Novel metallocene compound, catalyst composition containing the same, and method for preparing olefin polymer using the same

Abstract

The present invention relates to a novel metallocene compound, a catalyst composition comprising the metallocene compound and a method for preparing an olefin polymer using the catalyst composition.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 10-2020-0130132 filed on October 8, 2020, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety.

[0003] The present invention relates to a novel metallocene compound, a catalyst composition comprising the metallocene compound, and a method for preparing an olefin polymer using the catalyst composition. More specifically, the present invention relates to a novel metallocene compound having high activity in a polymerization reaction and capable of controlling the molecular weight and fine structure of the prepared olefin polymer, a catalyst composition comprising the metallocene compound, and a method for preparing an olefin polymer using the catalyst composition. Background Art

[0004] Olefin polymerization systems are divided into Ziegler-Natta catalyst systems and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics. Ziegler-Natta catalysts have been widely used in existing industrial production processes since their invention in the 1950s, but since it is a multi-site catalyst with multiple active sites, it is characterized by a wide molecular weight distribution of the polymer and is limited in its application areas. Due to the uneven composition distribution of the comonomer, it is limited in ensuring the desired performance.

[0005] At the same time, the metallocene catalyst is composed of a main catalyst whose main component is a transition metal compound and a co-catalyst. The co-catalyst is an organic metal compound including aluminum as the main component. The catalyst is a homogeneous composite catalyst and a single-site catalyst. According to the properties of the single-site catalyst, a polymer with a narrow molecular weight distribution and a uniform distribution of copolymer monomer composition is obtained, and the stereoregularity, copolymerization properties, molecular weight, crystallinity, etc. can be changed according to the modification of the ligand structure of the catalyst and the change of polymerization conditions.

[0006] At the same time, polyolefin resins for injection molding are required to have excellent long-term durability and processability. High-density polyethylene regions can generally exhibit high pressure resistance because the higher the crystallinity of the polyolefin resin, the greater the modulus, and the greater the force to withstand high pressure. However, if the density is high, the brittle fracture resistance may be reduced, so the long-term pressure resistance may be reduced. And, if the molecular weight is low or the molecular weight distribution is narrow, sagging (melt sagging) may occur during the processing of the injection molded product, making the processing difficult, therefore, a polyolefin resin with a high molecular weight and a very wide molecular weight distribution should be applied to solve the problem.

[0007] Although methods of controlling molecular weight distribution by synthesizing various supported metallocene catalysts have been developed to improve these problems, in the case of preparing olefin polymers using existing metallocene catalysts, economic efficiency may be reduced due to insufficient catalyst activity, or the molecular weight distribution of the prepared polymer may be narrow, making it difficult to prepare the target polymer.

[0008] Therefore, there is a continuous need for a method for preparing a metallocene catalyst having excellent activity and which can easily control the properties of olefin-based polymers. Summary of the invention

[0009] Technical issues

[0010] The object of the present invention is to provide a novel metallocene compound, a catalyst composition comprising the metallocene compound, and a method for preparing an olefin polymer using the catalyst composition.

[0011] Technical Solution

[0012] Provided is a metallocene compound represented by the following Chemical Formula 1:

[0013] [Chemical formula 1]

[0014]

[0015] In Chemical Formula 1,

[0016] M is a Group 4 transition metal,

[0017] A is carbon or silicon,

[0018] X1 and X2 are each independently hydrogen, halogen, or a substituted or unsubstituted C 1-30 alkyl;

[0019] R1 to R4 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 Aryl, wherein two adjacent substituents may be bonded to each other to form a C 5-30 Condensed ring;

[0020] R5 and R6 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30Alkenyl, substituted or unsubstituted C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 Aryl;

[0021] R7 and R8 are each independently a substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 aryl, and R7 and R8 may be bonded to each other to form a C 5-30 spiral ring;

[0022] R9 is a C with or without a substituent 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 Aryl;

[0023] Each R 10 are independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 Aryl, wherein two adjacent substituents may be bonded to each other to form a C 5-30 Condensed ring,

[0024] R 11 is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 Aryl,

[0025] m is an integer from 1 to 4,

[0026] n is an integer from 1 to 3, and

[0027] k is 0 or 1.

[0028] Also provided is a catalyst composition comprising:

[0029] A metallocene compound represented by the above Chemical Formula 1;

[0030] carrier; and

[0031] One or more co-catalyst compounds selected from the group consisting of compounds represented by the following Chemical Formula 2 and Chemical Formula 3:

[0032] [Chemical formula 2]

[0033] -[Al(R 12 )-O] a -

[0034] In chemical formula 2,

[0035] Each R 12 are independently halogen, C 1-20 Alkyl or C 1-20 Haloalkyl;

[0036] a is an integer greater than 2;

[0037] [Chemical formula 3]

[0038] J(R 13 )3

[0039] In chemical formula 3,

[0040] Each R 13 are independently halogen, C 1-20 Alkyl or C 1-20 haloalkyl; and

[0041] J is aluminum or boron.

[0042] Also provided is a method for preparing an olefin polymer, which comprises the step of polymerizing an olefin monomer in the presence of the above catalyst composition.

[0043] Beneficial Effects

[0044] The novel metallocene compound of the present invention is a compound having a novel structure unknown in the prior art, and an olefin polymer prepared using the novel metallocene compound can have a high SCB (short chain branch) content and show a wide molecular weight distribution.

[0045] Furthermore, the catalyst composition comprising the metallocene compound of the present invention exhibits a catalytic activity comparable to or higher than that of existing catalyst compositions during olefin polymerization, and the olefin polymer prepared using the catalyst composition of the present invention has a wide molecular weight distribution and a high SCB (short chain branch) content, thereby increasing the tie-molecule content, thereby improving the mechanical properties, especially improving the long-term durability of the final product. DETAILED DESCRIPTION

[0046] The terms used herein are only used to explain the specific embodiments and are not intended to limit the present invention. Singular expressions include their plural expressions unless explicitly stated or it is obvious from the context that it is not intended to do so. As used herein, the terms "including", "equipped with" or "having" are intended to specify the presence of practical features, quantities, steps, structural elements or their combinations, and they are not intended to exclude the possibility of the presence or addition of one or more other features, quantities, steps, structural elements or their combinations.

[0047] Although various modifications can be made to the present invention and the present invention can have various forms, specific examples will be described in detail and explained below. However, it should be understood that these are not intended to limit the present invention to specific disclosures, and the present invention includes all modifications, equivalents or replacements thereof without departing from the spirit and technical scope of the present invention.

[0048] Hereinafter, the present invention will be described in detail.

[0049] Explanation of terms

[0050] First, as used in this article, Refers to the bond to other substituents.

[0051] As used herein, the term "having a substituent or having no substituent" means substituted with one or more substituents selected from the group consisting of: deuterium, halogen; nitrile; nitro; hydroxyl; carbonyl; ester; imide; amino; phosphine oxide; alkoxy, aryloxy; alkylthiooxy; arylthiooxy; alkylsulfoxide; arylsulfoxide; silyl; boron; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; aralkenyl; alkaryl; alkylamine; aralkylamine; heteroarylamine; arylamine; arylphosphine; or a heterocyclic group containing one or more selected from N, O and S; or substituted with a substituent formed by connecting one or more of the above substituents, or having no substituent. For example, "a substituent formed by connecting two or more substituents" can be biphenyl. That is, the biphenyl group can be an aryl group, and it can also be interpreted as a substituent formed by connecting two phenyl groups.

[0052] The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0053] C 1-30 The alkyl group may be a linear, branched or cyclic alkyl group. 1-30 The alkyl group can be C 1-30 Straight chain alkyl; C 1-20 Straight chain alkyl; C 1-10 Straight chain alkyl; C 1-5 Straight chain alkyl; C 3-20 Branched or cyclic alkyl; C 3-15 Branched or cyclic alkyl; or C 3-10 More specifically, C 1-30 The alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl or cyclohexyl, etc.

[0054] C 2-30 The alkenyl group may be a straight chain, branched chain or cyclic alkenyl group. 2-30 The alkenyl group can be C 2-30 Straight chain alkenyl, C 2-20 Straight chain alkenyl, C 2-10 Straight chain alkenyl, C 2-5 Straight chain alkenyl, C 3-30 Branched alkenyl, C 3-20 Branched alkenyl, C 3-15 Branched alkenyl, C 3-10 Branched alkenyl, C 5-30 Cyclic alkenyl, C 5-20 Cyclic alkenyl or C 5-10 More specifically, C 2-30 The alkenyl group may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl, etc.

[0055] C 1-30 The alkoxy group may be a linear, branched or cyclic alkoxy group. 1-30 The alkoxy group can be C 1-30 Straight chain alkoxy; C 1-20 Straight chain alkoxy; C 1-10 Straight chain alkoxy; C 1-5 Straight chain alkoxy; C 3-30 Branched or cyclic alkoxy; C 3-20 Branched or cyclic alkoxy; C 3-15 Branched or cyclic alkoxy; or C 3-10 More specifically, C 1-30 The alkoxy group may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentyloxy, neopentyloxy or cyclohexyloxy, and the like.

[0056] C 2-30 Alkoxyalkyl is a group containing -R y-OR z The structure of alkyl (-R y ) can be replaced by an alkoxy group (-OR z ) is replaced. 2-30 Alkoxyalkyl in R y and R z The total number of carbon atoms included in is 2 to 30, and specifically, it can be methoxymethyl, methoxyethyl, ethoxymethyl, isopropoxymethyl, isopropoxyethyl, isopropoxyhexyl, tert-butoxymethyl, tert-butoxyethyl or tert-butoxyhexyl, etc.

[0057] C 2-30 Aryl refers to monocyclic, bicyclic or tricyclic aromatic hydrocarbons. 2-30 Aryl may be phenyl, naphthyl or anthracenyl, etc.

[0058] C 5-30 A fused ring may refer to a C 6-30 Aryl, C containing fused structure 5-30 Heteroaryl (heteroatoms: N, O, S) or C 5-30 Cycloalkanes.

[0059] C 5-30 Spirocyclic ring may refer to a C 5-30 Cycloalkanes.

[0060] As the Group 4 transition metal, titanium, zirconium, hafnium and the like can be mentioned.

[0061] The hydrocarbyl group refers to a monovalent hydrocarbon compound, and includes an alkyl group, an alkenyl group, an aryl group, an alkaryl group, an aralkyl group, and the like.

[0062] New metallocene compounds

[0063] The substituted carbazolyl group in the ligand of the metallocene compound according to one embodiment of the present invention exhibits a greater electron-donating effect than other aromatic groups, thereby increasing the electron density around the metal, so that the metallocene compound can show high activity during olefin polymerization. Various bonding forms and structural effects produced by the bonding direction and electron-donating effect of the bulky carbazolyl group have a wider molecular weight distribution and a larger weight-average molecular weight, and when copolymerized with alpha-olefins, olefin polymers with increased alpha-olefin percentages can be prepared. Especially in medium and large molecular weight olefin polymers, wide molecular weight and high short chain branching (SCB) content increase the interaction between olefin polymers, such as entanglement. Therefore, the content of the tie-molecule (tie-molecule) connecting the crystalline regions across the non-crystalline region increases, and therefore, the bonds between the olefin polymers are strengthened. The strengthening of this bond not only improves the mechanical properties, but also delays the damage of the polymer due to external impact or cracks, etc., and when this polymer is used in products, long-term durability can be improved.

[0064] Specifically, the metallocene compound according to one embodiment of the present invention is represented by the following Chemical Formula 1:

[0065] [Chemical formula 1]

[0066]

[0067] In chemical formula 1,

[0068] M is a Group 4 transition metal,

[0069] A is carbon or silicon,

[0070] X1 and X2 are each independently hydrogen, halogen, or a substituted or unsubstituted C 1-30 alkyl;

[0071] R1 to R4 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 Aryl, wherein two adjacent substituents may be bonded to each other to form a C 5-30 Condensed ring;

[0072] R5 and R6 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30Alkenyl, substituted or unsubstituted C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 Aryl;

[0073] R7 and R8 are each independently a substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 aryl, and R7 and R8 may be bonded to each other to form a C 5-30 spiral ring;

[0074] R9 is a C with or without a substituent 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 Aryl;

[0075] Each R 10 are independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 Aryl, wherein two adjacent substituents may be bonded to each other to form a C 5-30 Condensed ring,

[0076] R 11 is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, C 1-30 Alkoxy, substituted or unsubstituted C 2-30 Alkoxyalkyl, or a substituted or unsubstituted C 6-30 Aryl,

[0077] m is an integer from 1 to 4,

[0078] n is an integer from 1 to 3, and

[0079] k is 0 or 1.

[0080] In the metallocene compound represented by the above Chemical Formula 1, k is 0 or 1. In the case where k is 0, the bridge structure of -A- does not exist. Therefore, the metallocene compound represented by the chemical formula is represented by the following Chemical Formula 1-1 or 1-2:

[0081] [Chemical formula 1-1]

[0082]

[0083] [Chemical formula 1-2]

[0084]

[0085] In the formula,

[0086] M, X1, X2, A, R1 to R 11 , m and n are as defined above.

[0087] As the central metal of the metallocene compound represented by Chemical Formula 1, a Group 4 transition metal may be used, and preferably, in Chemical Formula 1, M is zirconium (Zr) or hafnium (Hf).

[0088] Preferably, in Chemical Formula 1, X1 and X2 are each independently chlorine or C 1-5 More preferably, X1 and X2 are each independently chlorine or methyl.

[0089] Preferably, in Chemical Formula 1, R1 to R4 are each independently hydrogen, C 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 an alkoxyalkyl group or a condensed ring selected from the group consisting of the following groups formed by two adjacent substituents being bonded to each other, and

[0090] Where two fused rings are present, they may be identical to or different from each other:

[0091]

[0092] in,

[0093] Each R' is independently C 1-10 alkyl, substituted or unsubstituted phenyl, 9-(C 1-10 alkyl)-9H-carbazolyl, 9-(C 2-10 alkoxyalkyl)-9H-carbazolyl or 9-phenyl-9H-carbazolyl,

[0094] R" is C1-10 Alkyl, and

[0095] Each o is independently an integer from 0 to 4.

[0096] Preferably, each R' is independently hydrogen, methyl, ethyl, isopropyl, butyl, tert-butyl, tert-butoxyhexyl; phenyl having no substituent or substituted with one or two tert-butyl groups, 9-methyl-9H-carbazolyl, 9-ethyl-9H-carbazolyl, 9-propyl-9H-carbazolyl, 9-butyl-9H-carbazolyl, 9-(tert-butoxyethyl)-9H-carbazolyl, 9-(tert-butoxyhexyl)-9H-carbazolyl or 9-phenyl-9H-carbazolyl.

[0097] Preferably, R" is methyl.

[0098] Preferably, in Chemical Formula 1, R5 and R6 are each independently hydrogen, C 1-10 Alkyl, C 2-10 Alkenyl or C 2-10 Alkoxyalkyl.

[0099] More preferably, R5 and R6 are each independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, vinyl, pentenyl, butenyl or tert-butoxyhexyl.

[0100] Preferably, in Chemical Formula 1, R7 and R8 are each independently C 1-10 Alkyl, C 2-10 Alkenyl or C 2-10 Alkoxyalkyl, unsubstituted or substituted with C 2-10 Phenyl of alkoxyalkyl, or spiro C formed by R7 and R8 bonded to each other 5-10 Cycloalkanes.

[0101] More preferably, R7 and R8 are each independently methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, vinyl, pentenyl, butenyl, tert-butoxyhexyl, or a spirocyclopentane or spirocyclohexane formed by R7 and R8 bonding to each other.

[0102] Preferably, in Chemical Formula 1, R9 is C 1-10 Alkyl or C 2-10 Alkoxyalkyl.

[0103] More preferably, R9 is methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, tert-butoxyhexyl or tert-butoxyethyl.

[0104] Preferably, in Chemical Formula 1, each R 10 are independently hydrogen, C 1-10 Alkyl or C 2-10 Alkoxyalkyl, or through two adjacent R 10Bonded condensed C 5-10 Cycloalkanes.

[0105] More preferably, each R 10 R is independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, tert-butoxyhexyl, tert-butoxyethyl, or through two adjacent R 10 The fused cyclopentane formed by the bond.

[0106] Preferably, in Chemical Formula 1, each R 11 are independently hydrogen, C 1-10 Alkyl or C 2-10 Alkoxyalkyl.

[0107] More preferably, each R 11 is independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, tert-butoxyhexyl or tert-butoxyethyl.

[0108] Preferably, the metallocene compound of Chemical Formula 1 is one selected from the group consisting of the following compounds.

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119] The metallocene compound represented by Chemical Formula 1 can be prepared by any known preparation method of an organic compound and a metallocene compound. The preparation method will be explained in more detail in the following preparation examples.

[0120] Catalyst composition

[0121] According to another embodiment of the present invention, a catalyst composition is provided, which includes a metallocene compound represented by Chemical Formula 1; a carrier; and a co-catalyst. In addition to the metallocene compound represented by Chemical Formula 1, the catalyst composition according to the present invention may include a carrier; and one or more co-catalyst compounds selected from the group consisting of compounds represented by the following Chemical Formulas 2 and 3.

[0122] [Chemical formula 2]

[0123] -[Al(R 12 )-O] a -

[0124] In chemical formula 2,

[0125] Each R 12 are independently halogen, C 1-20 Alkyl or C 1-20 Haloalkyl;

[0126] a is an integer greater than 2;

[0127] [Chemical formula 3]

[0128] J(R 13 )3

[0129] In chemical formula 3,

[0130] Each R 13 are independently halogen, C 1-20 Alkyl or C 1-20 haloalkyl; and

[0131] J is aluminum or boron.

[0132] As a carrier for supporting the metallocene compound represented by Chemical Formula 1, a carrier having a highly reactive hydroxyl group, a silanol group or a siloxane group on the surface may be used, and for this purpose, those in which the surface is modified by calcination or surface moisture is removed by drying may be used.

[0133] Preferably, silica prepared by calcining silica gel, high temperature dried silica, silica-alumina, silica-magnesia, etc. can be used, which generally can contain oxide, carbonate, sulfate and nitrate components such as Na2O, K2CO3, BaSO4 and Mg(NO3)2.

[0134] Preferably, the compound represented by Chemical Formula 2 used as a co-catalyst compound is not particularly limited as long as it is an alkylaluminoxane, but for example, aluminoxane compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane or butylaluminoxane can be mentioned, and one of them or a mixture thereof can be used.

[0135] Preferably, examples of the compound represented by Chemical Formula 3 used as a co-catalyst compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, and more specifically, it can be selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

[0136] The catalyst composition according to one embodiment of the present invention may be prepared by a method including the steps of: loading a co-catalyst in a carrier; and loading a metallocene compound in the carrier loaded with the co-catalyst.

[0137] In the preparation method, the loading conditions are not particularly limited and may be those known in the art. For example, a high temperature carrier and a low temperature carrier may be used to carry out the loading appropriately, for example, the loading temperature may be -30°C to 150°C, preferably 50°C to 98°C, or 50°C to 95°C. The loading time may be appropriately controlled according to the amount of the metallocene compound to be loaded. A supported catalyst may be used because it may be removed after filtering or distilling the reaction solvent under reduced pressure, and if necessary, Soxhlet filtration may be performed with an aromatic hydrocarbon such as toluene.

[0138] Furthermore, the preparation of the supported catalyst can be carried out in the presence of a solvent or without a solvent. If a solvent is used, a solvent known to be used for an organic metal catalyst can be used without particular limitation, for example, an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, nonane, decane and isomers thereof; an aromatic hydrocarbon solvent such as toluene, xylene, benzene; or a chlorinated hydrocarbon solvent such as dichloromethane, chlorobenzene, etc. can be used, and the content of the solvent used in the catalyst composition can be appropriately controlled according to the properties of the catalyst composition and the process conditions for preparing the olefin polymer.

[0139] In the preparation method of the metallocene compound or supported catalyst, equivalent (eq) refers to molar equivalent (eq / mol).

[0140] Method for preparing olefin polymer

[0141] Meanwhile, provided is a method for preparing an olefin polymer, which comprises the step of polymerizing an olefin monomer in the presence of a catalyst composition comprising the above metallocene compound.

[0142] In one embodiment of the present invention, the polymerization reaction may be performed while introducing hydrogen in an amount of 1500 ppm or less, 1000 ppm or less, or 850 ppm or less and 200 ppm or more, 250 ppm or more, or 300 ppm or more based on the monomer content.

[0143] In one embodiment of the present invention, the polymerization reaction may be performed at 10 to 150° C., preferably 60 to 130° C. If the polymerization temperature is too low, the reactivity of the olefin monomer may not be high, thus making it difficult to synthesize the olefin polymer, and if the polymerization temperature is too high, the olefin monomer may be thermally decomposed.

[0144] In one embodiment of the present invention, the polymerization reaction may be carried out at a pressure range of 1 to 20 bar, preferably 5 to 10 bar.

[0145] The polymerization reaction of the olefin monomer may be carried out by a continuous solution polymerization method, a bulk polymerization method, a suspension polymerization method or an emulsion polymerization method, but preferably, it may be carried out by a solution polymerization which is continuously carried out in a single reactor.

[0146] The catalyst composition can be dissolved or diluted in a C5-12 aliphatic hydrocarbon solvent suitable for olefin polymerization process, such as pentane, hexane, heptane, nonane, decane and isomers thereof; aromatic hydrocarbon solvents such as toluene, benzene; chlorinated hydrocarbon solvents such as dichloromethane, chlorobenzene, etc., and then introduced. The solvent used is preferably treated with a small amount of alkyl aluminum to remove a small amount of water or air as a catalyst poison, and a co-catalyst may be additionally used.

[0147] Examples of olefin monomers that can be polymerized using an organic metal compound and a co-catalyst include ethylene, α-olefins, cycloolefins, and the like. Diene olefin monomers or triene olefin monomers having two or more double bonds can also be polymerized. Specific examples of monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, α-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like. Two or more of these monomers can also be mixed and copolymerized.

[0148] In the case where the olefin polymer is a terpolymer prepared from ethylene, an α-olefin and a diene monomer, as the diene monomer, a non-conjugated diene monomer can be used. Specific examples thereof include 5-1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12-tetradecadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4 -octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-methyl-1,4-nonadiene, ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene 5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, 5-(2-ethyl-3-butenyl)-2-norbornene, 5-(6-heptenyl)-2-norbornene, 5-(3-methyl-hexenyl)-2-norbornene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornene, 5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene. Norbornene, 5-(2-methyl-6-heptenyl)-2-norbornene, 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(5-ethyl-5-hexenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, 5-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-butylidene-2-norbornene, 5-isobutylidene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene or 2-propenyl-2,2-norbornadiene, and one or more diene monomers selected therefrom can be used.

[0149] The metallocene catalyst having the above composition according to the present invention exhibits very high activity for olefin polymerization and prepares olefins having a wide molecular weight distribution and a high molecular weight, thereby increasing the number of tie molecules that can be connected between crystalline regions of the polymer. Also, it has a high short chain branching (SCB), thereby enabling the tie molecules to easily penetrate into the crystalline region.

[0150] In the general structure of olefin polymers, crystalline and non-crystalline regions are distributed in a matrix. At the boundary between the non-crystalline and crystalline regions, the load between the long molecular chain and another chain is transferred, and because the boundary exists between the energy-stable crystalline region and the relatively unstable non-crystalline region, it is internally subjected to pressure and is also susceptible to external influences.

[0151] Using the metallocene catalyst composition according to the present invention, the mechanical strength and durability of the olefin polymer can be improved due to the abundant tie molecules.

[0152] Specifically, a tie molecule refers to a specific long molecular chain that crosses the non-crystalline region to become part of the crystalline region or extends from the crystalline region and ends in the non-crystalline region. Alternatively, it extends from the crystalline region to the non-crystalline region, and the end sometimes returns to the crystalline region again. Through this entanglement, it plays the role of connecting the boundaries between regions. Since this tie molecule is fixed to the two crystalline regions, the shape of the boundary that is vulnerable to impact can be maintained and the growth of defects can be prevented.

[0153] Meanwhile, in the polymerization process, the metallocene catalyst composition of the present invention can show high catalytic activity. For example, when the weight (kgPE) of the olefin polymer produced per unit time (h) is divided by the weight (g) of the supported catalyst used, the catalytic activity of the metallocene catalyst composition can be more than 3.0kg PE / g·cat·hr, more than 4.0kg PE / g·cat·hr, more than 6.0kg PE / g·cat·hr, and less than 50kg PE / g·cat·hr, less than 40kg PE / g·cat·hr, less than 35kg PE / g·cat·hr.

[0154] Olefin polymers

[0155] Meanwhile, according to another aspect of the present invention, provided is an olefin polymer prepared by the method for preparing an olefin polymer.

[0156] The prepared polymer may have a weight average molecular weight of 100,000 to 1,500,000 g / mol or 200,000 to 1,000,000 g / mol as measured by GPC using PS standards, and a PDI of 4.0 to 15.0 or 5.5 to 13.0.

[0157] The number average molecular weight and weight average molecular weight of the polymer were determined as follows: The measurement was performed under the following GPC (gel permeation chromatography, PL GPC220, Agilent Technologies) analysis conditions:

[0158] - Column: PL MiniMixed B x 2

[0159] -Solvent: TCB (1,2,4-trichlorobenzene)

[0160] - Flow rate: 1.0mg / ml

[0161] -Sample concentration: 1.0mg / ml

[0162] -Introduction volume: 10μl

[0163] - Column temperature: 160℃

[0164] -Detector: Agilent RI detector

[0165] -Standard: Polystyrene (calibrated by cubic function)

[0166] -Data processing: ChemStation

[0167] Hereinafter, the functions and effects of the present invention will be explained in more detail by specific examples. However, these embodiments are presented only as an illustration of the present invention, and the scope of rights of the present invention is not determined thereby.

[0168] The following examples and comparative examples were carried out using a standard Schlenk and glove box under a nitrogen atmosphere to prevent contact with air and moisture, and the organic solvents used in the reactions were purified by standard methods. The synthesized ligands and catalysts were confirmed using 500 MHz NMR and MS detectors.

[0169] Preparation of Metallocene Compounds

[0170] Preparation Example 1: Preparation of Compound 1

[0171]

[0172] (Preparation of P1-1)

[0173] Under an argon atmosphere, S1-1 (10 g, 47.8 mmol) and S1-2 (10.8 g, 47.8 mmol) were introduced into 100 ml of tetrahydrofuran, and the mixture was stirred and refluxed. Then, potassium carbonate (19.8 g, 143.5 mmol) was dissolved in 20 ml of water, introduced, the mixture was fully stirred, and then tetrakis (triphenylphosphine) palladium (1.7 g, 1.4 mmol) was introduced. After reacting for 3 hours, the temperature was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was introduced into hexane (20x, 296 mL), dissolved again, washed with water twice, and then the organic layer was separated, anhydrous magnesium sulfate was introduced, it was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using hexane and ethyl acetate to obtain a light yellow solid compound P1-1 (8 g, 54%, MS: [M + H] + =310.4).

[0174] (Preparation of P1-2)

[0175] Under an argon atmosphere, P1-1 (5g, 16.2mmol) was dissolved in an anhydrous solution of 150ml ether:THF 3:1, the mixture was cooled to -78°C, n-BuLi (7.1ml, 17.78mmol) was introduced, and the mixture was stirred at room temperature for 4 hours. Copper cyanide (CuCN, 0.74g, 8.24mmol) was added thereto, the mixture was stirred at room temperature for 2 hours, and then cooled to -78°C again. Dimethyldichlorosilane (1.04ml, 8.56mmol) was added thereto, and then the temperature was raised to room temperature, and the mixture was stirred for 12 hours. After confirming that the reaction was complete, 1ml of water was quenched, anhydrous sodium sulfate was introduced to remove moisture, and then filtered through diatomaceous earth, washed with methyl tert-butyl ether, and then the filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using hexane and ethyl acetate to obtain a yellow solid compound P1-2 (3.1g, 57%, MS: [M+H] + =675.3).

[0176] (Preparation of Compound 1)

[0177] Under argon atmosphere, P1-2 (3 g, 4.44 mmol) was dissolved in 90 ml of ether, and then the mixture was cooled to -78 ° C, n-butyl lithium (3.73 ml, 9.33 mmol) was added dropwise thereto, and then the mixture was stirred at room temperature for 12 hours. ZrCl4 (THF) 2 (1.7 g, 4.44 mmol) was added thereto, and after the mixture was stirred at room temperature for 24 hours, it was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure to obtain a yellow solid. It was recrystallized in hexane to prepare compound 1 (2.95 g, 80%).

[0178] 1H NMR (500MHz, CDCl3): δ8.24(m,4H),8.13(m,4H),7.97-8.03(m,4H),7.89(m,4H),7.75(m,4H),7.54(m, 4H),7.19-7.44(m,16H),6.29(S,1H),6.13(s,1H),3.66(s,6H),2.42(s,6H),1.31(s,3H),1.12(s,3H)

[0179] Preparation Example 2: Preparation of Compound 2

[0180]

[0181] (Preparation of P2-1)

[0182] Under an argon atmosphere, S4-1 (10 g, 42.2 mmol) and S1-2 (9.5 g, 42.2 mmol) were introduced into 200 ml of tetrahydrofuran, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 17 ml of water, introduced, the mixed solution was fully stirred, and then tetrakis(triphenylphosphine)palladium (1.5 g, 1.3 mmol) was introduced. After reacting for 2 hours, the temperature was lowered to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was introduced into hexane (20x, 285 mL), dissolved again, washed with water twice, and then the organic layer was separated, anhydrous magnesium sulfate was introduced, it was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column using hexane and ethyl acetate to obtain a yellow solid compound P4-1 (10.8 g, 76%, MS: [M+H] + =338.5).

[0183] (Preparation of P2-2)

[0184] Under an argon atmosphere, P4-1 (5 g, 14.82 mmol) was dissolved in 30 ml of toluene / tetrahydrofuran (10 / 1), and then 6.2 ml of n-BuLi was slowly added dropwise at -78°C, and the mixture was stirred at room temperature for 3 hours. Dimethyldichlorosilane (1.89 ml, 15.56 mmol) was then introduced at -10°C, and the mixture was stirred at room temperature overnight. P1-1 (4.58 g, 14.82 mmol) was added to another reactor, dissolved in 22 ml of toluene / tetrahydrofuran (5 / 1), and then 6.2 ml of n-BuLi was slowly added dropwise at -78°C, and the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.03 g, 0.3 mmol) was added thereto, and then the reactant of P2-1 was introduced. Then, the mixture was stirred at room temperature overnight, treated with water and dried to prepare compound P2-2 (7.2 g, 69%, MS: [M+H] + =703.3).

[0185] (Preparation of Compound 2)

[0186] Under argon atmosphere, P2-2 (5g, 7.11mmol) was dissolved in 13ml of toluene / ether (2 / 1), and then 3ml of n-BuLi was slowly added dropwise at -78°C, and the mixture was stirred at room temperature for 5 hours. Then, a slurry of zirconium (IV) chloride (1.66g, 7.11mmol) in 42ml of toluene was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was vacuum dried and dichloromethane was introduced again, and LiCl was removed by glass frit filtration under nitrogen, and the filtrate was then vacuum dried. The obtained solid was recrystallized with hexane and dichloromethane, and the resulting solid was then filtered to prepare compound 2 (2.6g, 42%).

[0187] 1 H NMR (500MHz, CDCl3): δ8.27(m,4H),8.15(m,4H),7.98-8.00(m,4H),7.87(m,4H),7.72(m,4H),7.50(m,4H),7 .16-7.41(m,16H),6.24(S,1H),6.12(s,1H),3.65(s,6H),2.36(q,1H),1.66(d,6H),1.29(s,3H),1.10(s,3H)

[0188] Preparation Example 3: Preparation of Compound 3

[0189]

[0190] (Preparation of P3-1)

[0191] Under argon atmosphere, P1-1 (5 g, 16.16 mmol) was dissolved in 32 ml of toluene / tetrahydrofuran (10 / 1), and then n-butyl lithium (6.8 ml, 16.97 mmol) was slowly added thereto at -78°C, and the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.03 g, 0.32 mmol) was added thereto at room temperature, the mixture was stirred for 2 hours, and then dichloromethyl (6- (tert-butoxy) hexyl) silane (2.19 g, 8.08 mmol) was added. Then, the mixture was stirred at room temperature overnight, treated with water and dried to prepare compound P3-1 (7.6 g, 67%, MS: [M+H] + =817.5).

[0192] (Preparation of Compound 3)

[0193] P3-1 (3.5 g, 4.28 mmol) was introduced into a dry Schlenk flask, the flask was filled with argon, 44 ml of toluene / ether (10 / 1) was introduced to dissolve it, and then the mixture was cooled to -78 ° C. 3.6 ml of 2.5 M n-butyl lithium was slowly added thereto, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. Then, a slurry of zirconium (IV) chloride (1.02 g, 4.37 mmol) in 5 ml of toluene was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the temperature was lowered to -78 ° C, and a 3.0 M ether solution of methylmagnesium bromide (3.57 ml, 10.71 mmol) was slowly added thereto. The temperature was raised to room temperature and the mixture was stirred overnight. After the reaction was confirmed to be complete by NMR, the solvent was vacuum dried, dichloromethane was introduced again, and then 1,2-dimethoxyethane (1.34 ml, 12.85 mmol) was introduced and stirred at room temperature overnight. The inorganic matter was removed by filtration under nitrogen conditions, and the filtrate was then vacuum dried to prepare compound 3 (2.4 g, yield: 59%)

[0194] 1H NMR (500MHz, CDCl3): rac / meso mixed δ8.38-8.31(m,6H),8.25(m,2H),8.16(m,1H),8.14(m,1H),8.06-8.03(m,2H),7 .99(m,2H),7.72-7.66(m,7H),7.62(m,3H),7.42(m,6H),7.35(m,6H),7.23(m,2H),7.21(m,2H),6.37(S,2H),6.3 3(S,2H),3.79(s,6H),3.75(s,6H),3.37(t,2H),3.34(t,2H),1.8(s,6H),1.75(s,6H),1.51-1.20(m,16H),1.15( s,9H),1.11(s,9H),0.62(m,2H),0.58(m,2H),0.23(s,3H),0.18(s,3H),-0.87(s,6H),-0.93(s,3H),-1.03(s,3H)

[0195] Preparation Example 4: Preparation of Compound 4

[0196]

[0197] (Preparation of P4-2)

[0198] Under an argon atmosphere, S4-1 (2 g, 16.37 mmol) was dissolved in 33 ml of tetrahydrofuran, and then 6.9 ml of 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 3 hours. Then, dichloromethyl (6- (tert-butoxy) hexyl) silane (4.73 ml, 17.18 mmol) was introduced at -10 ° C, and the mixture was stirred at room temperature overnight. In another reactor, P1-1 (5.06 g, 16.37 mmol) was introduced and dissolved in 25 ml of toluene / tetrahydrofuran (5 / 1), and then 6.9 ml of 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.03 g, 0.33 mmol) was introduced at room temperature, and after stirring for 30 minutes, reactant P4-1 was added. Then, the mixture was stirred at room temperature overnight, treated with water and dried to prepare compound P4-2 (6.7 g, 65%, MS: [M+H] + =630.4).

[0199] (Preparation of Compound 4)

[0200] Under argon atmosphere, P4-2 (6g, 9.52mmol) was dissolved in 18ml toluene / ether (2 / 1), 4ml 2.5M n-butyl lithium was slowly added dropwise at -78°C, and then the mixture was stirred at room temperature for 5 hours. Then, a slurry of zirconium (IV) chloride (2.22g, 9.52mmol) in 56ml toluene was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, dichloromethane was introduced again, LiCl was removed by glass frit filtration under nitrogen conditions, and the filtrate was then dried in vacuo. The obtained solid was introduced into pentane, the mixture was stirred for 12 hours, and then the remaining solid was filtered to obtain compound 4 (6.4g, 85%).

[0201] 1 H NMR (500MHz, CDCl3): δ8.3(dd,1H),8.19(dd,1H),8(d,1H),7.92(s,1H),7.81(d,1H),7.63(m,1H),7.51-7.35(m,4H),6.40(s, 1H),3.80(s,3H),3.38(t,2H),2.16(s,6H),1.81(s,6H),1.79(s,3H),1.53-1.25(m,8H),1.15(s,9H),0.64(m,2H),0.24(s,3H)

[0202] Preparation Example 5: Preparation of Compound 5

[0203]

[0204] (Preparation of P5-2)

[0205] Under an argon atmosphere, S5-1 (3 g, 18.05 mmol) was dissolved in 36 ml of tetrahydrofuran, 7.6 ml of 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 3 hours. Then dichloromethyl (6- (tert-butoxy) hexyl) silane (5.21 ml, 18.95 mmol) was added at -10 ° C, and stirred overnight at room temperature. P1-1 (5.58 g, 18.05 mmol) was placed in another reactor and dissolved in 27 ml of toluene / tetrahydrofuran (5 / 1), 7.6 ml of 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C, and then the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.03 g, 0.36 mmol) was introduced therein at room temperature, and after the mixture was stirred for 30 minutes, reactant P5-1 was added. Then, the mixture was stirred at room temperature overnight, treated with water and dried to prepare compound P5-2 (5.4 g, 44%, MS: [M+H] + =674.4).

[0206] (Preparation of Compound 5)

[0207] Under argon atmosphere, P5-2 (5g, 7.42mmol) was dissolved in 14ml toluene / ether (2 / 1), 3.1ml 2.5M n-butyl lithium was slowly added dropwise at -78°C, and then the mixture was stirred at room temperature for 5 hours. Then, a slurry of zirconium chloride (IV) (1.73g, 7.42mmol) in 44ml toluene was introduced, and then the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, dichloromethane was introduced again, and LiCl was removed by glass frit filtration under nitrogen conditions, and then the filtrate was dried in vacuo. The obtained solid was introduced into pentane, and after stirring for 12 hours, the remaining solid was filtered to obtain compound 5 (3.04g, 49%).

[0208] 1 H NMR (500MHz, CDCl3): rac / meso mixed δ8.31(dd,1H),8.26(dd,1H),8.19(m,1H),8.15(m,1H),8.03(d,1H),7.97(d,1H) ,7.90-7.80(m,10H),7.66-7.62(m,2H),7.60-7.56(m,2H),7.50-7.35(m,3H),7.45-7.32(m,7H),7.12(d,1H),7.06 (d,1H),6.59(d,1H),6.56(d,1H),6.41-6.36(m,4H),3.79(s,3H),3.74(s,3H),3.36(t,2H),3.32(t,2H),1.82(s, 3H),1.78(s,3H),1.51-1.25(m,16H),1.17(s,9H),1.09(s,9H),0.62(m,2H),0.57(m,2H),0.24(s,3H),0.17(s,3H)

[0209] Preparation Example 6: Preparation of Compound 6

[0210]

[0211] (Preparation of P6-1)

[0212] Under a nitrogen atmosphere, S1-1 (5g, 23.9mmol) and S6-1 (5g, 23.9mmol) were introduced into 100ml tetrahydrofuran, and the mixture was stirred and refluxed. Then, potassium carbonate (9.9g, 71.7mmol) dissolved in 10ml water was introduced, and after sufficient stirring, tetrakis (triphenylphosphine) palladium (0.8g, 0.7mmol) was introduced. After 3 hours of reaction, the temperature was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. Hexane (20 times, 141mL) was introduced again and dissolved, washed with water 2 times, then the organic layer was separated, anhydrous magnesium sulfate was introduced, stirring was then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using hexane and ethyl acetate to obtain a light yellow solid compound P6-1 (5.7g, 80%, MS: [M+H] + =296.4).

[0213] (Preparation of P6-2)

[0214] Under nitrogen atmosphere, P6-1 (5 g, 16.9 mmol), S6-2 (4.8 g, 16.9 mmol), CTAB (0.12 g, 0.34 mmol) and sodium hydroxide (2 g, 50.8 mmol) were introduced into 50 ml of water and dissolved, and then the solution was introduced into 100 ml of toluene and stirred under reflux. After reacting for 12 hours, it was cooled to room temperature, and then introduced into ethyl acetate (30 times, 229 mL) and dissolved, washed with water twice, and then the organic layer was separated, anhydrous magnesium sulfate was introduced, stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column using hexane and ethyl acetate to obtain compound P6-2 (6 g, 79%, MS: [M+H] + =452.7).

[0215] (Preparation of P6-3)

[0216] Under an argon atmosphere, P6-2 (5 g, 11.07 mmol) was dissolved in 22 ml of toluene / ether (10 / 1), and 4.6 ml of 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C. Then, the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.02 g, 0.22 mmol) was added thereto at room temperature, the mixture was stirred for 2 hours, and then dimethyldichlorosilane (0.72 g, 5.54 mmol) was added. The mixture was then stirred at room temperature overnight, washed with water twice, and then the organic layer was separated, anhydrous magnesium sulfate was introduced, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using hexane and ethyl acetate to obtain compound P6-3 (6.8 g, 64%, MS: [M+H] + =959.6).

[0217] (Preparation of Compound 6)

[0218] Under argon atmosphere, P6-3 (4g, 4.17mmol) was dissolved in 8ml toluene / ether (2 / 1), 1.8ml 2.5M n-butyl lithium was slowly added dropwise at -78°C, and then the mixture was stirred at room temperature for 5 hours. Then, a slurry of zirconium chloride (IV) (0.97g, 4.17mmol) in 25ml toluene was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, dichloromethane was introduced again, LiCl was removed by glass frit filtration under nitrogen conditions, and the filtrate was then dried in vacuo to prepare compound 6 (3.2g, 69%).

[0219] 1 H NMR (500MHz, CDCl3): rac / meso mixed δ8.39-8.28(m,6H),8.26(m,2H),8.19(dd,1H),8.12(dd,1H),8.05-8.03(m ,4H),7.79-7.66(m,7H),7.73-7.62(m,3H),7.52-7.45(m,6H),7.46-7.41(m,6H),7.27-7.23(m,2H),7.18(m, 2H),6.4(s,2H),6.33(s,1H),6.30(s,1H),4.19(m,4H),4.14(m,4H),3.39(m,4H),3.31(m,4H),1.80-1.76(m, 12H),1.73-1.71(m,8H),1.51-1.27(m,12H),1.15(s,9H),1.10(s,9H),0.12(s,3H),0.09(s,6H),0.04(s,3H)

[0220] Preparation Example 7: Preparation of Compound 7

[0221]

[0222] (Preparation of P7-2)

[0223] Under argon atmosphere, P1-1 (3 g, 9.7 mmol) was dissolved in 19 ml toluene / tetrahydrofuran (10 / 1), 4.1 ml 2.5 M n-butyl lithium was slowly added dropwise at -78 °C, and then the mixture was stirred at room temperature for 3 hours. Then, dichloromethyl (6- (tert-butoxy) hexyl) silane (2.80 ml, 10.18 mmol) was introduced at -10 °C, and the mixture was stirred overnight at room temperature. In another reactor, S7-1 (2.54 g, 9.7 mmol) was introduced and dissolved in 15 ml toluene / tetrahydrofuran (5 / 1), 4.1 ml 2.5 M n-butyl lithium was slowly added dropwise at -78 °C, and then the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.02 g, 0.19 mmol) was added at room temperature, and after the mixture was stirred for 30 minutes, reactant P7-1 was added. Then, the mixture was stirred at room temperature overnight, treated with water and dried to prepare compound P7-2 (6.3 g, 84%, MS: [M+H] + =770.5).

[0224] (Preparation of Compound 7)

[0225] Under argon atmosphere, P7-2 (3g, 3.9mmol) is dissolved in 7ml toluene / ether (2 / 1), 1.6ml 2.5M n-butyl lithium is slowly added dropwise at -78 ° C, and then the mixture is stirred at room temperature for 5 hours. Then, 23ml slurry of zirconium chloride (IV) (0.91g, 3.9mmol) in 23ml toluene is introduced, and the mixture is stirred at room temperature overnight. After the reaction is completed by NMR confirmation, the solvent is vacuum dried, dichloromethane is introduced again, and LiCl is removed by glass frit filtration under nitrogen conditions, and then the filtrate is vacuum dried. The solid obtained is recrystallized using pentane and dichloromethane, and the resulting solid is then filtered to prepare compound 7 (2.5g, 69%).

[0226] 1H NMR (500MHz, CDCl3): rac / meso mixed δ8.31(dd,2H),8.27(dd,2H),8.20(m,1H),8.16(m,1H),8.01(d,1H),7.96(d ,1H),7.9(s,1H),7.85(s,1H),7.81(d,1H),7.75(d,1H),7.63(m,2H),7.53-7.33(m,12H),7.26-7.23(m,8H),6 .40(s,2H),6.32(s,2H),3.81(s,3H),3.73(s,3H),3.36(t,2H),3.34(t,2H),1.82(s,6H),1.76(s,6H),1.54-1 .25(m,23H),1.46-1.21(m,11H),1.17(s,9H),1.10(s,9H),0.62(m,2H),0.56(m,2H),0.25(s,3H),0.19(s,3H)

[0227] Preparation Example 8: Preparation of Compound 8

[0228]

[0229] (Preparation of P8-1)

[0230] Under a nitrogen atmosphere, S8-1 (7 g, 28.1 mmol) and S1-2 (6.3 g, 28.1 mmol) were introduced into 140 ml of tetrahydrofuran, and the mixture was stirred and refluxed. Then, potassium carbonate (11.6 g, 84.3 mmol) dissolved in 12 ml of water was introduced, the mixture was fully stirred, and then tetrakis (triphenylphosphine) palladium (1 g, 0.8 mmol) was introduced. After reacting for 1 hour, the temperature was cooled to room temperature, and after separating the organic layer and the aqueous layer, the organic layer was distilled. Chloroform (12 times, 118 mL) was introduced, dissolved again, washed with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a light yellow solid compound P8-1 (6.8 g, 69%, MS: [M+H] + =350.5).

[0231] (Preparation of P8-2)

[0232] Under argon atmosphere, P8-1 (6.5 g, 18.6 mmol) was dissolved in 37 ml toluene / ether (10 / 1), 7.8 ml 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C, and then the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.03 g, 0.37 mmol) was added at room temperature, the mixture was stirred for 2 hours, and then diethyldichlorosilane (1.46 g, 9.3 mmol) was introduced. Then, the mixture was stirred at room temperature overnight, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was introduced, stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column using hexane and ethyl acetate to prepare compound P8-2 (10.9 g, 75%, MS: [M+H] + =783.4).

[0233] (Preparation of Compound 8)

[0234] Under argon atmosphere, P8-2 (5g, 6.38mmol) was dissolved in 12ml ether, 2.7ml 2.5M n-butyl lithium was slowly added dropwise at -78 °C, and the mixture was stirred at room temperature for 5 hours. Then, a slurry of zirconium chloride (IV) (1.49g, 6.38mmol) in 38ml ether was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, methylene chloride was introduced again, and LiCl was removed by glass frit filtration under nitrogen conditions, and then the filtrate was dried in vacuo. The obtained solid was introduced into pentane, the mixture was stirred for 12 hours, and the remaining solid was then filtered to prepare compound 8 (4.9g, 81%).

[0235] 1 H NMR(500MHz,CDCl3):rac / meso mixδ8.37(m,1H),8.32(m,1H),8.16(m,2H),8.04(m,2H),8.00(m,2H),7.74-7.63(m,1 0H),7.49-7.34(m,8H),7.27(m,2H),7.19(m,2H),6.38(s,1H),6.35(s,2H),6.33(s,1 H),3.81(s,6H),3.75(s,6H),2.87-2.84(m,6H),2.82-2.76(m,10H),1.96(m,4H),1.9 3(m,4H),1.83(s,6H),1.75(s,6H),0.97(t,6H),0.93(t,6H),0.67(q,4H),0.65(q,4H)

[0236] Preparation Example 9: Preparation of Compound 9

[0237]

[0238] (Preparation of P9-2)

[0239] Under argon atmosphere, S9-1 (5g, 17.96mmol) was dissolved in 36ml of ether, 7.5ml of 2.5M n-butyl lithium was slowly added dropwise at -78°C, and the mixture was stirred at room temperature for 3 hours. Then, dichloromethyl (6- (tert-butoxy) hexyl) silane (5.19ml, 18.86mmol) was introduced at -10°C, and the mixture was stirred at room temperature overnight. In another reactor, P9-1 (6.28g, 17.96mmol) was introduced and dissolved in 31ml of toluene / ether (5 / 1), and 7.5ml of 2.5M n-butyl lithium was slowly added dropwise at -78°C, and then the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.03g, 0.36mmol) was introduced therein at room temperature, the mixture was stirred for 30 minutes, and then the reactant S9-1 was introduced. Then, the mixture was stirred at room temperature overnight, treated with water and dried to prepare compound P9-2 (11.5 g, 78%, MS: [M+H] + =826.5).

[0240] (Preparation of Compound 9)

[0241] Under argon atmosphere, P9-2 (5g, 6.05mmol) was dissolved in 11ml toluene / ether (2 / 1), 2.5ml 2.5M n-butyl lithium was slowly added dropwise at -78°C, and then the mixture was stirred at room temperature for 5 hours. Then, a slurry of zirconium (IV) chloride (1.41g, 6.05mmol) in 36ml toluene was introduced, and the mixture was stirred at room temperature overnight. After confirming that the reaction was complete by NMR, the solvent was dried in vacuo, tetrahydrofuran was introduced again, and LiCl was removed by filtration with glass powder under nitrogen conditions, and then the filtrate was dried in vacuo. The obtained solid was recrystallized using hexane and dichloromethane, and the resulting solid was then filtered to prepare compound 9 (2.8g, 47%).

[0242] 1 H NMR (500MHz, CDCl3): δ8.16(m,1H),7.95(d,1H),7.86(s,1H),7.81-7.76(m,3H),7.55(s,2H),7.41(m,3H),7.32(m,1H),6.34(s,1H ),3.75(s,3H),3.31(t,2H),2.82-2.77(m,4H),1.93(m,2H),1.77(s,3H),1.46-1.27(m,26H),1.11(s,9H),0.57(m,2H),0.18(s,3H)

[0243] Preparation Example 10: Preparation of Compound 10

[0244]

[0245] (Preparation of P10-2)

[0246] Under an argon atmosphere, S10-1 (5 g, 21.43 mmol) was dissolved in 43 ml of ether, 9 ml of 2.5 M n-butyl lithium was slowly added dropwise at -78 °C, and the mixture was stirred at room temperature for 3 hours. Then, dichloroethyl (6- (tert-butoxy) hexyl) silane (6.42 g, 22.5 mmol) was dissolved in 14 ml of hexane and introduced at -10 °C, and the mixture was stirred at room temperature overnight. In another reactor, P1-1 (6.63 g, 21.43 mmol) was introduced and dissolved in 31 ml of toluene / ether (10 / 1), 9 ml of 2.5 M n-butyl lithium was slowly added dropwise at -78 °C, and the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.04 g, 0.43 mmol) was added at room temperature and the mixture was stirred for 30 minutes, and then the reactant P10-1 was added. Then, the mixture was stirred at room temperature overnight, treated with water and dried to prepare compound P10-2 (10.9 g, 69%, MS: [M+H] + =741.4).

[0247] (Preparation of Compound 10)

[0248] Under argon atmosphere, P10-2 (5g, 6.75mmol) is dissolved in 13ml toluene / tetrahydrofuran (2 / 1), 2.8ml 2.5M n-butyl lithium is slowly added dropwise at -78 ° C, and then, the mixture is stirred at room temperature for 5 hours. Then, zirconium chloride (IV) (1.57g, 6.75mmol) slurry in 40ml toluene is introduced, and the mixture is stirred at room temperature overnight. After confirming that the reaction is completed by NMR, vacuum drying solvent is introduced again, and dichloromethane is removed by glass frit filtration under nitrogen conditions. LiCl is then vacuum dried to prepare compound 10 (3.6g, 59%).

[0249] 1H NMR (500MHz, CDCl3): δ8.39(s,1H),8.25(dd,1H),8.15(dd,1H),7.96(d,1H),7.88(s,1H),7.75(d,1H),7.63-7.59(m,3H),7.47-7.23(m,8 H),6.57(d,1H),6.38(d,1H),3.79(s,3H),3.73(s,3H),3.34(t,2H), 2.41(s,3H),1.49-1.22(m,8H),1.11(s,9H),0.93(t,3H),0.65(q,2H)

[0250] Preparation Example 11: Preparation of Compound 11

[0251]

[0252] (Preparation of P11-1)

[0253] Under a nitrogen atmosphere, S11-2 (20g, 102.5mmol) and S1-2 (23.1g, 102.5mmol) were introduced into 400ml tetrahydrofuran, and the mixture was stirred and refluxed. Then, potassium carbonate (42.5g, 307.6mmol) dissolved in 43ml water was introduced, the mixture was fully stirred, and then tetrakis (triphenylphosphine) palladium (3.6g, 3.1mmol) was introduced. After 3 hours of reaction, the temperature was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was then distilled. Introduced into chloroform (10 times, 303mL), dissolved again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was introduced, stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column using chloroform and ethyl acetate to prepare yellow solid compound P11-1 (15.7g, 52%, MS: [M+H] + =296.4).

[0254] (Preparation of P11-3)

[0255] Under an argon atmosphere, S11-1 (5 g, 24.96 mmol) was dissolved in 50 ml of ether, 10.5 ml of 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 3 hours. Then, dimethyldichlorosilane (3.19 ml, 26.21 mmol) was introduced at -10 ° C, and the mixture was stirred at room temperature overnight. P11-1 (7.37 g, 24.96 mmol) was placed in another reactor and dissolved in 37 ml of 37 ml of toluene / ether (5 / 1), 10.5 ml of 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.04 g, 0.5 mmol) was introduced therein at room temperature, and after the mixture was stirred for 30 minutes, the reactant S11-1 was introduced. Then, the mixture was stirred at room temperature overnight, worked up with water and dried to prepare compound P11-3 (10.7 g, 78%, MS: [M+H] + =552.2).

[0256] (Preparation of Compound 11)

[0257] Under argon atmosphere, P11-3 (5g, 9.06mmol) is dissolved in 17ml toluene / tetrahydrofuran (2 / 1), 3.8ml 2.5M n-butyl lithium is slowly added dropwise at -78 ° C, and then the mixture is stirred at room temperature for 5 hours. Then, a slurry of zirconium chloride (IV) (2.11g, 9.06mmol) in 53ml toluene is introduced, and the mixture is stirred at room temperature overnight. After the reaction is confirmed to be completed by NMR, the solvent is dried in vacuo, dichloromethane is introduced again, and LiCl is removed by glass frit filtration under nitrogen conditions, and then the filtrate is dried in vacuo. The obtained solid is recrystallized using hexane and dichloromethane, and the resulting solid is then filtered to prepare compound 11 (4.1g, 64%).

[0258] 1 H NMR(500MHz,CDCl3):rac / meso mixδ8.3(dd,1H),8.26(dd,1H),8.2(dd,1H),8.15(dd,1H),8.08-7.87(m,8H),7.78(d,1H),7.73(d,1H),7.6(m,1H),7.58(m,1H),7.51-7.32(m,1 2H),6.59(d,1H),6.56(m,1H),6.41(m,2H),3.81(s,3H),3.76(s,3H),2. 13(m,6H),1.8(s,3H),1.76(s,3H),0.24(s,3H),0.22(s,3H),0.16(s,6H)

[0259] Preparation Example 12: Preparation of Compound 12

[0260]

[0261] (Preparation of P12-1)

[0262] Under argon atmosphere, P1-1 (5 g, 16.16 mmol) was dissolved in 32 ml toluene / tetrahydrofuran (10 / 1), 6.8 ml 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C, and then the mixture was stirred at room temperature for 3 hours. Then, dichloromethyl (6- (tert-butoxy) hexyl) silane (4.67 ml, 16.97 mmol) was introduced at -10 ° C, and the mixture was stirred at room temperature overnight. In another reactor, S12-1 (1.94 g, 16.16 mmol) was placed and dissolved in 24 ml toluene / tetrahydrofuran (10 / 1), and then 6.8 ml 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C, and then the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.03 g, 0.32 mmol) was added at room temperature, the mixture was stirred for 30 minutes, and then the reactant P1-1 was added. Then, the mixture was stirred at room temperature overnight, treated with water and dried to prepare compound P12-1 (6.8 g, 67%, MS: [M+H] + =628.4).

[0263] (Preparation of Compound 12)

[0264] Under argon atmosphere, P12-1 (5g, 7.96mmol) was dissolved in 16ml toluene / tetrahydrofuran (3 / 1), 3.3ml 2.5M n-butyl lithium was slowly added dropwise at -78 °C, and then the mixture was stirred at room temperature for 5 hours. Then, a slurry of zirconium chloride (IV) (1.85g, 7.96mmol) in 47ml toluene was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, dichloromethane was introduced again, and LiCl was removed by glass frit filtration under nitrogen conditions, and then the filtrate was dried in vacuo. The obtained solid was recrystallized using hexane and dichloromethane, and the resulting solid was then filtered to prepare compound 12 (4.3g, 69%).

[0265] 1H NMR(500MHz,CDCl3):rac / meso mixδ8.33(dd,1H),8.28(dd,1H),8.21(dd,1H),8.15(dd,1H),8.02(d,1H),7.96(d,1H),7.93(s,1H),7. 87(s,1H),7.79(d,1H),7.76(d,1H),7.6(m,2H),7.51-7.4(m,6H),7.36(m,1H),7.29(m,1H),6.53(m,2H) ,6.41-6.32(m,4H),3.81(s,3H),3.74(m,3H),3.36(t,2H),3.34(t,2H),1.98-1.93(m,8H),1.83-1.61(m ,14H),1.48-1.26(m,16H),1.16(s,9H),1.12(s,9H),0.62(t,2H),0.59(t,2H),0.24(s,3H),0.18(s,3H)

[0266] Preparation Example 13: Preparation of Compound 13

[0267]

[0268] (Preparation of P13-1)

[0269] P13-1 was prepared by the same method as (Preparation of P1-1) except that (9-methyl-9H-carbazol-1-yl)boronic acid was used instead of S1-2.

[0270] (Preparation of P13-3)

[0271] Under argon atmosphere, P1-1 (5g, 16.16mmol) was dissolved in 32ml toluene / ether (10 / 1), 6.8ml 2.5M n-butyl lithium was slowly added at -78°C, and then the mixture was stirred at room temperature for 3 hours. Then, dimethyldichlorosilane (2.07ml, 16.97mmol) was introduced at -10°C, and the mixture was stirred overnight at room temperature. In another reactor, P13-1 (5g, 16.16mmol) was added and dissolved in 24ml toluene / ether (5 / 1), 6.8ml 2.5M n-butyl lithium was slowly added at -78°C, and then the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.03g, 0.32mmol) was introduced therein at room temperature, and after the mixture was stirred for 30 minutes, the reactant of P13-2 was added. Then, the mixture was stirred at room temperature overnight, treated with water and dried to prepare compound P13-3 (10.7 g, 98%, MS: [M+H] + =675.3).

[0272] (Preparation of Compound 13)

[0273] Under argon atmosphere, P13-3 (5g, 7.41mmol) was dissolved in 15ml toluene / tetrahydrofuran (2 / 1), 3.1ml 2.5M n-butyl lithium was slowly added dropwise at -78 °C, and then the mixture was stirred at room temperature for 5 hours. Then, a slurry of zirconium chloride (IV) (1.73g, 7.41mmol) in 44ml toluene was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, dichloromethane was introduced again, and LiCl was removed by glass frit filtration under nitrogen conditions, and then the filtrate was dried in vacuo. The obtained solid was recrystallized using hexane and dichloromethane, and the resulting solid was then filtered to prepare compound 13 (4.3g, 70%).

[0274] 1 H NMR (500MHz, CDCl3): rac / meso mixed δ8.47(m,2H),8.45(m,2H),8.40-8.30(m,6H),8.17-8.10(m,6H),7.72-7.67(m,4H),7.59-7.41(m,16H),7.26-7.23( m,4H),6.37(s,2H),6.34(s,1H),6.32(s,1H),3.84(s,6H),3.78(s,6H),1. 82(s,3H),1.77(s,6H),1.75(s,3H),0.17(s,3H),0.15(s,6H),0.13(s,3H)

[0275] Preparation Example 14: Preparation of Compound 14

[0276]

[0277] (Preparation of P14-1)

[0278] P14-1 was prepared by the same method as (Preparation of P1-1) except that 5-bromo-1H-indene was used instead of S1-1.

[0279] (Preparation of P14-2)

[0280] Under argon atmosphere, P14-1 (5 g, 16.93 mmol) was dissolved in 56 ml of toluene / tetrahydrofuran (10 / 1), 7.1 ml of 2.5 M n-butyl lithium was slowly added dropwise at -78 °C, and then the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.03 g, 0.34 mmol) was introduced thereinto at room temperature, and after the mixture was stirred for 2 hours, dimethyldichlorosilane (1.09 g, 8.46 mmol) was added. Then, the mixture was stirred at room temperature overnight, treated with water and dried to prepare compound P14-2 (6.2 g, 57%, MS: [M+H] + =647.3).

[0281] (Preparation of Compound 14)

[0282] Under argon atmosphere, P14-2 (4.5g, 6.96mmol) is dissolved in 14ml toluene / tetrahydrofuran (2 / 1), 2.9ml 2.5M n-butyl lithium is slowly added dropwise at -78 ° C, and then the mixture is stirred at room temperature for 5 hours. Then, a slurry of zirconium chloride (IV) (1.62g, 6.96mmol) in 41ml toluene is introduced, and the mixture is stirred at room temperature overnight. After the reaction is confirmed by NMR, the solvent is dried in vacuo, dichloromethane is introduced again, and LiCl is removed by glass frit filtration under nitrogen conditions, and then the filtrate is dried in vacuo. The solid obtained is recrystallized using hexane and dichloromethane, and the solid produced is then filtered to prepare compound 14 (3.8g, 68%).

[0283] 1 H NMR (500MHz, CDCl3): rac / meso mixed δ8.36-8.31(m,4H),8.16(m,1H),8.13(m,1H),8.05-7.95(m,8H),7.72-7.56(m,14H),7.45-7.36(m,4H) ,7.25-7.19(m,8H),6.83(d,2H),6.76(d,2H),6.42(d,2H),6.38(d,2H),3.79(s,6H),3.73(s,6H),0.22(s,3H),0.19(s,6H),0.17(s,3H)

[0284] Preparation Example 15: Preparation of Compound 15

[0285]

[0286] (Preparation of P15-2)

[0287] Under argon atmosphere, S15-1 (5 g, 22.49 mmol) was dissolved in 45 ml toluene / ether (10 / 1), 9.4 ml 2.5 M n-butyl lithium was slowly added dropwise at -78 °C, and then the mixture was stirred at room temperature for 3 hours. Dimethyldichlorosilane (2.87 ml, 23.61 mmol) was then introduced at -10 °C, and the mixture was stirred at room temperature overnight. P1-1 (6.96 g, 22.49 mmol) was placed in another reactor and dissolved in 34 ml toluene / ether (5 / 1), 9.4 ml 2.5 M n-butyl lithium was slowly added dropwise at -78 °C, and then the mixture was stirred at room temperature for 3 hours. Copper cyanide (0.04 g, 0.45 mmol) was introduced at room temperature and the mixture was stirred for 30 minutes, and then the reactant of P15-1 was introduced. Then, the mixture was stirred at room temperature overnight, treated with water and dried to prepare compound P15-2 (10.7 g, 81%, MS: [M+H]+=588.4).

[0288] (Preparation of Compound 15)

[0289] Under argon atmosphere, P15-2 (6 g, 9.27 mmol) was dissolved in 19 ml tetrahydrofuran, 3.9 ml 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 5 hours. Then, a slurry of zirconium chloride (IV) (2.16 g, 9.27 mmol) in 55 ml toluene was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, dichloromethane was introduced again, LiCl was removed by glass frit filtration under nitrogen conditions, and the filtrate was then dried in vacuo to prepare compound 15 (5.2 g, 75%).

[0290] 1 H NMR (500MHz, CDCl3): δ8.36(dd,1H),8.27(dd,1H),8.15(m,1H),7.75(m,1H),7.66(dd,1H),7.57(dd,1H),7.47-7.4(m,3H),7.17(m,1H),6. 49(m,1H),6.39-6.32(m,2H),6.15(s,1H),3.86(s,3H),3.33(t,2H), 1.92(t,2H),1.75(s,3H),1.48-1.25(m,8H),1.11(s,9H),0.21(s,6H)

[0291] Preparation Example 16: Preparation of Compound 16

[0292]

[0293] (Preparation of Compound 16)

[0294] Under argon atmosphere, P3-1 (3 g, 3.67 mmol) was dissolved in 7 ml toluene / tetrahydrofuran (2 / 1), 1.5 ml 2.5 M n-butyl lithium was slowly added dropwise at -78 ° C, and then the mixture was stirred at room temperature for 5 hours. Then, a slurry of hafnium (IV) chloride (1.18 g, 3.67 mmol) in 22 ml toluene was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, dichloromethane was introduced again, LiCl was removed by glass frit filtration under nitrogen conditions, and the filtrate was then dried in vacuo to prepare compound 16 (3.1 g, 80%).

[0295] 1 H NMR(500MHz,CDCl3):rac / meso mixδ8.38-8.26(m,8H),8.17(dd,1H),8.14(dd,1H),8.05-8.02(m,4H),7.69-7.6 4(m,10H),7.48-7.36(m,12H),7.26-7.21(m,4H),6.39(s,2H),6.32(s,2H),3.74 (d,12H),3.37(t,2H),3.33(t,2H),1.81(s,6H),1.75(s,6H),1.52-1.43(m,8H), 1.31-1.24(m,8H),1.17(s,9H),1.14(s,9H),0.6(t,2H),0.57(t,2H),0.2(d,6H)

[0296] Preparation Example 17: Preparation of Compound 17

[0297]

[0298] (Preparation of P17-1)

[0299] S15-1 (5 g, 22.49 mmol) was added to a dry Schlenk flask, and 45 ml of methanol and acetone (4.2 ml, 56.21 mmol) were placed, and the mixture was cooled to 0 ° C. Pyrrolidine (2.8 ml, 33.73 mmol) was slowly added dropwise, and then the temperature was slowly raised to room temperature, and the mixture was stirred for 7 hours. After confirming that the reaction was complete, a small amount of water was introduced to quench, and the mixture was extracted with ethyl acetate and water. The organic layers were combined, dried over anhydrous magnesium sulfate, and then vacuum dried to prepare compound P17-1 (5.7 g, 97%, MS: [M+H] + =263.2).

[0300] (Preparation of P17-2)

[0301] P1-1 (1.77 g, 5.72 mmol) was added to a dry Schlenk flask, the flask was filled with argon, and then 11 ml of ethyl acetate was introduced to dissolve, and then the mixture was cooled to -78 ° C. 2 ml of 2.5M n-butyl lithium was slowly added dropwise, the temperature was raised to room temperature, and then the mixture was stirred for 4 hours. P89-1 (3 g, 11.43 mmol) was dissolved in 16 ml of ethyl acetate, the mixture was cooled to -78 ° C, and then the lithiated P1-1 was slowly added dropwise, and the mixture was stirred at room temperature overnight. After confirming that the reaction was complete, a small amount of water was introduced to quench, the mixture was extracted twice with ethyl acetate and water, the organic layers were combined, dried over anhydrous magnesium sulfate, and then dried under reduced pressure. The concentrated compound was purified by silica gel column using hexane and ethyl acetate to prepare compound P17-2 (6.5 g, 70%, MS: [M+H] + =572.4).

[0302] (Preparation of Compound 17)

[0303] P17-2 (6 g, 10.49 mmol) was added to a dry Schlenk flask, filled with argon, and then 107 ml toluene / tetrahydrofuran (10 / 1) was introduced to dissolve, and the mixture was then cooled to -78 ° C. 8.8 ml 2.5 M n-butyl lithium 2 ml was slowly added dropwise, warmed to room temperature, and the mixture was then stirred for 12 hours. Then, a slurry of zirconium chloride (IV) (2.49 g, 10.7 mmol) in 15 ml toluene was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, hexane was introduced again, and LiCl was removed by glass frit filtration under nitrogen conditions, and then the filtrate was dried in vacuo. Hexane was introduced into the resulting solid and stirred, and the remaining solid was then filtered to prepare compound 17 (5 g, 65%).

[0304] 1 H NMR (500MHz, CDCl3): δ8.32(dd,1H),8.20(m,1H),8.01(d,1H),7.9(s,1H),7.81(d,1H),7.61(dd,1H),7.50-7.37(m,4H),6. 51(d,1H),6.43-6.37(m,3H),6.22(s,1H),3.8(s,3H),3.39(t,2H),1.82(s,3H),1.52-1.30(m,8H),1.15(s,9H),0.95(s,6H)

[0305] Preparation Example 18: Preparation of Compound 18

[0306]

[0307] (Preparation of P18-2)

[0308] P1-1 (4.23 g, 13.68 mmol) was placed in a dry Schlenk flask, argon was filled into the flask, and then 46 ml of ether was introduced to dissolve, and the mixture was cooled to -78 ° C. 6 ml of 2.5 M n-butyl lithium was slowly added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. P18-1 (4 g, 27.35 mmol) was dissolved in 39 ml of ether, the mixture was cooled to -78 ° C, and then the lithiated P1-1 was slowly added dropwise, and the mixture was stirred at room temperature overnight. After confirming that the reaction was complete, a small amount of water was introduced to quench, the mixture was extracted twice with ether and water, the organic layers were combined, dried over anhydrous magnesium sulfate, and then dried under reduced pressure. The concentrated compound was purified by silica gel column using hexane and ethyl acetate to obtain compound P18-2 (12.5 g, 63%, MS: [M+H] + =456.3).

[0309] (Preparation of Compound 18)

[0310] P18-2 (4g, 8.78mmol) was added to a dry Schlenk flask, argon was filled in the flask, and then 90ml tetrahydrofuran was introduced to dissolve, and the mixture was cooled to -78 ° C. 7.4ml 2.5M n-butyl lithium was slowly added dropwise, warmed to room temperature, and then the mixture was stirred for 12 hours. Then, a slurry of zirconium (IV) chloride (2.09g, 8.95mmol) in 13ml tetrahydrofuran was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, hexane was introduced again, LiCl was removed by glass frit filtration under nitrogen conditions, and then the filtrate was dried in vacuo. The obtained solid was recrystallized using hexane and dichloromethane, and the resulting solid was then filtered to prepare compound 18 (3.5g, 65%).

[0311] 1 H NMR (500MHz, CDCl3): δ8.26(dd,1H),8.13(m,1H),7.98(d,1H),7.85(s,1H),7.74(d,1H),7.58(dd,1 H),7.47-7.29(m,4H),6.48(m,2H),6.36-6.35(m,3H),3.76(s,3H),1.78(s,3H),1.49-1.40(m,10H)

[0312] Preparation Example 19: Preparation of Compound 19

[0313]

[0314] (Preparation of P19-1)

[0315] S15-1 (10 g, 44.97 mmol) was added to a dry Schlenk flask and dissolved in 90 ml of tetrahydrofuran, and then the mixture was cooled to -78 ° C. 2.5 M n-butyl lithium (18.9 ml, 47.22 mmol) was slowly added dropwise, the temperature of the mixture was slowly raised to room temperature, and the mixture was stirred for 5 hours. In addition, benzophenone (6.6 ml, 40.47 mmol) dissolved in 58 ml of tetrahydrofuran was added at 0 ° C, and then the mixture was stirred overnight. After confirming that the reaction was complete, a small amount of water was added to quench, and the mixture was extracted twice with ethyl acetate and water, the organic layers were combined, dried over anhydrous magnesium sulfate, and then dried under reduced pressure to prepare compound P19-1 (10.8 g, yield: 62%, MS: [M+H] + =387.3).

[0316] (Preparation of P19-2)

[0317] P11-1 (3.05 g, 10.35 mmol) was added to a dry Schlenk flask, the flask was filled with argon, and then 34 ml of tetrahydrofuran was introduced to dissolve, and the mixture was cooled to -78 ° C. 4 ml of 2.5 M n-butyl lithium was slowly added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. P19-1 (8 g, 20.69 mmol) was dissolved in 30 ml of tetrahydrofuran, the mixture was cooled to -78 ° C, and then the lithiated P11-1 was slowly added dropwise and stirred at room temperature overnight. After confirming that the reaction was complete, a small amount of water was introduced to quench, the mixture was extracted twice with ethyl acetate and water, the organic layers were combined, dried over anhydrous magnesium sulfate, and then dried under reduced pressure. The concentrated compound was purified by silica gel column using hexane and ethyl acetate to obtain compound P19-2 (14.1 g, 64%, MS: [M+H] + =682.4).

[0318] (Preparation of Compound 19)

[0319] P19-2 (8 g, 11.73 mmol) was placed in a dry Schlenk flask, argon was filled into the flask, and then 120 ml of tetrahydrofuran was introduced to dissolve it and cooled to -78 ° C. 9.9 ml of 2.5 M n-butyl lithium was slowly added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. Then, a slurry of hafnium (IV) chloride (3.83 g, 11.97 mmol) in 17 ml of tetrahydrofuran was added, and the mixture was stirred at 60 ° C overnight. After the reaction was confirmed to be complete by NMR, the temperature was lowered to -78 ° C, and a 3.0 M methylmagnesium bromide ether solution (9.78 ml, 29.33 mmol) was slowly added dropwise. The temperature of the mixture was raised to room temperature, and the mixture was stirred overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, hexane was introduced again, and 1,2-dimethoxyethane (3.66 ml, 35.19 mmol) was introduced, and the mixture was stirred at room temperature overnight. The inorganic matter was removed by filtration under nitrogen conditions, and the filtrate was then dried in vacuo to prepare Compound 19 (8.3 g, yield: 80%).

[0320] 1 H NMR (500MHz, CDCl3): δ8.33(dd,1H),8.21(dd,1H),8.04(dd,1H),7.91(d,1H),7.79(d,1H),7.64(dd,1H),7.52-7.44(m,3H),7.36-7.24(m,11 H),6.62(t,1H),6.53(dd,1H),6.45(m,2H),6.26(s,1H),3.85(s,3H), 3.38(t,2H),2.00(m,2H),1.55-1.33(m,8H),1.16(s,9H),-1.95(s,6H)

[0321] Preparation Example 20: Preparation of Compound 20

[0322]

[0323] (Preparation of Compound 20)

[0324] P19-2 (3 g, 4.4 mmol) was added to a dry Schlenk flask, which was filled with argon, and then 45 ml of toluene / tetrahydrofuran (10 / 1) was introduced to dissolve, and the mixture was cooled to -78 ° C. 3.7 ml of 2.5 M n-butyl lithium was slowly added dropwise, warmed to room temperature, and then the mixture was stirred for 12 hours. Then, a slurry of zirconium (IV) chloride (1.05 g, 4.49 mmol) in 6 ml of toluene was introduced, and the mixture was stirred at room temperature overnight. After the reaction was confirmed to be complete by NMR, the solvent was dried in vacuo, dichloromethane was introduced again, LiCl was removed by glass frit filtration under nitrogen conditions, and the filtrate was then dried in vacuo to prepare compound 20 (2.4 g, yield: 65%).

[0325] 1 H NMR (500MHz, CDCl3): δ8.32(dd,1H),8.19(dd,1H),8.03(dd,1H),7.92(d,1H),7.78(d,1H),7.62(dd,1H),7.51-7.44(m,3H),7.36-7.2 4(m,11H),6.61(t,1H),6.51(dd,1H),6.42(m,2H),6.22(s,1H),3.81(s,3H),3.36(t,2H),1.97(m,2H),1.53-1.30(m,8H),1.14(s,9H)

[0326] Preparation Example 21: Preparation of Compound 21

[0327]

[0328] (Preparation of P21-1)

[0329] S15-1 (8 g, 35.98 mmol) was placed in a dry Schlenk flask, 72 ml of tetrahydrofuran and acetophenone (10.5 ml, 89.94 mmol) were added, and the mixture was cooled to 0 ° C. In addition, pyrrolidine (4.4 ml, 53.96 mmol) was slowly added dropwise, and the temperature of the mixture was slowly raised to room temperature, and the mixture was stirred for 7 hours. After confirming that the reaction was complete, a small amount of water was introduced to quench, the mixture was extracted twice with ethyl acetate and water, the organic layers were combined, dried over anhydrous magnesium sulfate, and then dried under reduced pressure. The concentrated compound was purified by silica gel column using hexane and ethyl acetate to prepare compound P21-1 (6.8 g, 58%, MS: [M + H] + =325.3).

[0330] (Preparation of P21-2)

[0331] P21-1 (2.86 g, 9.24 mmol) was added to a dry Schlenk flask, the flask was filled with argon, and then 31 ml of tetrahydrofuran was added to dissolve, and the mixture was cooled to -78 ° C. 4 ml of 2.5 M n-butyl lithium was slowly added dropwise, the temperature was raised to room temperature, and then the mixture was stirred for 4 hours. P95-1 (6 g, 18.49 mmol) was dissolved in 26 ml of tetrahydrofuran, the mixture was cooled to -78 ° C, and then the lithiated P1-1 was slowly added dropwise, and the mixture was stirred at room temperature overnight. After confirming that the reaction was complete, a small amount of water was introduced to quench, the mixture was extracted twice with ethyl acetate and water, the organic layers were combined, dried over anhydrous magnesium sulfate, and then dried under reduced pressure. The concentrated compound was purified by silica gel column using hexane and ethyl acetate to prepare compound P21-2 (11.7 g, 65%, MS: [M+H] + =634.4).

[0332] (Preparation of Compound 21)

[0333] P21-2 (4 g, 6.31 mmol) was placed in a dry Schlenk flask, which was filled with argon, and then 64 ml of toluene / tetrahydrofuran (10 / 1) was introduced to dissolve, and the mixture was cooled to -78 ° C. 5.3 ml of 2.5 M n-butyl lithium was slowly added dropwise, warmed to room temperature, and then the mixture was stirred for 12 hours. Then, a slurry of zirconium (IV) chloride (1.5 g, 6.44 mmol) in 9 ml of toluene was introduced, and the mixture was stirred at room temperature overnight. After confirming that the reaction was complete by NMR, the solvent was vacuum dried, dichloromethane was introduced again, LiCl was removed by glass frit filtration under nitrogen conditions, and the filtrate was vacuum dried to prepare compound 21 (3.6 g, yield: 71%).

[0334] 1 H NMR (500MHz, CDCl3): δ8.31(d,1H),8.21(d,1H),8.01(d,1H),7.92(s,1H),7.78(d,1H),7.60(dd,1H),7.52-7.35(m,8H),7.25(m,1H),6.5 1(d,1H),6.43-6.40(m,2H),6.19(s,1H),3.81(s,3H),3.39(t,2H),1 .96(t,2H),1.82(s,3H),1.53-1.31(m,8H),1.15(s,9H),0.89(m,3H)

[0335] Preparation Example 22: Preparation of Compound 22

[0336]

[0337] (Preparation of Compound 22)

[0338] P11-1 (5 g, 15.41 mmol) was placed in a dry Schlenk flask, which was filled with argon, and then 51 ml of toluene / methyl tert-butyl ether (15 / 1) was introduced to dissolve, and the mixture was then cooled to -78 ° C. 6 ml of 2.5 M n-butyl lithium was slowly added dropwise, warmed to room temperature, and the mixture was then stirred overnight. The mixture was cooled to -78 ° C, and then a cyclopentadienyl zirconium trichloride (IV) solution (3.42 g, 13 mmol) dissolved in 22 ml of toluene was slowly added dropwise, and the mixture was stirred at room temperature overnight. After confirming that the reaction was complete, the solvent in the mixture was dried to a 1 / 10 volume ratio by vacuum decompression, and the same amount of hexane as the removed solvent was introduced again. The hexane slurry was filtered under argon, and the resulting filtrate was vacuum dried to prepare compound 22 (5.2 g, yield 53%).

[0339] 1 H NMR (500MHz, CDCl3): δ8.25(dd,1H),8.16(dd,1H),7.95(dd,1H),7.85(d,1H),7.73( d,1H),7.55(dd,1H),7.47-7.30(m,4H),6.55-6.36(m,6H),3.49(dd,1H),2.89(m,1H)

[0340] Preparation Example 23: Preparation of Compound 23

[0341]

[0342] (Preparation of Compound 23)

[0343] P11-1 (5g, 15.41mmol) was placed in a dry Schlenk flask, which was filled with argon, and then 51ml toluene / methyl tert-butyl ether (15 / 1) was introduced to dissolve, and the mixture was cooled to -78°C. 6ml2.5M n-butyl lithium was slowly added dropwise, warmed to room temperature, and then the mixture was stirred overnight. The mixture was cooled to -78°C, and then an indenyl zirconium trichloride (IV) solution (3.85g, 12.33mmol) dissolved in 18ml toluene was slowly added dropwise, and the mixture was stirred at room temperature overnight. After confirming that the reaction was complete, the solvent in the mixture was dried to a 1 / 10 volume ratio by vacuum decompression, and hexane as much as the solvent removed was introduced again. The hexane slurry was filtered under argon, and the resulting filtrate was vacuum dried to prepare compound 23 (4.7g, yield 53%).

[0344] 1H NMR (500MHz, CDCl3): δ8.26(dd,1H),8.15(dd,1H),7.98(dd,1H),7.87(d,1H),7.76(d,1H),7.58 (dd,1H),7.45-7.30(m,7H),7.16(td,1H),6.56(d,2H),6.37(dd,2H),3.73(s,3H),3.48(dd,2H)

[0345] Preparation of catalyst composition and use thereof to prepare olefin polymers

[0346] Example 1

[0347] 1) Preparation of catalyst composition (silicon dioxide supported metallocene catalyst in solid particle form)

[0348] In a Pico reactor, 50 mL of toluene was introduced and then 7 g of silica (952X) was transferred. 10 mmol of methylaluminoxane (MAO) was introduced and reacted at 95 ° C for 24 hours. After precipitation, the upper layer was removed and the residue was washed once with toluene. 60 μmol of the metallocene catalyst precursor compound 1 of Preparation Example 1 was dissolved in toluene and reacted at 80 ° C for 2 hours. After the reaction was completed and the precipitation was completed, the upper solution was removed and the remaining reaction product was washed with toluene. Washed again with hexane, then 2 wt % of Atmer was introduced into hexane and stirred for 10 minutes. After precipitation, the upper part was removed and the residue was vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

[0349] 2) Olefin polymerization

[0350] A 600 mL stainless steel reactor was dried under vacuum at 120° C., then cooled, 1 g of TMA was introduced into 250 g of hexane at room temperature, and the mixture was stirred for 10 minutes. After all the reacted hexane was removed, 250 g of hexane and 0.5 g of TiBAL were introduced, and the mixture was stirred for 5 minutes. 7 mg of the silica-supported metallocene catalyst prepared in 1) was added, and the mixture was stirred while the temperature was raised to 70° C. After stopping stirring at 70° C., 10 mL of 1-hexene was introduced, C2 was charged to 30 bar, and then stirring was started. After 30 minutes of polymerization, unreacted C2 was discharged.

[0351] Examples 2 to 23

[0352] The catalyst composition and polymerized olefin were prepared in the same manner as in Example 1, except that in the step of preparing the catalyst composition 1) in Example 1, the compounds prepared in Preparation Examples 2 to 23 were used instead of the metallocene catalyst precursor compound 1 of Preparation Example 1-1.

[0353] Comparative Examples 1 to 5

[0354] The catalyst composition and polymerized olefin were prepared in the same manner as in Example 1, except that in the step of 1) preparing the catalyst composition of Example 1, the following compounds A to E were used instead of the metallocene catalyst precursor compound 1 of Preparation Example 1-1.

[0355]

[0356] <Experimental example>

[0357] The polymerization activity of each catalyst composition of Examples and Comparative Examples was measured, and the melting point, weight average molecular weight, molecular weight distribution and SCB of the olefin polymer polymerized using the catalyst composition were measured. The results are shown in Table 1 below.

[0358] (1) Polymerization activity (kg / mmol cat·hr): calculated as the ratio of the weight (kg) of the polymer produced per unit time (hr) to the weight (gCat) of the catalyst used.

[0359] (2) Melting point (Tm, °C)

[0360] The temperature of the polymer was raised to 200°C and maintained for 5 minutes, then lowered to 30°C, and then raised again, and the top of the curve was measured as Tm using a DSC (differential scanning calorimeter, manufactured by TA Corporation), and then the temperature was lowered to 30°C, and the top of the curve was Tc.

[0361] The heating and cooling rates were 10°C / min, and Tm and Tc were the results measured in the second heating and cooling stages, respectively.

[0362] (2) Weight average molecular weight (Mw, g / mol) and polydispersity index (PDI)

[0363] Using GPC (gel permeation chromatography, manufactured by Water), the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured, and the polydispersity index (PDI) was measured by dividing the weight average molecular weight by the number average molecular weight. Specifically, as a GPC device, a Waters PL-GPC220 device was used, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. Among them, the measurement temperature was 160° C., 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL / min.

[0364] The polymer sample was dissolved in 1,2,4-trichlorobenzene containing 0.0125% BHT at 160°C for 10 hours, pretreated using a GPC analyzer (PL-GP220), formulated to a concentration of 10 mg / 10 mL, and then supplied in an amount of 200 μL. The Mw and Mn values ​​were derived using a calibration curve formed using a polystyrene standard sample. As polystyrene standard samples, 9 samples with weight average molecular weights of 2000 g / mol, 10000 g / mol, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 g / mol, 4000000 g / mol, and 10000000 g / mol were used.

[0365] (3) SCB (short chain branching) content (number / C1000)

[0366] For the prepared polymer, 1 H NMR analysis of SCB content (number / C1000). Using a Bruker DMX600MHzNMR / BBFO (1H / 19F / broadband) probe, the sample was dissolved in TCE-d2 solvent at high temperature and measured at 100°C. 1 HNMR. Determination 1 From the H NMR spectrum, the comonomer content of the polymer was calculated based on the terminal CH3 peak of 1-hexene appearing in the region of 0.8 ppm to 1.0 ppm.

[0367] SCB content refers to the number of C2-7 branches per 1000 main chain carbon atoms.

[0368]

Table 1

[0369]

[0370] As confirmed by the data in Table 1, the catalyst composition using the metallocene compound of Chemical Formula 1 of the present invention exhibits excellent catalytic activity. Therefore, an olefin polymer having a wide molecular weight distribution, a large weight average molecular weight, and a high SCB content can be prepared through various bonding forms, and the finally prepared polymer has excellent durability, so it can be easily applied to various products requiring long-term durability.

Claims

1. A metallocene compound represented by the following Chemical Formula 1-1 or 1-2: [Chemical Formula 1-1] [Chemical formula 1-2] In Chemical Formulas 1-1 and 1-2, M is zirconium or hafnium, A is carbon or silicon, X1 and X2 are each independently halogen or C 1-30 alkyl; R1 to R4 are each independently hydrogen, C 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 an alkoxyalkyl group, a phenyl group, or a condensed ring selected from the group consisting of the following groups formed by two adjacent substituents being bonded to each other, and Where two fused rings are present, they may be identical to or different from each other: in, Each R' is independently C 1-10 alkyl, phenyl which has no substituent or is substituted by one or two tert-butyl groups, 9-(C 1-10 alkyl)-9H-carbazolyl, 9-(C 2-10 alkoxyalkyl)-9H-carbazolyl or 9-phenyl-9H-carbazolyl, R" is C 1-10 Alkyl, and Each o is independently an integer from 0 to 4; R5 and R6 are each independently hydrogen, C 1-30 Alkyl, C 2-30 Alkenyl, C 1-30 Alkoxy or C 2-30 Alkoxyalkyl; R7 and R8 are each independently C 1-10 Alkyl, C 2-10 Alkenyl or C 2-10 Alkoxyalkyl, substituted with C 2-10 Alkoxyalkyl or unsubstituted phenyl, or R7 and R8 are bonded to form a spiro group 5-10 Cycloalkanes; R9 is C 1-30 Alkyl, C 2-30 Alkenyl, C 1-30 Alkoxy, C 2-30 Alkoxyalkyl, or phenyl; Each R 10 are independently hydrogen, C 1-30 Alkyl, C 2-30 Alkenyl, C 1-30 Alkoxy or C 2-30 Alkoxyalkyl, wherein two adjacent substituents may be bonded to each other to form a fused C 5-10 Cycloalkanes, R 11 It is hydrogen, C 1-30 Alkyl, C 2-30 Alkenyl, C 1-30 Alkoxy or C 2-30 Alkoxyalkyl, m is an integer from 1 to 4, and n is an integer of 1 to 3.

2. The metallocene compound according to claim 1, wherein X1 and X2 are each independently chlorine or C 1-5 alkyl.

3. The metallocene compound of claim 1, wherein R5 and R6 are each independently hydrogen, C 1-10 Alkyl, C 2-10 Alkenyl or C 2-10 Alkoxyalkyl.

4. The metallocene compound according to claim 1, wherein R9 is C 1-10 Alkyl or C 2-10 Alkoxyalkyl.

5. The metallocene compound according to claim 1, characterized in that Each R 10 are independently hydrogen, C 1-10 Alkyl or C 2-10 Alkoxyalkyl, or through two adjacent R 10 Bonding to form fused C 5-10 Cycloalkanes.

6. The metallocene compound of claim 1, wherein each R 11 are independently hydrogen, C 1-10 Alkyl or C 2-10 Alkoxyalkyl.

7. The metallocene compound of claim 1, wherein the metallocene compound represented by Chemical Formula 1 is selected from the group consisting of the following compounds:

8. A catalyst composition comprising: The metallocene compound according to any one of claims 1 to 7; Carrier; and One or more co-catalyst compounds selected from the group consisting of compounds represented by the following Chemical Formula 2 and Chemical Formula 3: [Chemical formula 2] <h2 style=";text-align:left;direction:ltr">-[Al(R<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> )-O]<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> - In chemical formula 2, Each R 12 are independently halogen, C 1-20 Alkyl or C 1-20 Haloalkyl; a is an integer greater than 2; [Chemical formula 3] J(R 13 )3 In chemical formula 3, Each R 13 are independently halogen, C 1-20 Alkyl or C 1-20 haloalkyl; and J is aluminum or boron.

9. A method for preparing an olefin polymer, comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition according to claim 8.

10. The method for preparing an olefin polymer according to claim 9, characterized in that: The olefin monomers include one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, styrene, α-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

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