New metallocene catalysts and their applications

Abstract

The present invention relates to a compound represented by formula (I) TIFF2024522262000063.tif62114 [R in the formula 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 has the meaning defined in the description and claims. The invention also relates to a catalyst composition comprising at least one catalyst according to the invention, an optional activator; an optional support; and an optional cocatalyst. The invention also relates to the use of the catalyst or catalyst composition according to the invention for the preparation of an olefin polymer. The invention also relates to an olefin polymerization process comprising contacting the catalyst or 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 at least one catalyst composition, and optionally hydrogen, to obtain an olefin polymer. The invention also relates to an olefin polymer and to articles comprising said olefin polymer.

Description

[Technical Field]

[0001] Field of Invention This invention relates to a novel metallocene catalyst. The invention also relates to the use of a novel metallocene catalyst in polymerization reactions. Furthermore, the invention relates to polyolefins obtained using a novel metallocene catalyst, and articles produced therefrom. [Background technology]

[0002] Background of the Invention Metallocene catalysts have been used for many years in the production of polyolefins. Countless academic and patent documents describe the use of these catalysts in olefin polymerization. Although much research has been done in the field of metallocene catalysts, several issues remain, mainly concerning the productivity or activity of the catalysts.

[0003] Metallocene catalysts possess several advantages, such as good functional and optical properties, as well as some peculiarities, such as a narrow distribution. However, polypropylene with high melting temperatures or low melt flow rates is not always readily produced using these catalysts.

[0004] Many metallocene structures were synthesized, some of which allowed for the production of polypropylene with low melt flow rates or high melting temperatures, but had disadvantages in other parameters such as low activity. [Overview of the project]

[0005] Thus, there is room to improve catalytic behavior. Therefore, it is desirable to find a catalyst system that provides highly stable activity and, in addition to the other properties mentioned above, also offers a wide molecular weight range or a higher degree of crystallinity in the final product.

[0006] Summary of the present invention Therefore, the object of the present invention is to provide a new catalyst that avoids the aforementioned drawbacks. In a first embodiment, the present invention relates to formula (I) [Chemical formula] [In the formula, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are each independently selected from the group consisting of hydrogen or alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, -OR 15 , alkylaryl, arylalkyl, halogen, Si(R 12 )3, and heteroalkyl; each of the said groups may be unsubstituted or substituted with one or more substituents Z 1 ; Z 1 is selected from -OR 16 , alkyl, and alkenyl; R 15 , R 16 are each independently selected from the group consisting of alkyl, arylalkyl, alkylaryl and aryl; preferably R 15 , R[[ID=�8]] 16 are each independently alkyl; R 3 , R 4 , R 5 , R 6 , R 7 at least one of is -OR 15 ; R 8 , R 9 , R 10 , R 11 are each independently selected from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 12 )3, and heteroalkyl; L 1 is SiR 13 R 14 , -[CR 13 R 14 h -, GeR 13 R​14 , or BR 13 And; h is an integer selected from 1, 2, or 3; R 13 and R 14 Each of them is independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R 13 and R 14 They form cycloalkyl, cycloalkenyl, or heterocyclyl groups with the atoms to which they are bonded; M 1 is a transition metal selected from the group including zirconium, titanium, hafnium, and vanadium; preferably, M is zirconium; Q 1 and Q 2 Each is independently a halogen, alkyl, and -N(R) 17 )2, selected from the group comprising alkoxy, cycloalkoxy, aryloxy, arylalkyloxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; each R 17 These are independently hydrogen, alkyl, and Si(R 12 )3, selected from the group comprising cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; Each R 12 [These are independently hydrogen, alkyl, or alkenyl atoms.] We provide metallocene catalysts.

[0007] In a second embodiment, the present invention provides a catalyst composition comprising a catalyst according to a first embodiment of the present invention, an optional activator; an optional support; and an optional co-catalyst.

[0008] In a third embodiment, the present invention provides an olefin polymerization method comprising contacting at least one catalyst according to the first embodiment or a catalyst composition according to the second embodiment with an olefin monomer, optionally hydrogen, and optionally one or more olefin comonomers; and polymerizing the monomer and optionally one or more olefin comonomers in the presence of at least one catalyst or catalyst composition and optional hydrogen to obtain an olefin polymer.

[0009] In a fourth embodiment, the present invention provides an olefin polymer that is at least partially catalyzed by at least one catalyst according to the first embodiment or at least one catalyst composition according to the second embodiment, or produced by a method according to the third embodiment of the present invention.

[0010] The present invention also includes articles comprising olefin polymers according to a fourth embodiment. The independent and dependent claims describe the defining and preferred features of the invention. The features of the dependent claims may be combined with the features of the independent or other dependent claims as necessary. [Modes for carrying out the invention]

[0011] The present invention is described further below. Various aspects of the present invention are defined in more detail in the following description. Each of the aspects defined in this way may be combined with any one or more other aspects unless otherwise clearly indicated. In particular, any feature or provision indicated as preferred or advantageous may be combined with any other feature or provision indicated as preferred or advantageous.

[0012] Detailed description of the invention Before describing the compositions, catalysts, compounds, methods, articles, and uses encompassed by the present invention, it should be understood that such compositions, catalysts, compounds, methods, articles, and uses are not limited to the specific compositions, catalysts, compounds, methods, articles, and uses described, as such compositions, catalysts, compounds, methods, articles, and uses are naturally subject to change. Furthermore, it should be understood that the scope of the present invention is limited only by the appended claims, and therefore the terminology used herein is not intended to be limiting.

[0013] Unless otherwise defined, all terms used in disclosing this invention, including technical and scientific terms, have the meanings commonly understood by those skilled in the art to which this invention pertains. Definitions of terms used herein, provided by further guidance, are included to better understand the teachings of this invention. When describing the compounds, methods, articles, and uses of this invention, terms used should be interpreted according to the following definitions unless the circumstances indicate otherwise.

[0014] As used herein, the singular forms “a,” “an,” and “the” refer to both singular and plural objects unless the context clearly indicates otherwise. For example, “a resin” means one resin or more than one resin.

[0015] The terms “comprising,” “comprises,” and “comprised of,” as used herein, are synonymous with “including,” “includes,” or “containing,” and are inclusive or open-ended, and do not exclude additional, unlisted members, elements, or method steps. The terms “comprising,” “comprises,” and “comprised of” also include the term “consisting of.”

[0016] Enumerations of numerical ranges by endpoints include all integers and, where appropriate, fractions within that range (for example, 1–5 may include 1, 2, 3, and 4 when referring to the number of elements, and may also include 1.5, 2, 2.75, and 3.80 when referring to measured values). The description of an endpoint also includes the value of the endpoint itself (for example, 1.0–5.0 includes both 1.0 and 5.0). Any numerical range enumerated herein is intended to include all subranges contained therein.

[0017] Throughout this specification, any reference to “one embodiment” or “a certain embodiment” means that the specific features, structures, or characteristics described in relation to that embodiment are included in at least one embodiment of the present invention. Therefore, the appearance of the expression “in one embodiment” or “in a certain embodiment” in various parts throughout this specification does not necessarily mean that all of them refer to the same embodiment, although they may. Furthermore, specific features, structures, or characteristics can be combined in any suitable manner in one or more embodiments, as will be apparent to those skilled in the art from this disclosure. Furthermore, as will be understood to those skilled in the art, some embodiments described herein include some features included in other embodiments but do not include others, however, combinations of features from different embodiments are within the scope of the present invention and are intended to form different embodiments. For example, any embodiment may be used in any combination within the following claims and paragraphs.

[0018] When the term “substituted” is used herein, it means that one or more hydrogen atoms on the atom indicated in the expression using “substituted” have been replaced with a selection from the group indicated, provided that the substitution does not exceed the normal valence of the atom indicated and that the substitution results in a chemically stable compound, i.e., a compound robust enough to survive isolation from the reaction mixture. Preferred substituents for the indenyl, cyclopentadienyl, and fluorenyl groups are alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 )3. Can be selected from the group including heteroalkyl groups; each R 10 These are independently hydrogen, alkyl, or alkenyl. Preferably, each indenyl is substituted with at least one aryl or heteroaryl, more preferably aryl; preferably, the aryl substituent or heteroaryl substituent is at the 3-position of each indenyl; indenyl can further be alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, or Si(R 10 )3, may be substituted with one or more substituents selected from the group including heteroalkyl groups; each R 10 These are independently hydrogen, alkyl, or alkenyl.

[0019] The term "halo" or "halogen," as a group or part of a group, is a general term for fluoro, chloro, bromo, and iodine groups.

[0020] The term "alkyl" as a group or part of a group is derived from the formula C n H 2n+1This refers to a hydrocarbyl group, where n is a number of 1 or more. The alkyl group may be linear or branched and may be substituted as shown herein. Generally, the alkyl groups of this invention contain 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Where a subscript is used following a carbon atom herein, the subscript indicates the number of carbon atoms that the named group may contain. For example, the term "C" as a group or part of a group. 1~20 "Alkyl" is a formula where n is a number in the range of 1 to 20 - C n H 2n+1 This refers to the hydrocarbyl group. Therefore, for example, "C 1~8 "Alkyl" includes all linear or branched alkyl groups having 1 to 8 carbon atoms, and therefore includes methyl, ethyl, n-propyl, i-propyl, butyl and their isomers (e.g., n-butyl, i-butyl, and t-butyl); pentyl and its isomers, hexyl and its isomers, etc. "Substituted alkyl" means an alkyl group substituted with one or more substituents (e.g., 1 to 3 substituents, e.g., 1, 2, or 3 substituents) at any of the available bonding sites.

[0021] When the suffix "ene" is used in relation to an alkyl group, i.e., "alkylene," it is intended to mean an alkyl group as defined herein that has two single bonds as bonding sites to other groups. The term "alkylene," also called "alkanediyl," when used herein by itself or as part of another substituent, means a divalent alkyl group that has two single bonds for bonding to two other groups. The alkylene group may be linear or branched and may be substituted as shown herein. Non-limiting examples of alkylene groups include methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH(CH3)-), 1-methylethylene (-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.

[0022] The term “alkenyl” as a group or part of a group refers to an unsaturated hydrocarbyl group which may be linear or branched and contain one or more carbon-carbon double bonds. Generally, the alkenyl groups of this invention contain 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and preferably 3 to 8 carbon atoms. Where a subscript is used following a carbon atom in this specification, the subscript indicates the number of carbon atoms that the named group may contain. 3~20 Examples of alkenyl groups include ethenyl, 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl and its isomers, 2-hexenyl and its isomers, 2,4-pentadienyl, and the like.

[0023] The terms "alkoxy" or "alkyloxy" as a group or part of a group are R b Formula -OR is an alkyl as defined above in this specification. bThis refers to a group having [a specific characteristic]. Suitable non-limiting examples of alkoxys include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, and hexyloxy.

[0024] The term “cycloalkyl” as a group or part of a group refers to a cyclic alkyl group that is a monovalent saturated hydrocarbyl group having one or more cyclic structures and containing 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms; more preferably 3 to 6 carbon atoms. Cycloalkyls include all saturated hydrocarbon groups containing one or more rings, including monocyclic, bicyclic, or tricyclic groups. Further rings in polycyclic cycloalkyls may be fused, bridged, and / or bonded via one or more spiro atoms. Where a subscript is used following a carbon atom in this specification, the subscript indicates the number of carbon atoms that the named group may contain. For example, the term “C 3~20 A "cycloalkyl" is a cyclic alkyl group containing 3 to 20 carbon atoms. For example, the term "C 3~10 A "cycloalkyl" is a cyclic alkyl group containing 3 to 10 carbon atoms. For example, the term "C 3~8 A "cycloalkyl" is a cyclic alkyl group containing 3 to 8 carbon atoms. For example, the term "C 3~6 A "cycloalkyl" is a cyclic alkyl group containing 3 to 6 carbon atoms. 3~12 Examples of cycloalkyl groups include, but are not limited to, adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptan-2-yl, (1S,4R)-norbornan-2-yl, (1R,4R)-norbornan-2-yl, (1S,4S)-norbornan-2-yl, and (1R,4S)-norbornan-2-yl.

[0025] When the suffix "ene" is used in relation to a cycloalkyl group, i.e., cycloalkylene, it is intended to mean a cycloalkyl group as defined herein, having two single bonds as bonding sites 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.

[0026] When an alkylene or cycloalkylene group is present, the connection to the molecular structure in which it forms part may be via a common carbon atom or a different carbon atom. Using the asterisk nomenclature of this invention, the C3 alkylene group may be, for example, *-CH2CH2CH2-*, *-CH(-CH2CH3)-*, or *-CH2CH(-CH3)-*. Similarly, the C3 cycloalkylene group is [ka] It is possible.

[0027] The term “cycloalkenyl” as a group or part of a group refers to a non-aromatic cyclic alkenyl group having at least one (usually 1 to 3, preferably 1) unsaturated carbon-carbon sp2 double bond; preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, and more preferably 5 to 6 carbon atoms. Cycloalkenyls encompass all unsaturated hydrocarbon groups containing one or more rings, including monocyclic, bicyclic, or tricyclic groups. Further rings may be fused, bridged, and / or bonded via one or more spiro atoms. Where a subscript is used following a carbon atom in this specification, the subscript indicates the number of carbon atoms that the named group may contain. For example, the term “C 5~20 A "cycloalkenyl" is a cyclic alkenyl group containing 5 to 20 carbon atoms. For example, the term "C 5~10A "cycloalkenyl" is a cyclic alkenyl group containing 5 to 10 carbon atoms. For example, the term "C 5~8 A "cycloalkenyl" is a cyclic alkenyl group containing 5 to 8 carbon atoms. For example, the term "C 5~6 A "cycloalkyl" is a cyclic alkenyl group containing 5 to 6 carbon atoms. Examples, though not limited to them, include cyclopentenyl (-C5H7), cyclopentenylpropylene, methylcyclohexenylene, and cyclohexenyl (-C6H9). The double bond may be in either a cis or trans configuration.

[0028] The term "cycloalkenylalkyl" as a group or part of a group means an alkyl group as defined herein, in which at least one hydrogen atom is replaced by at least one cycloalkenyl as defined herein.

[0029] The term "cycloalkoxy" as a group or part of a group is R h Formula -OR is a cycloalkyl as defined above in this specification. h This refers to a group that has [a certain characteristic].

[0030] The term "aryl" as a group or part of a group refers to a polyunsaturated aromatic hydrocarbyl group having a single ring (i.e., phenyl) or multiple aromatic rings fused to each other (e.g., naphthyl), or covalently bonded, typically containing 6 to 20 atoms; preferably 6 to 10, with at least one ring being aromatic. The aromatic ring may optionally contain one or two additional rings fused to it (either cycloalkyl, heterocyclyl, or heteroaryl). A suitable example of an aryl is C 6~20 Aryl, preferably C 6~10 Aryl, more preferably C 6~8There are aryl groups. Non-limiting examples of aryl groups include phenyl, biphenylyl, biphenylenyl, or 1- or 2-naphthanelyl; 1-, 2-, 3-, 4-, 5- or 6-tetralinyl (also known as "1,2,3,4-tetrahydronaphthalene"); 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-azlenyl, 4-, 5-, 6- or 7-indenyl; 4- or 5-indanyl; 5-, 6-, 7- or 8-tetrahydronaphthyl; 1,2,3,4-tetrahydronaphthyl; and 1,4-dihydronaphthyl; and 1-,2, 3-, 4- or 5-pyrenyl. A "substituted aryl" is an aryl group having one or more substituents (e.g., one, two or three substituents, or one to two substituents) at any of the available bonding sites.

[0031] The term "aryloxy" as a group or part of a group is R g The expression -OR is an aryl as defined above in this specification. g This refers to a group that has [a certain characteristic].

[0032] The term “arylalkyl” as a group or part of a group means an alkyl group as defined herein, in which at least one hydrogen atom is replaced by at least one aryl group as defined herein. Non-limiting examples of arylalkyl groups include benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl, 3-(2-naphthyl)butyl, and the like.

[0033] The term "alkylaryl" as a group or part of a group means an aryl group as defined herein in which at least one hydrogen atom is replaced by at least one alkyl group as defined herein. Non-limiting examples of alkylaryl groups include R g p-CH3-R is the aryl defined herein as described above. g - exists.

[0034] The term "arylalkyloxy" or "arylalkyloxy" as a group or part of a group is R gis aryl, and R a Formula -OR is an alkylene as defined above in this specification. a -R g This refers to a group that has [a certain characteristic].

[0035] The term "heteroalkyl" as a group or part of a group means an acyclic alkyl group in which one or more carbon atoms are replaced by at least one heteroatom selected from the group including O, Si, S, B, and P, wherein the chain may not contain two adjacent heteroatoms. This means that one or more -CH3 groups of the acyclic alkyl group may be replaced by, for example, -OH groups, and / or one or more -CR2- groups of the acyclic alkyl group may be replaced by O, Si, S, B, and P groups.

[0036] The term "aminoalkyl" as a group or part of a group is R j It is alkylene, and R k is hydrogen or an alkyl as defined herein, and R l The group -R is hydrogen or an alkyl group as defined herein. j -NR k R l It refers to.

[0037] The term "heterocyclyl," as a group or part of a group, refers to a non-aromatic, fully saturated or partially unsaturated cyclic group having at least one heteroatom in at least one ring containing carbon atoms (e.g., a 3- to 7-membered monocyclic, a 7- to 11-membered bicyclic, or containing a total of 3 to 10 ring atoms). Each ring of a heterocyclic group containing heteroatoms may have 1, 2, 3, or 4 heteroatoms selected from N, S, Si, and Ge, where the nitrogen and sulfur heteroatoms may optionally be oxidized, and the nitrogen heteroatom may optionally be quaternized. Heterocyclic groups may be bonded at any heteroatom or carbon atom in the ring or ring system, where the valence allows. The rings of polycyclic heterocycles may be fused, bridged, and / or bonded via one or more spiroatoms.

[0038] Non-restrictive, representative heterocyclic groups include azilidinyl, oxyranyl, thiiranyl, piperidinyl, azetidinyl, 2-imidazolinyl, and pyrazolidinyl. Imidazolidinil, isoxazolidinil, oxazolidinil, isoxazolidinil, thiazolidinil, isothiazolidinil, piperidinil, succinimidyl, 3H-indolyl, indolinil, isoindolinil, 2H-pyrrolyl, 1-pyrrolinil, 2-pyrrolinil, 3-pyrrolinil, pyrrolidinil, 4H-quinolidinil, 2-oxopiperazinil, piperazinil, homopiperazinil, 2-pyrazolinil, 3-pyrazolinil, tetrahydro-2H-pyranil, 2H-pyranil, 4H-pyranil, 3,4-dihydro-2H-pyranil, oxetanil, thietanyl, 3-dioxolanil, 1,4-dioxanil, 2,5-dioxymidazolidinil These include 1H-pyrrolidinyl, 2-oxopiperidinyl, 2-oxopyrrodinyl, indolinyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydroquinolinyl, 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-dioxolanyl, 1,4-oxathianyl, 1,4-dithianyl, 1,3,5-trioxanyl, 1H-pyrrolidinyl, tetrahydro-1,1-dioxothiophenyl, N-formylpiperazinyl, and morpholine-4-yl.

[0039] Preferred terms (features) and embodiments of the composition, catalyst, compound, method, polymer, article, and use of this invention are described below. Each term and embodiment of this invention as so defined can be combined with any other term and / or embodiment, unless clearly indicated to the contrary. In particular, any feature shown to be preferred or advantageous can be combined with any other feature or term shown to be preferred or advantageous. In this regard, this invention is particularly captured by any combination of any one or more of the terms and embodiments numbered below and any other aspect and / or embodiment.

[0040] 1. Formula (I) [Chemical formula] [Wherein, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are each independently selected from the group consisting of hydrogen or alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, -OR 15 , alkylaryl, arylalkyl, halogen, Si(R 12 )3, and heteroalkyl; each of the above groups is unsubstituted or may be substituted with one or more substituents Z 1 ; Z 1 is selected from -OR 16 , alkyl, and alkenyl; R 15 , R 16 are each independently selected from the group consisting of alkyl, arylalkyl, alkylaryl and aryl; preferably, R 15 , R 16 are each independently alkyl; R 3 , R 4 , R 5 , R 6 , R 7 at least one of which is -OR15 and; R 8 , R 9 , R 10 , R 11 Each is independently hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 12 )3, and selected from the group including heteroalkyl groups; L 1 is SiR 13 R 14 ,-[CR 13 R 14 ] h -, GeR 13 R 14 , or BR 13 And; h is an integer selected from 1, 2, or 3; R 13 and R 14 Each of them is independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R 13 and R 14 They form cycloalkyl, cycloalkenyl, or heterocyclyl groups with the atoms to which they are bonded; M 1 is a transition metal selected from the group including zirconium, titanium, hafnium, and vanadium; preferably, M is zirconium; Q 1 and Q 2 Each is independently a halogen, alkyl, and -N(R) 17 )2, selected from the group comprising alkoxy, cycloalkoxy, aryloxy, arylalkyloxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; each R 17 These are independently hydrogen, alkyl, and Si(R 12 )3, selected from the group comprising cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl; Each R 12[These are independently hydrogen, alkyl, or alkenyl atoms.] Metallocene catalyst.

[0041] 2.R 2 , R 3 , R 4 , R 5 , R 6 , R 7 Each of them independently consists of hydrogen or C 1~20 Alkyl, C 2~20 Alkenil, C 3~20 Cycloalkyl, C 5~20 Cycloalkenyl, C 5~20 Cycloalkenyl C 1~20 Alkyl, C 6~20 Ariel, -OR 15 , C 1~20 Alkyl C 6~20 Ariel, C 6~20 Aryl C 1~20 Alkyl, halogen, Si(R 12 )3, and hetero C 1~12 Selected from the group including alkyl groups; each of the group is either unsubstituted or has one or more substituents Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , C 1~20 Alkyl, and C 2~20 Selected from Alkenil; R 15 , R 16 Each is independently C 1~20 Alkyl, C 6~20 Aryl C 1~20 Alkyl, C 1~20 Alkyl C 6~20 Aryl and C 6~20 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~20 It is alkyl; R 3 , R 4 , R 5 , R 6 , R 7 At least one of them is -OR 15 And, R 8 , R9 , R 10 , R 11 Each of them independently produces hydrogen and C 1~20 Alkyl, C 2~20 Alkenil, C 3~20 Cycloalkyl, C 5~20 Cycloalkenyl, C 5~20 Cycloalkenyl C 1~20 Alkyl, C 6~20 Ariel, C 1~20 Alkoxy, C 1~20 Alkyl C 6~20 Ariel, C 6~20 Aryl C 1~20 Alkyl, halogen, Si(R 12 )3, and hetero C 1~12 Selected from the group including alkyl groups; L 1 SiR 13 R 14 ,-[CR 13 R 14 ] h -, GeR 13 R 14 , or BR 13 And; h is an integer selected from 1, 2, or 3; R 13 and R 14 Each of them independently contains hydrogen and C 1~20 Alkyl, C 2~20 Alkenil, 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 Selected from the group including alkyl groups; or R 13 and R 14 C 3~20 Cycloalkyl, C 5~20 Forming cycloalkenyls or 3-14 member heterocyclines; M 1 is a transition metal selected from the group including zirconium, titanium, hafnium, and vanadium; preferably, M is zirconium; Q 1 and Q 2 Each of them independently produces halogen and C 1~20 Alkyl, -N(R 17 )2, C 1~20 Alkoxy, C 3~20 Cycloalkoxy, C 6~20 Aryl C 1~20 Alkyloxy, C 3~20 Cycloalkyl, C 6~20 Ariel, C 6~20 Aryloxy, C 1~20 Alkyl C 6~20 Ariel, C 6~20 Aryl C 1~20 Alkyl and hetero C 1~20 Selected from the group consisting of alkyl; each R 17 Hydrogen and C are independent of each other. 1~20 Alkyl, Si(R 12 )3, C 3~20 Cycloalkyl, C 6~20 Ariel, C 1~20 Alkyl C 6~20 Ariel, C 6~20 Aryl C 1~20 Alkyl and hetero C 1~20 Selected from the group including alkyl groups; preferably, Q 1 and Q 2 Each of them independently emits a halogen or C 1~20 Selected from the group consisting of alkyl groups; Each R 12 Hydrogen and C are independent of each other. 1~20 Alkyl, or C 2~20 The catalyst relating to item 1, which is an alkenyl.

[0042] 3.R 2 , R 3 , R 4 , R 5 , R 6 , R 7 Each of them independently consists of hydrogen or C 1~8 Alkyl, C 2~8 Alkenil, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 5~8 Cycloalkenyl C 1~8 Alkyl, C6~10 Ariel, -OR 15 , C 1~8 Alkyl C 6~10 Ariel, C 6~10 Aryl C 1~8 Alkyl, halogen, Si(R 12 )3, and hetero C 1~8 Selected from the group including alkyl groups; each of the group is either unsubstituted or has one or more substituents Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , C 1~8 Alkyl, and C 2~8 Selected from Alkenil; each R 12 Hydrogen and C are independent of each other. 1~8 Alkyl, or C 2~8 It is an alkenil; R 15 , R 16 Each is independently C 1~8 Alkyl, C 6~10 Aryl C 1~8 Alkyl, C 7~8 Alkyl C 6~10 Aryl and C 6~10 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~8 It is alkyl; R 3 , R 4 , R 5 , R 6 , R 7 At least one of them is -OR 15 And; preferably, R 4 , R 5 , R 6 , R 7 At least one of them is -OR 15 And; preferably, R 4 , R 5 , R 6 At least one of them is -OR 15 And; preferably, R 4 , R 5 , R 6 At least one of them is -OR 15 And; preferably, R 5 , R 6At least one of them is -OR 15 and; Preferably, R 2 , R 3 , R 4 , R 6 , R 7 Each of them independently consists of hydrogen or C 1~8 Alkyl, C 2~8 Alkenil, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 5~8 Cycloalkenyl C 1~8 Alkyl, C 6~10 Ariel, -OR 15 , C 1~8 Alkyl C 6~10 Ariel, C 6~10 Aryl C 1~8 Alkyl, halogen, Si(R 12 )3, and hetero C 1~8 Selected from the group including alkyl groups; each of the group is either unsubstituted or has one or more substituents Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , C 1~8 Alkyl, and C 2~8 Selected from Alkenil; each R 12 Hydrogen and C are independent of each other. 1~8 Alkyl, or C 2~8 It is an alkenil; R 15 , R 16 Each is independently C 1~8 Alkyl, C 6~10 Aryl C 1~8 Alkyl, C 7~8 Alkyl C 6~10 Aryl and C 6~10 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~8 It is alkyl; R 5 ga-OR 15 and; Preferably, R 2 , R 3 , R 6 , R 7 Each of them independently consists of hydrogen or C 1~8Alkyl, C 2~8 Alkenil, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 5~8 Cycloalkenyl C 1~8 Alkyl, C 6~10 Ariel, -OR 15 , C 1~8 Alkyl C 6~10 Ariel, C 6~10 Aryl C 1~8 Alkyl, halogen, Si(R 12 )3, and hetero C 1~8 Selected from the group including alkyl groups; each of the groups is either unsubstituted or contains one or more Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , C 1~8 Alkyl, and C 2~8 Selected from Alkenil; each R 12 Hydrogen and C are independent of each other. 1~8 Alkyl, or C 2~8 It is an alkenil; R 15 , R 16 Each is independently C 1~8 Alkyl, C 6~10 Aryl C 1~8 Alkyl, C 7~8 Alkyl C 6~10 Aryl and C 6~10 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~8 It is alkyl; R 4 C 6~10 It is an aryl, and the C 6~10 The aryl is either unsubstituted or has one or more substituents Z. 1 It is also fine if it is replaced with;R 5 ga-OR 15 and; Preferably, R 2 , R 3 , R 6 , R 7 Each of them independently consists of hydrogen or C 1~8 Alkyl, C 2~8 Alkenil, C 6~10 Ariel, -OR15 , halogens, and hetero C 1~8 Selected from the group including alkyl groups; each of the groups is either unsubstituted or contains one or more Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , and C 1~8 Selected from alkyl; R 15 , R 16 Each is independently C 1~8 Alkyl, and C 6~10 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~8 It is alkyl; R 4 C 6~10 It is an aryl, and the C 6~10 The aryl is either unsubstituted or has one or more substituents Z. 1 It is also fine if it is replaced with;R 5 ga-OR 15 and; Preferably, R 3 , R 7 Each of them independently consists of hydrogen or C 1~8 Alkyl, C 2~8 Alkenil, C 6~10 Ariel, -OR 15 , halogens, and hetero C 1~8 Selected from the group including alkyl groups; each of the groups is either unsubstituted or contains one or more Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , and C 1~8 Selected from alkyl; R 15 , R 16 Each is independently C 1~8 Alkyl, and C 6~10 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~8 It is alkyl; R 2 and R 6 Each of them is independent of C 1~8 Alkyl, C 6~10 Ariel, -OR 15 , halogens, and hetero C1~8 Selected from the group including alkyl groups; R 4 C 6~10 It is an aryl, and the C 6~10 The aryl is either unsubstituted or has one or more substituents Z. 1 It is also fine if it is replaced with;R 5 ga-OR 15 and; Preferably, R 3 , R 7 Each of them independently consists of hydrogen or C 1~8 Selected from alkyl groups, preferably hydrogen; R 2 and R 6 Each of them is independent of C 1~8 Alkyl, C 6~10 Ariel, -OR 15 , halogens, and hetero C 1~8 Selected from the group including alkyl groups, preferably C 1~8 It is alkyl; R 4 C 6~10 It is an aryl, and the C 6~10 The aryl is either unsubstituted or has one or more substituents Z. 1 It is also fine if it is replaced with;R 5 ga-OR 15 A catalyst relating to one of items 1 or 2.

[0043] 4.R 8 , R 9 , R 10 , R 11 Each of them independently produces hydrogen and C 1~8 Alkyl, C 2~8 Alkenil, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 5~8 Cycloalkenyl C 1~8 Alkyl, C 6~10 Ariel, C 1~8 Alkoxy, C 1~8 Alkyl C 6~10 Ariel, C 6~10 Aryl C 1~8 Alkyl, halogen, Si(R 12 )3, and hetero C 1~8 Selected from the group including alkyl groups; each R12 Hydrogen and C are independent of each other. 1~8 Alkyl, or C 2~8 It is an alkenyl; preferably, R 8 , R 9 , R 10 , R 11 Each of them independently produces hydrogen and C 1~8 Alkyl, C 2~8 Alkenil, C 6~10 Ariel, C 1~8 Alkoxy, halogens, and Si(R 12 ) Selected from the group including 3; each R 12 These independently consist of hydrogen, or C 1~6 It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each of them independently produces hydrogen and C 1~6 Selected from alkyl or halogen; preferably, R 8 , R 9 , R 10 , R 11 Each of them independently contains hydrogen, or C 1~4 It is alkyl; preferably R 8 , R 9 , R 10 , R 11 Each of them independently contains hydrogen, or C 1~2 It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each is independently hydrogen or methyl; preferably, R 8 , R 9 , R 10 , R 11 A catalyst relating to any one of items 1 to 3, wherein each of the elements is independently methyl.

[0044] 5.L 1 SiR 13 R 14 ,-[CR 13 R 14 ] h -, GeR 13 R 14 , or BR 13And; h is an integer selected from 1, 2, or 3; R 13 and R 14 Each of them independently contains hydrogen and C 1~8 Alkyl, C 2~8 Alkenil, 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 Selected from the group including alkyl groups; or R 13 and R 14 C 3~8 Cycloalkyl, C 5~8 Forms a cycloalkenyl or a 3-8 membered heterocyclyl; preferably, L 1 SiR 13 R 14 , or -[CR 13 R 14 ] h - is an integer selected from 1 or 2; R 13 and R 14 Each of them independently contains hydrogen and C 1~8 Alkyl, C 2~8 Alkenil, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, and C 6~10 Selected from the group containing aryl; or R 13 and R 14 C 3~8 Cycloalkyl, C 5~8 Forms a cycloalkenyl; preferably, L 1 SiR 13 R 14 , or -[CR 13 R 14 ]-and;R 13 and R 14 Each of them independently contains hydrogen and C 1~8 Alkyl, and C 3~8 Selected from the group including cycloalkyl; or R 13 and R14 C 3~8 Forms a cycloalkyl group; preferably, L 1 SiR 13 R 14 , or -[CR 13 R 14 ]-and;R 13 and R 14 Each of them is independently hydrogen, or C 1~6 Selected from alkyl groups; preferably, L 1 SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~4 Selected from alkyl groups; preferably, L 1 SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~2 Selected from alkyl groups; preferably, L 1 SiR 13 R 14 And; R 13 and R 14 Each of them is independently selected from hydrogen or methyl; preferably, L 1 The catalyst is SiMe2, relating to one of items 1 to 4.

[0045] 6.M 1 is a transition metal selected from the group including zirconium, titanium, hafnium, and vanadium; preferably, M is zirconium; Q 1 and Q 2 Each of them independently produces halogen and C 1~8 Alkyl, -N(R 17 )2, C 1~8 Alkoxy, C 3~8 Cycloalkoxy, C 6~10 Aryl C 1~8 Alkyloxy, C 3~8 Cycloalkyl, C 6~10 Ariel, C 6~10 Aryloxy, C 1~8Alkyl C 6~10 Ariel, C 6~10 Aryl C 1~8 Alkyl and hetero C 1~8 Selected from the group consisting of alkyl; each R 17 Hydrogen and C are independent of each other. 1~8 Alkyl, Si(R 12 )3, C 3~8 Cycloalkyl, C 6~10 Ariel, C 1~8 Alkyl C 6~10 Ariel, C 6~10 Aryl C 1~8 Alkyl and hetero C 1~8 Selected from the group including alkyl groups; preferably, each R 17 Hydrogen and C are independent of each other. 1~20 Alkyl, Si(R 12 )3, C 3~20 Cycloalkyl, C 6~20 Ariel, C 1~20 Alkyl C 6~20 Ariel, C 6~20 Aryl C 1~20 Alkyl and hetero C 1~20 Selected from the group including alkyl groups, preferably each R 17 These are independently hydrogen or C 1~8 Selected from alkyl groups; each R 12 These are independently hydrogen, or C 1~8 It is alkyl; preferably, Q 1 and Q 2 Each of them independently produces halogen and C 1~8 Alkyl, C 1~8 Alkoxy and hetero C 1~8 Selected from the group consisting of alkyl groups; preferably, Q 1 and Q 2 Each of them independently emits a halogen or C 1~8 Selected from the group consisting of alkyl groups; preferably, Q 1 and Q 2 Each of them independently uses halogen or C 1~8 Selected from the group consisting of alkyl groups; preferably, Q 1 and Q 2 A catalyst relating to any one of items 1 to 5, wherein each of the elements is independently a halogen, preferably chloro.

[0046] 7.R 2 , R 3 , R 4 , R 5 , R 6 , R 7 Each of them independently consists of hydrogen or C 1~8 Alkyl, C 2~8 Alkenil, C 6~10 Ariel, -OR 15 Selected from the group including; each of the group is either unsubstituted or has one or more substituents Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , C 1~6 Alkyl, and C 2~6 Selected from Alkenil; R 15 , R 16 Each is independently C 1~6 Alkyl, C 6~10 Aryl C 1~8 Alkyl, C 7~8 Alkyl C 6~10 Aryl and C 6~10 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~6 It is alkyl; R 3 , R 4 , R 5 , R 6 , R 7 At least one of them is -OR 15 And, R 8 , R 9 , R 10 , R 11 Each of them independently produces hydrogen and C 1~8 Alkyl, C 2~8 Alkenil, C 6~10 Aryl, and C 1~8 Selected from the group including alkoxys; L 1 SiR 13 R 14 , or -[CR 13 R 14 ] h- is an integer selected from 1 or 2; R 13 and R 14 Each of them independently contains hydrogen and C 1~8 Alkyl, C 2~8 Alkenil, C 3~8 Cycloalkyl, C 5~8 Selected from the group including cycloalkenyls; or R 13 and R 14 C 3~8 Cycloalkyl, or C 5~8 Forming cycloalkenyls; M 1 is zirconium or titanium; preferably, M is zirconium; Q 1 and Q 2 Each of them independently produces halogen and C 1~8 Alkyl, and C 1~8 Selected from the group consisting of alkoxys; preferably, Q 1 and Q 2 Each of them independently emits a halogen or C 1~8 A catalyst selected from the group consisting of alkyl groups, relating to any one of items 1 to 6.

[0047] 8.R 2 , R 3 , R 4 , R 5 , R 6 , R 7 Each of them independently consists of hydrogen or C 1~6 Alkyl, C 6~10 aryl, or -OR 15 Selected from a group chosen from; each of the group is either unsubstituted or has one or more substituents Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , or C 1~6 Selected from alkyl; R 15 , R 16 Each is independently C 1~6 It is alkyl; R 3 , R 4 , R 5 , R 6, R 7 At least one of them is -OR 15 And, R 8 , R 9 , R 10 , R 11 Each of them independently produces hydrogen and C 1~6 Alkyl, and C 2~6 Selected from the group including alkenyls; preferably, R 8 , R 9 , R 10 , R 11 Each of them independently contains hydrogen, or C 1~6 Selected from alkyl groups; preferably, R 8 , R 9 , R 10 , R 11 Each of them independently contains hydrogen, or C 1~4 Selected from alkyl groups; preferably, R 8 , R 9 , R 10 , R 11 Each of them independently contains hydrogen, or C 1~2 Selected from alkyl groups; 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 of them is independently methyl; L 1 SiR 13 R 14 , or -[CR 13 R 14 ] h - is an integer selected from 1 or 2; R 13 and R 14 Each of them independently contains hydrogen and C 1~6 Alkyl, C 3~6 Selected from the group including cycloalkyl; or R 13 and R 14 C 3~6 Forms a cycloalkyl group; preferably, L 1 SiR 13 R14 , or -[CR 13 R 14 ] h - is; h is 1; R 13 and R 14 Each of them is independently hydrogen, or C 1~6 Selected from alkyl groups; preferably, L 1 SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~6 Selected from alkyl groups; preferably, L 1 SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~4 Selected from alkyl groups; preferably, L 1 SiR 13 R 14 And; R 13 and R 14 Each of them is independently selected from hydrogen or methyl; preferably, L 1 It is SiMe2; M is zirconium; Q 1 and Q 2 Each of them independently emits a halogen or C 1~6 Selected from alkyl groups; preferably, Q 1 and Q 2 Each of these is independently chloro, fluoro, or C 1~4 Selected from the group consisting of alkyl groups, preferably Q 1 and Q 2 A catalyst relating to any one of items 1 to 7, wherein each of the elements is independently chloro.

[0048] 9.R 5 ga-OR 15 A catalyst relating to any one of items 1 to 8.

[0049] 10.Formula (II) [ka] [In the formula, 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 [This has the same meaning as any one of items 1-9] A catalyst relating to any one of items 1 to 9, having the following characteristics.

[0050] 11.R 4 is unsubstituted or contains one or more Z 1 A catalyst relating to any one of items 1 to 10, wherein the aryl is substituted with [a specific aryl compound].

[0051] 12. Equation (III) or (IV) [ka] [wherein n is an integer selected from 0, 1, 2, 3 or 4; m is an integer selected from 0, 1, 2 or 3; 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 [This has the same meaning as any one of items 1-11] A catalyst relating to any one of items 1 to 11, having the following characteristics.

[0052] 13.R 8 , R 9 , R 10 , R 11 Each of them independently contains hydrogen, or C 1~8It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each of them independently produces hydrogen and C 1~6 It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each of them independently contains hydrogen, or C 1~4 It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each of them independently contains hydrogen, or C 1~2 It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each is independently hydrogen or methyl; preferably, R 8 , R 9 , R 10 , R 11 A catalyst relating to any one of items 1 to 12, wherein each of the elements is independently methyl.

[0053] 14. Equation (V) or (VI) [ka] [wherein n is an integer selected from 0, 1, 2, 3 or 4, and m is an integer selected from 0, 1, 2 or 3; R 2 , R 3 , R 15 , R 16 , R 6 , R 7 , L 1 , Z 1 M 1 Q 1 Q 2 [This has the same meaning as any one of items 1-13] A catalyst relating to any one of items 1 to 13, having the following characteristics.

[0054] 15.L 1 SiR 13 R 14 , or -[CR13 R 14 - is, and R 13 , R 14 has the same meaning as defined in any one of items 1 to 14, and preferably, L 1 is preferably SiR 13 R 14 and preferably, R 13 , R 14 are each independently selected from hydrogen or alkyl, and preferably, R 13 , R 14 are each independently alkyl, preferably C 1~6 alkyl, preferably C 1~4 alkyl, preferably C 1~2 alkyl, preferably methyl, a catalyst according to any one of items 1 to 14.

[0055] 16. Formula (VII) or (VIII) [Chemical formula] [wherein, n is an integer selected from 0, 1, 2, 3 or 4, m is an integer selected from 0, 1, 2 or 3; R 2 , R 3 , R 15 , R 16 , R 6 , R 7 , Z 1 , M 1 , Q 1 , Q 2 has the same meaning as any one of items 1 to 15] having, a catalyst according to any one of items 1 to 15.

[0056] 17. Formula (IX) or (X) [Chemical formula] [wherein, n is an integer selected from 0, 1, 2, 3 or 4, m is an integer selected from 0, 1, 2 or 3; R 2 , R 3 , R 15 , R16 , R 6 , R 7 , Z 1 Q 1 Q 2 [This has the same meaning as any one of items 1-16] A catalyst relating to any one of items 1 to 16, having the following characteristics.

[0057] 18. Equation (XI) or (XII) [ka] [wherein n is an integer selected from 0, 1, 2, 3 or 4, and m is an integer selected from 0, 1, 2 or 3; R 2 , R 3 , R 15 , R 16 , R 6 , R 7 , Z 1 [This has the same meaning as any one of items 1-17] A catalyst relating to any one of items 1 to 17, having the following characteristics.

[0058] 19. Equation (XIII) or (XIV) [ka] [wherein n is an integer selected from 0, 1, 2, 3 or 4, and m is an integer selected from 0, 1, 2 or 3; R 2 , R 6 , R 15 , R 16 , Z 1 [This has the same meaning as any one of items 1-18] A catalyst relating to any one of items 1 to 18, having the following characteristics.

[0059] 20.R 2 , R 3 Each of them independently consists of hydrogen or C 1~6 A catalyst related to one of items 1 to 18, selected from alkyl groups.

[0060] 21. Equation (XV) or (XVI) [ka] [wherein n is an integer selected from 0, 1, 2, 3 or 4, and m is an integer selected from 0, 1, 2 or 3; R 6 , Z 1 [This has the same meaning as any one of items 1-20] A catalyst relating to any one of items 1 to 20, having the following characteristics.

[0061] 22. Equation (XVII) or (XVIII) [ka] [wherein n is an integer selected from 0, 1, 2, 3 or 4; m is an integer selected from 0, 1, 2 or 3; Z 1 [This has the same meaning as any one of items 1-21] A catalyst relating to any one of items 1 to 21.

[0062] 23. Equation (XIX) or (XX) [ka] A catalyst relating to any one of items 1 to 22, having the following characteristics.

[0063] 24. A supported catalyst comprising a catalyst relating to any one of items 1 to 23, and a support, preferably an inorganic porous support.

[0064] 25. A catalyst composition comprising at least one catalyst relating to any one of items 1 to 24; an optional activator; an optional support; and an optional co-catalyst.

[0065] 26. The catalyst composition according to item 25, wherein the catalyst composition comprises an activator, preferably an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof; preferably the activator is methylalmoxane.

[0066] 27. The activator is of formula (A1) or (A2) R a -(Al(R a )-O) x -AlR a 2(A1); or (-Al(R a )-O-) y (A2) [In the formula, x is between 1 and 40, preferably between 10 and 20; y is 3 to 40, preferably 3 to 20; Each R a C is independent 1~8 Selected from alkyl groups, preferably methyl groups. A catalyst composition according to any one of claims 25 to 26, comprising at least one almoxane compound.

[0067] 28. A catalyst composition according to any one of items 25 to 27, wherein the activator is methylarmoxane.

[0068] 29. A catalyst composition according to any one of items 25 to 28, wherein the catalyst composition includes a co-catalyst.

[0069] 30. A catalyst composition according to any one of claims 25 to 29, wherein the catalyst composition comprises an organoaluminum co-catalyst.

[0070] 31. A catalyst composition according to any one of claims 25 to 30, wherein the catalyst composition comprises a co-catalyst, preferably an organoaluminum co-catalyst selected from the group comprising trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and any combination thereof.

[0071] 32. A catalyst composition according to any one of items 25 to 31, or a supported catalyst according to item 24, wherein the support comprises a solid oxide, preferably a solid inorganic oxide, preferably the solid oxide being titanated silica, silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any mixture thereof; preferably, silica, titanated silica, fluoride-treated silica, silica-alumina, fluoride-treated alumina, sulfated alumina, fluoride-treated silica-alumina, sulfated silica-alumina, silica-coated alumina, fluoride-treated silica, sulfated silica-coated alumina, or any combination thereof.

[0072] 33. A catalyst composition according to any one of items 25 to 32, wherein the support comprises solid oxides including titanated silica, silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any mixture thereof.

[0073] 34. A catalyst composition according to any one of claims 25 to 33, comprising an almoxane activator; a titanated silica or silica solid support; and an optional co-catalyst.

[0074] 35. Use of a catalyst according to any one of items 1 to 24, or use of a catalyst composition according to any one of items 25 to 34, for the preparation of an olefin polymer.

[0075] 36. Use of a catalyst according to any of the preceding items 1 to 24, or use of a catalyst composition according to any one of items 25 to 34, for the preparation of polypropylene, preferably propylene homopolymer, propylene random copolymer and heterogeneous propylene copolymer.

[0076] 37. A method for olefin polymerization comprising contacting a catalyst according to any one of items 1 to 24 or a catalyst composition according to any one of items 25 to 34 with an olefin monomer, optionally hydrogen, and optionally one or more olefin comonomers; and polymerizing the monomer and optionally one or more olefin comonomers in the presence of at least one catalyst composition and optionally hydrogen to obtain an olefin polymer.

[0077] 38. The method relating to item 37, wherein the method is carried out in a slurry phase, a gas phase, or a liquid phase.

[0078] 39. A method relating to any one of items 37 to 38, wherein the method is carried out in one or more batch reactors, slurry reactors, gas-phase reactors, solution reactors, high-pressure reactors, tubular reactors, autoclave reactors, or a combination thereof.

[0079] 40. A method relating to any one of items 37-39, wherein the method is carried out in a single reaction zone.

[0080] 41. A method according to any one of claims 37 to 40, wherein the olefin monomer is propylene and the olefin comonomer comprises ethylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-l-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

[0081] 42. A method according to any one of claims 37 to 41, wherein the olefin monomer is ethylene and the olefin comonomer comprises propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-l-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.

[0082] 43. A method for preparing polypropylene, comprising polymerizing propylene in the presence of a catalyst according to any one of items 1 to 24, or in the presence of a catalyst composition according to any one of items 25 to 34, to form polypropylene.

[0083] 44. An olefin polymer at least partially catalyzed by at least one catalyst according to any one of items 1 to 24, or by at least one catalyst composition according to any one of items 24 to 34, or produced by a method according to any one of items 37 to 43.

[0084] 45. The olefin polymer according to item 44, wherein the olefin polymer is polypropylene.

[0085] Articles containing olefin polymers relating to any one of headings 44 to 45.

[0086] As used herein, the term "catalyst" refers to a substance that causes a change in the rate of a reaction. In the present invention, it particularly applies to catalysts suitable for polymerization, preferably polymerization from olefins to olefin polymers.

[0087] The term "metallocene catalyst" is used herein to describe a transition metal complex containing a metal atom bonded to one or more ligands. A metallocene catalyst is a compound of a Group IV transition metal of the periodic table such as titanium, zirconium, hafnium, etc., and has a coordination structure of a metal compound and a ligand. A metallocene contains a single metal site that enables better control of polymer branching and molecular weight distribution. Monomers are inserted between the metal and the growing chain of the polymer.

[0088] In some embodiments, the present invention provides a metallocene catalyst of any one of formulas (I) to (XVIII), wherein R 2 、R 3 、R 4 、R 5 、R 6 、R 7 are each independently 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 hetero C 1~8 alkyl, and each of the above groups is unsubstituted or may be substituted with one or more substituents Z 1 ; Z 1 is -OR 16 、C 1~8 alkyl, and C 2~8 alkenyl; each R 12 is independently hydrogen, C1~8 Alkyl, or C 2~8 It is an alkenil; R 15 , R 16 Each is independently C 1~8 Alkyl, C 6~10 Aryl C 1~8 Alkyl, C 7~8 Alkyl C 6~10 Aryl and C 6~10 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~8 It is alkyl; R 3 , R 4 , R 5 , R 6 , R 7 At least one of them is -OR 15 And; preferably, R 4 , R 5 , R 6 , R 7 At least one of them is -OR 15 And; preferably, R 4 , R 5 , R 6 At least one of them is -OR 15 And; preferably, R 5 , R 6 At least one of them is -OR 15 and; R 8 , R 9 , R 10 , R 11 Each of them is independently hydrogen, C 1~8 Alkyl, C 2~8 Alkenil, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 5~8 Cycloalkenyl C 1~8 Alkyl, C 6~10 Ariel, C 1~8 Alkoxy, C 1~8 Alkyl C 6~10 Ariel, C 6~10 Aryl C 1~8 Alkyl, halogen, Si(R 12 )3, and hetero C 1~8 Selected from the group including alkyl groups; each R12 Hydrogen and C are independent of each other. 1~8 Alkyl, or C 2~8 It is an alkenil; L 1 is SiR 13 R 14 , or -[CR 13 R 14 ] h - is an integer selected from 1 or 2; R 13 and R 14 Each of them independently contains hydrogen and C 1~8 Alkyl, C 2~8 Alkenil, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, and C 6~10 Selected from the group containing aryl; or R 13 and R 14 C 3~8 Cycloalkyl, C 5~8 Forms a cycloalkenyl; preferably, L 1 is SiR 13 R 14 , or -[CR 13 R 14 ]-and;R 13 and R 14 Each of them independently contains hydrogen and C 1~8 Alkyl, and C 3~8 Selected from the group including cycloalkyl; or R 13 and R 14 C 3~8 Forms a cycloalkyl group; preferably, L 1 is SiR 13 R 14 , or -[CR 13 R 14 ]-and;R 13 and R 14 Each of them is independently hydrogen, or C 1~6 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~4Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~2 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently selected from hydrogen or methyl; preferably, L 1 It is SiMe2.

[0089] In some embodiments, the present invention provides a metallocene catalyst of any one of the formulas (I) to (XVI), wherein, R 2 , R 3 , R 4 , R 6 , R 7 Each is independently hydrogen or C 1~8 Alkyl, C 2~8 Alkenil, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 5~8 Cycloalkenyl C 1~8 Alkyl, C 6~10 Ariel, -OR 15 , C 1~8 Alkyl C 6~10 Ariel, C 6~10 Aryl C 1~8 Alkyl, halogen, Si(R 12 )3, and hetero C 1~8 Selected from the group including alkyl groups; each of the group is either unsubstituted or has one or more substituents Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , C 1~8 Alkyl, and C 2~8 Selected from Alkenil; each R 1 Hydrogen and C are independent of each other. 1~8 Alkyl, or C 2~8 It is an alkenil; R 15 , R 16 Each is independently C1~8 Alkyl, C 6~10 Aryl C 1~8 Alkyl, C 7~8 Alkyl C 6~10 Aryl and C 6~10 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~8 It is alkyl; R 5 は-OR 15 and; R 8 , R 9 , R 10 , R 11 Each of them is independently hydrogen, C 1~8 Alkyl, C 2~8 Alkenil, C 6~10 Ariel, C 1~8 Alkoxy, halogens, and Si(R 12 ) Selected from the group including 3; each R 12 These are independently hydrogen, or C 1~6 It is alkyl; L 1 is SiR 13 R 14 , or -[CR 13 R 14 ]-and;R 13 and R 14 Each of them independently contains hydrogen and C 1~8 Alkyl, and C 3~8 Selected from the group including cycloalkyl; or R 13 and R 14 C 3~8 Forms a cycloalkyl group; preferably, L 1 is SiR 13 R 14 , or -[CR 13 R 14 ]-and;R 13 and R 14 Each of them is independently hydrogen, or C 1~6 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14Each of them is independently hydrogen, or C 1~4 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~2 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently selected from hydrogen or methyl; preferably, L 1 It is SiMe2.

[0090] In some embodiments, the present invention provides a metallocene catalyst of any one of the formulas (I) to (XVIII), wherein, R 2 , R 3 , R 6 , R 7 Each is independently hydrogen or C 1~8 Alkyl, C 2~8 Alkenil, C 3~8 Cycloalkyl, C 5~8 Cycloalkenyl, C 5~8 Cycloalkenyl C 1~8 Alkyl, C 6~10 Ariel, -OR 15 , C 1~8 Alkyl C 6~10 Ariel, C 6~10 Aryl C 1~8 Alkyl, halogen, Si(R 12 )3, and hetero C 1~8 Selected from the group including alkyl groups; each of the groups is either unsubstituted or contains one or more Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , C 1~8 Alkyl, and C 2~8 Selected from Alkenil; each R 12 Hydrogen and C are independent of each other. 1~8 Alkyl, or C 2~8 It is an alkenil; R 15 , R16 Each is independently C 1~8 Alkyl, C 6~10 Aryl C 1~8 Alkyl, C 7~8 Alkyl C 6~10 Aryl and C 6~10 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~8 It is alkyl; R 4 is C 6~10 It is an aryl, and the C 6~10 The aryl is either unsubstituted or has one or more substituents Z. 1 It is also fine if it is replaced with;R 5 は-OR 15 and; R 8 , R 9 , R 10 , R 11 Each is independently hydrogen, or C 1~4 It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each is independently hydrogen, or C 1~2 It is alkyl; preferably R 8 , R 9 , R 10 , R 11 Each is independently hydrogen or methyl; preferably R 8 , R 9 , R 10 , R 11 Each of these is independently a methyl group.

[0091] L 1 is SiR 13 R 14 , or -[CR 13 R 14 ]-and;R 13 and R 14 Each of them is independently hydrogen, or C 1~6 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14Each of them is independently hydrogen, or C 1~4 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~2 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently selected from hydrogen or methyl; preferably, L 1 It is SiMe2.

[0092] In some embodiments, the present invention provides a metallocene catalyst of any one of the formulas (I) to (XVIII), wherein, R 2 , R 3 , R 6 , R 7 Each is independently hydrogen or C 1~8 Alkyl, C 2~8 Alkenil, C 6~10 Ariel, -OR 15 , halogens, and hetero C 1~8 Selected from the group including alkyl groups; each of the groups is either unsubstituted or contains one or more Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , and C 1~8 Selected from alkyl; R 15 , R 16 Each is independently C 1~8 Alkyl, and C 6~10 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~8 It is alkyl; R 4 is C 6~10 It is an aryl, and the C 6~10 The aryl is either unsubstituted or has one or more substituents Z. 1 It is also fine if it is replaced with;R 5 は-OR 15 and; R 8 , R 9 , R 10 , R 11 Each of them is independently hydrogen, C 1~6 Selected from alkyl or halogen; preferably, R 8 , R 9 , R 10 , R 11 Each is independently hydrogen, or C 1~4 It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each is independently hydrogen, or C 1~2 It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each is independently hydrogen or methyl; preferably, R 8 , R 9 , R 10 , R 11 Each of these is independently a methyl group.

[0093] L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~2 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently selected from hydrogen or methyl; preferably, L 1 It is SiMe2.

[0094] In some embodiments, the present invention provides a metallocene catalyst of any one of the formulas (I) to (XVIII), wherein, R 3 , R 7 Each is independently hydrogen or C 1~8 Alkyl, C 2~8 Alkenil, C 6~10 Ariel, -OR 15, halogens, and hetero C 1~8 Selected from the group including alkyl groups; each of the groups is either unsubstituted or contains one or more Z 1 It is also fine if it is replaced with;Z 1 は-OR 16 , and C 1~8 Selected from alkyl; R 15 , R 16 Each is independently C 1~8 Alkyl, and C 6~10 Selected from the group including aryls; preferably, R 15 , R 16 Each is independently C 1~8 It is alkyl; R 2 and R 6 Each is independently C 1~8 Alkyl, C 6~10 Ariel, -OR 15 , halogens, and hetero C 1~8 Selected from the group including alkyl groups; R 4 is C 6~10 It is an aryl, and the C 6~10 The aryl is either unsubstituted or has one or more substituents Z. 1 It is also fine if it is replaced with;R 5 は-OR 15 and; R 8 , R 9 , R 10 , R 11 Each is independently hydrogen, or C 1~6 It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each is independently hydrogen, or C 1~2 It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each is independently hydrogen or methyl; preferably, R 8 , R 9 , R 10 , R 11 Each of these is independently a methyl group.

[0095] L 1is SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~4 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~2 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently selected from hydrogen or methyl; preferably, L 1 It is SiMe2.

[0096] In some embodiments, the present invention provides a metallocene catalyst of any one of the formulas (I) to (XVIII), wherein, R 3 , R 7 Each is independently hydrogen or C 1~8 Selected from alkyl groups, preferably hydrogen; R 2 and R 6 Each is independently C 1~8 Alkyl, C 6~10 Ariel, -OR 15 , halogens, and hetero C 1~8 A group including alkyl groups, preferably C 1~8 Selected from alkyl; R 4 is C 6~10 It is an aryl, and the C 6~10 The aryl is either unsubstituted or has one or more substituents Z. 1 It is also fine if it is replaced with;R 5 は-OR 15 That is the case.

[0097] R 8 , R 9 , R 10 , R 11 Each is independently hydrogen, or C 1~6 It is alkyl; preferably, R 8, R 9 , R 10 , R 11 Each is independently hydrogen, or C 1~2 It is alkyl; preferably, R 8 , R 9 , R 10 , R 11 Each is independently hydrogen or methyl; preferably, R 8 , R 9 , R 10 , R 11 Each of these is independently a methyl group.

[0098] L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~4 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently hydrogen, or C 1~2 Selected from alkyl groups; preferably, L 1 is SiR 13 R 14 And; R 13 and R 14 Each of them is independently selected from hydrogen or methyl; preferably, L 1 It is SiMe2.

[0099] In some embodiments, the present invention provides a metallocene catalyst of any one of the formulas (I) to (X), where M 1 is zirconium or titanium; preferably, M is zirconium; Q 1 and Q 2 Each of them independently controls halogen and C 1~8 Alkyl, and C 1~8 Selected from the group consisting of alkoxys; preferably, Q 1 and Q 2 Each of these is independently a halogen like chloroform, or C 1~8 Selected from the group consisting of alkyl groups.

[0100] In the present invention, the catalyst is preferably provided on a solid support.

[0101] The support can be an inert organic or inorganic solid that is chemically unreactive with any of the components of conventional crosslinked metallocene catalysts. Suitable support materials for supported catalysts include silica, alumina, magnesium oxide, titanium oxide, thorium oxide, and mixed oxides of silica and one or more group 2 or 13 metal oxides, such as silica-magnesia and silica-alumina mixed oxides. Silica, alumina, and mixed oxides of silica and one or more group 2 or 13 metal oxides are preferred support materials. A preferred example of such a mixed oxide is silica-alumina. For example, the solid oxides include titanated silica, silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any mixture thereof, preferably silica, titanated silica, fluoride-treated silica, silica-alumina, fluoride-treated alumina, sulfated alumina, fluoride-treated silica-alumina, sulfated silica-alumina, silica-coated alumina, fluoride-treated silica, sulfated silica-coated alumina, or any combination thereof. Most preferably titanated silica or silica compounds. In a preferred embodiment, the crosslinked metallocene catalyst is provided on a solid support, preferably titanated silica, or a silica support. The silica may be granular, lumpy, fumed, or in other forms.

[0102] In some embodiments, the support for the catalyst component is a porous support, preferably porous titanated silica, or 200-900 m 2The silica support has a surface area contained between / g. In another embodiment, the support for the polymerization catalyst is a porous support, preferably porous titanated silica, or a silica support having an average pore volume contained between 0.5 and 4 ml / g. In yet another embodiment, the support for the polymerization catalyst is a porous support, preferably porous titanated silica, or a silica support having an average pore diameter contained between 50 and 300 Å, preferably 75 and 220 Å.

[0103] 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 in which 50 weight percent of the particles are smaller than D50. Particle size can be measured in accordance with the International Standard ISO 13320:2009 ("Particle size analysis - Laser diffraction methods"). For example, D50 can be measured by sieving, BET surface measurement, or laser diffraction analysis. For example, laser diffraction systems from Malvern Instruments can be advantageously used. Particle size can be measured by laser diffraction analysis with a Malvern-type analyzer. Particle size can be measured by laser diffraction analysis with a Malvern-type analyzer after suspending the supported catalyst in cyclohexane. Suitable Malvern systems include the Malvern 2000, Malvern MasterSizer (e.g., Mastersizer S), Malvern 2600, and Malvern 3600 series. Such instruments, along with their operating manuals, meet or even exceed the requirements of the ISO 13320 standard. The Malvern MasterSizer (e.g., Mastersizer S) can also be useful because, by applying Mie's theory, it is possible to more accurately measure D50 toward the lower limit of the average particle size range of less than 8 μm using appropriate optical means.

[0104] Preferably, the catalyst is activated by an activator. The activator may be any activator known for this purpose, such as an aluminum-containing activator, a boron-containing activator, or a fluorinated activator. Aluminum-containing activators may include almoxanes, alkylaluminums, Lewis acids, and / or fluorinated catalyst supports.

[0105] In some embodiments, an almoxane is used as a catalyst activator. The almoxane can be used in conjunction with the catalyst during the polymerization reaction to improve its activity.

[0106] As used herein, the terms “alumoxane” and “aluminoxane” are used synonymously and refer to substances capable of activating crosslinked metallocene catalysts. In some embodiments, alumoxanes include oligomeric linear and / or cyclic alkylalumoxanes. In further embodiments, alumoxanes are of formula (A1) or (A2) R a -(Al(R a )-O) x -AlR a 2(A1); or (-Al(R a )-O-) y (A2) (wherein x is 1 to 40, preferably 10 to 20; y is 3 to 40, preferably 3 to 20; Each R a C is independent 1~8 It has an alkyl group (selected from alkyl groups, preferably methyl). In a preferred embodiment, the almoxane is a methylalmoxane (MAO).

[0107] The catalyst composition may include a co-catalyst, preferably an organoaluminum co-catalyst. Preferably, the formula is AIR. b xOne or more alkylaluminums represented by the formula can be used as additional co-catalysts, and each R in the formula b x is the same or different and is selected from halogens or alkoxy or alkyl groups having 1 to 12 carbon atoms, and x is 1 to 3. Non-limiting examples include triethylaluminum (TEAL), tri-isobutylaluminum (TIBAL), tri-methylaluminum (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. Particularly suitable are trialkylaluminums, with triisobutylaluminum (TIBAL) and triethylaluminum (TEAL) being the most preferred.

[0108] The catalyst composition may be particularly useful in a method for preparing a polymer, which involves contacting at least one monomer with at least one catalyst composition. Preferably, the polymer is an olefin polymer, and preferably, the monomer is an alpha-olefin.

[0109] Therefore, the catalyst composition of the present invention is particularly suitable for use in the preparation of olefin polymers. The present invention also relates to the use of catalyst compositions in olefin polymerization.

[0110] The present invention also encompasses olefin polymerization methods, which include contacting a catalyst composition according to the present invention with an olefin monomer, optionally hydrogen, and optionally one or more olefin comonomers; and polymerizing the monomer and optionally one or more olefin comonomers in the presence of at least one catalyst composition and optional hydrogen to obtain an olefin polymer.

[0111] The term "olefin" as used herein means a molecule composed of carbon and hydrogen and containing at least one carbon-carbon double bond. An olefin containing one carbon-carbon double bond is used herein to mean a monounsaturated hydrocarbon with the chemical formula C n H 2n The formula has a double bond at the primary or alpha(α) position. "Alpha-olefin," "α-olefin," "1-alkene," or "terminal olefin" are used herein as synonyms and mean an olefin or alkene having a double bond at the primary or alpha(α) position.

[0112] Throughout this application, the terms “olefin polymer,” “polyolefin,” and “polyolefin polymer” may be used synonymously.

[0113] Suitable polymerizations include, but are not limited to, homopolymerization of alpha-olefins, or copolymerization of alpha-olefins with at least one other alpha-olefin comonomer.

[0114] As used herein, the term “comonomer” refers to an olefin comonomer suitable for polymerization with an alpha-olefin monomer. Comonomers, if present, differ from olefin monomers in that they are selected for their suitability for copolymerization with olefin monomers. Comonomers are not limited to aliphatic C2-C2 compounds. 20 May contain alpha-olefins. Suitable aliphatic C3-C3 20Examples of alpha-olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Further examples of suitable comonomers are vinyl acetate (H3C-C(=O)O-CH=CH2) or vinyl alcohol ("HO-CH=CH2"). Examples of suitable olefin copolymers that can be prepared may be random copolymers of propylene and ethylene, random copolymers of propylene and 1-butene, heterogeneous 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).

[0115] In some embodiments, the olefin monomer is ethylene, and the olefin comonomer includes propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or mixtures thereof.

[0116] In some embodiments, the olefin monomer is propylene, and the olefin comonomer includes ethylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or mixtures thereof.

[0117] Olefin polymers can be prepared in bulk, gas, solution, and / or slurry phases. The methods can be carried out in one or more batch reactors, slurry reactors, gas-phase reactors, solution reactors, high-pressure reactors, tubular reactors, autoclave reactors, or combinations thereof.

[0118] The terms “slurry,” “polymerization slurry,” or “polymer slurry” as used herein mean a substantially 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 polymerized monomers.

[0119] In some embodiments, the liquid phase contains a diluent. As used herein, the term “diluent” means any organic diluent that does not dissolve the synthesized polyolefin. As used herein, the term “diluent” means a diluent in liquid form that is liquid at room temperature, preferably under pressure conditions, in a loop reactor. Suitable diluents are not limited to but include hydrocarbon diluents, such as aliphatic, cyclic aliphatic, and aromatic hydrocarbon solvents, or halogenated forms of such solvents. Preferred solvents are C 12 Alternatively, the solvent may be a lower linear or branched saturated hydrocarbon, a C5-C9 saturated alicyclic or aromatic hydrocarbon, or a C2-C6 halogenated hydrocarbon. Non-limiting 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.

[0120] Polymerization can also be carried out in the gas phase under gas phase conditions. The term "gas phase conditions," as used herein, refers to the temperature and pressure suitable for polymerizing one or more gas phase olefins to produce a polymer.

[0121] The polymerization process can be carried out over a wide temperature range. In certain embodiments, the polymerization process may be carried out at temperatures of 20°C to 125°C, preferably 60°C to 110°C, more preferably 75°C to 100°C, and most preferably 78°C to 98°C. Preferably, the temperature range may be within the range of 75°C to 100°C, most preferably 78°C to 98°C. The aforementioned temperatures may fall under the terminology of more general polymerization conditions.

[0122] In certain embodiments, under slurry conditions, the polymerization process may be carried out at a pressure of about 20 bar to about 100 bar, preferably about 30 bar to about 50 bar, and more preferably about 37 bar to about 45 bar. The aforementioned pressures may fall under the more general terminology of polymerization conditions.

[0123] The present invention also includes polymers at least partially catalyzed by at least one catalyst composition according to the present invention or produced by the method according to the present invention.

[0124] The present invention also includes polymers, preferably olefin polymers, produced by the methods defined herein. In some embodiments, the olefin polymer is polyethylene. In some embodiments, the olefin polymer is polypropylene.

[0125] After the polymer is produced, various articles can be formed from it. Such articles may include, but are not limited to, various polyethylene articles in extrusion and injection applications, including film products, caps and closures, rotational molding, glass yarn, pipes, etc. Such articles may include, but are not limited to, various polypropylene articles in extrusion and injection applications, including injection molding, blow molding, injection stretch blow molding (ISBM), cast or inflation film extrusion, sheet extrusion, thermoforming, fibers, etc.

[0126] Therefore, the present invention also includes articles comprising polymers as defined herein; preferably olefin polymers as defined herein, or polymers obtained according to the methods defined herein.

[0127] The following embodiments are merely illustrative and should not be construed as limiting the scope in any way. Although only some forms of the invention have been shown, as will be apparent to those skilled in the art, the invention is not limited thereto and can be varied and modified without departing from its scope. [Examples]

[0128] Test method The properties referred to herein and hereafter were determined according to the following test procedures. Any of these properties, if referenced in the appended claims, are measured according to the specified test procedures.

[0129] Melt flow index The melt flow index (MI2) of the ethylene polymer 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 die. The melt flow index (HLMI) of ethylene polymers was determined using a 2.096 mm die at a temperature of 190°C and a load of 21.6 kg, according to ISO 1133:2005 Method B, Condition G. 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 die.

[0130] Molecular weight, molecular distribution Molecular weight (M n (number average molecular weight), M w (Weight-average molecular weight) and molecular weight distribution D(M w / M n ), and D'(Mz / M w The polymer was determined by size exclusion chromatography (SEC), particularly by gel permeation chromatography (GPC). Briefly, using Polymer Char's GPC-IR5: 10 mg of polymer sample was dissolved in 10 ml of trichlorobenzene (technical 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) and one Styragel HT6E (Waters) column were used at a flow rate of 1 ml / min. Mobile phase: 1000 wt ppm butylhydroxytoluene (BHT) stabilized trichlorobenzene filtered through a 0.45 μm PTFE filter. Detector: Infrared detector (2800~3000 cm²). -1 ), measure concentration with one narrow filter center 2928cm² -1 , and one narrow filter center 2959cm -1 Calibration: Narrow polystyrene (PS) standard (commercially available). In polyethylene, the molecular weight M of each fraction i of the eluted polymer i The calculation is done using the Mark-Houwink relation (log 10 (M PE ) = 0.965909 × log 10 (M PS )-0.28264)(M PE Based on a cutoff of 1000 for low molecular weight end values. In polypropylene, the molecular weight M of each fraction i of the eluted polymer i The calculation is done using the Mark-Houwink relation (log 10 (M PP )=log 10 (M PS )-0.25323)(M PP Based on a cutoff of 1000 for low molecular weight end values.

[0131] The molecular weight average used when establishing molecular weight / property relationships is the number average (M n ), weighted average (M w) and z-mean (M z ) is the molecular weight. These averages are defined by the following formula and calculated as M i Determined by:

number

[0132] Xylene soluble content The xylene-soluble content was determined by dissolving propylene polymer in refluxing xylene, cooling the solution to 25°C, filtering the solution, and then evaporating the solvent. The residue was the xylene-soluble portion of the propylene polymer, which was then dried and weighed. The protocol was as follows: Approximately 2.5 g of propylene polymer was weighed and placed in a flask, and 250 ml of xylene was added. The xylene was heated with stirring, and then refluxed for 15 minutes until dissolved. Heating and stirring were stopped, and the solution was allowed to stand for exactly 15 minutes. The flask was then placed in a constant temperature bath set to 25°C ± 1°C for 1 hour. The solution was filtered through Whatman No. 4 filter paper, and exactly 50 ml of the solution was collected. The solution was then evaporated, and the residue was dried and weighed. The percentage of xylene-soluble content ("XS") was then calculated according to the following formula. XS(wt.%) = (weight of residue / initial total weight of PP) * 500 All weights are in the same unit.

[0133] Differential scanning calorimetry (DSC) for determining crystallization and melting temperatures. Peak crystallization temperature (T c ), peak melting temperature (T mThe heat of fusion (ΔH) and the heat of melting (T) were calibrated with indium and measured by differential scanning using a TA Instruments DQ 2000 instrument in T-zero mode. Polymer analysis was performed on polymer samples of 2–10 mg. The sample was first equilibrated at 20°C and then heated to 220°C at a heating rate of 20°C / min (first heating). The sample was held at 220°C for 5 minutes to erase the previous heat and crystallization history. The sample was then cooled to 20°C at a constant cooling rate of 20°C / min (first cooling). The sample was 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 (T) corresponding to the cooling rate of 20°C / min was determined. c The endothermic peak of 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 ) was determined. Unless otherwise indicated, the T reported in this invention c , T m The values ​​represent cooling and heating rates of 20°C / min, respectively.

[0134] 13 C NMR / stereoregularity The three-dimensional regularity is 13 This was determined by 13C-NMR spectroscopy. 13¹³C-NMR spectroscopy was performed using a 500 MHz Bruker NMR spectrometer with a high-temperature 10 mm cryoprobe at an operating frequency of 125 MHz, under conditions where the signal intensity of the spectrum was directly proportional to the total number of contributing carbon atoms in the sample. 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 obtained using proton decoupling at 240 scans per spectrum, a pulse repetition delay of 11 s, a spectral width of 26,000 Hz, and a temperature of 130 °C. Samples were prepared by dissolving a sufficient amount of polymer in 1,2,4-trichlorobenzene (TCB, 99%, spectroscopic grade) at 130 °C, homogenizing the sample with occasional stirring, and then adding hexaduterobenzene (C6D6, spectroscopic grade) and a small amount of hexamethyldisiloxane (HMDS, 99.5+%). HMDS served as an internal standard. For example, approximately 600 mg of polymer was dissolved in 2.0 mL of TCB, and then 0.5 mL of C6D6 and 2-3 drops of HMDS were added.

[0135] After data acquisition, the chemical shift is compared to the signal of the internal standard HMDS. The internal standard signal is assigned a value of 2.03 ppm.

[0136] Isotacticity is relative to the total polymer according to procedures well known in the art. 13 The pentads mmmm, mmmr, mmrr, and mrrm are determined by 13C-NMR spectroscopy. In the spectral region of the methyl group, signals corresponding to the pentads mmmm, mmmr, mmrr, and mrrm are assigned using published data, e.g., A. Razavi, Macromol.Symp., Vol. 89, pp. 345-367. Only the pentads mmmm, mmmr, mmrr, and mrrm are considered. The remaining pentads are ignored due to the weak intensity of the corresponding signals. The signal associated with the mmrr pentad is corrected for its overlap with the methyl signal associated with 2,1-insertion. The percentage of the mmmm pentad is then calculated according to the following formula. %mmmm=Area mmmm / (Area mmmm+Area mmmr+Area mmrr+Area mrrm)*100

[0137] The regio-defect content of polypropylene is the percentage of 2,1-insertions in polypropylene.

[0138] In the case of propylene homopolymers, the signal corresponding to the 2,1-insertion is identified with the help of published data, e.g., HNCheng, J. Ewen, Makromol. Chem., Vol. 190 (1989), pp. 1931–1940.

[0139] In the case of propylene copolymers, the determination of the percentage of 2,1-insertion is detailed below using ethylene as the comonomer, but it can be applied to other comonomers as well.

[0140] The percentage of 2,1-insertions in the copolymer of propylene and ethylene comonomer is determined by two contributions: (i) Percentage of 2,1-insertions defined above for propylene homopolymer, and (ii) Percentage of 2,1-insertion, 2,1-inserted propylene is adjacent to ethylene. Therefore, the total percentage of 2,1-insertion corresponds to the sum of these two contributions. The first area, area 1, is defined as the average area of ​​the signals corresponding to 2,1-insertion. The second area, area 2, is defined as the average area of ​​the signals corresponding to 1,2-insertion. The signal assignments related to 1,2-insertion are well known to those skilled in the art. The percentage of 2,1-insertion is calculated according to the following formula: 2,1 - Insertion (%) = Area 1 / (Area 1 + Area 2) * 100 The percentage of 2,1-insertion is given as the molar percentage of 2,1-inserted propylene relative to the total propylene. The signal assignment for case (ii) can be done by using a reference spectrum or by referring to published literature.

[0141] Comonomer content Comonomer content of polypropylene: The total comonomer content (especially ethylene (C2), i.e., C2 by weight) relative to the total weight of the polypropylene composition is 13 The determination was made using 13C NMR. Samples were prepared by dissolving a sufficient amount of polymer in 1,2,4-trichlorobenzene (TCB 99% spectroscopic grade) at 130°C, homogenizing the sample with occasional stirring, and then adding hexaduterobenzene (C6D6, spectroscopic grade) and a small amount of hexamethyldisiloxane (HMDS, 99.5+%). HMDS served 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 2-3 drops of HMDS.

[0142] 13 The 13C NMR signals were recorded on a Bruker 500MHz using a 10mm probe under the conditions listed in Table 1. [Table 1]

[0143] 13 C{ 1 The 1H NMR spectrum was obtained by performing a Fourier transform on 131 K points after a light Gaussian multiplication. The spectrum was phased, baseline corrected, and the chemical shift scale was compared to an internal standard HMDS of 2.03 ppm.

[0144] The chemical shift of the signal is peak-picked, and the peaks are integrated as shown in Figure 2 and Table 2 below. [Table 2] The chemical shift (chemical shit) is given as + / - 0.05 ppm. The main peak A shows 1,2 PP units. Peak I represents 1.3 PP units. Peaks B, C, D, E, F, G, and H represent 2,1 PP units. Peaks T, U, V, W, X, and Y indicate ethylene incorporation in units of 1,2 PP. Peaks P, Q, R, and S indicate ethylene incorporation after 2.1 PP units. The weight percentage of C2 content is obtained by the following combination of areas (A). A C3 1,2 =A A 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 A C3 1,3 =A I / 2 A C2 E1 1,2 =(0.5*A T +A Y ) / 2 A C2 E2 1,2 =( A U -A I +A X ) / 2-A V 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 A C2 2,1 =(0.5*A P +0.5*A Q +0.5*A S+ A R ) / 4 A C2 =( A C2 E1 1,2 +A C2 E2 1,2 +A C2 E3 1,2 +AC2 2,1 ) A C3 =( A C3 1,2 +A C3 2,1 +A C3 1,3 ) %(wt.)C2=(28*A C2 ) / (28*A C2 +42*A C3 ) x 100 Randomness (%) = A C2 E1 1,2 / A C2

[0145] Determination of Al and Zr content Al and Zr content was determined using inductively coupled plasma atomic emission spectroscopy (ICP-AES) after mineralization of the sample and recovery of the acid medium residue. The spectrometer used was Spectro's ICP-AES ARCOS.

[0146] The elements were determined by atomizing the solution in an argon plasma, measuring the intensity of the most sensitive and uninterfering emission line, and comparing these intensities with those of a calibration solution (external calibration method).

[0147] Preparation of the test solution: Under an inert atmosphere (in a glove box), approximately 0.3 g of catalyst was placed in a platinum crucible, and 3-5 ml of isopropyl alcohol was added to "deactivate" the catalyst. The mixture was heated to dryness in a sand bath (30 minutes). The platinum crucible was placed in a 600°C oven for 10 minutes. After cooling, Milli-Q® deionized water was added to impregnate all the ash, and 1 ml of concentrated HCl and concentrated HF were added. The crucible was placed in a sand bath, and the contents of the crucible were mixed by adding Milli-Q® deionized water. After 24 hours, 1 ml of concentrated HCl, 0.5 ml of concentrated HF and Milli-Q® deionized water were added, and the mixture was stirred under heat to achieve complete dissolution. After cooling, the mixture was transferred to a 50 ml polypropylene tube, and the volume was increased to 50 ml with Milli-Q® deionized water. The test solution was then diluted 25-fold to ensure that a 2% HCl / 1% HF medium was maintained.

[0148] Preparation of calibration standards and control solutions: Standard solutions were prepared by diluting commercially available single-element solutions of guaranteed concentration. Standard solutions were prepared by transferring the required volume of guaranteed solution to a 50 ml polypropylene tube, rinsing the sides of the tube with Milli-Q® deionized water, adding 1 ml of HCl and 0.5 ml of concentrated HF per 50 ml to obtain the same acid content in the solution as the sample solution, and finally diluting with Milli-Q® deionized water. Control solutions were prepared by diluting commercially available multi-element solutions of guaranteed concentration. The presence of other elements in the solution allowed for verification of the presence / absence of possible interference.

[0149] Expression of the result: The measured elemental content (ppm) in the sample was calculated as follows: Elemental concentration in solution (mg / l) × Volume (50 ml) × Dilution ratio / Mass (g) The Limit of Quantification (LOQ) was calculated for each element from 10 blank measurements: LOQ in solution (mg / l) = Standard deviation of 10 blank replicates × 10 LOQ (ppm) of a sample = LQ in solution × volume (50 ml) × dilution ratio / mass (g).

[0150] A. Catalyst Catalyst 1: Metallocene catalyst 1 (Cata1) was prepared as described below and shown in Scheme 1. [ka]

[0151] A solution of 2-tert-butylanisole: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 at room temperature overnight. The mixture was then filtered and concentrated to obtain a pale yellow liquid, which was dried under vacuum (20.2 g, 93%). 1 H NMR (400 MHz, CDCl3, 25℃): δ 7.40 (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). [ka]

[0152] A mixture of 6-tert-butyl-5-methoxy-2-methyl-1-indanone:2-tert-butylanisole (17.8 g, 0.11 mol) and methacrylic acid (11.7 g, 0.14 mol) was added dropwise at 60°C to a well-mixed Eaton reagent prepared from 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, then at room temperature overnight. It was then poured into ice water (400 mL) and extracted with toluene (2 × 200 mL). The combined organic layer was washed with water and aqueous NaHCO3 solution (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%). 1H NMR (400 MHz, CDCl3, 25℃): δ 7.70 (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). [ka]

[0153] 4-Bromo-6-tert-butyl-5-methoxy-2-methyl-1-indanone:Bromine (5.95 mL, 0.12 mol) was added dropwise at 0°C 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), and water (90 mL) containing tetrabutylammonium bromide (0.75 g, 2 mol%) in CH2Cl2 (30 mL). The mixture was then stirred overnight at room temperature. After 16 hours, bromine (3.4 mL, 0.066 mol) was added together with NaOAc (16.2 g, 0.2 mol), and the mixture was stirred at rt for 6 hours. The organic phase was separated and washed with aqueous Na2S2O3 (1.0 M, 300 mL), saturated aqueous NaHCO3, and water. The compound was dried on MgSO4 and evaporated to obtain the desired compound as a viscous orange oil (35.3 g, 98%). 1 H NMR (400 MHz, CDCl3, 25℃): δ 7.69 (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). [ka]

[0154] 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 under argon flush to a well-mixed mixture of 4-bromo-6-(tert-butyl)-5-methoxy-2-methyl-1-indanone (5.1 g, 0.017 mol), phenylboronic acid (2.82 g, 0.023 mol), and K2CO3 (6.39 g, 0.046 mol) in 1,2-dimethoxyethane (60 mL) and water (20 mL). 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 water and an aqueous solution of Na2CO3 (2.0 M, 100 mL), dried on MgSO4, and evaporated under reduced pressure to obtain an orange liquid (5.3 g, 83%). 1 H NMR (400 MHz, CDCl3, 25℃): δ 7.76 (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-ind), 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). [ka]

[0155] 6-tert-butyl-5-methoxy-4-phenyl-2-phenyl-1H-indenone (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 aqueous HCl (10 mL) were added to separate the organic phase. The mixture was washed with aqueous Na2CO3 solution (2.0 M, 200 mL), dried on 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 minutes, cooled, washed with water, dried on MgSO4, and evaporated. A brownish oily substance was obtained, which was purified by flash column chromatography (Al2O3-petroleum ether) to obtain the desired product as a colorless, viscous oil (2.8 g, 48%). 1 H NMR (400 MHz, CDCl3, 25℃): δ 7.51-7.41 (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). [ka]

[0156] (1,2,3,4-tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)-dimethylsilane(proligand C) OMe,tBu):6-tert-butyl-5-methoxy-4-phenyl-2-methyl-1H-indene (0.62 g, 0.0021 mol) was dissolved in dry Et2O (20 mL) and cooled to -78 °C. To this solution, n-BuLi (2.26 M solution in 0.93 mL of hexane, 0.0021 mol) was added by syringe, and the temperature was raised to room temperature. The color of the solution changed 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 warmed 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 × 30 mL). The combined organic phase was dried over Na2SO4 and then evaporated to dryness to obtain a yellow, viscous oily substance (0.90 g, 91%), which was used without further purification. 1 H NMR (300 MHz, CDCl3, 25℃): δ 7.53-7.30 (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). [ka]

[0157] Cata1:C OMe,tBu -ZrCl2(1,2,3,4-tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)-dimethylsilane-dichlorozirconium-(IV):n-BuLi (2.26 M solution in 2.30 mL of hexane, 0.0052 mol) is added to proligand C OMe,tBu(1.00 g, 0.0026 mol) was added dropwise to a solution in Et2O (30 mL) at -78°C, and the resulting mixture was stirred overnight. To this solution, ZrCl4 (0.61 g, 0.0026 mol, 1 equivalent) was added at -78°C, and the resulting mixture was warmed at room temperature and stirred overnight. The mixture was evaporated to dryness, and dichloromethane / heptane (40 mL, 1:1 v / v) was added. The precipitated LiCl was filtered through a cannula to obtain an orange solution. The latter was concentrated to approximately 1 / 3 v, 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 (400 MHz, CD2Cl2, 25℃): δ 7.64 (s, 2H), 7.46 (q, J = 7.4, 6.3, 4H), 7.41-7.32 (m, 1H), 6.59 (s, 1H, H in 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 C NMR (400 MHz, 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. 32 H 40 The calculated value of Cl2OSiZr is 628.1273, and the measured value (m / z) is 630.1266. [ka]

[0158] Comparative example 1C: Comparative catalyst 1C (Comp1C) is described below and was prepared as shown in Scheme 2. [ka] 2-Bromo-4-tert-butyltoluene:8.3 mL, 0.16 mol of bromine was slowly added at room temperature to a solution of 4-tert-butyltoluene (20.0 g, 0.14 mol) in glacial acetic acid (62 mL), and the solution was 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 phase was washed with water, dried over Na2SO4, evaporated, and distilled (90°C / 0.05 mg / L) to obtain the desired compound as a yellow liquid (24.4 g, 77%). 1 H NMR (300 MHz, CDCl3, 25℃): δ 7.26 (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). [ka]

[0159] 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 formed succinimide was removed by filtration. The filtrate was evaporated by rotation and distilled (0.06 mg, 75-84 °C) to obtain a yellow liquid (13.1 g, 70%). 1H NMR (300 MHz, CDCl3, 25℃): δ 7.58 (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). [ka]

[0160] 2-(2-bromo-4-tert-butylbenzyl)-2-methylmalonate: Diethyl-2-methylmalonate (5.42 g, 0.031 mol) was slowly added at -30°C to a suspension of NaH (0.821 g, 0.034 mol) dispersed in dry THF (40 mL), and the mixture was stirred for 1 hour. 2-bromo-4-tert-butylbenzene bromide (10.0 g, 0.0327 mol) dissolved in dry THF (10 mL) was added at 0°C, and the mixture was stirred for 1 hour, and then under reflux for 16 hours. The precipitated NaBr was filtered over silica, and the filtrate was concentrated to obtain a yellow oily substance (12.0 g, 96%). 1 H NMR (300 MHz, 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-malonic acid)), 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). [ka]

[0161] 3-(2-bromo-4-tert-butylbenzyl)-2-methylmalonic acid: 2-(2-bromo-4-tert-butylbenzyl)-2-methylmalonate (12.0 g, 0.03 mol) was added to H2O / MeOH (70 mL, 1:1 v / v) and NaOH (4.80 g, 0.12 mol), and the resulting mixture was heated overnight under reflux. Then, H2O (30 mL) and 12 M HCl (pH 1) were added to the reaction mixture to precipitate an orange, viscous oily substance. The latter oily substance 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 the white solid (5.6 g, 55%). 1 H NMR (300 MHz, THF-d8, 25℃): δ 7.56 (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). [ka]

[0162] 3-(2-bromo-4-tert-butylphenyl)-2-methylpropanoic acid:3-(2-bromo-4-tert-butylbenzyl)-2-methylmalonic acid was heated under reflux at 160°C in air for 4 hours to obtain an extremely viscous yellow oily substance (4.88 g, 99%). 1 H NMR (300 MHz, THF-d8, 25℃): δ 7.55 (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). [ka]

[0163] 3-(2-bromo-4-tert-butylphenyl)-2-methylpropanoyl chloride: 3-(2-bromo-4-tert-butylphenyl)-2-methylpropanoic 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 the addition was complete, the resulting solution was stirred overnight under reflux at 40°C. Excess thionyl chloride was removed under vacuum to obtain a yellow liquid, which was dried overnight under vacuum (5.0 g, 96%). 1 H NMR (300 MHz, CDCl3, 25℃): δ 7.56 (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). [ka]

[0164] A solution of 3-(2-bromo-4-tert-butylphenyl)-2-methylpropanoyl chloride (4.95 g, 0.016 mol) in 4-bromo-6-tert-butyl-2-methyl-1-indanone:CH2Cl2 (20 mL) was slowly added dropwise to a suspension of AlCl3 (2.52 g, 0.19 mol) dispersed in CH2Cl2 (20 mL) at 0°C for 30 minutes. The resulting mixture was heated, 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 and then over Na2SO4, and evaporated to dryness to obtain a yellow solid (3.54 g, 80%). 1H NMR (300 MHz, CDCl3, 25℃): δ 7.80 (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). [ka]

[0165] 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 well-mixed 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), and K2CO3 (4.90 g, 0.035 mol) in 1,2-dimethoxyethane (42 mL) and water (14 mL) under Ar flushing. The mixture was then poured into water (200 mL) and extracted with CH2Cl2 (3 × 100 mL). The combined organic phase was washed with water and aqueous Na2CO3 solution (2 M, 100 mL), dried over Na2SO4, and evaporated. The crude product was extracted with hexane (200 mL), and the volatile components were evaporated under vacuum to obtain a viscous red oily substance (3.40 g, 96%). 1 H NMR (300 MHz, CDCl3, 25℃): δ 7.80 (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). [ka]

[0166] 4-phenyl-6-tert-butyl-2-methyl-1H-indene:4-phenyl-6-tert-butyl-2-methyl-1-indanone (3.40 g, 0.012 mol) was dissolved in Et2O (20 mL) and added dropwise to LiAlH4 (0.23 g, 0.0061 mol) in Et2O (50 mL) at 0°C. After stirring for 1 hour, water (40 mL) and 5% w / v aqueous HCl (10 mL) were added to separate the organic phase, which was washed with Na2CO3 aqueous solution (2.0 M, 100 mL), dried on MgSO4, and evaporated. The residue was dissolved in toluene (50 mL), p-TSA (0.21 g, 9 mol%) was added, the resulting mixture was refluxed for 20 minutes, cooled, washed with water, dried on Na2SO4, and evaporated to obtain a brown oily substance, which was crystallized at 0°C (2.80 g, 88%). 1 H NMR (300 MHz, CDCl3, 25℃): δ 7.60-7.53 (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). [ka]

[0167] (1,2,3,4-tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenyl-6-tert-butyl-indenyl)-dimethylsilane(proligand C) tBu):6-tert-butyl-4-phenyl-2-methyl-1H-indene (2.40 g, 0.0092 mol) was dissolved in dry Et2O (40 mL) and cooled to -78°C. To this solution, n-BuLi (2.26 M solution in 4.05 mL of hexane, 0.0092 mol) was added by syringe and the temperature was raised to room temperature. The resulting mixture was stirred overnight. Then Conch (0.33 g, 0.0037 mol) was 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 warmed to 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 × 50 mL). The combined organic phases were dried on Na2SO4 and then evaporated to dryness to obtain a yellow, viscous oily substance (3.80 g, 94%), which was used without further purification. 1 H NMR (300 MHz, CDCl3, 25℃): δ 7.65-7.20 (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). [ka]

[0168] Comp1C:C tBu -ZrCl2(1,2,3,4-tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenyl-6-tert-butyl-indenyl)-dimethylsilane-dichlorozirconium-(IV):n-BuLi (2.26 M solution in 2.00 mL of hexane, 0.0045 mol) is added to proligand C tBu(1.00 g, 0.0023 mol) was added dropwise at -78°C to a solution in Et2O (15 mL), and the resulting mixture was stirred overnight. To this solution, ZrCl4 (0.53 g, 0.0023 mol) was added at -80°C, and the resulting mixture was warmed at room temperature and stirred overnight. The mixture was evaporated to dryness, dichloromethane / heptane (40 mL, 1:1 v / v) was added, and the precipitated LiCl was filtered through a cannula to obtain an orange solution. The latter was concentrated to approximately 1 / 3 v, and the resulting yellow microcrystalline powder was separated from the solution by cannula filtration and then dried under vacuum (0.62 g, 45%). 1 H NMR (400 MHz, CD2Cl2, 25℃): δ 7.68 (d, J = 7.6, 2H), 7.54-7.43 (m, 4H), 7.40 (d, J = 7.2, 2H), 6.94 (s, 1H, H in 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 C NMR (400 MHz, 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. 31 H 38 The calculated value for Cl2SiZr is 598.1167, and the measured value (m / z) is 600.1155. [ka]

[0169] Comparative Example 2C: The comparative catalyst 2C (Comp2C) was prepared as described below: 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. Then, 4-bromo-2-methyl-1H-indene (4.00 g, 0.019 mol) and K2CO3 (7.40 g, 0.054 mol) were added. The mixture was stirred and placed under Ar. Then, Pd(OAc)2 (0.13 g, 3 mol%) and PPh3 (0.30 g, 6 mol%) were 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 phase was washed with water (3 × 100 mL) and aqueous Na2CO3 solution (2 M, 100 mL), dried on MgSO4, and evaporated. The crude product was extracted with hot hexane (200 mL) to obtain an orange oily substance after evaporation of volatile components (3.53 g, 90%). This was purified by column chromatography (eluent system: 95:5 v / v hexane / siRNA) to obtain the desired compound as a colorless, viscous liquid (2.60 g, 66%). 1 ¹H NMR (300 MHz, 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). [ka]

[0170] (1,2,3,4-tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenylindenyl)-dimethylsilane (proligand C) H): 2-methyl-4-phenylindene (4.30 g, 0.021 mol) was dissolved in dry Et2O (50 mL) and cooled to -78°C. To this solution, n-BuLi (2.26 M solution in 9.2 mL of hexane, 0.021 mol, 1 equivalent) was added by syringe, and the temperature was raised to room temperature. The color of the solution changed from yellow to orange with the first drop of n-BuLi, 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 warmed at 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 ether (2 × 70 mL). The combined organic phase was dried over Na₂SO₄ and then evaporated to dryness to obtain a yellow, viscous oily substance (7.2 g, 90%), which was used without any purification. [ka]

[0171] Comp2C:C H -ZrCl2(1,2,3,4-tetramethyl-1,3-cyclopentadienyl)-(2-methyl-4-phenylindenyl)-dimethylsilane-dichlorozirconium-(IV):n-BuLi (2.26 M solution in 2.30 mL of hexane, 0.0052 mol) is added to proligand C H (1.00 g, 0.0026 mol) was added dropwise at -78°C to a solution in Et2O (30 mL), and the resulting mixture was stirred overnight. To this solution, ZrCl4 (0.61 g, 0.0026 mol) was added at -80°C, and the resulting mixture was warmed at room temperature and stirred overnight. The mixture was evaporated to dryness, and dichloromethane / heptane (40 mL, 1:1 v / v) was added. The precipitated LiCl was filtered through a cannula to obtain an orange solution. The latter was concentrated to approximately 1 / 3 v; the resulting yellow microcrystalline powder was separated from the solution by cannula filtration and then dried under vacuum (0.60 g, 42%). 1H NMR (400 MHz, CDCl3, 25℃): δ 7.71-7.65 (m, 2H), 7.57 (d, J = 8.7 Hz, 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 C NMR (500 MHz, 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. 27 H 30 The calculated value for Cl2SiZr is 542.0541, and the measured value (m / z) is 544.0535. [ka]

[0172] Catalyst 2: Catalyst 2 (Cata2) was prepared as described below and shown in Scheme 3. [ka]

[0173] 1,3-di-tert-butyl-2-methoxybenzene:2,6-di-tert-butylphenol (50.0 g, 0.18 mol) was added to degassed dry DMF (300 mL) under an Ar atmosphere, followed by barite (74.0 g, 0.23 mol) and CH3I (36.0 mL, 0.58 mol). The reaction mixture was stirred overnight. Et2O (300 mL) was then added. The organic layer was extracted with H2O (500 mL), NaOH aqueous solution (1.0 M, 300 mL), and H2O (2 × 400 mL). The combined extracts were dried over MgSO4 and concentrated under vacuum. The crude residue was purified by distillation (123 °C, 3 mmbar) to obtain an orange crystalline solid (30.0 g, 58%). 1 H NMR (300 MHz, CDCl3, 25℃): δ 7.34 (s, 2H), 3.69 (s, 3H), 1.42 (s, 18H). [ka]

[0174] 3,5-di-tert-butyl-4-methoxyphenyl)boronic acid:4-bromo-2,6-di-tert-butylanisole (30.0 g, 0.1 mol) was placed in a three-necked round-bottom flask and flushed with nitrogen for 10 minutes. Anhydrous THF (400 mL) was added via cannula, and the solution was cooled to -78°C. n-BuLi (2.5 M solution in 48.0 mL of hexane, 0.12 mol, 1.2 equivalents) was added dropwise using a syringe. The solution was stirred at -78°C for 1 hour. Then, (iPrO)3B (56.0 mL, 0.3 mol) was slowly added using a syringe, the reaction was warmed, and stirred overnight to obtain a milky yellow solution. Solid NH4Cl was added to the solution to quench the excess n-BuLi, then 1 M aqueous HCl was added dropwise to adjust the pH to 6.5, and finally 6 M HCl was added to adjust the pH to 1. The reaction layers were separated, and the aqueous layer was extracted with dichloromethane. The combined organic layer was reduced in volume under vacuum, and a yellow-white solid precipitated, which was then diluted with dichloromethane. Excess heptane was then added, and the mixture was stored in a freezer for one day. A solid formed, which was then filtered. This process was repeated twice to obtain the desired product (18.0 g, 68%).1 H NMR (400 MHz, CDCl3, 25℃): δ 8.16 (s, 2H), 3.76 (s, 3H), 1.52 (s, 18H). [ka]

[0175] 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 under Ar flush to a well-mixed mixture of 4-bromo-6-(tert-butyl)-5-methoxy-2-methyl-1-indanone (pre-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), and K3PO4 (12.0 g, 0.057 mol) in THF (72 mL) and water (14 mL). 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 Na2CO3 aqueous solution (2M, 200 mL), dried on MgSO4, and evaporated under vacuum. A concentrated solution of the crude product was then prepared in dichloromethane, and the desired product was precipitated as a white solid by adding excess hexane (6.0 g, 70%). 1 H NMR (300 MHz, CDCl3, 25℃): δ 7.73 (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). [ka]

[0176] 3,5-di-tert-butyl-4-methoxyphenyl-1-indene:3,5-di-tert-butyl-4-methoxyphenyl-1-indanone 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% w / v aqueous HCl (20 mL). The organic phase was separated, washed with Na2CO3 aqueous solution (5% w / w, 100 mL), dried on 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 on MgSO4, and evaporated to obtain a white crystalline solid (5.2 g, 89%). 1 H NMR (400 MHz, CDCl3, 25℃): δ 7.37 (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). [ka]

[0177] Starting with (1,2,3,4-tetramethyl-1,3-cyclopentadienyl)-[2-methyl-4-(3,5-di-tbutyl-4-methoxy)-6-tert-butyl-indenyl]-dimethylsilane(proligand C1[di-tBu,OMe)-Ph]):3,5-di-tert-butyl-4-methoxyphenyl-1-indene (0.54 g, 0.00012 mmol), the same experimental procedure as that used for the previously synthesized ligand was followed. A yellow, viscous oily substance was obtained, which was used in the next step without further purification (0.85 g, 98%). 1H NMR (400 MHz, CDCl3, 25℃): δ 7.35 (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). [ka]

[0178] Cata2:C1[(di-tBu,OMe)-Ph]-ZrCl2(1,2,3,4-tetramethyl-1,3-cyclopentadienyl))-[2-methyl-4-(3,5-di-tbutyl-4-methoxy)-6-tert-butyl-indenyl]-dimethylsilane-dichlorozirconium-(IV): The complex C1[(di-tBu,OMe)-Ph]-Zr was synthesized from the proligand C1[(tBu)2,OMe-Ph] (0.80 g, 1.31 mmol) using a procedure similar to that described above for other metallocene complexes, and isolated as a yellow microcrystalline powder (0.32 g, 30%). 1 H NMR (400 MHz, CDCl3, 25℃): δ 7.41 (s, 3H), 6.67 (s, 1H, H in Cp ring), 3.73 (s, 3H, ind-OCH3), 3.32 (s, 3H, 4-(OMe)-Ph), 2.22 (s, 3H, C-CH3), 2.04 (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). 13C NMR (101 MHz, 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. piASAP C 41 H 58 The calculated value for Cl2O2SiZr is 770.2625, and the measured value (m / z) is 772.2628. [ka]

[0179] Reference 1: rac-Cyclohexyl(methyl)silanediylbis[2-methyl-4-(4'-tert-butylphenyl)indenyl]zirconium dichloride (Ref1) was purchased from SPCI (South Pacific Chemical Industries) (CAS 888227-55-2). [ka]

[0180] B. Heterogeneous polymerization of propylene All catalysts were supported using the ACM methodology with a Radley apparatus as described below: 20.011 g of dry silica (TS-F202) was suspended in 200 mL of dry toluene and stirring was started. 38 mL of MAO (30 wt%) was added dropwise, aiming for a 16 wt% Al deposition. An additional 87 mL of dry 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 dry toluene and dry pentane, and then dried. Metallocene (approximately 10 mg, to reach 1.25 wt% supported metallocene) was dissolved in 5 mL of dry toluene. 8 g of silica / MAO (prepared as described above) was added, and the glassware was washed with 5 mL of dry toluene and added to the mixture. The mixture was stirred at room temperature for 3 hours and then filtered. The solid was washed three times with dry toluene and three times with dry pentane, and then dried in vacuum. Next, the supported catalyst was dispersed in dried oil (Finavestan A 360 B) to achieve a solid content of approximately 20 wt%.

[0181] The zirconium and aluminum content (%wt) of the samples was analyzed using an ICP-AES spectrometer. The ICP-AES analysis results of the supported catalyst are shown in Table 3. [Table 3]

[0182] Homopolymerization PPH An 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 started, and once the reactor stabilized, 1 mL of TIBAL, a mixture of the supported catalyst and co-catalyst was added to the reactor along with 1.5 L of propylene. The reactor was then raised to 70°C, and once that temperature was reached, the reaction was allowed to proceed for 1 hour. The reactor was then evacuated, and the polymer was dried under a light flow of N2. The polymer was then collected and dried for a further 2 hours. [Table 4]

[0183] The polymerization results are shown in Table 5. [Table 5] The activity of the comparative example is quite low. When the methoxy group is grafted onto the indenyl group, especially when a second methoxy group is added to the 4-position of the phenyl ring, the activity increases. This last metallocene has almost the same activity as Ref1. Low xylene solubility values ​​were measured.

[0184] The DSC and NMR analysis results are shown in Table 6. [Table 6] A lower content of site defects is observed (compared to bis-indenyl Ref1). All of these defects with different values ​​along the chain affect the melting and crystallization temperatures.

[0185] Table 7 shows the information and NMR results at the end of the experiment. [Table 7]

[0186] Random Copolymer PPR Polymerization was carried out in an 8-liter reactor at 70°C for 30 minutes in the presence of 15 g of ethylene, 0.5 NL of hydrogen, and TIBAL as a scavenger. Unless otherwise specified, the reaction conditions were as listed in Table 8. The reactor was then evacuated and the polymer was dried under a flow of light nitrogen. The polymer was then collected and dried for a further 2 hours. [Table 8]

[0187] The polymerization results are shown in detail in Table 9. [Table 9] It can be seen that the ethylene conversion rate was high.

[0188] The results of NMR, GPC, and DSC analysis are shown in Table 10. [Table 10] The GPC results shown in Table 10 are consistent with the MFI analysis results. The lower melting and crystallization temperatures are also noteworthy in the new metallocene-based PPR compared to Ref1. This is due to higher ethylene incorporation and lower melting and crystallization temperatures in homopolymerization (see above). The higher melting and crystallization temperatures compared to polymerization with comparative catalysts Comp1C and 2C are also noteworthy. Compared to comparative catalysts 1C and 2C, increased activity was possible when using indenyl catalysts with -OR groups such as methoxy groups. Compared to catalyst Ref1, higher stereoregularity defects and lower site defects were observed.

[0189] C. Homogeneous polymerization of propylene 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 mantle with a circulating water bath. Toluene (150 mL) and MAO (5000 equivalents of PMAO 13 wt.% Al in toluene) were charged into the reactor. After 30 minutes, propylene (5 bar, liquid air, 99.99%) was introduced, and then the propylene pressure was reduced to 1 bar. A solution of the catalyst precursor in toluene (2.0 μmol, dependent on the catalyst MW and catalyst concentration) was added by syringe. Immediately, the propylene pressure was increased to 5 bar (maintained constant with a back regulator), and the solution was stirred for 30 minutes. The temperature inside the reactor was monitored using a thermocouple. Polymerization was stopped by evacuating the vessel and quenching with a 10% aqueous HCl solution in MeOH. The polymer was precipitated in methanol (500 mL) with a 10% c.HCl solution. The polymer was collected by filtration, washed with methanol (200 mL), and dried in a vacuum (60°C, 3 hours).

[0190] The polymerization results are shown in Table 11. [Table 11]

[0191] D. Heterogeneous polymerization of ethylene The polymerization reaction was carried out in a 132 ml autoclave equipped with a stirrer, temperature controller, and inlets for supplying ethylene and hydrogen. The reactor was dried with nitrogen at 110°C for 1 hour, and then cooled to 40°C.

[0192] All polymerization was carried out under the conditions listed in Table 12 (unless otherwise specified). 75 ml of isobutane and 1.6 ml of 1-hexene were charged into the reactor and pressurized to 23.8 bar with ethylene containing 800 ppm hydrogen. Catalyst (3.5 mg) and co-catalyst were added. Polymerization began upon injection of the catalyst suspension and proceeded at 85°C, stopping after 60 minutes by depressurizing the reactor. The reactor was flushed with nitrogen before opening. [Table 12]

[0193] The polymerization results are shown in Table 13. [Table 13]

Claims

1. A catalyst of formula (I) for the polymerization of olefins. 【Chemistry 1】 [In the formula, R ２ 、R ３ 、R ６ 、R ７ are each independently hydrogen or selected from the group consisting of alkyl, alkenyl, aryl, and -OR １５ ; each of said groups is unsubstituted or may be substituted with one or more substituents Z １ ; Z １ is selected from -OR １６ , alkyl, and alkenyl; R １５ , R １６ are each independently alkyl; R ４ is unsubstituted or one or more Z １ It is an aryl substituted with R ５ ha-OR １５ And; R ８ , R ９ , R １０ , R １１ Each is independently selected from the group comprising hydrogen, alkyl, alkenyl, aryl, and alkoxy; L １ is SiR １３ R １４ or -[CR １３ R １４ ] ｈ - is true; h is an integer selected from 1, 2, or 3; R １３ and R １４ Each of them is independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, and cycloalkenyl; or R １３ and R １４ They form cycloalkyl or cycloalkenyl groups with the atoms to which they are bonded; M １ It is zirconium; Q １ and Q ２ Each is independently selected from the group comprising halogens, alkyls, and alkoxys.

2. R ２ , R ３ , R ６ , R ７ Each of them independently is hydrogen or C １～８ Alkyl, C ２～８ Alkenil, C ６～１０ aryl, and -OR １５ A group is selected from the group including; each of the group is either unsubstituted or has one or more substituents Z １ It may be replaced with; Z １ ha-OR １６ , C １～８ Alkyl and C ２～８ Selected from Alkenil; R １５ , R １６ Each is independently C １～８ It is alkyl; R ４ is unsubstituted or one or more Z １ It is an aryl substituted with R ５ ha-OR １５ The catalyst according to claim 1.

3. R ８ , R ９ , R １０ , R １１ Each of them independently produces hydrogen and C １～８ Alkyl, C ２～８ Alkenil, C ６～１０ Aryl, and C １～８ The catalyst according to claim 1, selected from the group comprising alkoxys.

4. L １ is SiR １３ R １４ or -[CR １３ R １４ ] ｈ - is true; h is an integer selected from 1, 2, or 3; R １３ , and R １４ Each of them independently contains hydrogen and C １～８ Alkyl, C ２～８ Alkenil, C ３～８ Cycloalkyl, and C ５～８ Selected from the group including cycloalkenyls; or R １３ and R １４ C ３～８ Cycloalkyl or C ５～８ The catalyst according to claim 1, which forms a cycloalkenyl.

5. M １ is zirconium; Q １ and Q ２ Each of them independently controls halogen and C １～８ The catalyst according to claim 1, selected from the group including alkyl groups.

6. Formula (III) or (IV) 【Chemistry 2】 [where n is an integer selected from 0, 1, 2, 3 or 4; m is an integer selected from 0, 1, 2 or 3; 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 has the same meaning as in claim 1] The catalyst according to claim 1, having the following characteristics.

7. Equation (V) or (VI) 【Transformation 3】 [wherein, n is an integer selected from 0, 1, 2, 3 or 4, m is an integer selected from 0, 1, 2, or 3; R ２ , R ３ , R １５ , R １６ , R ６ , R ７ , L １ , Z １ , M １ , Q １ , Q ２ have the same meaning as in claim 1] The catalyst according to claim 1, having the following characteristics.

8. Formula (VII) or (VIII) 【Chemistry 4】 [wherein n is an integer selected from 0, 1, 2, 3 or 4, and m is an integer selected from 0, 1, 2 or 3; R ２ , R ３ , R １５ , R １６ , R ６ , R ７ Z １ M １ Q １ Q ２ This has the same meaning as claim 1. The catalyst according to claim 1, having the following characteristics.

9. Formula (XIX) or (XX) 【Transformation 5】 The catalyst according to claim 1, having the following characteristics.

10. A supported catalyst comprising the catalyst according to any one of claims 1 to 9, and a support.

11. At least one catalyst according to any one of claims 1 to 9; Optional activator; optional support; and optional co-catalyst. A catalyst composition containing the following:

12. The catalyst composition according to claim 11, wherein the catalyst composition comprises an activator.

13. The catalyst composition according to claim 11, comprising an almoxane activator; a titanated silica or silica solid support; and an optional co-catalyst.

14. Use of the catalyst according to any one of claims 1 to 9 for the preparation of an olefin polymer.

15. Use of the catalyst composition according to claim 11 for the preparation of olefin polymers.

16. A method for olefin polymerization comprising contacting the catalyst composition according to claim 11 with an olefin monomer, one or more olefin comonomers, and an optional hydrogen; and polymerizing the monomer and one or more olefin comonomers in the presence of at least one of the catalyst compositions and an optional hydrogen to obtain an olefin polymer.

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