Hybride supported metallocene catalyst and method for preparing polyethylene copolymer using same

Abstract

The present invention relates to: a hybride supported metallocene catalyst which has excellent catalytic activity in polyethylene polymerization and improves high crystalline molecular weight, and thus is useful for preparing a biaxially oriented polyethylene having improved heat resistance; and a method for preparing a polyethylene using same.

Description

Hybrid supported metallocene catalyst and method for producing polyethylene copolymer using the same

[0001] The present invention relates to a hybrid supported metallocene catalyst and a method for producing a polyethylene copolymer using the same.

[0002] Cross-citation with related applications

[0003] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0086290, filed July 1, 2024, and Korean Patent Application No. 10-2025-0049748, filed April 16, 2025, the entire contents of which are incorporated herein by reference.

[0004]

[0005] Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems. These two highly active catalyst systems have been developed to suit their respective characteristics.

[0006]

[0007] Ziegler-Natta catalysts have been widely applied in existing commercial processes since their invention in the 1950s. However, since they are multi-site catalysts with multiple active sites, they are characterized by a wide molecular weight distribution of polymers and an uneven distribution of comonomer composition, which limits the ability to secure desired properties.

[0008]

[0009] Meanwhile, metallocene catalysts are composed of a combination of a main catalyst, which is mainly composed of a transition metal compound, and a cocatalyst, which is mainly composed of an organometallic compound, which is mainly composed of aluminum. This type of catalyst is a homogeneous complex catalyst and exhibits the characteristics of a single-site catalyst. Due to the single-site characteristic, a narrow molecular weight distribution is obtained, and a polymer with a uniform comonomer composition distribution is obtained. In addition, it has the characteristics of being able to change the stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the polymer depending on the modification of the ligand structure of the catalyst and the change in polymerization conditions.

[0010]

[0011] Recent shifts in environmental awareness have led many product groups to pursue reductions in volatile organic compounds (VOCs). However, Ziegler-Natta (Z / N) catalysts used in the production of polyethylene (PE) have been problematic for generating high levels of total volatile organic compounds (TVOCs). While Ziegler-Natta catalysts are the dominant catalyst for various commercially available polyethylenes, the transition to products utilizing metallocene catalysts, which offer lower odor and lower emission, is accelerating.

[0012]

[0013] In particular, research and development of biaxially-oriented polyethylene (BOPE) film, a single-material shrink film that can be used for packaging while maintaining the shape of the product, instead of a composite material that cannot be recycled, is being conducted. However, commercial polyethylene (PE) resin does not have sufficient stretching stability, and phenomena such as fracture and melting occur during stretching, making it difficult to apply the biaxial stretching process. In order to have stretching properties and stretching stability, it must have a structure of low MI-high density / high MI-low density, and a technology has been reported to derive resin crystallization and molecular weight separation using a dual-reactor for the production of the corresponding PE resin, but this has high production costs.

[0014]

[0015] Accordingly, there is a need to develop a method for manufacturing biaxially oriented polyethylene that can be manufactured in a single reactor using a metallocene catalyst, has a molecular structure advantageous for stretching, exhibits stretching stability during biaxial stretching, and exhibits good film mechanical properties.

[0016]

[0017] The present invention aims to provide a hybrid supported metallocene catalyst useful for producing biaxially oriented polyethylene having improved heat resistance by improving high crystal molecular weight and excellent catalytic activity in polyethylene polymerization.

[0018] In addition, the present invention aims to provide a method for producing polyethylene using the hybrid supported metallocene catalyst.

[0019]

[0020] The present invention comprises: at least one first metallocene compound selected from compounds represented by the following chemical formula 1; at least one second metallocene compound selected from compounds represented by the following chemical formula 2; and a carrier carrying the first metallocene compound and the second metallocene compound.

[0021] Provided are hybrid supported metallocene catalysts:

[0022] [Chemical Formula 1]

[0023]

[0024] In the above chemical formula 1,

[0025] M1 is a group 4 transition metal,

[0026] X 11 and X 12 are each independently substituted or unsubstituted C 1-20 Alkyl or halogen,

[0027] R1 to R5 and R7 to R 12 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-60 Aryl, or -(CH2) n1 -OR 13 And,

[0028] R6 is substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-60 Aryl, or -(CH2) n1 -OR 13 However,

[0029] R1 to R 12 At least one of them is -(CH2) n1 -OR 13 And,

[0030] R 13 Silver substituted or unsubstituted C 1-20 It is alkyl,

[0031] n1 is an integer from 0 to 10,

[0032] [Chemical Formula 2]

[0033]

[0034] In the above chemical formula 2,

[0035] M2 is a group 4 transition metal,

[0036] X 21 , X 22are each independently substituted or unsubstituted C 1-20 Alkyl or halogen,

[0037] T2 is C (carbon) or Si (silicon),

[0038] Q 21 and Q 22 are each independently substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-60 Aryl, or -(CH2) n2 -OR 32 This or Q 21 and Q 22 C, which is substituted or unsubstituted by combining with each other 3-20 Forming a cycloalkyl ring,

[0039] R 20 Inland R 31 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-60 Aryl, or -(CH2) n2 -OR 32 This or R 20 Inland R 31 C, which is substituted or unsubstituted, is formed by combining two adjacent C's. 3-20 Forming a cycloalkyl ring,

[0040] R 20 Inland R 31 , Q 21 and Q 22 At least one of them is -(CH2) n2 -OR 32 And,

[0041] R 32 is substituted or unsubstituted C 1-20 It is alkyl,

[0042] n2 is an integer from 0 to 10.

[0043]

[0044] The present invention also provides a method for producing a polyethylene copolymer, comprising a step of copolymerizing ethylene and alpha-olefin in the presence of the hybrid supported metallocene catalyst.

[0045]

[0046] The hybrid supported metallocene catalyst according to the present invention enables biaxial stretching of polyethylene by hybridly supporting a metallocene compound exhibiting high molecular weight and high crystallinity and a metallocene compound exhibiting low molecular weight and low crystallinity, and can produce polyethylene with improved heat resistance by increasing the high crystal molecular weight.

[0047]

[0048] The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprise," "include," or "have" indicate the presence of a feature, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, steps, components, or combinations thereof.

[0049]

[0050] Additionally, in the present invention, (co)polymer means both a homopolymer and a copolymer.

[0051]

[0052] Unless otherwise defined herein, “copolymerization” may mean block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization, and “copolymer” may mean block copolymer, random copolymer, graft copolymer or alternating copolymer.

[0053]

[0054] The present invention is susceptible to various modifications and takes various forms. Specific examples are illustrated and described in detail below. However, this does not limit the invention to a specific disclosed form, but rather encompasses all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0055]

[0056] Hereinafter, the present invention will be described in detail.

[0057]

[0058] In this specification, the substituents of the chemical formulae 1 and 2 are described more specifically as follows.

[0059] The halogen can be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0060] C 1-20 Alkyl may be straight-chain, branched-chain or cyclic alkyl. Specifically, the C 1-20 Alkyl may be a straight chain alkyl having 1 to 20 carbon atoms; a straight chain alkyl having 1 to 10 carbon atoms; a straight chain alkyl having 1 to 5 carbon atoms; a branched chain or cyclic alkyl having 3 to 20 carbon atoms; a branched chain or cyclic alkyl having 3 to 15 carbon atoms; or a branched chain or cyclic alkyl having 3 to 10 carbon atoms. More specifically, C 1-20 The alkyl group may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, or a cyclohexyl group.

[0061] C 3-20 The cycloalkyl ring may be a ring composed of carbon atoms. It may be a hydrocarbon ring having 3 to 20 carbon atoms; a hydrocarbon ring having 3 to 15 carbon atoms; or a hydrocarbon ring having 3 to 10 carbon atoms. More specifically, C 3-20The cycloalkyl ring may be a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, or a cyclohexene ring.

[0062] C 2-20 Alkenyl may be straight-chain, branched-chain or cyclic alkenyl. Specifically, the above C 2-20 The alkenyl may be a straight chain alkenyl having 2 to 20 carbon atoms; a straight chain alkenyl having 2 to 10 carbon atoms; a straight chain alkenyl having 2 to 5 carbon atoms; a branched chain alkenyl having 3 to 20 carbon atoms; a branched chain alkenyl having 3 to 15 carbon atoms; a branched chain alkenyl having 3 to 10 carbon atoms; a cyclic alkenyl having 5 to 20 carbon atoms; or a cyclic alkenyl having 5 to 10 carbon atoms. More specifically, C 2-20 The alkenyl may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl.

[0063] C 1-20 Alkoxy may be a straight-chain, branched-chain or cyclic alkoxy group. Specifically, the above C 1-20 The alkoxy may be a straight chain alkoxy group having 1 to 20 carbon atoms; a straight chain alkoxy group having 1 to 10 carbon atoms; a straight chain alkoxy group having 1 to 5 carbon atoms; a branched chain or cyclic alkoxy group having 3 to 20 carbon atoms; a branched chain or cyclic alkoxy group having 3 to 15 carbon atoms; or a branched chain or cyclic alkoxy group having 3 to 10 carbon atoms. More specifically, the alkoxy group having 1 to 20 carbon atoms may be a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a tert-butoxy group, an n-pentoxy group, an iso-pentoxy group, a neo-pentoxy group, or a cyclohexene group.

[0064] C 2-20 Alkoxyalkyl is -R y -OR z Alkyl (-R) with a structure containing y ) is one or more hydrogens of alkoxy (-OR z ) may be a substituent substituted with C. Specifically, the above C 2-20The alkoxyalkyl may be a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhectyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, or a tert-butoxyhexyl group.

[0065] C 6-60 Aryl may mean a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, the above C 6-60 The aryl group may be a phenyl group, a naphthyl group, or anthracenyl group.

[0066] C 7-20 The alkylaryl of may mean a substituent in which one or more hydrogens of the aryl are replaced by alkyl. Specifically, the C 7-20 The alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl or cyclohexylphenyl.

[0067] The above group 4 transition metals include titanium, zirconium, and hafnium.

[0068]

[0069] The hybrid supported metallocene catalyst of the present invention is a hybrid catalyst comprising a first metallocene compound having a high molecular weight and high crystallinity and a second metallocene compound having a low molecular weight and low crystallinity.

[0070] In copolymerization in a single reactor using a hybrid supported metallocene catalyst, it is important to control the expression of differences in polymerization characteristics between the metallocene compounds constituting the hybrid supported metallocene catalyst under a single copolymerization condition. In particular, to obtain a polyethylene copolymer suitable for biaxial stretching, a high molecular weight, high crystallinity component and a low molecular weight, low crystallinity component must be composed together. Accordingly, the present invention has invented a polyethylene copolymer that expresses each characteristic under a single copolymerization condition by using a hybrid supported metallocene catalyst obtained by combining the first metallocene compound and the second metallocene compound.

[0071] The first metallocene compound represented by the above chemical formula 1 has the characteristics of a lower polymerization rate of the comonomer and a higher polymerization rate of the ethylene monomer compared to the second metallocene compound due to the structure of the non-bridged ligand bonded to the central metal. As a result, under ethylene / 1-hexene copolymerization conditions, it can express a high molecular weight, high crystallinity polyethylene with a small number of SCBs and a high Mw.

[0072] Meanwhile, the second metallocene compound represented by Chemical Formula 2 has a higher polymerization rate of the comonomer and a lower polymerization rate of the ethylene monomer compared to the first metallocene compound due to the bridge-type ligand structure bonded to the central metal. As a result, it can express a low molecular weight, low crystallinity polyethylene with a high SCB and a low Mw under ethylene / 1-hexene copolymerization conditions.

[0073]

[0074] Preferably, the central metal (M1) of the chemical formula 1 may be a Group 4 transition metal, specifically Ti, Zr, or Hf, and more specifically Hf or Zr.

[0075]

[0076] Preferably, X 11 , X 12can each independently be methyl or chloro, more preferably X 11 , X 12 can be all methyl or all chloro.

[0077]

[0078] Preferably, R1 to R5 and R7 to R 12 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl, or -(CH2) n1 -OR 13 , and R6 is substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl, or -(CH2) n1 -OR 13 However, R1 to R 12 One or both of them are -(CH2) n1 -OR 13 It could be.

[0079]

[0080] Preferably, either R7 or R8 is -(CH2) n1 -OR 13 And the rest of R1 to R5 and R9 to R 12 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-60 Aryl, or -(CH2) n1 -OR 13 , and R6 is substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-60 Aryl, or -(CH2) n1 -OR 13 It could be.

[0081]

[0082] Preferably, R1 to R5 are each independently hydrogen, methyl, isopropyl, n-butyl, phenyl, or -(CH2) n1 -OR 13may be. More preferably, R1 to R5 may each independently be hydrogen, methyl, n-butyl, phenyl, or tertbutoxyhexyl.

[0083]

[0084] Preferably, R6 is unsubstituted or C 6-10 C substituted with aryl or Si(R')3 1-20 Alkyl, or C 6-20 It can be aryl, where R' is C 1-20 Alkyl or C 6-10 It may be aryl. More preferably, R6 is C unsubstituted or substituted with phenyl, trimethylsilyl, or triphenylsilyl. 1-20 Alkyl, or C 6-20 It can be aryl. Most preferably, R6 can be methyl, ethyl, isopropyl, benzyl, trimethylsilyl methyl, or phenyl.

[0085]

[0086] Preferably, either R7 or R8 is -(CH2) n1 -OR 13 And the rest of R9 to R 12 Each of R7 and R8 may be hydrogen. More preferably, one of R7 or R8 is tert-butoxy hexyl, and the other and R9 to R 12 Each can be hydrogen.

[0087]

[0088] Preferably, R 13 It may be tert-butyl.

[0089]

[0090] Preferably, n1 may be an integer from 4 to 10, more preferably, n1 may be an integer from 4 to 7, and most preferably, n1 may be 6.

[0091]

[0092] Preferably, the first metallocene compound represented by the above chemical formula 1 may be any one selected from the group consisting of:

[0093]

[0094] .

[0095]

[0096] Meanwhile, the method for producing the first metallocene compound represented by the above chemical formula 1 is not particularly limited, but may be produced by a method such as the following reaction scheme 1, for example.

[0097] The compound represented by the above chemical formula 1 is difficult to synthesize due to the steric hindrance of the indene ligand, but the compound represented by the above chemical formula 1 can be produced in high yield and high purity according to a method such as the following reaction scheme 1.

[0098]

[0099] Accordingly, according to one embodiment of the present invention, the compound represented by the chemical formula 1 is

[0100] A step of preparing a ligand of chemical formula 1-3 by reacting a compound represented by chemical formula 1-1 with a compound represented by chemical formula 1-2; and

[0101] It can be produced by a production method including a step of reacting a ligand of Chemical Formula 1-3, a compound represented by Chemical Formula 1-4, and a halogen salt of a transition metal represented by Chemical Formula 1-5:

[0102] [Reaction Formula 1]

[0103]

[0104] In the above reaction formula 1,

[0105] M1, X 11 , X 12 and R1 to R 12 is as defined in the above chemical formula 1,

[0106] X' is each independently a halogen.

[0107]

[0108] Preferably, the central metal (M2) of chemical formula 2 may be a Group 4 transition metal, specifically Ti, Zr, or Hf, and more specifically Zr.

[0109]

[0110] Preferably, X 21 , X 22 can each independently be methyl or chloro, more preferably X 21 , X 22 Each can be chloro.

[0111]

[0112] Preferably, T2 may be C (carbon).

[0113]

[0114] Preferably, R 20 Inland R 31 , Q 21 and Q 22 At least one of them is -(CH2) n2 -OR 32 It can be. More preferably, R 20 Inland R 25 , Q 21 and Q 22 At least one of them is -(CH2) n2 -OR 32 It can be. More preferably, R 20 Inland R 31 , Q 21 and Q 22 One or both of them are -(CH2) n2 -OR 32 It can be. More preferably, R 20 Inland R 25 , Q 21 and Q 22 One or both of them are -(CH2) n2 -OR 32 It can be. Most preferably, R 20 Inland R 25 , Q 21 and Q22 Either one or both may be tert-butoxyhexyl.

[0115]

[0116] Preferably, Q 21 and Q 22 are each independently substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl, or -(CH2) n2 -OR 32 This or Q 21 and Q 22 C, which is substituted or unsubstituted by combining with each other 3-20 A cycloalkyl ring can be formed. More preferably, Q 21 and Q 22 are each independently methyl, ethyl, isopropyl, phenyl, or -(CH2) n2 -OR 32 This or Q 21 and Q 22 can combine with each other to form a cyclopentene ring or a cyclohexene ring.

[0117]

[0118] Preferably, R 20 Inland R 23 are each independently hydrogen, C 1-20 Alkyl, C 6-20 Aryl, or -(CH2) n2 -OR 32 It may be, and more preferably, R 20 Inland R 23 Each independently may be hydrogen, methyl, n-butyl, phenyl, or tertbutoxyhexyl. More preferably, R 20 Inland R 23 One of them is tert-butoxyhexyl or n-butyl, and the other is hydrogen, or R 20 Inland R 23 Two of them can be independently methyl, n-butyl, or phenyl, and the remainder can be hydrogen.

[0119]

[0120] Preferably, R 24 Inland R 31 are each independently hydrogen, C 1-10 Alkyl, C 6-20 Aryl, or -(CH2) n2 -OR 32 This or R 24 Inland R 31 C, which is substituted or unsubstituted, is formed by combining two adjacent C's. 3-10 A cycloalkyl ring can be formed. More preferably, R 24 Inland R 31 are each independently hydrogen, tert-butyl or tert-butoxyhexyl, or R 24 Inland R 31 Two adjacent ones can combine to form a cyclohexane ring substituted with four methyl groups.

[0121]

[0122] Preferably, R 32 may be tertbutyl.

[0123]

[0124] Preferably, n2 may be an integer from 4 to 10, more preferably, n2 may be an integer from 4 to 7, and most preferably, n2 may be 6.

[0125]

[0126] Preferably, the metallocene compound represented by the above chemical formula 2 may be any one selected from the group consisting of:

[0127]

[0128] .

[0129]

[0130] Meanwhile, the method for producing the second metallocene compound represented by the above chemical formula 2 is not particularly limited, but may be produced by a method such as the following reaction formula 2, for example.

[0131] The compound represented by the above chemical formula 2 is difficult to synthesize due to the steric hindrance of the indene ligand, but the compound represented by the above chemical formula 2 can be produced in high yield and high purity according to a method such as the following reaction scheme 2.

[0132]

[0133] Accordingly, according to one embodiment of the present invention, the compound represented by the chemical formula 2 is

[0134] A step of producing a compound represented by chemical formula 2-3 by reacting a compound represented by chemical formula 2-1 with a compound represented by chemical formula 2-2;

[0135] A step of preparing a ligand of chemical formula 2-5 by reacting a compound represented by chemical formula 2-3 with a compound represented by chemical formula 2-4; and

[0136] It can be produced by a production method including a step of reacting a ligand of Chemical Formula 2-5 with a halogen salt of a transition metal represented by Chemical Formula 2-6:

[0137] [Reaction Formula 2]

[0138]

[0139] In the above reaction formula 2,

[0140] M2, X 21 , X 22 , T2, Q 21 , Q 22 and R 20 Inland R 31 is as defined in the above chemical formula 2,

[0141] X" is each independently a halogen.

[0142]

[0143] In the hybrid supported metallocene catalyst of the present invention, the first metallocene compound and the second metallocene compound may be supported at a molar ratio of 1:1 to 25:1, 2:1 to 25:1, 3:1 to 25:1, 3:1 to 23:1, or 3:1 to 20:1. When the ratio of the first metallocene compound and the second metallocene compound is less than 1:1, the high crystallinity content is low, making it difficult for the stretched film to have heat resistance, and when the ratio of the first metallocene compound and the second metallocene compound exceeds 25:1, the low crystallinity content is low, making biaxial stretching processability difficult.

[0144]

[0145] In the hybrid supported metallocene catalyst of the present invention, a carrier containing a hydroxyl group on the surface can be used as a carrier for supporting the first metallocene compound and the second metallocene compound. Preferably, the carrier can be a carrier having a highly reactive hydroxyl group, silanol group, or siloxane group on the surface. For this purpose, a carrier whose surface has been modified by calcination or whose surface has had moisture removed by drying can be used.

[0146] For example, silica manufactured by calcining silica gel, silica such as silica dried at high temperature, silica-alumina, and silica-magnesia can be used, and these can typically contain oxide, carbonate, sulfate, and nitrate components such as Na2O, K2CO3, BaSO4, and Mg(NO3)2.

[0147]

[0148] The drying temperature of the carrier is preferably from about 200°C to about 800°C, more preferably from about 300°C to about 600°C, and most preferably from about 300°C to about 400°C. If the drying temperature of the carrier is less than 200°C, the moisture content is too high, causing the moisture on the surface to react with the cocatalyst described below, and if the drying temperature is less than 800°C, the cocatalyst described below will react with the moisture on the surface. When the temperature exceeds ℃, the pores on the surface of the carrier merge, reducing the surface area. In addition, many hydroxyl groups on the surface disappear, leaving only siloxane groups, which is not desirable because the reaction sites with the cocatalyst decrease.

[0149]

[0150] The amount of hydroxyl groups on the surface of the carrier is preferably about 0.1 mmol / g to about 10 mmol / g, and more preferably about 0.5 mmol / g to about 5 mmol / g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the manufacturing method and conditions of the carrier or drying conditions, such as temperature, time, vacuum or spray drying.

[0151]

[0152] If the amount of the above hydroxyl group is less than about 0.1 mmol / g, there are few reaction sites with the cocatalyst, and if it exceeds about 10 mmol / g, it is not preferable because there is a possibility that it is caused by moisture other than the hydroxyl group present on the surface of the carrier particle.

[0153]

[0154] When used in a supported catalyst state, the particle shape and bulk density of the polymer produced are excellent, and it can be suitably used in conventional slurry polymerization, bulk polymerization, and gas phase polymerization processes. In addition, among various supports, the silica support is supported by chemical bonding of the functional group of the transition metal compound, so that almost no catalyst is liberated from the support surface during the ethylene polymerization process, and as a result, when producing a polyethylene copolymer by slurry or gas phase polymerization, fouling caused by adhesion of the reactor wall or polymer particles to each other can be minimized.

[0155] The above-mentioned carrier may have an average particle diameter (D50) of 20 to 60 μm. When the above-mentioned particle size is present, the transition metal compound can be supported with superior efficiency, and as a result, the catalytic activity can be enhanced. More specifically, the carrier may have an average particle diameter of 20 μm or more, or 25 μm or more, and 60 μm or less, or 50 μm or less.

[0156] Meanwhile, in the present invention, the average particle diameter (D50) of the carrier refers to the particle diameter at the 50% point of the cumulative distribution of the number of particles according to particle size (particle diameter). The D50 can be measured using a laser diffraction method. Specifically, the target carrier is dispersed in a dispersion medium such as deionized water, and then introduced into a commercially available laser diffraction particle size measuring device (e.g., Microtrac S3500), and when the particles pass through the laser beam, the difference in the diffraction pattern according to the particle size is measured to calculate the particle size distribution. The particle size at the point where it becomes 50% of the cumulative distribution of the number of particles according to the particle diameter in the measuring device is calculated, and this is taken as the average particle size.

[0157] In addition, when supported on the carrier, the first and second metallocene compounds may be supported in an amount of, for example, 1 mmol or more, 10 mmol or more, 15 mmol or more, 20 mmol or more, 25 mmol or more, or 30 mmol or more, and 500 mmol or less, 400 mmol or less, 300 mmol or less, 200 mmol or less, 100 mmol or less, 80 mmol or less, 60 mmol or less, or 52.5 mmol or less, based on 1,000 g of the carrier. When supported in the above amount range, it may exhibit appropriate supported catalytic activity, which may be advantageous in terms of maintaining the activity of the catalyst and economic efficiency.

[0158]

[0159] In addition, the above hybrid metallocene catalyst may further include a cocatalyst in order to improve high activity and process stability.

[0160] Specifically, the cocatalyst may include at least one compound represented by the following chemical formula 3.

[0161] [Chemical Formula 3]

[0162] -[Al(R 41 )-O]a-

[0163] In the above chemical formula 3,

[0164] R 41 is a halogen; or C substituted or unsubstituted with a halogen 1-20 It is hydrocarbyl;

[0165] a is an integer greater than or equal to 2.

[0166] Meanwhile, in the present specification, a hydrocarbyl group is a monovalent functional group in the form of removing a hydrogen atom from a hydrocarbon, and may include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenylaryl group, and an alkynylaryl group. In addition, the hydrocarbyl group having 1 to 20 carbon atoms may be a hydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. Specifically, the hydrocarbyl group having 1 to 20 carbon atoms is a straight-chain, branched-chain, or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, or a cyclohexyl group; Or it may be an aryl group such as a phenyl group, a naphthyl group, or anthracenyl group.

[0167] Examples of compounds represented by the above chemical formula 3 include alkylaluminoxane compounds such as modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane, and one or a mixture of two or more of these may be used.

[0168] Among the above compounds, the cocatalyst may be, more specifically, an alkylaluminoxane cocatalyst such as methylaluminoxane.

[0169] The above alkylaluminoxane cocatalyst can further enhance catalytic activity by including a metal element that stabilizes the first and second transition metal compounds and acts as a Lewis acid to form a bond through a Lewis acid-base interaction with a functional group introduced into a bridge group of the first and second transition metal compounds.

[0170] In addition, the amount of the cocatalyst used can be appropriately adjusted depending on the properties or effects of the desired catalyst and the polyethylene copolymer. For example, when silica is used as the carrier, the cocatalyst can be supported in an amount of 100 g or more, or 1000 g or more, or 2000 g or more, and 6000 g or less, or 5500 g or less, or 5400 g or less, based on 1,000 g of silica.

[0171]

[0172] The hybrid metallocene catalyst according to the present invention having the above-described configuration can be manufactured by a manufacturing method including a step of supporting a promoter compound on a support, and a step of supporting the first and second metallocene compounds on the support. At this time, the supporting order of the promoter and the first and second metallocene compounds can be changed as needed, and the supporting order of the first and second metallocene compounds can also be changed as needed. The first and second metallocene compounds may be supported simultaneously. Considering the effect of the supported catalyst having a structure determined according to the supporting order, among these, supporting the first and second metallocene compounds sequentially after supporting the promoter on the support can enable the manufactured supported catalyst to implement high catalytic activity and better process stability in the manufacturing process of a polyethylene copolymer.

[0173] As described above, the hybrid supported metallocene catalyst can exhibit excellent catalytic activity by including first and second metallocene compounds having specific structures. Accordingly, the hybrid supported metallocene catalyst can be suitably used for the polymerization of ethylene and olefin monomers.

[0174]

[0175] In the above method, the supporting conditions are not particularly limited and can be carried out within a range well known to those skilled in the art. For example, high-temperature supporting and low-temperature supporting can be appropriately utilized. For example, the supporting temperature can be in the range of about -30°C to about 150°C, and preferably about 30°C to about 98°C, or about 40°C to about 95°C. The supporting time can be appropriately adjusted depending on the amount of the metallocene compound to be supported. The reacted supported catalyst can be used as is by removing the reaction solvent by filtration or distillation under reduced pressure, or, if necessary, can be used after Soxhlet filtering with an aromatic hydrocarbon such as toluene.

[0176]

[0177] And, the production of the supported catalyst can be carried out under a solvent or solventless conditions. When a solvent is used, usable solvents include aliphatic hydrocarbon solvents such as hexane or pentane, aromatic hydrocarbon solvents such as toluene or benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, ether solvents such as diethyl ether or tetrahydrofuran (THF), acetone, ethyl acetate, and most organic solvents, with hexane, heptane, toluene, or dichloromethane being preferred.

[0178]

[0179] The above-described hybrid supported catalyst can improve the average molecular weight of the excellent supporting performance, catalytic activity and high crystallinity fraction, and can produce a polyethylene copolymer having stretching stability advantageous for biaxial stretching under such a hybrid supported catalyst.

[0180]

[0181] Meanwhile, as the olefin monomer polymerized with ethylene, ethylene, alpha-olefin, cyclic olefin, diene olefin or triene olefin having two or more double bonds can be used.

[0182] Specific examples of the above olefin 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, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc., and two or more of these monomers may be mixed and copolymerized. More specifically, the above olefin monomer may be 1-hexene.

[0183] The amount of the olefin monomer added may be determined depending on the properties of the polyethylene copolymer to be manufactured. For example, considering the properties of the polyethylene copolymer to be implemented in the present invention, the olefin monomer may be added in an amount of 3.0 to 10.0 wt% relative to the total weight of ethylene.

[0184]

[0185] The above polymerization reaction is carried out under the condition of hydrogen input.

[0186] Specifically, the hydrogen may be introduced in an amount of 5 to 120 ppm based on the total weight of ethylene, which is a monomer. More specifically, it may be introduced in an amount of 5 ppm or more, 10 ppm or more, 15 ppm or more, 20 ppm or more, or 21 ppm or more, and 100 ppm or less, 95 or less, 90 ppm or less, 85 ppm or less, or 80 ppm or less, based on the total weight of ethylene.

[0187] When injected within the above range, it is easier to implement the properties of the polyethylene copolymer described above.

[0188]

[0189] The above polymerization reaction can be carried out as a gas phase polymerization reaction or a slurry polymerization reaction.

[0190] Accordingly, it can be performed using a single gas phase polymerization reactor, a continuous slurry polymerization reactor, or a loop slurry reactor.

[0191]

[0192] In addition, the above hybrid supported catalyst can be dissolved or diluted and injected into an aliphatic hydrocarbon solvent having 4 to 12 carbon atoms, such as isobutane, pentane, hexane, heptane, nonane, decane, and their isomers, an aromatic hydrocarbon solvent such as toluene and benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene, etc. It is preferable to use the solvent used here after removing a small amount of water or air, etc. that act as catalyst poisons, by treating it with a small amount of alkyl aluminum, and it is also possible to carry out the process using an additional cocatalyst.

[0193]

[0194] In addition, the polymerization reaction may be carried out at a temperature of 40°C or higher, or 60°C or higher, or 80°C or higher, and 110°C or lower, or 100°C or lower, or 90°C or lower. In addition, when the pressure conditions during the polymerization reaction are further controlled, the polymerization reaction may be carried out under a pressure of 5 bar or higher, or 10 bar or higher, or 20 bar or higher, and 50 bar or lower, or 45 bar or lower, or 40 bar or lower. When polymerization is carried out under such temperature and pressure, the desired physical properties of the polyethylene copolymer can be more easily realized.

[0195]

[0196] The above polyethylene copolymer is produced using a catalyst that hybridizes a metallocene compound exhibiting high molecular weight and high crystallinity with a metallocene compound exhibiting low molecular weight and low crystallinity, thereby having a high crystallinity content of 45 wt% or more and improving the main chain average molecular weight of the high crystallinity fraction. Accordingly, when a biaxially oriented film is produced using the above polyethylene copolymer, the heat resistance, such as tensile modulus and shrinkage rate, of the oriented film can be improved.

[0197]

[0198] According to another embodiment of the invention, a polyethylene copolymer obtained by the above-described manufacturing method is provided. In this case, the polyethylene produced may be an ethylene-1-hexene copolymer.

[0199]

[0200] The above method for producing a polyethylene copolymer can provide a polyethylene copolymer having excellent mechanical properties by polymerizing in the presence of the hybrid supported catalyst described above.

[0201]

[0202] The polyethylene copolymer of the present invention has the characteristic of having an improved main chain average molecular weight of a highly crystalline fraction eluted at an elution temperature exceeding 90°C during cross fractionation chromatography (CFC) analysis using the above-described hybrid supported metallocene catalyst. The hybrid supported metallocene catalyst supports a metallocene compound exhibiting a high molecular weight and high crystallinity together with a metallocene compound exhibiting a low molecular weight and low crystallinity, thereby enabling production in a single reactor, thereby reducing production costs. In addition, the polyethylene copolymer has the characteristic of being suitable for the production of a biaxially oriented film with improved heat resistance due to the improved main chain average molecular weight of the highly crystalline fraction.

[0203]

[0204] The above polyethylene copolymer has a main chain average molecular weight (Mw) of a high-crystalline fraction eluted at an elution temperature exceeding 90°C when analyzed by cross fractionation chromatography (CFC). ,T>90℃ ) may be 90,000 g / mol or more. Preferably, the main chain average molecular weight (Mw) of the high-crystalline fraction ,T>90℃ ) may be 100,000 g / mol or more, 103,000 g / mol or more, or 105,000 g / mol or more, and 200,000 g / mol or less.

[0205]

[0206] The above polyethylene copolymer has a content ratio (TREF) of a high-crystalline fraction eluted at an elution temperature exceeding 90°C when analyzed by cross fractionation chromatography (CFC). T>90℃ ) may be 45.0 wt% or more of the total elution fraction. Preferably, the content ratio of the high crystallinity fraction (TREF T>90℃) may be 47.0 wt% or more, 48.0 wt% or more, or 48.3 wt% or more and 70 wt% or less, 60 wt% or less, or 56.1 wt% or less.

[0207]

[0208] In the present invention, a specific test method related to cross fractionation chromatography (CFC) analysis is as described in Experimental Example 1 described below. However, the cross fractionation chromatography (CFC) analysis is not limited thereto and may be measured by other methods known in the technical field to which the present invention pertains.

[0209]

[0210] Meanwhile, the polyethylene copolymer has a density of 0.920 g / cm as measured according to ASTM D 792. 3 Above 0.940 g / cm 3 It may be less than or equal to 0.923 g / cm. Preferably, the density is 0.923 g / cm. 3 Above, 0.925 g / cm 3 or 0.926 g / cm 3 Ideally, 0.937 g / cm 3 Below, 0.935 g / cm 3 or less, or 0.933 g / cm 3 It could be as follows:

[0211]

[0212] In addition, the polyethylene copolymer has a melt index (MI) measured according to ASTM D 1238. 2.16 ) may be 0.5 g / 10 min or more and 5.0 g / 10 min or less. Preferably, the melting index (MI 2.16, 190 ℃, 2.16 kg load) may be 0.7 g / 10 min or more, 1.0 g / 10 min or more, 1.2 g / 10 min or more, or 1.33 g / 10 min or more, but 4.0 g / 10 min or less, 3.5 g / 10 min or less, 3.0 g / 10 min or less, 2.5 g / 10 min or less, 2.2 g / 10 min or less, 2.0 g / 10 min or less, 1.9 g / 10 min or less, or 1.88 g / 10 min or less.

[0213]

[0214] In addition, the above polyethylene copolymer has MFRR (MFR 21.6 / MFR 2.16 ) may be 15 or more and 40 or less. Preferably, the MFRR (MFR) 21.6 / MFR 2.16 ) may be 20 or more and 35 or less, 23 or more and 35 or less, 25.2 or more and 30 or less, or 25.2 or more and 29.8 or less. The MFR of the above MFRR 21.6 is measured at 190 ℃ and under a load of 21.6 kg according to ISO 1133, and MFR 2.16 It is measured at 190°C and under a load of 2.16 kg according to ISO 1133.

[0215]

[0216] Accordingly, the polyethylene copolymer manufactured by the above manufacturing method can be used for various purposes requiring such properties, and in particular, can be used for stretch films requiring biaxial stretching, to which it is difficult to apply conventional low-density polyethylene or high-density polyethylene.

[0217]

[0218] Hereinafter, the present invention will be described in more detail to aid understanding. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following examples.

[0219]

[0220] <Preparation of metallocene compounds>

[0221] Synthesis Example 1-1: Preparation of Metallocene Compound A1

[0222]

[0223] (1) Synthesis of ligands

[0224] Under Ar, 27.2 g (100 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene and 250 mL of n-hexane were added to a dried 2 L Schlenk flask. After cooling to -78 °C, 42 mL (1.05 eq., 105 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling again to -78 °C, 21.3 g (1.5 eq., 150 mmol) of iodomethane was added dropwise. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 24.1 g (84.2 mmol, 84.2% yield) of 3-(6-tert-butoxyhexyl)-1-methyl-1H-indene.

[0225] 1 H NMR (500 MHz, CDCl3): 1.12 (9H, s), 1.29 (3H, d), 1.42 (4H, m), 1.56 (2H, m), 1.70 (2H, m), 2.52 (2H, t), 3.34 (2H, t), 3.42 (1H, m), 6.25 (1H, brs), 7.21 (1H, t), 7.25-7.32 (2H, m), 7.40 (1H, d).

[0226]

[0227] (2) Synthesis of metallocene compounds

[0228] ​Under Ar, 5.73 g (20 mmol) of the ligand synthesized above and 70 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 8.4 mL (1.05 eq., 21 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 8.46 g (1.0 eq., 20 mmol) of (1-n-butyl-3-methylcyclopentadienyl)ZrCl3dimethoxyethane complex and 30 mL of diethyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure, and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 7.52 g (12.9 mmol, 64.5% yield) of metallocene compound A1 in solid form.

[0229] 1 H NMR (500 MHz, CDCl3): 0.77-0.81 (3H, m), 1.09 (9H, s), 1.16-1.28 (6H, m), 1.48-1.56 (6H, m), 1.95 (3H, d), 2.14 (1H, m), 2.42 (4H, m), 2.68 (1H, m), 2.90 (1H, m), 3.23 (2H, t), 4.97 (1H, dt), 5.11 (1H, dt), 5.76 (1H, t), 6.41 (1H, brs), 7.13-7.15 (2H, m), 7.46-7.48 (2H, m).

[0230]

[0231] Synthesis Example 1-2: Preparation of Metallocene Compound A2

[0232]

[0233] (1) Synthesis of ligands

[0234] Under Ar, 54.5 g (200 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene and 500 mL of n-hexane were added to a dried 2 L Schlenk flask. After cooling to -78 °C, 84 mL (1.05 eq., 210 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling again to -78 °C, 46.8 g (1.5 eq., 300 mmol) of iodoethane was added dropwise. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 43.3 g (144 mmol, 72% yield) of 3-(6-tert-butoxyhexyl)-1-ethyl-1H-indene.

[0235] 1 H NMR (500 MHz, CDCl3): 0.94 (3H, t), 1.12 (9H, s), 1.29 (2H, m), 1.32-1.90 (8H, m), 2.52 (2H, t), 3.34 (2H, t), 3.45 (1H, m), 6.27 (1H, brs), 7.22 (1H, t), 7.25-7.35 (2H, m), 7.39 (1H, d).

[0236]

[0237] (2) Synthesis of metallocene compounds

[0238] ​Under Ar, 6.61 g (22 mmol) of the ligand synthesized above and 80 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 9.3 mL (1.06 eq., 23.3 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 9.00 g (1.0 eq., 22 mmol) of (n-butylcyclopentadienyl)ZrCl3dimethoxyethane complex and 30 mL of diethyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure, and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 8.10 g (13.9 mmol, 63.2% yield) of metallocene compound A2 in solid form.

[0239] 1 H NMR (500 MHz, CDCl3): 0.75-0.85 (3H, m), 0.87 (3H, m), 1.11 (9H, s), 1.18-1.29 (6H, m), 1.47-1.56 (6H, m), 2.16 (1H, m), 2.40-2.65 (4H, m), 2.89 (1H, m), 3.26 (2H, t), 4.96-5.94 (4H, m), 6.40 (1H, brs), 7.11-7.17 (2H, m), 7.44-7.48 (2H, m).

[0240]

[0241] Synthesis Example 1-3: Preparation of Metallocene Compound A3

[0242]

[0243] (1) Synthesis of ligands

[0244] Under Ar, 27.3 g (100 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene and 250 mL of n-hexane were added to a dried 2 L Schlenk flask. After cooling to -78 °C, 42 mL (1.05 eq., 105 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling again to -78 °C, 13.6 g (1.1 eq., 111 mmol) of 2-bromopropane was added dropwise. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 26.4 g (84 mmol, 84% yield) of 3-(6-tert-butoxyhexyl)-1-isopropyl-1H-indene.

[0245] 1 H NMR (500 MHz, CDCl3): 0.88 (6H, d), 1.24 (9H, s), 1.34 (4H, m), 1.47 (3H, m), 1.57 (2H, m), 1.73 (2H, m), 2.55 (2H, t), 3.39 (2H, t), 3.45 (1H, m), 6.17 (1H, brs), 7.23 (1H, t), 7.31 (2H, m), 7.44 (1H, d).

[0246] (2) Synthesis of metallocene compounds

[0247] Under Ar, 6.29 g (20 mmol) of the ligand synthesized above and 70 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 8.4 mL (1.05 eq., 21 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 8.46 g (1.0 eq., 20 mmol) of (1-n-butyl-3-methylcyclopentadienyl)ZrCl3dimethoxyethane complex and 30 mL of diethyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure, and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 7.70 g (12.6 mmol, 63% yield) of metallocene compound A3 in solid form.

[0248] 1 H NMR (500 MHz, CDCl3): 0.79-0.91 (9H, m), 1.19 (9H, s), 1.29-1.30 (6H, m), 1.52-1.54 (4H, m), 1.65-1.71 (2H, m), 2.03 (3H, s), 2.11-2.22 (2H, m), 2.51-2.55 (1H, m), 2.77-2.86 (1H, m), 2.99-3.07 (1H, m), 3.34 (2H, t), 4.53 (1H, dt), 5.22 (1H, dt), 5.82 (1H, t), 6.62 (1H, brs), 7.11-7.28 (2H, m), 7.56-7.63 (2H, m).

[0249]

[0250] Synthesis Example 1-4: Preparation of Metallocene Compound A4

[0251]

[0252] (1) Synthesis of ligands

[0253] Under Ar, 120 g (440 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene and 1.1 L of n-hexane were added to a dried 2 L Schlenk flask. After cooling to -78 °C, 185 mL (1.05 eq., 462.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling again to -78 °C, 82.8 g (1.1 eq., 484 mmol) of benzyl bromide was added dropwise. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 137 g (377 mmol, 85.7% yield) of 3-(6-tert-butoxyhexyl)-1-benzyl-1H-indene.

[0254] 1 H NMR (500 MHz, CDCl3): 1.22 (9H, s), 1.32 (4H, m), 1.44 (2H, m), 1.57 (2H, m), 1.73 (2H, m), 2.59 (2H, m), 3.38 (2H, t), 3.75 (1H, m), 6.14 (1H, brs), 7.14-7.45 (9H, m).

[0255] (2) Synthesis of metallocene compounds

[0256] Under Ar, 9.06 g (25 mmol) of the ligand synthesized above and 90 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11 mL (1.05 eq., 27.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 10.6 g (1.0 eq., 25 mmol) of (1-n-butyl-3-methylcyclopentadienyl)ZrCl3dimethoxyethane complex and 30 mL of diethyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure, and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 8.76 g (13.3 mmol, 53.2% yield) of metallocene compound A4 in solid form.

[0257] 1 H NMR (500 MHz, CDCl3): 0.88-0.91 (3H, m), 1.22 (9H, s), 1.29-1.40 (8H, m), 1.52-1.76 (4H, m), 2.06 (3H, s), 2.11-2.22 (2H, m), 2.59-2.68 (2H, m), 2.99-3.07 (2H, m), 3.34 (2H, t), 4.43 (1H, dt), 5.21 (1H, dt), 5.78 (1H, t), 6.47 (1H, brs), 7.11-7.63 (9H, m).

[0258]

[0259] Synthesis Example 1-5: Preparation of Metallocene Compound A5

[0260]

[0261] (1) Synthesis of ligands

[0262] Under Ar, 35.4 g (130 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene and 350 mL of n-hexane were added to a dried 2 L Schlenk flask. After cooling to -78 °C, 55 mL (1.05 eq., 137 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling again to -78 °C, 23.9 g (1.5 eq., 195 mmol) of (chloromethyl)trimethylsilane was added dropwise. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 27.6 g (77 mmol, 59.2% yield) of 3-(6-tert-butoxyhexyl)-1-(trimethylsilyl)methyl-1H-indene.

[0263] 1 H NMR (500 MHz, CDCl3): 0.05 (9H, s), 0.88 (2H, m), 1.24 (9H, s), 1.33 (4H, m), 1.45 (2H, m), 1.57 (2H, m), 2.57 (2H, m), 3.35 (2H, t), 3.71 (1H, m), 6.16 (1H, brs), 7.12-7.45 (4H, m).

[0264] (2) Synthesis of metallocene compounds

[0265] Under Ar, 9.68 g (27 mmol) of the ligand synthesized above and 100 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11.4 mL (1.06 eq., 28.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 8.61 g (1.0 eq., 27 mmol) of (tetramethylcyclopentadienyl)ZrCl3 and 30 mL of diethyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure, and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 8.76 g (13.3 mmol, 53.2% yield) of metallocene compound A5 in solid form.

[0266] 1 H NMR (500 MHz, CDCl3): -0.05 (9H, s), 0.75 (2H, m), 1.24 (9H, s), 1.25-1.42 (4H, m), 1.52-1.76 (4H, m), 1.81 (12H, brs), 2.10-2.22 (2H, m), 3.33 (2H, t), 5.01 (1H, brs), 6.41 (1H, brs), 7.10-7.58 (4H, m).

[0267]

[0268] Synthesis Example 1-6: Preparation of Metallocene Compound A6

[0269]

[0270] (1) Synthesis of ligands

[0271] Under Ar, 44.2 g (230 mmol) of 3-phenyl-1H-indene and 600 mL of tetrahydrofuran were added to a dried 2 L Schlenk flask. After cooling to -78 °C, 97 mL (1.06 eq., 243 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling again to -78 °C, 44.4 g (1.0 eq., 230 mmol) of 6-tert-butoxyhexyl chloride was added dropwise. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 31.7 g (91.0 mmol, 39.5% yield) of 1-(6-tert-butoxyhexyl)-3-phenyl-1H-indene.

[0272] 1 H NMR (500 MHz, CDCl3): 1.18 (9H, s), 1.32 (4H, m), 1.42 (2H, m), 1.55 (2H, m), 1.97 (2H, m), 3.32 (2H, t), 3.61 (1H, m), 6.66 (1H, brs), 7.08-7.50 (9H, m).

[0273] (2) Synthesis of metallocene compounds

[0274] Under Ar, 11.5 g (33 mmol) of the ligand synthesized above and 120 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 13.9 mL (1.05 eq., 34.8 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 11.0 g (1.0 eq., 33 mmol) of (pentamethylcyclopentadienyl)ZrCl3 and 30 mL of diethyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure, and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 15.3 g (23.7 mmol, 71.8% yield) of metallocene compound A6 in solid form.

[0275] 1 H NMR (500 MHz, CDCl3): 1.21 (9H, s), 1.26-1.43 (4H, m), 1.55-1.71 (4H, m), 1.74 (15H, brs), 2.24 (2H, m), 3.32 (2H, t), 6.61 (1H, brs), 7.10-7.65 (9H, m).

[0276]

[0277] Synthesis Example 1-7: Preparation of Metallocene Compound A7

[0278]

[0279] Under Ar, 7.25 g (20 mmol) of the ligand synthesized in (1) of Synthesis Example 1-4 and 70 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 8.4 mL (1.05 eq., 21 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 6.66 g (1.0 eq., 20 mmol) of (pentamethylcyclopentadienyl)ZrCl3 and 30 mL of diethyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure, and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 7.45 g (11.3 mmol, 56.5% yield) of metallocene compound A7 in solid form.

[0280] 1 H NMR (500 MHz, CDCl3): 1.23 (9H, s), 1.25-1.41 (4H, m), 1.54-1.75 (4H, m), 1.79 (15H, brs), 2.21 (2H, m), 2.93 (2H, m), 3.32 (2H, t), 6.45 (1H, brs), 7.05-7.64 (9H, m).

[0281]

[0282] Synthesis Example 1-8: Preparation of Metallocene Compound A8

[0283]

[0284] Under Ar, 9.43 g (26 mmol) of the synthesized ligand synthesized in (1) of Synthesis Example 1-4 and 90 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11 mL (1.06 eq., 27.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 11.5 g (1.0 eq., 26 mmol) of (1-phenyl-3-methylcyclopentadienyl)ZrCl3dimethoxyethane complex was added together with 30 mL of diethyl ether. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 10.9 g (16.1 mmol, 61.9% yield) of metallocene compound A8 in solid form.

[0285] 1 H NMR (500 MHz, CDCl3): 1.23 (9H, s), 1.25-1.41 (4H, m), 1.54-1.75 (4H, m), 2.17 (5H, m), 2.61 (2H, m), 3.32 (2H, t), 4.45 (1H, dt), 5.22 (1H, dt), 5.99 (1H, t), 6.45 (1H, brs), 7.09-7.58 (14H, m).

[0286]

[0287] Synthesis Example 1-9: Preparation of Metallocene Compound A9

[0288]

[0289] (1) Synthesis of ligands

[0290] Under Ar, 54.5 g (200 mmol) of 2-(6-tert-butoxyhexyl)-1H-indene and 500 mL of tetrahydrofuran were added to a dried 2 L Schlenk flask. After cooling to -78 °C, 84 mL (1.05 eq., 210 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling again to -78 °C, 46.8 g (1.5 eq., 300 mmol) of iodoethane was added dropwise. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 41.2 g (137 mmol, 68.5% yield) of 2-(6-tert-butoxyhexyl)-1-ethyl-1H-indene.

[0291] 1 H NMR (500 MHz, CDCl3): 0.96 (3H, t), 1.11 (9H, s), 1.22-1.90 (10H, m), 3.34 (3H, m), 6.46 (1H, brs), 7.12-7.55 (4H, m).

[0292]

[0293] (2) Synthesis of metallocene compounds

[0294] ​Under Ar, 8.11 g (27 mmol) of the ligand synthesized above and 90 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11.4 mL (1.06 eq., 28.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 13.7 g (1.0 eq., 27 mmol) of ((6-tert-butoxyhexyl)cyclopentadienyl)ZrCl3dimethoxyethane complex was added together with 30 mL of diethyl ether. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 11.5 g (16.8 mmol, 62.2% yield) of metallocene compound A9 in solid form.

[0295] 1 H NMR (500 MHz, CDCl3): 0.88 (3H, m), 1.14 (18H, brs), 1.19-1.35 (8H, m), 1.51-1.70 (8H, m), 2.18 (1H, m), 2.40-2.65 (4H, m), 2.77 (1H, m), 3.25 (4H, m), 4.86-5.90 (4H, m), 6.66 (1H, brs), 7.07-7.21 (2H, m), 7.40-7.51 (2H, m).

[0296]

[0297] Synthesis Example 1-10: Preparation of Metallocene Compound A10

[0298]

[0299] Under Ar, 10.9 g (30 mmol) of the ligand synthesized in (1) of Synthesis Example 1-4 and 110 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 12.6 mL (1.05 eq., 31.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 15.3 g (1.0 eq., 30 mmol) of ((6-tert-butoxyhexyl)cyclopentadienyl)ZrCl3dimethoxyethane complex was added together with 30 mL of diethyl ether. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 13.3 g (17.8 mmol, 59.3% yield) of metallocene compound A10 in solid form.

[0300] 1 H NMR (500 MHz, CDCl3): 1.13 (18H, brs), 1.17-1.35 (8H, m), 1.52-1.66 (8H, m), 2.16 (1H, m), 2.40-2.65 (2H, m), 2.74 (1H, m), 2.98 (2H, m), 3.22 (4H, m), 4.89-5.88 (4H, m), 6.36 (1H, brs), 7.05-7.54 (9H, m).

[0301]

[0302] Synthesis Example 1-11: Preparation of Metallocene Compound A11

[0303]

[0304] Under Ar, 9.06 g (25 mmol) of the ligand synthesized in (1) of Synthesis Example 1-4 and 90 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11 mL (1.05 eq., 27.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 12.8 g (1.0 eq., 25 mmol) of (1-n-butyl-3-methylcyclopentadienyl)HfCl3dimethoxyethane complex was added together with 30 mL of diethyl ether. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and toluene was added. The resulting suspension was filtered under Ar to remove LiCl, and 25 mL (3.0 eq., 75 mmol) of 3.0 M methylmagnesium bromide in diethyl ether was added dropwise to the filtrate. The reaction mixture was heated to 80 °C and stirred for 2 days. After cooling to room temperature, 1,4-dioxane was added. The resulting suspension was filtered under Ar to remove the Mg salt, and the reaction mixture was dried under reduced pressure to obtain 12.9 g (18.3 mmol, 73.2% yield) of metallocene compound A11 in the form of an oil.

[0305] 1H NMR (500 MHz, CDCl3): -1.19 (6H, d), 0.85-0.88 (3H, m), 1.20 (9H, s), 1.22-1.37 (8H, m), 1.50-1.66 (4H, m), 2.01 (3H, s), 2.10-2.18 (2H, m), 2.52-2.58 (2H, m), 2.95-3.03 (2H, m), 3.32 (2H, t), 4.81 (1H, dt), 5.35 (1H, dt), 5.54 (1H, t), 5.71 (1H, brs), 7.05-7.53 (9H, m).

[0306]

[0307] Synthesis Example 1-12: Preparation of Metallocene Compound A12

[0308]

[0309] Under Ar, 5.73 g (20 mmol) of the ligand synthesized in (1) of Synthesis Example 1-1 and 70 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 8.4 mL (1.05 eq., 21 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 8.12 g (1.0 eq., 20 mmol) of (tetramethylcyclopentadienyl)HfCl3 and 30 mL of diethyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and toluene was added. The resulting suspension was filtered under Ar to remove LiCl, and 20 mL (3.0 eq., 60 mmol) of 3.0 M methylmagnesium bromide in diethyl ether was added dropwise to the filtrate. The reaction mixture was heated to 80 °C and stirred for 2 days. After cooling to room temperature again, 1,4-dioxane was added. The resulting suspension was filtered under Ar to remove the Mg salt, and the reaction mixture was dried under reduced pressure to obtain 7.80 g (12.7 mmol, 63.4% yield) of metallocene compound A12 in the form of an oil.

[0310] 1 H NMR (500 MHz, CDCl3): -1.39 (6H, d), 1.17 (9H, s), 1.30-1.37 (4H, m), 1.45-1.70 (4H, m), 1.81-1.90 (12H, m), 2.27 (3H, s), 2.30-2.41 (1H, m), 2.72-2.80 (1H, m), 3.30 (2H, t), 4.92 (1H, brs), 5.56 (1H, brs), 7.10-7.19 (2H, m), 7.39-7.46 (2H, m).

[0311]

[0312] Synthesis Example 1-13: Preparation of Metallocene Compound A13

[0313]

[0314] Under Ar, 9.06 g (25 mmol) of the ligand synthesized in (1) of Synthesis Example 1-4 and 90 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11 mL (1.05 eq., 27.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling again to -78 °C, 10.5 g (1.0 eq., 25 mmol) of (pentamethylcyclopentadienyl)HfCl3 and 30 mL of diethyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and toluene was added. The resulting suspension was filtered under Ar to remove LiCl, and 25 mL (3.0 eq., 75 mmol) of 3.0 M methylmagnesium bromide in diethyl ether was added dropwise to the filtrate. The reaction mixture was heated to 80 °C and stirred for 2 days. After cooling to room temperature again, 1,4-dioxane was added. The resulting suspension was filtered under Ar to remove the Mg salt, and the reaction mixture was dried under reduced pressure to obtain 9.45 g (13.4 mmol, 53.7% yield) of metallocene compound A13 in the form of an oil.

[0315] 1H NMR (500 MHz, CDCl3): -1.25 (6H, d), 1.19 (9H, s), 1.22-1.37 (4H, m), 1.50-1.66 (4H, m), 1.85-2.05 (15H, m), 2.28 (1H, m), 2.78 (1H, m), 2.92-3.01 (2H, m), 3.32 (2H, t), 5.69 (1H, brs), 7.05-7.53 (9H, m).

[0316]

[0317] Synthesis Example 2-1: Preparation of Metallocene Compound B1

[0318]

[0319] (1) Synthesis of ligands

[0320] Under Ar, 7.33 g (60 mmol) of n-butylcyclopentadiene, 6.97 g (2.0 eq., 120 mmol) of acetone, and 120 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 6.40 g (1.5 eq., 90 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 h. After cooling to 0 °C, 120 mL of 10 vol% aq. acetic acid was added and stirred for 30 min. The organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 9.17 g (56.5 mmol, 94.1% yield) of 2-n-butyl-5-isopropylidene-cyclopenta-1,3-diene.

[0321] Under Ar, 12.9 g (40 mmol) of 2-(6-tert-butoxyhexyl)fluorene and 160 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 19.2 mL (1.2 eq., 48 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 °C, 6.49 g (1.0 eq., 40 mmol) of 2-n-butyl-5-isopropylidene-cyclopenta-1,3-diene synthesized above was added together with 30 mL of tetrahydrofuran. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 17.8 g (36.7 mmol, 91.8% yield) of ligand.

[0322] 1 H NMR (500 MHz, CDCl3): 0.91-0.97 (9H, m), 1.12 (9H, s), 1.25-1.62 (12H, m), 2.15 (2H, m), 2.68 (2H, m), 2.92 (4H, m), 3.36 (2H, t), 3.73 (1H, brs), 6.13 (1H, m), 6.28 (1H, brs), 7.21-8.01 (7H, m).

[0323]

[0324] (2) Synthesis of metallocene compounds

[0325] ​Under Ar, 14.5 g (30 mmol) of the ligand synthesized above, 30 mL of methyl t-butyl ether, and 120 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 26.4 mL (2.2 eq., 66 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 211.3 g (1.0 eq., 30 mmol) of ZrCl4(THF) and 10 mL of methyl t-butyl ether were added. The temperature was slowly warmed to room temperature and stirred for 24 hours, and then the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 8.25 g (12.8 mmol, 42.7% yield) of a solid metallocene compound B1.

[0326] 1 H NMR (500 MHz, C6D6): 0.91-1.04 (9H, m), 1.13 (9H, s), 1.25-1.38 (6H, m), 1.44-1.65 (6H, m), 2.25 (2H, m), 2.85 (2H, m), 3.37 (2H, t), 5.42-6.21 (3H, m), 7.26-7.39 (3H, m), 7.42-7.55 (2H, m), 7.78 (1H, d), 7.93 (2H, d).

[0327]

[0328] Synthesis Example 2-2: Preparation of Metallocene Compound B2

[0329]

[0330] (1) Synthesis of ligands

[0331] Under Ar, 100 g (450 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 103 g (2.0 eq., 900 mmol) of 2,4-dimethyl-3-pentanone, and 1 L of ethanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 48.0 g (1.5 eq., 675 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 h. After cooling the reaction mixture to 0 °C, 1 L of 10 vol% aq. acetic acid was added and stirred for 30 min. The organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 44.9 g (141 mmol, 31.3% yield) of 2-(6-tert-butoxyhexyl)-5-(2,4-dimethylpentan-3-ylidene)-cyclopenta-1,3-diene.

[0332] Under Ar, 1.66 g (10 mmol) of fluorene and 40 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 4.8 mL (1.2 eq., 12 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 °C, 3.19 g (1.0 eq., 10 mmol) of 2-(6-tert-butoxyhexyl)-5-(2,4-dimethylpentan-3-ylidene)-cyclopenta-1,3-diene synthesized above was added together with 10 mL of tetrahydrofuran. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 3.94 g (8.12 mmol, 81.2% yield) of ligand.

[0333] 1 H NMR (500 MHz, CDCl3): 0.87 (12H, d), 1.12 (9H, s), 1.34 (2H, m), 1.41 (2H, m), 1.46 (2H, m), 1.55 (4H, m), 2.18 (2H, t), 2.91 (2H, d), 3.36 (2H, t), 3.73 (1H, s), 6.15 (1H, t), 6.25 (1H, brs), 7.25-7.44 (4H, m), 7.55 (2H, dd), 7.90 (2H, dd).

[0334]

[0335] (2) Synthesis of metallocene compounds

[0336] Under Ar, 3.94 g (8.12 mmol) of the ligand synthesized above, 5 mL of methyl t-butyl ether, and 20 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 7.1 mL (2.2 eq., 17.8 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 23.06 g (1.0 eq., 8.12 mmol) of ZrCl4(THF) and 5 mL of methyl t-butyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 2.61 g (4.04 mmol, 49.8% yield) of metallocene compound B2 in solid form.

[0337] 1 H NMR (500 MHz, C6D6): 1 ​H NMR (500 MHz, C6D6): 0.91 (12H, d), 1.13 (9H, s), 1.15-1.38 (6H, m), 1.40-1.55 (6H, m), 3.22 (2H, t), 5.32-6.12 (3H, m), 7.20-7.32 (2H, t), 7.47-7.55 (2H, dd), 7.72 (2H, d), 7.93 (2H, t).

[0338]

[0339] Synthesis Example 2-3: Preparation of Metallocene Compound B3

[0340]

[0341] (1) Synthesis of ligands

[0342] Under Ar, 4.45 g (20 mmol) of 2-tert-butylfluorene and 80 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 9.6 mL (1.2 eq., 24 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 °C, 6.38 g (1.0 eq., 20 mmol) of 2-(6-tert-butoxyhexyl)-5-(2,4-dimethylpentan-3-ylidene)-cyclopenta-1,3-diene synthesized in B2 was added together with 10 mL of tetrahydrofuran. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 7.30 g (13.5 mmol, 67.5% yield) of ligand.

[0343] 1H NMR (500 MHz, CDCl3): 0.85 (12H, d), 1.14 (9H, s), 1.25 (9H, s), 1.31-1.60 (10H, m), 2.22 (2H, m), 2.92 (2H, m), 3.33 (2H, t), 3.76 (1H, brs), 6.11 (1H, m), 6.35 (1H, brs), 7.25-7.42 (3H, m), 7.50-7.62 (2H, d), 7.81-7.92 (2H, d).

[0344]

[0345] (2) Synthesis of metallocene compounds

[0346] Under Ar, 7.30 g (13.5 mmol) of the ligand synthesized above, 10 mL of methyl t-butyl ether, and 40 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11.9 mL (2.2 eq., 29.8 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 25.09 g (1.0 eq., 13.5 mmol) of ZrCl4(THF) and 10 mL of methyl t-butyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 5.31 g (7.57 mmol, 56.1% yield) of a solid metallocene compound B3.

[0347] 1 ​H NMR (500 MHz, C6D6): 0.90 (12H, d), 1.12 (9H, s), 1.15-1.38 (15H, m), 1.44-1.55 (6H, m), 3.21 (2H, t), 5.30-6.15 (3H, m), 7.23-7.55 (5H, m), 7.73 (1H, d), 7.92 (1H, d).

[0348]

[0349] Synthesis Example 2-4: Preparation of Metallocene Compound B4

[0350]

[0351] (1) Synthesis of ligands

[0352] Under Ar, 5.01 g (18 mmol) of 2,7-di-tert-butylfluorene and 80 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 8.6 mL (1.2 eq., 21.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 °C, 5.73 g (1.0 eq., 18 mmol) of 2-(6-tert-butoxyhexyl)-5-(2,4-dimethylpentan-3-ylidene)-cyclopenta-1,3-diene synthesized in B2 was added together with 10 mL of tetrahydrofuran. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 6.92 g (11.6 mmol, 64.4% yield) of ligand.

[0353] 1H NMR (500 MHz, CDCl3): 0.85 (12H, d), 1.14 (9H, s), 1.27 (18H, s), 1.31-1.60 (10H, m), 2.22 (2H, m), 2.92 (2H, m), 3.33 (2H, t), 3.76 (1H, brs), 6.11 (1H, m), 6.35 (1H, brs), 7.40 (2H, m), 7.49-7.62 (2H, m), 7.78-7.91 (2H, m).

[0354]

[0355] (2) Synthesis of metallocene compounds

[0356] Under Ar, 6.92 g (11.6 mmol) of the ligand synthesized above, 10 mL of methyl t-butyl ether, and 40 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 10.2 mL (2.2 eq., 25.5 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 24.38 g (1.0 eq., 11.6 mmol) of ZrCl4(THF) and 10 mL of methyl t-butyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 4.12 g (5.44 mmol, 46.9% yield) of metallocene compound B4 in solid form.

[0357] 1 ​H NMR (500 MHz, C6D6): 0.90 (12H, d), 1.12 (9H, s), 1.15-1.38 (24H, m), 1.44-1.55 (6H, m), 3.21 (2H, t), 5.30-6.15 (3H, m), 7.44 (2H, dd), 7.65 (2H, d), 7.91 (2H, d).

[0358]

[0359] Synthesis Example 2-5: Preparation of Metallocene Compound B5

[0360]

[0361] (1) Synthesis of ligands

[0362] Under Ar, 10.2 g (45.8 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 7.71 g (2.0 eq., 91.6 mmol) of cyclopentanone, and 100 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 4.89 g (1.5 eq., 68.7 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 h. After cooling the reaction mixture to 0 °C, 100 mL of 10 vol% aq. acetic acid was added and stirred for 30 min. The organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 11.3 g (39.2 mmol, 85.6% yield) of 2-(6-tert-butoxyhexyl)-5-(cyclopentylidene)-cyclopenta-1,3-diene.

[0363] Under Ar, 7.80 g (28 mmol) of 2,7-di-tert-butylfluorene and 100 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 13.4 mL (1.2 eq., 33.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 °C, 8.08 g (1.0 eq., 28 mmol) of 2-(6-tert-butoxyhexyl)-5-(cyclopentylidene)-cyclopenta-1,3-diene synthesized above was added together with 15 mL of tetrahydrofuran. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 11.8 g (20.8 mmol, 74.3% yield) of ligand.

[0364] 1 H NMR (500 MHz, CDCl3): 1.11 (9H, s), 1.25 (18H, s), 1.31-1.60 (14H, m), 1.64-1.88 (4H, m), 2.26 (2H, m), 2.94 (2H, m), 3.36 (2H, t), 3.74 (1H, brs), 6.12 (1H, m), 6.32 (1H, brs), 7.41 (2H, m), 7.47-7.62 (2H, m), 7.75-7.89 (2H, m).

[0365]

[0366] (2) Synthesis of metallocene compounds

[0367] ​Under Ar, 11.8 g (20.8 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 18.3 mL (2.2 eq., 45.8 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 27.85 g (1.0 eq., 20.8 mmol) of ZrCl4(THF) and 15 mL of methyl t-butyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 10.1 g (13.9 mmol, 66.8% yield) of a solid metallocene compound B5.

[0368] 1 H NMR (500 MHz, C6D6): 1.12 (9H, s), 1.15-1.36 (26H, m), 1.44-1.55 (4H, m), 1.62-1.81 (4H, m), 3.31 (2H, t), 5.30-6.25 (3H, m), 7.42-7.51 (2H, dd), 7.68 (2H, d), 7.87 (2H, d).

[0369]

[0370] Synthesis Example 2-6: Preparation of Metallocene Compound B6

[0371]

[0372] (1) Synthesis of ligands

[0373] Under Ar, 5.57 g (25 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 4.91 g (2.0 eq., 50 mmol) of cyclohexanone, and 50 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 2.67 g (1.5 eq., 37.5 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 h. After cooling the reaction mixture to 0 °C, 50 mL of 10 vol% aq. acetic acid was added and stirred for 30 min. The organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 5.54 g (18.3 mmol, 73.2% yield) of 2-(6-tert-butoxyhexyl)-5-(cyclohexylidene)-cyclopenta-1,3-diene.

[0374] Under Ar, 2.49 g (15 mmol) of fluorene and 50 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 7.2 mL (1.2 eq., 18 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 °C, 4.54 g (1.0 eq., 15 mmol) of 2-(6-tert-butoxyhexyl)-5-(cyclohexylidene)-cyclopenta-1,3-diene synthesized above was added together with 10 mL of tetrahydrofuran. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 5.06 g (10.8 mmol, 72% yield) of ligand.

[0375] 1H NMR (500 MHz, CDCl3): 1.22 (9H, s), 1.29-1.71 (16H, m), 1.81-1.91 (2H, t), 2.24-2.47 (2H, m), 2.63-2.93 (2H, m), 3.37 (2H, t), 3.94 (1H, brs), 5.66-6.17 (2H, m), 7.14-7.36 (6H, m), 7.65-7.77 (2H, m).

[0376]

[0377] (2) Synthesis of metallocene compounds

[0378] Under Ar, 5.06 g (10.8 mmol) of the ligand synthesized above, 10 mL of methyl t-butyl ether, and 40 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 9.5 mL (2.2 eq., 23.8 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 24.07 g (1.0 eq., 10.8 mmol) of ZrCl4(THF) and 10 mL of methyl t-butyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 4.15 g (6.60 mmol, 61.1% yield) of a solid metallocene compound B6.

[0379] 1 ​H NMR (500 MHz, C6D6): 1.18 (9H, s), 1.20-1.64 (18H, m), 1.77-1.96 (2H, m), 3.30 (2H, t), 5.40-6.14 (3H, m), 7.25-7.61 (4H, m), 7.72 (2H, dd), 7.89 (2H, t).

[0380]

[0381] Synthesis Example 2-7: Preparation of Metallocene Compound B7

[0382]

[0383] (1) Synthesis of ligands

[0384] Under Ar, 22.3 g (100 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 36.4 g (2.0 eq., 200 mmol) of benzophenone, and 200 mL of ethanol were added to a dried 500 mL Schlenk flask. After cooling to 0 °C, 10.7 g (1.5 eq., 150 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 h. After cooling the reaction mixture to 0 °C, 200 mL of 10 vol% aq. acetic acid was added and stirred for 30 min. The organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 28.4 g (73.5 mmol, 73.5% yield) of 2-(6-tert-butoxyhexyl)-5-(diphenylmethylidene)-cyclopenta-1,3-diene.

[0385] Under Ar, 5.45 g (16.9 mmol) of 2-(6-tert-butoxyhexyl)fluorene and 50 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 8.1 mL (1.2 eq., 20.3 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 °C, 6.53 g (1.0 eq., 16.9 mmol) of 2-(6-tert-butoxyhexyl)-5-(diphenylmethylidene)-cyclopenta-1,3-diene synthesized above was added together with 10 mL of tetrahydrofuran. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 9.71 g (13.7 mmol, 81.1% yield) of ligand.

[0386] 1 H NMR (500 MHz, CDCl3): 1.12 (18H, brs), 1.22-1.67 (16H, m), 2.12 (2H, t), 2.68 (2H, t), 2.93 (2H, m), 3.33 (4H, m), 4.73 (1H, brs), 6.11 (1H, m), 6.33 (1H, brs), 7.21-8.01 (17H, m).

[0387]

[0388] (2) Synthesis of metallocene compounds

[0389] ​Under Ar, 9.71 g (13.7 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 12 mL (2.2 eq., 30 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 25.17 g (1.0 eq., 13.7 mmol) of ZrCl4(THF) and 15 mL of methyl t-butyl ether were added. The temperature was slowly warmed to room temperature and stirred for 24 hours, and then the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 6.25 g (7.19 mmol, 52.5% yield) of a solid metallocene compound B7.

[0390] 1 H NMR (500 MHz, C6D6): 1.06-1.15 (18H, brs), 1.23-1.72 (16H, m), 2.21 (2H, t), 2.75 (2H, t), 3.33 (2H, t), 5.52-6.41 (3H, m), 7.16-7.69 (15H, m), 7.91 (2H, d).

[0391]

[0392] Synthesis Example 2-8: Preparation of Metallocene Compound B8

[0393]

[0394] (1) Synthesis of ligands

[0395] Under Ar, 5.45 g (18.6 mmol) of 2-tert-butylfluorene and 60 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 8.9 mL (1.2 eq., 22.3 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 °C, 7.19 g (1.0 eq., 18.6 mmol) of 2-(6-tert-butoxyhexyl)-5-(diphenylmethylidene)-cyclopenta-1,3-diene synthesized in B7 was added together with 10 mL of tetrahydrofuran. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 9.68 g (15.9 mmol, 85.5% yield) of ligand.

[0396] 1 H NMR (500 MHz, CDCl3): 1.10 (9H, s), 1.24 (9H, s), 1.27-1.66 (8H, m), 2.13 (2H, t), 2.91 (2H, m), 3.34 (2H, t), 4.53 (1H, brs), 6.21 (1H, m), 6.36 (1H, brs), 7.05-7.90 (17H, m).

[0397]

[0398] (2) Synthesis of metallocene compounds

[0399] ​Under Ar, 9.68 g (15.9 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 14 mL (2.2 eq., 35 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 26.00 g (1.0 eq., 15.9 mmol) of ZrCl4(THF) and 15 mL of methyl t-butyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 6.37 g (8.28 mmol, 52.1% yield) of a solid metallocene compound B8.

[0400] 1 H NMR (500 MHz, C6D6): 1.15 (9H, s), 1.21 (9H, s), 1.24-1.68 (16H, m), 2.24 (2H, t), 3.34 (2H, t), 5.62-6.44 (3H, m), 7.10-7.73 (13H, m), 7.75-7.94 (2H, m).

[0401]

[0402] Synthesis Example 2-9: Preparation of Metallocene Compound B9

[0403]

[0404] (1) Synthesis of ligands

[0405] Under Ar, 4.45 g (20 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 8.01 g (2.0 eq., 40 mmol) of 8-tert-butoxy-2-octanone, and 50 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 2.13 g (1.5 eq., 30 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 h. After cooling the reaction mixture to 0 °C, 50 mL of 10 vol% aq. acetic acid was added and stirred for 30 min. The organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 6.31 g (15.6 mmol, 78% yield) of 2-(6-tert-butoxyhexyl)-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene.

[0406] Under Ar, 3.47 g (15.6 mmol) of 2-tert-butylfluorene and 50 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 7.4 mL (1.2 eq., 18.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 °C, 6.31 g (1.0 eq., 15.6 mmol) of 2-(6-tert-butoxyhexyl)-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene synthesized above was added together with 10 mL of tetrahydrofuran. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 8.59 g (13.7 mmol, 87.8% yield) of ligand.

[0407] 1 H NMR (500 MHz, CDCl3): 0.97 (3H, brs), 1.11 (18H, brs), 1.17 (2H, m), 1.25 (9H, s), 1.27-1.65 (16H, m), 2.10 (2H, t), 2.90 (2H, m), 3.33 (2H, m), 3.83 (1H, brs), 6.13 (1H, m), 6.26 (1H, brs), 7.21-7.44 (3H, m), 7.51-7.65 (2H, m), 7.78 (1H, d), 7.91 (1H, d).

[0408]

[0409] (2) Synthesis of metallocene compounds

[0410] ​Under Ar, 8.59 g (13.7 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 12 mL (2.2 eq., 30 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 25.17 g (1.0 eq., 13.7 mmol) of ZrCl4(THF) and 15 mL of methyl t-butyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 6.35 g (8.07 mmol, 58.9% yield) of a solid metallocene compound B9.

[0411] 1 H NMR (500 MHz, C6D6): 1.04 (3H, brs), 1.12 (20H, brs), 1.27 (9H, s), 1.34-1.70 (16H, m), 2.27 (2H, t), 3.34 (4H, m), 5.42-6.36 (3H, m), 7.12-7.39 (3H, m), 7.48-7.61 (2H, m), 7.73-7.94 (2H, m).

[0412]

[0413] Synthesis Example 2-10: Preparation of Metallocene Compound B10

[0414]

[0415] (1) Synthesis of ligands

[0416] Under Ar, 2.72 g (20 mmol) of 1-methyl-3-n-butylcyclopenta-1,3-diene, 8.01 g (2.0 eq., 40 mmol) of 8-tert-butoxy-2-octanone, and 50 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 2.13 g (1.5 eq., 30 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 h. After cooling the reaction mixture to 0 °C, 50 mL of 10 vol% aq. acetic acid was added and stirred for 30 min. The organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 4.56 g (14.3 mmol, 78% yield) of 1-methyl-3-n-butyl-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene.

[0417] Under Ar, 3.98 g (14.3 mmol) of 2,7-di-tert-butylfluorene and 50 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 6.8 mL (1.2 eq., 17 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 °C, 4.56 g (1.0 eq., 14.3 mmol) of 1-methyl-3-n-butyl-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene synthesized above was added together with 10 mL of tetrahydrofuran. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 6.92 g (11.6 mmol, 81.2% yield) of ligand.

[0418] 1 H NMR (500 MHz, CDCl3): 0.95 (6H, m), 1.10 (9H, s), 1.16 (2H, m), 1.28 (18H, brs), 1.30-1.65 (12H, m), 1.81 (3H, m), 2.16 (2H, t), 2.91 (2H, m), 3.34 (2H, t), 3.78 (1H, brs), 6.30 (1H, brs), 7.41 (2H, dd), 7.61 (2H, d), 7.87 (2H, d).

[0419]

[0420] (2) Synthesis of metallocene compounds

[0421] ​Under Ar, 6.92 g (11.6 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 10.2 mL (2.2 eq., 25.5 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 24.38 g (1.0 eq., 11.6 mmol) of ZrCl4(THF) and 15 mL of methyl t-butyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 5.25 g (6.93 mmol, 59.7% yield) of a solid metallocene compound B10.

[0422] 1 H NMR (500 MHz, C6D6): 0.88 (3H, s), 1.07 (3H, m), 1.16 (9H, s), 1.20 (2H, m), 1.31 (18H, brs), 1.34-1.69 (12H, m), 1.85 (3H, s), 2.20 (2H, t), 3.30 (2H, t), 6.02-6.36 (2H, m), 7.36 (2H, dd), 7.51 (2H, d), 7.79 (2H, d).

[0423]

[0424] Synthesis Example 2-11: Preparation of Metallocene Compound B11

[0425]

[0426] (1) Synthesis of ligands

[0427] Under Ar, 3.12 g (20 mmol) of 1-methyl-3-phenylcyclopenta-1,3-diene, 8.01 g (2.0 eq., 40 mmol) of 8-tert-butoxy-2-octanone, and 50 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 2.13 g (1.5 eq., 30 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 h. After cooling the reaction mixture to 0 °C, 50 mL of 10 vol% aq. acetic acid was added and stirred for 30 min. The organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 4.57 g (13.5 mmol, 67.5% yield) of 1-methyl-3-phenyl-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene.

[0428] Under Ar, 3.76 g (13.5 mmol) of 2,7-di-tert-butylfluorene and 50 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 6.4 mL (1.2 eq., 16 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 °C, 4.57 g (1.0 eq., 13.5 mmol) of 1-methyl-3-phenyl-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene synthesized above was added together with 10 mL of tetrahydrofuran. After slowly warming to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 6.60 g (10.7 mmol, 79.3% yield) of ligand.

[0429] 1 H NMR (500 MHz, CDCl3): 0.93 (3H, m), 1.15 (9H, s), 1.19 (2H, m), 1.23 (18H, s), 1.26-1.61 (8H, m), 1.91 (3H, m), 2.95 (2H, m), 3.37 (2H, t), 3.75 (1H, brs), 6.79 (2H, m), 7.11-7.25 (3H, m), 7.44 (2H, dd), 7.61 (2H, d), 7.83 (2H, d).

[0430]

[0431] (2) Synthesis of metallocene compounds

[0432] ​Under Ar, 6.60 g (10.7 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 9.4 mL (2.2 eq., 23.5 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 24.04 g (1.0 eq., 10.7 mmol) of ZrCl4(THF) and 15 mL of methyl t-butyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 4.47 g (5.75 mmol, 53.7% yield) of a solid metallocene compound B11.

[0433] 1 H NMR (500 MHz, C6D6): 1.05 (3H, m), 1.18 (9H, s), 1.22 (2H, m), 1.30 (18H, brs), 1.32-1.59 (8H, m), 1.91 (3H, s), 3.34 (2H, t), 6.12-6.76 (2H, m), 7.16 (2H, m), 7.30-7.45 (5H, m), 7.66 (2H, d), 7.99 (2H, d).

[0434]

[0435] Synthesis Example 2-12: Preparation of Metallocene Compound B12

[0436]

[0437] (1) Synthesis of ligands

[0438] Under Ar, 5.57 g (25 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 4.31 g (2.0 eq., 50 mmol) of 3-pentanone, and 60 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 2.67 g (1.5 eq., 37.5 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 h. After cooling the reaction mixture to 0 °C, 60 mL of 10 vol% aq. acetic acid was added and stirred for 30 min. The organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 3.49 g (12.0 mmol, 48% yield) of 2-(6-tert-butoxyhexyl)-5-(pentan-3-ylidene)-cyclopenta-1,3-diene.

[0439] Under Ar, 4.64 g (12 mmol) of 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorene and 50 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 5.7 mL (1.2 eq., 14.3 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 ℃, 3.49 g (1.0 eq., 12 mmol) of 2-(6-tert-butoxyhexyl)-5-(pentan-3-ylidene)-cyclopenta-1,3-diene synthesized above was added together with 10 mL of tetrahydrofuran. The temperature was slowly raised to room temperature and stirred for 24 hours. The organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 4.64 g (6.85 mmol, 57.1% yield) of the ligand.

[0440] 1 H NMR (500 MHz, CDCl3): 0.86 (30H, m), 1.12 (9H, s), 1.19 (4H, m), 1.26-1.61 (16H, m), 2.21 (2H, t), 2.91 (2H, m), 3.32 (2H, t), 3.71 (1H, brs), 6.01-6.48 (2H, m), 7.49 (2H, s), 7.84 (2H, s).

[0441]

[0442] (2) Synthesis of metallocene compounds

[0443] ​Under Ar, 4.64 g (6.85 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 6 mL (2.2 eq., 15 mmol) of 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 22.58 g (1.0 eq., 6.85 mmol) of ZrCl4(THF) and 10 mL of methyl t-butyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 2.70 g (3.22 mmol, 47% yield) of a solid metallocene compound B12.

[0444] 1 H NMR (500 MHz, C6D6): 0.75 (6H, t), 0.87 (24H, s), 1.15 (9H, s), 1.25 (4H, m), 1.30-1.57 (16H, m), 2.34 (2H, t), 3.37 (2H, t), 6.02-6.57 (3H, m), 7.39 (2H, s), 7.90 (2H, s).

[0445]

[0446] Synthesis Example 2-13: Preparation of Metallocene Compound B13

[0447]

[0448] (1) Synthesis of ligands

[0449] Under Ar, 6.57 g (17 mmol) of 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorene and 80 mL of tetrahydrofuran were added to another dried 250 mL Schlenk flask. After cooling to -78 °C, 8.1 mL (1.2 eq., 20.3 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After cooling to -78 ℃, 5.42 g (1.0 eq., 17 mmol) of 2-(6-tert-butoxyhexyl)-5-(2,4-dimethylpentan-3-ylidene)-cyclopenta-1,3-diene synthesized in B2 was added together with 10 mL of tetrahydrofuran. The temperature was slowly raised to room temperature and stirred for 24 hours. The organic layer was separated using water and diethyl ether and dried over MgSO4 to obtain 5.24 g (7.43 mmol, 43.7% yield) of the ligand.

[0450] 1 H NMR (500 MHz, CDCl3): 0.82 (12H, m), 0.92 (24H, s), 1.10 (9H, s), 1.26-1.65 (18H, m), 2.15 (2H, t), 2.91 (2H, m), 3.34 (2H, t), 3.78 (1H, brs), 6.02-6.50 (2H, m), 7.43 (2H, s), 7.82 (2H, s).

[0451]

[0452] (2) Synthesis of metallocene compounds

[0453] ​Under Ar, 5.24 g (7.43 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 6.5 mL (2.2 eq., 16.3 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 8 hours. After cooling to -78 °C, 22.80 g (1.0 eq., 7.43 mmol) of ZrCl4(THF) and 10 mL of methyl t-butyl ether were added. After slowly warming to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, and the filtrate was dried under reduced pressure at 50°C and n-hexane was added. The resulting suspension was filtered under Ar to obtain 2.93 g (3.39 mmol, 45.6% yield) of a solid metallocene compound B13.

[0454] 1 H NMR (500 MHz, C6D6): 0.71 (12H, m), 0.84 (24H, s), 1.13 (9H, s), 1.27-1.57 (20H, m), 2.24 (2H, t), 3.32 (2H, t), 5.82-6.47 (3H, m), 7.49 (2H, s), 7.77 (2H, s).

[0455]

[0456] <Manufacture of supported catalysts>

[0457] Manufacturing Example 1: Manufacturing of Catalyst 1

[0458] Silica (SP 952, manufactured by Grace Davision) was dehydrated and dried under vacuum at 200°C for 12 hours.

[0459] 800 g of dried silica was placed in a 20 L SUS reactor, and 6 kg of methylaluminoxane (MAO) solution (10 wt% in toluene) in toluene solution was added, and the mixture was slowly reacted with stirring at 70 ° C. for 1 hour. After completion of the reaction, the mixture was washed several times with a sufficient amount of toluene until the unreacted aluminum compound was completely removed. A solution prepared by dissolving 25.4 g of metallocene compound A1 and 2.8 g of metallocene compound B2 in toluene was sequentially added to the reactor, and the mixture was reacted with stirring at 40 ° C. for 4 hours. After washing with a sufficient amount of toluene, the mixture was vacuum-dried to obtain a hybrid supported metallocene catalyst 1 as a solid powder.

[0460]

[0461] Manufacturing Examples 2 to 25: Manufacturing of Catalysts 2 to 25

[0462] Hybrid supported metallocene catalysts 2 to 25 were prepared in the same manner as in Preparation Example 1, except that the types and contents of metallocene compounds were used as described in Table 1 below instead of 25.4 g of metallocene compound A1 and 2.8 g of metallocene compound B2.

[0463]

[0464] Manufacturing Examples 26 to 29: Manufacturing of Catalysts 26 to 29

[0465] Hybrid supported metallocene catalysts 26 to 29 were prepared in the same manner as in Preparation Example 1, except that the types and contents of metallocene compounds were used as described in Table 1 below instead of 25.4 g of metallocene compound A1 and 2.8 g of metallocene compound B2. The structures of metallocene compounds A14, A15, B14, and B15 used in Preparation Examples 26 to 29 are as follows.

[0466]

[0467]

[0468] Manufacturing example Catalyst Metallocene compound 1 Metallocene compound 2 Ratio Metallocene compound 1 (g) Metallocene compound 2 (g) Manufacturing example 1 Catalyst 1 A1B 2 10 25.4 2.8 Manufacturing example 2 Catalyst 2 A2B 2 7 24.5 3.9 Manufacturing example 3 Catalyst 3 A3B 2 8 26.13.4 Manufacturing example 4 Catalyst 4 A4B 2 20 30.11.5 Manufacturing example 5 Catalyst 5 A5B 2 6 26.4 4.4 Manufacturing example 6 Catalyst 6 A6B 2 15 29.01.9 Manufacturing example 7 Catalyst 7A7B2425.36.2 Manufacturing example 8 Catalyst 8A8B2324.47.7 Manufacturing example 9 Catalyst 9A9B2728.73.9 Manufacturing example 10 Catalyst 10A10B21733.81.7 Manufacturing example 11 Catalyst 11A11B21231.32.4 Manufacturing example 12 Catalyst 12A12B2322.17.7 Manufacturing example 13 Catalyst 13A13B2528.25.2 Manufacturing example 14 Catalyst 14A3B11126.92.8 Manufacturing example 15 Catalyst 15A3B3926.43.4 Manufacturing example 16 Catalyst 16A3B41227.13.0 Manufacturing example 17 Catalyst 17A3B5826.13.8 Manufacturing example 18 Catalyst 18A3B61627.61.8 Manufacturing example 19 Catalyst 19A3B71427 .41.9 Manufacturing Example 20 Catalyst 20A3B81227.13.0 Manufacturing Example 21 Catalyst 21A3B9625.14.0 Manufacturing Example 22 Catalyst 22A3B10725.74.3 Manufacturing Example 23 Catalyst 23A3B11524.45.6 Manufacturing Example 24 Catalyst 24A3B121327.21.8 Manufacturing Example 25 Catalyst 25A3B13625.12.9 Manufacturing Example 26 Catalyst 26A14B14314.66.1 Manufacturing Example 27 Catalyst 27A15B15213.46.8 Manufacturing Example 28 Catalyst 28B14B21022.82.9 Manufacturing Example 29 Catalyst 29A3A15825.02.1

[0469] (The ratio in Table 1 above means ‘number of moles of metallocene compound 1 / number of moles of metallocene compound 2.’)

[0470] <Manufacture of polyethylene copolymer>

[0471] Examples 1-1 to 1-25 and Comparative Examples 1-1 to 1-4

[0472] The polymerization reactor was a continuous isobutane slurry loop process reactor with a reactor volume of 140 L and a reaction flow rate of approximately 7 m / s. The gases (ethylene, hydrogen) and comonomers required for polymerization were continuously fed at a constant rate, and the individual flow rates were adjusted to suit the target product. The concentrations of all gases and the comonomer 1-hexene were confirmed by online gas chromatography. The supported catalyst was fed as isobutane slurry, the reactor pressure was maintained at 40 bar, and the polymerization temperature was 80°C.

[0473] The ethylene input amount, the input amount of the solvent i-butane, the 1-hexene / ethylene input ratio, and the hydrogen / ethylene input ratio for the production of the polyethylene copolymers of Examples 1-1 to 1-25 and Comparative Examples 1-1 to 1-4 are shown in Table 2 below.

[0474]

[0475] Catalytic process conditions Ethylene (kg / h) i-butane (kg / h) 1-hexene / ethylene (wt%) Hydrogen / ethylene (ppmw) Example 1-1 Catalyst 1 25.2 24 7.230 Example 1-2 Catalyst 2 25.1 25 6.648 Example 1-3 Catalyst 3 25 30 6.522 Example 1-4 Catalyst 4 25 28 6.752 Example 1-5 Catalyst 5 25.1 26 8.345 Example 1-6 Catalyst 6 25 25 8.738 Example 1-7 Catalyst 7 25.2 28 829 Example 1-8 Catalyst 8 25.1 30 7.132 Example 1-9 Catalyst 9 25 22 6.845 Example 1-10 Catalyst 10 25 29 7.780 Example 1-11 Catalyst 1125.1257.852 Example 1-12 Catalyst 1225.1256.848 Example 1-13 Catalyst 1325.1286.955 Example 1-14 Catalyst 1425307.733 Example 1-15 Catalyst 1525277.849 Example 1-16 Catalyst 1625306.577 Example 1-17 Catalyst 1725.1286.932 Example 1-18 Catalyst 1825.2296.621 Example 1-19 Catalyst 1925236.858 Example 1-20 Catalyst 2025277.261 Example 1-21 Catalyst 2125.2277.566 Example 1-22 Catalyst 2225.1267.674 Example 1-23 Catalyst 2325287.461 Example 1-24 Catalyst 2425306.825 Example 1-25 Catalyst 2525306.936 Comparative Example 1-1 Catalyst 2625.1301023 Comparative Example 1-2 Catalyst 2725.0195.554 Comparative Example 1-3 Catalyst 2825.1285.431 Comparative Example 1-4 Catalyst 2925.1246.038

[0476] <Experimental Example 1: Evaluation of Physical Properties of Polyethylene Copolymer>

[0477] The physical properties of the polyethylene copolymers manufactured in Examples 1-1 to 1-25 and Comparative Examples 1-1 to 1-4 were evaluated and are shown in Table 3 below. The method for evaluating the physical properties of the polyethylene copolymer is as follows.

[0478]

[0479] (1) MI 2.16 and MFRR(MFR 21.6 / MFR 2.16 )

[0480] Melt Index (MI 2.16 ) was measured according to ASTM D1238 (Condition E, 190 ℃, 2.16 kg load). Melt Flow Rate Ratio (MFRR, MFR) 21.6 / MFR 2.16 ) is MFR 21.6 MFR 2.16 It was calculated by dividing by MFR 21.6 is measured at a temperature of 190 ℃ and a load of 21.6 kg according to ISO 1133, and MFR 2.16 was measured at a temperature of 190 ℃ and a load of 2.16 kg according to ISO 1133.

[0481]

[0482] (2) Density (g / cm) 3 )

[0483] Density (g / cm) according to ASTM D 792, American Society for Testing and Materials 3 ) was measured.

[0484]

[0485] (3) Molecular structure analysis: Cross Fractionation Chromatography (CFC) analysis

[0486] - Analysis equipment: Polymer Char CFC (Detector: Integrated Detector IR5 MCT)

[0487] - Sample preparation and loading: Place polyethylene copolymer (32 mg) in a 10 mL vial, place in the autosampler position, add 8 mL of trichlorobenzene (TCB), dissolve at 160°C for 90 minutes, extract after nitrogen purge, and load onto TREF column.

[0488] - Crystallization: Cool the sample loaded on the TREF column from 100 ℃ to 35 ℃ at a rate of 0.5 ℃ / min.

[0489] - Temperature rising elution temperature (TREF) analysis: The crystallized sample was heated from 35 ℃ to 120 ℃ in 1 ℃ increments, and the amount released at that temperature was analyzed for 25 minutes (extraction / analysis at 35 ℃ for 25 minutes → extraction / analysis at 36 ℃ for 25 minutes → .... → extraction / analysis at 120 ℃ for 25 minutes)

[0490] - GPC-IR analysis: Molecules eluted at each temperature in TREF analysis are transferred to the GPC column, and the molecular weight and number of short-chain branches (scb) of the eluted molecules are analyzed.

[0491]

[0492] 1) Method for measuring high-crystallinity, medium-crystallinity, low-crystallinity content and soluble fraction

[0493] From the TREF analysis graph, the content ratio of the soluble fraction (SF) eluted in the region of the elution temperature 35 ℃ or lower (T≤35 ℃), the content ratio of the polymer fraction (low crystallinity; M1) eluted in the region of the elution temperature exceeding 35 ℃ and 70 ℃ or lower (35 ℃ <T≤70℃), 그리고 용리 온도 90 ℃ 초과의 영역에서 용출되는 중합체 분획(고결정; M3)의 함량 비율(T> 90℃) were calculated respectively (wt%).

[0494] <fraction temperature>

[0495] 35℃ / 40℃ / 43℃ / 46℃ / 49℃ / 52℃ / 55℃ / 58℃ / 61℃ / 64℃ / 67℃ / 70℃ / 73℃ / 76℃ / 79℃ / 82℃ / 85℃ / 88℃ / 91℃ / 94℃ / 97℃ / 100℃ / 105℃ / 120℃

[0496]

[0497] 2) The main chain average molecular weight (Mw) of the high-crystalline fraction T>90℃ ) calculate

[0498] The average molecular weight of the main chain (main chain) portion of the fraction, excluding the short-chain branch (scb) portion of molecules eluted above 90°C as confirmed through CFC analysis, was calculated using the following mathematical formula 1.

[0499] [Mathematical Formula 1]

[0500] Main chain Mw of high crystallinity fraction =

[0501] In the above mathematical formula 1,

[0502] M T,i and C T,i : Molecular weight and concentration of each molecule eluted at different temperatures

[0503] n scb T,i : Number of scb in each molecule

[0504] M scb : scb molecular weight

[0505]

[0506] 3) Main chain average molecular weight (Mw) of low crystallinity fraction ,35<T≤70℃ ) calculate

[0507] : 35 confirmed through CFC analysis <T≤70 ℃에서 용출되는 분자들의 short-chain branch(scb) 부분을 제외한 분획의 주쇄(주사슬) 부분의 평균 분자량을 하기 수학식 2로 계산하였다.

[0508] [Equation 2]

[0509] Main chain Mw of low crystallinity fraction =

[0510] In the above mathematical expression 2,

[0511] M T,i and C T,i : Molecular weight and concentration of each molecule eluted at different temperatures

[0512] n scb T,i : Number of scb in each molecule

[0513] M scb : scb molecular weight

[0514]

[0515] Catalyst basic molecular structure (CFC) MI2.16 (g / 10min) MFRR density (g / cm) 3)SolubleFraction(T≤35℃)LowCrystallinity(35℃) <T≤70℃)함량고결정(90℃<T)함량저결정Mw고결정Mw실시예 1-1촉매11.3426.10.92711.32551.140k129k실시예 1-2촉매21.3729.10.9317.721.355.237k125k실시예 1-3촉매31.3325.80.9320.712.148.345k112k실시예 1-4촉매41.4129.10.9312.515.556.136k118k실시예 1-5촉매51.5827.60.9288.220.149.138k108k실시예 1-6촉매61.5426.70.9307.417.252.242k107k실시예 1-7촉매71.4427.20.9298.119.951.644k120k실시예 1-8촉매81.5128.50.9295.220.252.342k116k실시예 1-9촉매91.3429.20.9308.817.755.539k103k실시예 1-10촉매101.6929.50.92710.223.851.836k105k실시예 1-11촉매111.5328.50.92911.32551.140k129k실시예 1-12촉매121.5229.80.9327.721.355.237k125k실시예 1-13촉매131.4529.10.9332.515.556.136k118k실시예 1-14촉매141.8827.20.9260.712.148.345k112k실시예 1-15촉매151.6827.70.9278.220.149.138k108k실시예 1-16촉매161.7326.20.9307.417.252.242k107k실시예 1-17촉매171.3827.80.9298.119.951.644k120k실시예 1-18촉매181.5727.70.9305.220.252.342k116k실시예 1-19촉매191.7626.80.9318.817.755.539k103k실시예 1-20촉매201.8626.80.92910.223.851.836k105k실시예 1-21촉매211.7526.10.9285.215.250.841k110k실시예 1-22촉매221.7626.10.9280.311.550.242k108kExample 1-23Catalyst231.4527.30.9293.217.251.845k122kExample 1-24Catalyst241.5926.80.9302.224.152.638k108kExample 1-25Catalyst251.6625.20.9301.722.353.144k101kComparative Example 1-1Catalyst260.9318.80.9167.716.911.3160k101kComparative Example 1-2Catalyst270.3164.40.9270.52.63.114k103kComparative Example 1-3 Catalyst 281.4322.10.92111.943.95.3155k90k Comparative example 1-4 Catalyst 291.2144.80.9350.62.132.330k101k.

[0516] (The 'k' in the low-crystal Mw and high-crystal Mw in Table 3 above means 1000 times.)

[0517] It was confirmed that the polyethylene copolymers of Examples 1-1 to 1-25 manufactured using the first metallocene compound and the second metallocene compound have a structure having a high crystallinity high molecular weight and a low crystallinity low molecular weight, in which the main chain molecular weight of the high crystallinity fraction is high and the main chain molecular weight of the low crystallinity fraction is low.

[0518] Comparative Examples 1-1 and 1-2, which used catalysts containing metallocene compounds of different structures as precursors, were confirmed to have a predominantly medium-crystalline content and a very low high-crystalline content. In addition, Comparative Examples 1-1 and 1-3 have a structure in which the main chain molecular weight of the low-crystalline fraction is higher than that of the high-crystalline fraction. In particular, Comparative Example 1-3 was confirmed to have a predominantly low-crystalline content.

[0519]

[0520] <Manufacturing of Stretch Film>

[0521] Examples 2-1 to 2-10 and Comparative Examples 2-1 to 2-4

[0522] According to the stretching conditions in Table 4 below, stretched films of Examples 2-1 to 2-10 and Comparative Examples 2-1 to 2-4 were manufactured under the following conditions. At this time, the stretched films of Comparative Examples 2-1 to 2-4 could not be preheated and stretched under the conditions of 120 to 127°C.

[0523] - Manufacture of 0.75 mm thick polyethylene copolymer sheet using Bruckner Lab extruder line (L / D ratio: 42, Screw diameter: 25 mm, Melt / T-Die temperature: 220 ℃)

[0524] - Biaxial stretching of polyethylene copolymer sheet with width and length of 50 mm x 50 mm was performed using Ocean Science COAD.521 stretching equipment.

[0525] - After preheating for 90 seconds each, sequential stretching (MD→TD) is performed under the conditions in Table 4 below.

[0526]

[0527] Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 Example 2-6 Example 2-7 Example 2-8 Example 2-9 Example 2-10 Comparative Example 2-1 Comparative Example 2-2 Comparative Example 2-3 Comparative Example 2-4 Catalyst Catalyst 1 Catalyst 3 Catalyst 4 Catalyst 7 Catalyst 11 Catalyst 14 Catalyst 16 Catalyst 18 Catalyst 20 Catalyst 22 Catalyst 26 Catalyst 27 Catalyst 28 Catalyst 29 Use PE Example 1-1 Example 1-3 Example 1-4 Example 1-7 Example 1-11 Example 1-14 Example 1-16 Example 1-18 Example 1-20 Example 1-22 Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 Comparative Example 1-4 Oven Temperature (℃) 125 125 125 124 124 125 124 124 124 124 ---- Stretch ratio 5 x 55 x 55 x 55 x 55 x 55 x 55 x 55 x 5 ---- Stretch speed (% / s) 200 200 200 200 200 200 200 200 200 200 ----

[0528] <Experimental Example 2: Evaluation of Physical Properties of Biaxially Stretched Film>

[0529] The properties of the stretched films manufactured in Examples 2-1 to 2-10 and Comparative Examples 2-1 to 2-4 were evaluated and are shown in Tables 5 and 6 below. The method for evaluating the properties of the stretched films is as follows.

[0530]

[0531] (1) Haze: Measured according to ASTM 1003

[0532] (2) Tensile properties (tensile modulus (1% modulus), elongation): Measured in each MD / TD direction according to ASTM D 882

[0533] (3) Tear strength: Measured in each MD / TD direction according to ASTM 1922

[0534] (4) Shrinkage: Measure the change in length after shrinkage for 7 minutes at 100 ℃ or 120 ℃ according to ASTM D 1204. Specifically, shrinkage (%) is measured as "[1 - (length after shrinkage) / (length before shrinkage)] * 100".

[0535]

[0536] Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 Example 2-6 Example 2-7 Example 2-8 Example 2-9 Example 2-10 Catalyst Catalyst 1 Catalyst 3 Catalyst 4 Catalyst 7 Catalyst 11 Catalyst 14 Catalyst 16 Catalyst 18 Catalyst 20 Catalyst 22 PE used Example 1-1 Example 1-3 Example 1-4 Example 1-7 Example 1-11 Example 1-14 Example 1-16 Example 1-18 Example 1-20 Example 1-22 Thickness (μm) 21~28 19~20 18~23 19~24 20~27 18~25 20~28 17~25 19~24 21~23 Haze (%)9.08.55.68.05.28.27.65.98.16.21%Modulus(MPa)MD452389488452392401443452415378TD509515681502508520598559508424MD+TD961904116995490092110411011923802Tensile Elongation(%)MD2271249123312914310211598109TD9910693130110129172178110135MD+TD326230184363239272274293208244Tear Strength( g / μm)MD0.380.210.290.430.220.260.360.410.110.52TD0.320.250.290.3 50.270.280.470.440.750.78MD+TD0.70.460.580.780.490.540.830.850.8 61.3Shrinkage (%,@120˚C)MD4.995.78.710.19.17.16.49.28.8TD7.512.59.812.912.210.78.27.710.111.2MD+TD12.421.515.521.622.319.815.314.119.320

[0537] Comparative Example 2-1 Comparative Example 2-2 Comparative Example 2-3 Comparative Example 2-4 Catalyst Catalyst 26 Catalyst 27 Catalyst 28 Catalyst 29 PE used Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 Comparative Example 1-4 Thickness (μm)----Haze (%)----1%Modulus (MPa)MD----TD----MD+TD----Tensile Elongation (%)MD----TD----MD+TD----Tear Strength (g / μm)MD----TD----MD+TD----Shrinkage (%,@120˚C)MD----TD----MD+TD----

[0538] According to the above table, it can be confirmed that the biaxially oriented films of Examples 2-1 to 2-10, which were obtained by stretching the polyethylene copolymers of Examples 1-1 to 1-10, exhibit excellent stretching properties, and that the 1% modulus, which is a representative factor of stiffness, is superior to that of the comparative examples. In other words, it was confirmed that the 1% modulus tends to improve as the high-crystal content increases or the main chain molecular weight of the high-crystal fraction increases.

Claims

1. At least one first metallocene compound selected from compounds represented by the following chemical formula 1; At least one second metallocene compound selected from compounds represented by the following chemical formula 2; and A carrier comprising the first metallocene compound and the second metallocene compound; Hybrid supported metallocene catalysts: [Chemical Formula 1] In the above chemical formula 1, M1 is a group 4 transition metal, X 11 and X 12 are each independently substituted or unsubstituted C 1-20 Alkyl or halogen, R1 to R5 and R7 to R 12 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-60 Aryl, or -(CH2) n1 -OR 13 And, R6 is substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-60 Aryl, or -(CH2) n1 -OR 13 However, R1 to R 12 At least one of them is -(CH2) n1 -OR 13 And, R 13 Silver substituted or unsubstituted C 1-20 It is alkyl, n1 is an integer from 0 to 10, [Chemical Formula 2] In the above chemical formula 2, M2 is a group 4 transition metal, X 21 , X 22 are each independently substituted or unsubstituted C 1-20 Alkyl or halogen, T2 is C (carbon) or Si (silicon), Q 21 and Q 22 are each independently substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-60 Aryl, or -(CH2) n2 -OR 32 This or Q 21 and Q 22 C, which is substituted or unsubstituted by combining with each other 3-20 Forming a cycloalkyl ring, R 20 Inland R 31 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-60 Aryl, or -(CH2) n2 -OR 32 This or R 20 Inland R 31 C, which is substituted or unsubstituted, is formed by combining two adjacent C's. 3-20 Forming a cycloalkyl ring, R 20 Inland R 31 , Q 21 and Q 22 At least one of them is -(CH2) n2 -OR 32 And, R 32 is substituted or unsubstituted C 1-20 It is alkyl, n2 is an integer from 0 to 10.

2. In paragraph 1, M1 is Hf or Zr, X 11 and X 12 are each independently methyl or chloro, Hybrid supported metallocene catalyst.

3. In paragraph 1, R1 to R5 and R7 to R 12 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl, or -(CH2) n1 -OR 13 And, R6 is substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl, or -(CH2) n1 -OR 13 However, R1 to R 12 One or both of them are -(CH2) n1 -OR 13 person, Hybrid supported metallocene catalyst.

4. In paragraph 1, R1 to R5 are each independently hydrogen, methyl, n-butyl, phenyl, or tertbutoxyhexyl, R6 is methyl, ethyl, isopropyl, benzyl, trimethylsilyl methyl, or phenyl, Hybrid supported metallocene catalyst.

5. In paragraph 1, Either R7 or R8 is tert-butoxy hexyl, and the remainder and R9 to R 12 are hydrogen, respectively, R 13 Silver tertbutyl, Hybrid supported metallocene catalyst.

6. In paragraph 1, n1 is 6 people, Hybrid supported metallocene catalyst.

7. In paragraph 1, The first metallocene compound represented by the above chemical formula 1 is any one selected from the group consisting of: Hybrid supported metallocene catalysts: .

8. In paragraph 1, M2 is Zr, X 21 , X 22 are each independently methyl or chloro, Hybrid supported metallocene catalyst.

9. In paragraph 1, T2 is C (carbon), R 20 Inland R 25 , Q 21 and Q 22 One or both of them are -(CH2) n2 -OR 32 person, Hybrid supported metallocene catalyst.

10. In paragraph 1, Q 21 and Q 22 are each independently methyl, ethyl, isopropyl, phenyl, or -(CH2) n2 -OR 32 This or Q 21 and Q 22 are combined with each other to form a cyclopentene ring or a cyclohexene ring, Hybrid supported metallocene catalyst.

11. In paragraph 1, R 20 Inland R 23 One of them is tert-butoxyhexyl or n-butyl, and the other is hydrogen, or R 20 Inland R 23 Two of them are independently methyl, n-butyl, or phenyl, and the remainder is hydrogen. Hybrid supported metallocene catalyst.

12. In paragraph 1, R 24 Inland R 31 are each independently hydrogen, tert-butyl or tert-butoxyhexyl, or R 24 Inland R 31 Two adjacent ones combine to form a cyclohexane ring substituted with four methyls, Hybrid supported metallocene catalyst.

13. In paragraph 1, R 32 is tertbutyl, n2 is 6 people, Hybrid supported metallocene catalyst.

14. In paragraph 1, The second metallocene compound represented by the above chemical formula 2 is any one selected from the group consisting of: Hybrid supported metallocene catalysts: .

15. In paragraph 1, The first metallocene compound and the second metallocene compound are supported in a molar ratio of 1:1 to 25:

1. Hybrid supported metallocene catalyst.

16. A method for producing a polyethylene copolymer, comprising a step of copolymerizing ethylene and an olefin monomer in the presence of a hybrid supported metallocene catalyst of paragraph 1.

17. In paragraph 16, The above olefin monomer is at least one 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, and mixtures thereof. Method for producing polyethylene copolymer.

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