7.39(d,J=8.1,1H,o-Ph(t-Bu)),7 .32(dd,J=8.1,1.9,1H,m-Ph(t-Bu)), 4.60(s,2H,allylic-H2), 1.31(d,J=2.5,9H,t-Bu).

[0318]

[0319] 2-(2-Bromo-4-tert-butylbenzyl)-2-methylmalonate: Diethyl-2-methylmalonate (5.42 g, 0.031 mol) was slowly added to a suspension prepared by dispersing NaH (0.821 g, 0.034 mol) in anhydrous THF (40 mL) at -30 °C, and then stirred for 1 hour. 2-Bromo-4-tert-butylbromobenzene (10.0 g, 0.0327 mol) dissolved in anhydrous THF (10 mL) was added at 0 °C, stirred for 1 hour, and then stirred under reflux for 16 hours. The precipitated NaBr was filtered off silica, and the filtrate was concentrated to give a yellow oil (12.0 g, 96%). 1 ¹H NMR (300MHz, CDCl₃, 25℃): δ 7.52 (d, J = 2.0, 1H, o-PhBr), 7.20 (dd, J = 8.1, 2.1, 1H, Ph(t-Bu)), 7.07 (d, J = 8.1, 1H, Ph(Me-malonate)), 4.21 (qd, J = 7.1, 1.9, 4H, OCH₂), 3.47 (s, 2H, CH), 1.38 (s, 3H, CH₃), 1.33–1.21 (m, 15H, (CH₃)₃, O-CH₃).

[0320]

[0321] 3-(2-bromo-4-tert-butylbenzyl)-2-methylmalonic acid: 2-(2-bromo-4-tert-butylbenzyl)-2-methylmalonic acid ester (12.0 g, 0.03 mol) was added together with H₂O / MeOH (70 mL, 1:1 volume / volume) and NaOH (4.80 g, 0.12 mol), and the resulting mixture was heated under reflux overnight. Then, H₂O (30 mL) and 12 M HCl to pH 1 were added to the reaction mixture to precipitate an orange viscous oil. This orange viscous oil was dissolved in CH₂Cl₂ (100 mL) and washed with water. A white solid began to precipitate from the solution. After evaporation of the solvent, petroleum ether (150 mL) was added to precipitate a white solid (5.6 g, 55%). 1 H NMR (300MHz, THF-d8, 25°C): δ7.56 (t, J = 1.1, 1H, o-PhBr), 7.24 (d, J = 1.1, 2H, Ph), 3.43 (s, 2H, CH), 1.27 (m, J = 3.6, 12H, (CH3) 3, CH3).

[0322]

[0323] 3-(2-bromo-4-tert-butylphenyl)-2-methylpropionic acid: 3-(2-bromo-4-tert-butylbenzyl)-2-methylmalonic acid was heated in air under reflux at 160°C for 4 hours to obtain a highly viscous yellow oil (4.88 g, 99%). 1 HNMR (300MHz, THF-d8, 25℃): δ7.55 (d, J=2.0, 1H, o-PhBr), 7.27 (dd, J=8.0, 2.0, 1H,Ph),7.19(d,J=8.1,1H,Ph),3.18-3.03(m,1H,CH),2.84-2.64(m,2H,allylic CH2),1.28(s,9H,(CH3)3),1.16-1.07(m,3H,CH3).

[0324]

[0325] 3-(2-bromo-4-tert-butylphenyl)-2-methylpropionyl chloride: 3-(2-bromo-4-tert-butylphenyl)-2-methylpropionic acid (4.88 g, 0.016 mol) was dissolved in CH₂Cl₂ (5 mL), and then thionyl chloride (5.82 g, 0.049 mol) was added dropwise at 0 °C. After complete addition, the resulting solution was stirred overnight under reflux at 40 °C. Excess thionyl chloride was removed under vacuum, leaving a yellow liquid, which was dried under vacuum overnight (5.0 g, 96%). 1 H NMR (300MHz, CDCl3, 25℃): δ7.56(d,J=2.0,1H,o-PhBr),7.30-7.23(m,1H,Ph),7.15(d,J=8 .0,1H,Ph),3.40-3.20(m,2H,CH2),2.91-2.75(m,1H,CH),1.40-1.25(m,12H,(CH3)3,CH3).

[0326]

[0327] 4-Bromo-6-tert-butyl-2-methyl-1-indanone: A solution of 3-(2-bromo-4-tert-butylphenyl)-2-methylpropionyl chloride (4.95 g, 0.016 mol) in CH2Cl2 (20 mL) was slowly added dropwise at 0 °C to a suspension in which AlCl3 (2.52 g, 0.19 mol) was dispersed in CH2Cl2 (20 mL) for 30 minutes. The resulting mixture was heated and stirred under reflux for 3 hours, cooled to room temperature, and poured into ice water (150 mL). The organic layer was separated, and the aqueous phase was extracted with Et2O (3 × 100 mL). The combined extracts were dried over K2CO3, then over Na2SO4, and evaporated to dryness to give a yellow solid (3.54 g, 80%). 1 H NMR (300MHz, CDCl3, 25℃): δ7.80(d,J=1.7,1H,o-PhBr),7.72(d,J=1.7,1H,Ph),3.31(dd,J= 17.5,7.8,1H,2-(CH3)-ind),2.84-2.53(m,2H,3H-ind),1.32(m,J=6.3,12H,(CH3)3,CH3).

[0328]

[0329] 4-Phenyl-6-tert-butyl-2-methyl-1-indanone: Pd(OAc)₂ (0.085 g, 3% mol) and PPh₃ (0.20 g, 6% mol) were added to a homogenized mixture of 4-bromo-6-tert-butyl-2-methyl-1-indanone (3.54 g, 0.013 mol), PhB(OH)₂ (2.15 g, 0.018 mol), K₂CO₃ (4.90 g, 0.035 mol) in 1,2-dimethoxyethane (42 mL), and water (14 mL). This mixture was then poured into water (200 mL) and extracted with CH₂Cl₂ (3 × 100 mL). The combined organic phases were washed with an aqueous solution of water and Na₂CO₃ (2 M, 100 mL), dried over Na₂SO₄, and evaporated. The crude product was extracted with hexane (200 mL), and the evaporation was evaporated under vacuum to give a viscous red oil (3.40 g, 96%). 1H NMR (300MHz, CDCl3, 25℃): δ7.80(d,J=1.9,1H,o-Ph-ind),7.66(d,J=1.9,1H,o-tBu-Ph),7.50-7.46(m,5H,4- Ph-ind),3.46-3.31(m,1H,2H-ind),2.80-2.65(m,2H,3H-ind),1.39(s,9H,(CH3)3),1.31(d,J=7.2,3H,CH3).

[0330]

[0331] 4-Phenylacetyl-6-tert-butyl-2-methyl-1H-indene: 4-Phenylacetyl-6-tert-butyl-2-methyl-1-indene (3.40 g, 0.012 mol) was dissolved in Et₂O (20 mL) and LiAlH₄ (0.23 g, 0.0061 mol) was added dropwise to Et₂O (50 mL) at 0 °C. After stirring for 1 hour, water (40 mL) and 5% HCl aqueous solution (10 mL) were added, and the organic phase was separated. The mixture was washed with an aqueous solution of Na₂CO₃ (2.0 M, 100 mL), dried with MgSO₄, and evaporated. The residue was dissolved in toluene (50 mL), p-TSA (0.21 g, 9% mol) was added, and the resulting mixture was refluxed for 20 minutes, cooled, washed with water, dried with Na₂SO₄, and evaporated to obtain a brown oil, which was crystallized at 0 °C (2.80 g, 88%). 1 H NMR (300MHz, CDCl3, 25℃): δ7.60-7.53(m,2H),7.52-7.42(m,3H),7.41-7.31(m,2H),6.54(br,s,J =1.6,1H,1H-ind),3.36(dd,J=1.6,0.8,2H,2H-ind),2.18-2.11(m,3H,CH3),1.40(s,9H,(CH3)3).

[0332]

[0333] (1,2,3,4-Tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenyl-6-tert-butyl-indenyl)-dimethylsilane (proligand C) tBu6-tert-butyl-4-phenyl-2-methyl-1H-indene (2.40 g, 0.0092 mol) was dissolved in anhydrous Et₂O (40 mL) and cooled at -78 °C. n-BuLi (4.05 mL of a 2.26 M solution in hexane, 0.0092 mol) was added to the solution via syringe, and the temperature was raised to room temperature. The resulting mixture was stirred overnight. Conch (0.33 g, 0.0037 mol) was then added at -25 °C. After stirring for 10 minutes, 5-(chlorodimethylsilyl)-1,2,3,4-tetramethyl-1,3-cyclopentadiene (1.67 g, 0.0092 mol) was added dropwise at the same temperature, and the resulting mixture was allowed to warm at room temperature and stirred overnight. The mixture was poured into water (50 mL), the organic layer was separated, and the aqueous layer was extracted with ether (2 x 50 mL). The combined organic phases were dried with Na2SO4 and then evaporated to dryness to give a yellow viscous oil (3.80 g, 94%), which was used without further purification. 1 H NMR (300MHz, CDCl3, 25℃): δ7.65-7.20(m,9H),6.78-6.67(m,1H,3H-ind),3.67(d,J=3.5,1H,1H-ind),3.24(s,1H ), 2.22 (s, 4H), 2.01 (d, J = 13.0, 8H), 1.89-1.75 (m, 8H), 1.38 (d, J = 4.1, 11H), -0.26 (dd, J = 11.2, 2.4, 6H, Si-CH3).

[0334]

[0335] Comp 1C:C tBu -ZrCl2(1,2,3,4-tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenyl-6-tert-butyl-indenyl)-dimethylsilane-zirconium dichloride-(IV): n-BuLi (2.00 mL of 2.26 M solution in hexane, 0.0045 mol) was added dropwise to the preligand C at -78 °C. tBuA solution of 1.00 g (0.0023 mol) in Et₂O (15 mL) was prepared and stirred overnight. ZrCl₄ (0.53 g, 0.0023 mol) was added to this solution at -80 °C, and the resulting mixture was allowed to warm to room temperature while stirring overnight. The mixture was evaporated to dryness, and dichloromethane / heptane (40 mL, 1:1 volume / volume) was added. The precipitated LiCl was filtered through a sleeve to give an orange solution. The latter was concentrated to approximately 1 / 3 volume, and the resulting yellow microcrystalline powder was separated from the solution by filtration through a sleeve and then dried under vacuum (0.62 g, 45%). 1 H NMR (400MHz, CD2Cl2, 25℃): δ7.68(d,J=7.6,2H),7.54-7.43(m,4H),7.40(d,J=7.2,2H),6.94(s,1H,H of Cp ring),2.28(s,3H,C-CH3 ),2.07(s,3H,Me-Cp),2.00(s,3H,Me-Cp),1.91(d,J=14.9,6H,Me-Cp),1.31(s,10H,tBu),(1.24(s,3H),1.11(s,3H),Si-CH3). 13 C10 NMR (400MHz, CD2Cl2, 25℃): δ 147.66, 140.26, 137.42, 137.08, 134.78, 134.60, 131.60, 128.61, 128.48, 127.53, 127.48, 126.53, 125.78, 120.41, 118.99, 94.15, 83.19, 34.93, 30.51, 17.90, 15.93, 15.35, 12.24, 11.94, 2.89, 2.86. For C10 NMR... 31 H 38 The calculated piASAP of Cl2SiZr is 598.1167, and the m / z is found to be 600.1155.

[0336]

[0337] Comparative Example 2C:

[0338] The comparative catalyst 2C (Comp 2C) is prepared as described below:

[0339] 2-Methyl-4-phenylindene: Phenylboronic acid (3.27 g, 0.027 mol) was dissolved in DME / H₂O (64.0 mL, 3:1 v / v) and transferred to a Schlenk flask. 4-Bromo-2-methyl-1H-indene (4.00 g, 0.019 mol) and K₂CO₃ (7.40 g, 0.054 mol) were then added to the Schlenk flask. The mixture was stirred and placed under Ar. Pd(OAc)₂ (0.13 g, 3% mol) and PPh₃ (0.30 g, 6% mol) were then added, and the mixture was refluxed for 16 hours. The reaction mixture was then poured into water and extracted with CH₂Cl₂ (3 × 100 mL). The combined organic phases were washed with water (3 × 100 mL) and an aqueous solution of Na₂CO₃ (2 M, 100 mL), dried on MgSO₄, and evaporated. The crude product was extracted with hot hexane (200 mL) to obtain an orange oil (3.53 g, 90%) after evaporation of the volatiles. The orange oil was purified by column chromatography (elution system: 95:5 v / v hexane / EtOAc) to give the desired compound (2.60 g, 66%) in the form of a colorless viscous liquid. 1 ¹H NMR (300MHz, CDCl₃, 25℃): δ 7.55 (tt, J = 6.4, 1.5, 2H, o-Ph), 7.51–7.42 (m, 2H, m-Ph), 7.42–7.33 (m, 2H, o-, m-Ph-indene), 7.33–7.24 (m, 1H, p-Ph), 7.24–7.13 (m, 1H, p-Ph-indene), 6.63 (ddq, J = 39.7, 3.1, 1.6, 1H, 3H-indene), 3.40 (dq, J = 2.8, 1.0, 2H, 1H-indene), 2.17 (dd, J = 2.8, 1.5, 3H, CH₃).

[0340]

[0341] (1,2,3,4-Tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenylindenyl)-dimethylsilane (proligand C) H2-Methyl-4-phenylindene (4.30 g, 0.021 mol) was dissolved in anhydrous Et₂O (50 mL) and cooled at -78 °C. n-BuLi (9.2 mL of a 2.26 M solution in hexane, 0.021 mol, 1 equivalent) was added to this solution via syringe, and the temperature was raised to room temperature. From the first drop of n-BuLi, the color of the solution changed from yellow to orange, and the product precipitated as a yellow solid. The resulting mixture was stirred overnight. CuCN (0.75 g, 0.083 mol) was added at 25 °C. After stirring for 10 minutes, 5-(chlorodimethylsilyl)-1,2,3,4-tetramethyl-1,3-cyclopentadiene (4.48 g, 0.021 mol, 1 equivalent) was added dropwise at the same temperature, and the resulting mixture was allowed to warm to room temperature and stirred overnight. The mixture was poured into water (100 mL), the organic layer was separated, and the aqueous layer was extracted with diethyl ether (2 x 70 mL). The combined organic phases were dried over Na2SO4 and then evaporated to dryness to give a yellow viscous oil (7.2 g, 90%), which was used without any purification.

[0342]

[0343] Comp 2C:C H -ZrCl2(1,2,3,4-tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenylindenyl)-dimethylsilane zirconium dichloride-(IV): n-BuLi (2.30 mL of 2.26 M solution in hexane, 0.0052 mol) was added dropwise to the preligand C at -78 °C. H A solution of 1.00 g (0.0026 mol) of LiCl was prepared in 30 mL of Et₂O, and the resulting mixture was stirred overnight. ZrCl₄ (0.61 g, 0.0026 mol) was added to this solution at -80 °C, and the resulting mixture was allowed to warm at room temperature while stirring overnight. The mixture was evaporated to dryness, and dichloromethane / heptane (40 mL, 1:1 volume / volume) was added. The precipitated LiCl was filtered through a sleeve to give an orange solution. The latter was concentrated to approximately 1 / 3 volume; a yellow microcrystalline powder was formed, which was separated from the solution by filtration through a sleeve and then dried under vacuum (0.60 g, 42%). 1H NMR (400MHz, CDCl3, 25℃): δ7.71-7.65(m,2H),7.57(d,J=8.7Hz,1H),7.46(t,J=7.5,3H),7.37(t,J=7.4,2H),7.31 (s,1H),7.09-7.02(m,2H),2.30(s,3H),2.09(s,3H),2.01(s,3H),1.92(d,J=10.2,6H),1.22(s,3H),1.11(s,3H). 13 C10 NMR (500MHz, CD2Cl2, 25℃): δ 139.87, 137.85, 135.52, 134.61, 133.73, 128.62, 128.50, 128.31, 127.85, 127.61, 125.96, 125.67, 124.66, 94.49, 83.87, 18.03, 15.71, 15.44, 12.27, 11.89, 2.82, 2.73. For C10 NMR... 27 H 30 The calculated piASAP of Cl2SiZr is 542.0541, and the m / z is found to be 544.0535.

[0344]

[0345] Catalyst 2:

[0346] Catalyst 2 was prepared as described below and is shown in Scheme 3.

[0347]

[0348] 1,3-Di-tert-butyl-2-methoxybenzene: Under an Ar atmosphere, barite (74.0 g, 0.23 mol) and CH3I (36.0 mL, 0.58 mol) were successively added to 2,6-di-tert-butylphenol (50.0 g, 0.18 mol) in degassed anhydrous DMF (300 mL). The reaction mixture was stirred overnight. Then Et2O (300 mL) was added. The organic layer was extracted with H2O (500 mL), an aqueous solution of NaOH (1.0 M, 300 mL), and H2O (2 x 400 mL). The combined extracts were dried over MgSO4 and concentrated under vacuum. The crude residue was purified by distillation (123 °C, 3 mbar) to give an orange crystalline solid (30.0 g, 58%). 1 H NMR (300MHz, CDCl3, 25°C): δ7.34 (s, 2H), 3.69 (s, 3H), 1.42 (s, 18H).

[0349]

[0350] 3,5-Di-tert-butyl-4-methoxyphenyl)boronic acid: 30.0 g (0.1 mol) of 4-bromo-2,6-di-tert-butylanisole was added to a three-necked round-bottom flask, which was purged with nitrogen for 10 minutes. Anhydrous THF (400 mL) was added via a sleeve, the solution was cooled to -78 °C, and n-BuLi (48.0 mL of 2.5 M solution in hexane, 0.12 mol, 1.2 equivalent) was added dropwise via a syringe. The solution was stirred at -78 °C for 1 hour. Then, (iPrO)3B (56.0 mL, 0.3 mol) was slowly added via a syringe, allowing the reaction to proceed warm and stirring overnight to obtain a milky yellow solution. Solid NH4Cl was added to the solution to quench the excess n-BuLi, followed by dropwise addition of 1 M aqueous HCl to adjust the pH to 6.5, and finally dropwise addition of 6 M HCl to pH 1. The reaction layers were separated, and the aqueous layer was extracted with dichloromethane. The combined organic layers decreased in volume under vacuum, and a yellowish-white solid precipitated, which was then diluted in dichloromethane. Excess heptane was then added, and the mixture was stored in a freezer for one day. A solid formed and was filtered. This step was repeated twice. The desired product was obtained (18.0 g, 68%). 1 H NMR (400MHz, CDCl3, 25°C): δ8.16 (s, 2H), 3.76 (s, 3H), 1.52 (s, 18H).

[0351]

[0352] 3,5-Di-tert-butyl-4-methoxyphenyl-1-indanone: Pd(OAc)₂ (0.13 g, 3% mol) and RuPhos (0.53 g, 6% mol) were added to a well-mixed mixture of 4-bromo-6-(tert-butyl)-5-methoxy-2-methyl-1-indanone (previously purified by column chromatography) (5.9 g, 0.019 mol), 3,5-di-tert-butyl-4-methoxyphenyl)boronic acid (8.0 g, 0.03 mol), K₃PO₄ (12.0 g, 0.057 mol) in THF (72 mL) and water (14 mL) under Ar rinsing. The reaction mixture was refluxed overnight. The reaction mixture was then poured into water (100 mL) and extracted with CH₂Cl₂ (3 × 100 mL). The combined organic phases were washed with water (200 mL) and an aqueous solution of Na₂CO₃ (2 M, 200 mL), dried over MgSO₄, and evaporated under vacuum. A concentrated solution of the crude product in dichloromethane was then prepared, and the desired product was precipitated as a white solid by adding excess hexane (6.0 g, 70%). 1H NMR (300MHz, CDCl3, 25℃): δ7.73(s,1H,ind-ArH),7.27(s,2H,Ar-H),3.75(d,J=4.8,3H,4-(OMe)-Ph),3.25(s,3H,OMe-ind ), 3.18 (dd, J = 17.4, 7.8, 1H, 2H-ind), 2.76-2.37 (m, 2H, 3H-ind), 1.44 (d, J = 10.1, 29H, tBu), 1.27 (d, J = 7.4, 3H, ind-CH3).

[0353]

[0354] 3,5-Di-tert-butyl-4-methoxyphenyl-1-indene: 3,5-Di-tert-butyl-4-methoxyphenyl-1-indene was dissolved in THF (100 mL) and added dropwise at 0 °C to a mixture of LiAlH4 (0.25 g, 6.7 mol) in THF (50 mL). After stirring for 1 hour, water was slowly added, followed by 5 wt% HCl aqueous solution (20 mL). The organic phase was separated, washed with an aqueous solution of Na2CO3 (5 wt%, 100 mL), dried over MgSO4, and evaporated. The residue was dissolved in toluene (80 mL), p-TSA (0.23 g, 9% mol) was added, and the resulting mixture was refluxed for 30 minutes, cooled, washed with water, dried over MgSO4, and evaporated to obtain a white crystalline solid (5.2 g, 89%). 1 H NMR (400MHz, CDCl3, 25℃): δ7.37(s,2H),7.21(s,1H),6.45(q,J=1.5,1H,1H-ind),3.74(s,3H,-OCH3),2.10-2.07(m,3H C-CH3), 1.45 (d, J = 7.2, 28H, tBu).

[0355]

[0356] (1,2,3,4-Tetramethyl-1,3-cyclopentadienyl)-[2-methyl-4-(3,5-di-tert-butyl-4-methoxy)-6-tert-butyl-indene]-dimethylsilane (preligand C1[di-tBu,OMe)-Ph]): Starting with 3,5-di-tert-butyl-4-methoxyphenyl-1-indene (0.54 g, 0.00012 mmol), the same experimental procedure as for the ligands used in the previous synthesis was followed. A yellow viscous oil was obtained, which was used in the next step without further purification (0.85 g, 98%). 1H NMR (400MHz, CDCl3, 25℃): δ7.35(d,J=9.4,3H),6.46(s,1H),3.74(d,J=3.0,5H),3.56(s,1H),3.18(s,4H),2.17(d,J=1.3, 3H), 2.06-1.93 (m, 9H), 1.84 (td, J = 7.4, 4.6, 11H), 1.44 (d, J = 11.0, 34H), 0.07 (s, 1H), -0.06 (s, 2H), -0.23 (d, J = 4.7, 6H).

[0357]

[0358] Cata 2: C1[(di-tBu,OMe)-Ph]-ZrCl2(1,2,3,4-tetramethyl-1,3-cyclopentadienyl))-[2-methyl-4-(3,5-di-tert-butyl-4-methoxy)-6-tert-butyl-indenyl]-dimethylsilane-zirconium dichloride-(IV): Using a procedure similar to that described above for other metallocene complexes, the complex C1[(ditBu,OMe)-Ph]-Zr was synthesized from the preligand C1[(tBu)2,OMe-Ph] (0.80 g, 1.31 mmol) and isolated as a yellow microcrystalline powder (0.32 g, 30%). 1 H NMR (400MHz, CDCl3, 25℃): δ7.41(s,3H),6.67(s,1H,H of Cp ring),3.73(s,3H,ind-OCH3),3.32(s,3H,4-(OMe)-Ph),2.22(s,3H,C-CH3),2.0 4(d,J=17.9,6H,Cp-CH3), 1.91(d,J=12.4,6H,Cp-CH3), 1.43(s,21H,tBu), 1.36(s,9H,tBu), 1.19(s,3H,Si-CH3), 1.07(s,3H,Si-CH3). 13 CNMR (101MHz, CDCl3, 25℃): δ 159.47, 158.61, 143.37, 137.35, 135.89, 135.00, 134.72, 131.19, 127.31, 126.97, 126.75, 121.91, 120.73, 120.13, 93.80, 82.45, 64.44, 62.22, 35.87, 32.47, 32.05, 30.51, 22.86, 18.34, 16.10, 15.65, 14.28, 12.66, 12.35, 3.25, 3.14. For C 41 H 58The calculated piASAP of Cl2O2SiZr is 770.2625, and the m / z is found to be 772.2628.

[0359]

[0360] Reference 1:

[0361] Racemic-cyclohexyl(methyl)silane dimethylbis[2-methyl-4-(4'-tert-butylphenyl)indenyl]zirconium dichloride (Ref 1) was purchased from SPCI (South Pacific Chemical Industries) (CAS 888227-55-2).

[0362]

[0363] B. Heterogeneous polymerization of propylene

[0364] All catalysts have been loaded onto Radley devices using the ACM method, as described below:

[0365] 20.011 g of dry silica (TS-F202) was suspended in 200 mL of anhydrous toluene and stirring was initiated. 38 mL of MAO (30 wt%) was added dropwise to deposit 16 wt% Al. Another 87 mL of anhydrous toluene was added, and the mixture was heated at 110 °C for 4 hours. The mixture was then filtered, and the solid was washed three times with both anhydrous toluene and anhydrous pentane, and then dried. Metallocene (approximately 10 mg, to achieve 1.25 wt% of supported metallocene) was dissolved in 5 mL of anhydrous toluene. 8 g of silica / MAO (prepared as described above) was added, the glassware was washed with 5 mL of anhydrous toluene, and then added to the mixture. The mixture was stirred at room temperature for 3 hours, and then filtered. The solid was washed three times with anhydrous toluene and three times with anhydrous pentane, and then dried under vacuum. The supported catalyst was then dispersed in anhydrous oil (Finavestan A 360B) to have a solids content of about 20% by weight.

[0366] The zirconium and aluminum content (wt%) of the samples were analyzed using ICP-AES spectrometry. The ICP-AES analysis results of the supported catalysts are shown in Table 3.

[0367] Table 3

[0368]

[0369]

[0370] Homopolymer PPH.

[0371] The 8-liter reactor was heated to 130°C and flushed with N2 before use. The reactor was then flushed with 1 L of propylene and cooled to 40°C. Unless otherwise specified, the reaction conditions were as listed in Table 4. Subsequently, 3 L of propylene was added to the reactor along with the required amount of H2. Stirring was initiated, and once the reactor stabilized, 1 mL of a mixture of TIBAL, the supported catalyst, and the co-catalyst was injected into the reactor along with 1.5 L of propylene. The reactor was then heated to 70°C, and once this temperature was reached, the reaction was allowed to proceed for 1 hour. The reactor was then vented, and the polymer was dried under a light N2 stream. The polymer was then collected and allowed to dry even further for 2 hours.

[0372] Table 4

[0373] <![CDATA[H2]]> 0.5 NL <![CDATA[Propylene (C3)]]> 4.5 L temperature 70℃ time 1 hour

[0374] The aggregation results are shown in Table 5.

[0375] Table 5

[0376]

[0377] The comparative example showed rather low activity. Activity increased when the methoxy group was grafted onto the indene group, especially when a second methoxy group was added at position 4 on the benzene ring. This final metallocene was almost as active as Ref 1.

[0378] A low xylene soluble content has been measured.

[0379] DSC and NMR analyses are shown in Table 6.

[0380] Table 6

[0381] Catalyst composition <![CDATA[T m (℃)]]> <![CDATA[T c (℃)]]> [mmmm](%) [2,1-region defects](%) TS-F202 / MAO / Ref1 151 103. 98.1 0.8 TS-F202 / MAO / Comp 2C 147.8 109 91.9 0.2 TS-F202 / MAO / Cata 1 150.7 107 95.4 0.3 TS-F202 / MAO / Comp 1C 144.5 104 91.7 0.3 TS-F202 / MAO / Cata 2 155.2 109 96.6 0.2

[0382] Low levels of regional defects can be observed (compared to bis-indene Ref 1). All these different values ​​of defects along the chain are influenced by melting and crystallization temperatures.

[0383] End information and NMR results are shown in Table 7.

[0384] Table 7

[0385] catalyst Ref 1 Comp 2C Cata 1 Comp 1C Cata 2 1,2C3- 99.09 99.63 99.53 99.42 99.63 2,1C3- 0.81 0.16 0.30 0.33 0.18 1,3C3- 0.03 0.00 0.00 traces 0.00

[0386] Random copolymer PPR.

[0387] Polymerization occurred in an 8-liter reactor at 70°C for 30 minutes in the presence of 15 g ethylene, 0.5 NL hydrogen, and TIBAL as a scavenging agent. Unless otherwise specified, the reaction conditions were as listed in Table 8. The reactor was then vented, and the polymer was placed under a light N2 stream for drying. The polymer was then collected and allowed to dry even further for 2 hours.

[0388] Table 8

[0389] <![CDATA[H2]]> 0.5NL <![CDATA[Propylene (C3)]]> 4.5L <![CDATA[Ethylene (C2)]]> 15g temperature 70℃ time 0.5 hours

[0390] The results of the polymerization reaction are detailed in Table 9.

[0391] Table 9

[0392]

[0393] It can be seen that the ethylene conversion rate is high.

[0394] The results of NMR, GPC and DSC measurements are shown in Table 10.

[0395] Table 10

[0396]

[0397]

[0398] The GPC results shown in Table 10 are consistent with the MFI analysis. The lower melting and crystallization temperatures of the novel metallocene-based PPRs are also significant compared to Ref 1. This is due to the higher ethylene incorporation in the homopolymerization reaction and the lower melting and crystallization temperatures (see above). The higher melting and crystallization temperatures are also significant compared to polymerizations using the comparative catalysts Comp 1C and 2C.

[0399] Compared to the contrast catalysts 1C and 2C, using an indenyl group with an -OR group, such as a methoxy group, allows for increased activity. Higher stereodefects and lower reticulum defects have been observed compared to the Ref 1 catalyst.

[0400] C. Homogeneous polymerization of propylene

[0401] Polymerization was carried out in a 300 mL high-pressure glass reactor equipped with a mechanical stirrer (Pelton turbine) and externally heated by a double-layered hood with a circulating water bath. Toluene (150 mL) and MAO (5000 equivalents of PMAO in toluene, 13% by weight Al) were added to the reactor. After 30 minutes, propylene (5 bar, air liquid, 99.99%) was introduced, and the propylene pressure was subsequently reduced to 1 bar, and a solution of the catalyst precursor in toluene (2.0 μmol, depending on the catalyst MW and concentration) was added via syringe. The propylene pressure was immediately increased to 5 bar (maintained constant using a back regulator), and the solution was stirred for 30 minutes. The temperature inside the reactor was monitored using thermocouples. Polymerization was stopped by venting the vessel and quenching in MeOH with a 10% HCl aqueous solution. The polymer was precipitated in methanol (500 mL) with a 10% HCl solution. The polymer was collected by filtration, washed with methanol (200 mL), and dried under vacuum (60 °C, 3 h).

[0402] The results of the aggregation are shown in Table 11.

[0403] Table 11

[0404]

[0405]

[0406] D. Multiphase polymerization of ethylene

[0407] The polymerization reaction was carried out in a 132 ml autoclave equipped with a stirrer, temperature controller, and inlets for ethylene and hydrogen feed. The reactor was dried with nitrogen at 110 °C for 1 hour and then cooled to 40 °C.

[0408] All polymerizations were carried out under the conditions described in Table 12 (unless otherwise noted). The reactor was loaded with 75 ml of isobutane, 1.6 ml of 1-hexene, and pressurized with ethylene at 23.8 bar and 800 ppm hydrogen. A catalyst (3.5 mg) and a co-catalyst were added. Polymerization was initiated upon injection of the catalyst suspension, carried out at 85°C, and stopped by depressurization of the reactor after 60 minutes. The reactor was purged with nitrogen before restarting.

[0409] Table 12

[0410] condition unit reactor Isobutane (iC4) L 0.075 Triisobutylaluminum (TIBAL) ppm 100 hydrogen ppm 800 temperature ℃ 85 Ethylene pressure -bar 23.8

[0411] The aggregation results are shown in Table 13.

[0412] Table 13

[0413] catalyst Comp 2C Cata 1 Comp 1C Reference 1 Cata 2 active (g / g / h) 1000 1022 714 1498 847 active (kg / mmol / h) 50 56 37 105 62 <![CDATA[MI2]]> (g / 10 minutes) 0.79 1.35 HLMI (g / 10 minutes) 1.69 <![CDATA[M w ]]> (g / mol) 106064 119851 83679 231534 88979 <![CDATA[M w / M n ]]> 4 3.8 3.5 5.7 3.4 <![CDATA[T m ]]> (℃) 133 134 132 133 133

Claims

1. Catalyst of Formula (I) (I) Where R 2 R 3 R 6 R 7 Each is independently selected from hydrogen or alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, -OR 15 Alkyl aryl, arylalkyl, halogen, Si(R) 12 )3 and heteroalkyl; wherein each of the said groups may be unsubstituted or substituted by one or more substituents Z 1 Replace; where Z 1 Selected from -OR 16 alkyl and alkenyl groups; wherein R 15 R 16 Each is independently selected from alkyl, arylalkyl, alkylaryl, and aryl; And R 4 For not replaced or by one or more Z 1 Substituted aryl, and R 5 For -OR 15 ; R 8 R 9 R 10 R 11 Each is independently selected from hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R) 12 )3 and heteroalkyl; L 1 For SiR 13 R 14 -[CR 13 R 14 ] h -、GeR 13 R 14 or BR 13 Where h is an integer selected from 1, 2, or 3; R 13 and R 14 Each is independently selected from hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R 13 and R 14 The atoms attached to them together form cycloalkyl, cycloalkenyl, or heterocyclic groups; M 1 It is a transition metal selected from zirconium, titanium, hafnium, and vanadium; Q 1 and Q 2 Each is independently selected from halogens, alkyl groups, and -N(R) groups. 17 2. Alkoxy, cycloalkoxy, aryloxy, arylalkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; wherein each R 17 Independently selected from hydrogen, alkyl, Si(R) 12 3. Cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; and Each R 12 It can be hydrogen, alkyl, or alkenyl on its own.

2. The catalyst according to claim 1, wherein... R 2 R 3 R 6 R 7 Each is independently selected from hydrogen or C. 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, -OR 15 C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, halogen, Si(R) 12 )3 and miscellaneous C 1-8 Alkyl group; wherein each of the said groups may be unsubstituted or substituented by one or more substituents. 1 Replace; where Z 1 Selected from -OR 16 C 1-8 Alkyl and C 2-8 alkenyl; each R 12 Independently hydrogen, C 1-8 Alkyl or C 2-8 alkenyl; wherein R 15 R 16 Each was independently selected from C 1-8 Alkyl, C 6-10 Aryl C 1-8 Alkyl, C 7-8 Alkyl C 6-10 Aryl and C 6-10 Aryl; and R in which 4 For not replaced or by one or more Z 1 Substituted aryl, and R 5 For -OR 15 .

3. The catalyst according to claim 1, wherein... R 8 R 9 R 10 R 11 Each is independently selected from hydrogen and C. 1-8 Alkyl, C 2-8 alkenyl, C 3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, C 1-8 Alkoxy, C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, halogen, Si(R) 12 )3 and miscellaneous C 1-8 Alkyl; and each R 12 Independently hydrogen, C 1-8 Alkyl or C 2-8 Alkenyl group.

4. The catalyst according to claim 1, wherein... L 1 For SiR 13 R 14 -[CR 13 R 14 ] h -、GeR 13 R 14 or BR 13 Where h is an integer selected from 1, 2, or 3; R 13 and R 14 Each is independently selected from hydrogen and C. 1-8 Alkyl, C 2-8 alkenyl, C3-8 cycloalkyl, C 5-8 Cycloalkenyl, C 5-8 Cycloalkenyl C 1-8 Alkyl, C 6-10 Aryl, amino C 1-8 Alkyl and C 6-10 Aryl C 1-8 Alkyl; or R 13 and R 14 Together with the atoms they are attached to, they form C 3-8 cycloalkyl, C 5-8 Cycloalkenyl or 3-8 membered heterocyclic groups.

5. The catalyst according to claim 1, wherein... M 1 For zirconium; and Q 1 and Q 2 Each is independently selected from halogens, C 1-8 Alkyl, -N(R) 17 2. C 1-8 Alkoxy, C 3-8 Cycloalkoxy, C 6-10 Aryl C 1-8 Alkoxy, C 3-8 cycloalkyl, C 6-10 Aryl, C 6-10 aryloxy group, C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl and heterocarbon 1-8 Alkyl; wherein each R 17 Independently selected from hydrogen and C 1-8 Alkyl, Si(R) 12 3. C 3-8 cycloalkyl, C 6-10 Aryl, C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl and heterocarbon 1-8 alkyl.

6. The catalyst according to any one of claims 1-5, having formula (II) (II) Where R 2 R 3 R 4 R 15 R 6 R 7 R 8 R 9 R 10 R 11 L 1 M 1 Q 1 Q 2 It has the same meaning as in any one of claims 1-5.

7. The catalyst according to any one of claims 1-5, having formula (III) or (IV), (III) (IV) Where n is an integer selected from 0, 1, 2, 3, or 4; m is an integer selected from 0, 1, 2, or 3; and R 2 R 3 R 15 R 16 R 6 R 7 R 8 R 9 R 10 R 11 L 1 Z 1 M 1 Q 1 Q 2 It has the same meaning as in any one of claims 1-5.

8. The catalyst according to any one of claims 1-5, having formula (V) or (VI), (V) (VI) Where n is an integer selected from 0, 1, 2, 3, or 4; m is an integer selected from 0, 1, 2, or 3; and R 2 R 3 R 15 R 16 R 6 R 7 L 1 Z 1 M 1 Q 1 Q 2 It has the same meaning as in any one of claims 1-5.

9. The catalyst according to any one of claims 1-5, wherein L 1 For SiR 13 R 14 or -[CR 13 R 14 ]-, and R 13 R 14 It has the same meaning as defined in any one of claims 1-5.

10. The catalyst according to any one of claims 1-5, having formula (VII) or (VIII), (VII) (VIII) Where n is an integer selected from 0, 1, 2, 3, or 4; m is an integer selected from 0, 1, 2, or 3; and R 2 R 3 R 15 R 16 R 6 R 7 Z 1 M 1 Q 1 Q 2 It has the same meaning as in any one of claims 1-5.

11. A supported catalyst comprising the catalyst according to any one of claims 1-10, and a support.

12. A catalyst composition comprising: At least one catalyst according to any one of claims 1-10; Optional activator; optional support; and optional co-catalyst.

13. The catalyst composition according to claim 12, wherein the catalyst composition comprises an activator.

14. The catalyst composition according to any one of claims 12-13, comprising an aluminoxane activator; a titanated silica or silica solid support; and optionally a co-catalyst.

15. Use of the catalyst according to any one of claims 1 to 11, or use of the catalyst composition according to any one of claims 12 to 14, said use for the preparation of olefin polymers.

16. An olefin polymerization process, which includes: The catalyst according to any one of claims 1-11 or the catalyst composition according to any one of claims 12-14 is contacted with an olefin monomer, optional hydrogen and optional one or more olefin comonomers. And to polymerize the monomer and the optional one or more olefin comonomers in the presence of at least one of the catalyst compositions and optional hydrogen, thereby obtaining an olefin polymer.

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