Polyethylene copolymer and biaxially stretched film comprising same

Abstract

The present invention relates to a polyethylene copolymer and a film comprising same, the polyethylene copolymer, through the improvement of a high-crystal molecular weight, being suitable for manufacturing a biaxially stretched film having improved heat resistance.

Description

Polyethylene copolymer and biaxially oriented film comprising the same

[0001] The present invention relates to polyethylene and a film comprising the same, which is suitable for producing a biaxially oriented film having improved heat resistance by improving the molecular weight of a high-crystallinity fraction.

[0002] Cross-citation with related applications

[0003] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0086289, filed July 1, 2024, and Korean Patent Application No. 10-2025-0049749, filed April 16, 2025, the entire contents of which are incorporated herein by reference.

[0004]

[0005] Thin film products manufactured from linear low-density polyethylene (LLDPE) and / or high-density polyethylene (HDPE) are widely used in packaging applications such as merchandise bags, grocery bags, food and specialty packaging, and industrial liners. In these applications, shrink film is primarily used to preserve the shape of the product while protecting it from touch during display.

[0006] In particular, among these shrink films, biaxially oriented polymer films are widely used for packaging purposes due to their excellent mechanical properties, productivity, and printability. Commercialized packaging films generally use biaxially oriented polypropylene (BOPP), biaxially oriented polyethylene terephthalate (BOPET), or biaxially oriented polyamide (BOPA) for the print layer, and LLDPE film for the sealing layer. These composite material forms are not recyclable, and the demand for single-material products is increasing due to the expansion of packaging material recycling regulations. Therefore, research and development is being conducted to manufacture single-material packaging films by replacing the print layer film with biaxially oriented polyethylene (BOPE) film.

[0007] However, commercial polyethylene (PE) resins lack sufficient stretching stability, and phenomena such as fracture and melting occur during stretching, making biaxial stretching difficult to apply. To achieve stretching properties and stretching stability, they must possess a low MI-high density / high MI-low density structure. A technology has been reported to produce the corresponding PE resin using a dual-reactor to derive resin crystallization and molecular weight separation, but this method incurs high production costs.

[0008] Accordingly, there is a need to select a polyethylene resin having a molecular structure advantageous for stretching that can be manufactured in a single reactor, and to develop a polyethylene copolymer for biaxial stretching that exhibits stretching stability during biaxial stretching and good film mechanical properties.

[0009]

[0010] The present invention relates to a polyethylene copolymer suitable for manufacturing a biaxially oriented film having improved heat resistance by improving a high crystal molecular weight, and a film comprising the same.

[0011]

[0012] In one embodiment of the present invention,

[0013] The main chain average molecular weight (Mw) of the highly crystalline fraction eluted at an elution temperature exceeding 90 ℃ during cross fractionation chromatography (CFC) analysis ,T>90℃ ) is 90,000 g / mol or more,

[0014] The content ratio of highly crystalline fractions eluted at an elution temperature exceeding 90 ℃ during cross fractionation chromatography (CFC) analysis (TREF) T>90℃ ) is more than 45.0 wt% of the total elution fraction,

[0015] Provides a polyethylene copolymer.

[0016]

[0017] In addition, in another embodiment of the present invention, a biaxially oriented film comprising the polyethylene copolymer of the above embodiment is provided.

[0018]

[0019] The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the present invention.

[0020]

[0021] Singular expressions include plural expressions unless the context clearly indicates otherwise.

[0022]

[0023] In this specification, the terms “comprise,” “include,” or “have” are intended to describe a feature, number, step, component, or combination thereof implemented, but do not exclude the possibility of one or more other features, numbers, steps, components, combinations, or additions thereof.

[0024]

[0025] In addition, the terms "about," "substantially," and the like used throughout this specification are used in a meaning that is at or close to the numerical value when manufacturing and material tolerances inherent to the meanings mentioned are presented, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosure in which exact or absolute values ​​are mentioned to aid understanding of the present invention.

[0026]

[0027] Additionally, in the present invention, (co)polymer means both a homopolymer and a copolymer.

[0028]

[0029] 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.

[0030]

[0031] 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.

[0032]

[0033] Hereinafter, the present invention will be described in detail.

[0034]

[0035] According to one aspect of the present invention, the main chain average molecular weight (Mw) of a high crystallinity fraction eluted at an elution temperature exceeding 90° C. during cross fractionation chromatography (CFC) analysis ,T>90℃) is 90,000 g / mol or more,

[0036] The content ratio of highly crystalline fractions eluted at an elution temperature exceeding 90 ℃ during cross fractionation chromatography (CFC) analysis (TREF) T>90℃ ) is provided, wherein the polyethylene copolymer is at least 45.0 wt% of the total elution fraction.

[0037]

[0038] For reference, in this specification, "part by weight" means a relative concept that expresses the weight of a substance as a ratio based on the weight of the remaining substance. For example, in a mixture containing 50 g of substance A, 20 g of substance B, and 30 g of substance C, the amounts of substance B and substance C are 40 parts by weight and 60 parts by weight, respectively, based on 100 parts by weight of substance A.

[0039]

[0040] Meanwhile, "% by weight (wt%)" refers to an absolute concept that expresses the weight of a certain substance as a percentage of the total weight. In the mixture in the example above, the contents of substance A, substance B, and substance C are 50 wt%, 20 wt%, and 30 wt%, respectively, out of 100% of the total weight of the mixture.

[0041]

[0042] 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 by using a hybrid supported metallocene catalyst comprising two types of metallocene compounds described below. 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 having the effect of 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.

[0043]

[0044] 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, 180,000 g / mol or less, 150,000 g / mol or less, 130,000 g / mol or less, or 129,000 g / mol or less.

[0045]

[0046] 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.

[0047]

[0048] 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.

[0049]

[0050] 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:

[0051]

[0052] 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.

[0053]

[0054] 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.

[0055]

[0056] Meanwhile, the polyethylene copolymer may be an ethylene / alpha-olefin copolymer, and preferably an ethylene / 1-hexene copolymer.

[0057]

[0058] Meanwhile, the polyethylene copolymer having the above physical properties may be a polyethylene copolymer prepared by polymerizing an olefin monomer in the presence of a hybrid supported metallocene catalyst, which comprises at least one non-bridged metallocene compound including an indenyl ligand and a cyclopentadienyl ligand; at least one bridged-metallocene compound including a fluorenyl ligand and a cyclopentadienyl ligand; and a carrier supporting the non-bridged metallocene compound and the bridged metallocene compound.

[0059]

[0060] Preferably, the polyethylene copolymer may be a polyethylene copolymer prepared by polymerizing an olefin monomer in the presence of a hybrid supported metallocene catalyst, comprising: 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 supporting the first and second metallocene compounds:

[0061] [Chemical Formula 1]

[0062]

[0063] In the above chemical formula 1,

[0064] M1 is a group 4 transition metal,

[0065] X 11 , X 12 are each independently substituted or unsubstituted C 1-20 Alkyl or halogen,

[0066] 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,

[0067] R6 is substituted or unsubstituted C 1-20Alkyl, substituted or unsubstituted C 6-60 Aryl, or -(CH2) n1 -OR 13 However,

[0068] R1 to R 12 At least one of them is -(CH2) n1 -OR 13 And,

[0069] R 13 Silver substituted or unsubstituted C 1-20 It is alkyl,

[0070] n1 is an integer from 0 to 10,

[0071] [Chemical Formula 2]

[0072]

[0073] In the above chemical formula 2,

[0074] M2 is a group 4 transition metal,

[0075] X 21 , X 22 are each independently substituted or unsubstituted C 1-20 Alkyl or halogen,

[0076] T2 is C (carbon) or Si (silicon),

[0077] 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,

[0078] 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 -OR32 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,

[0079] R 20 Inland R 31 , Q 21 and Q 22 At least one of them is -(CH2) n2 -OR 32 And,

[0080] R 32 is substituted or unsubstituted C 1-20 It is alkyl,

[0081] n2 is an integer from 0 to 10.

[0082]

[0083] In the present invention, the substituents of the chemical formula are described more specifically as follows.

[0084] The halogen can be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0085] C above 1-20 Alkyl may be straight-chain, branched-chain or cyclic alkyl. Specifically, the C 1-20 The 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, the alkyl having 1 to 20 carbon atoms 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.

[0086] C 3-20The 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 3-20 The cycloalkyl ring may be a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, or a cyclohexene ring.

[0087] 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.

[0088] 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.

[0089] C 2-20 Alkoxyalkyl is -Ry -OR z Alkyl (-R) with a structure containing y ) is one or more hydrogens of alkoxy (-OR z ) may be a substituent substituted with. Specifically, the alkoxyalkyl having C2 to C20 carbon atoms 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.

[0090] C 6-60 Aryl may refer to a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon. Specifically, the C6 to C60 aryl may be a phenyl group, a naphthyl group, an anthracenyl group, or the like.

[0091] C 7-20 Alkylaryl may mean a substituent in which one or more hydrogens of aryl are replaced by alkyl. Specifically, the above C 7-20 The alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl or cyclohexylphenyl.

[0092] C 7-20 Arylalkyl may mean a substituent in which one or more hydrogens of alkyl are replaced by aryl. Specifically, the above C 7-20 The arylalkyl group may be benzyl, phenylpropyl or phenylhexyl.

[0093] Also, group 4 transition metals can include titanium, zirconium, and hafnium.

[0094]

[0095] The above hybrid supported metallocene catalyst is a hybrid catalyst comprising a first metallocene compound, which is a non-bridged metallocene compound including a high molecular weight, high crystallinity indenyl ligand and a cyclopentadienyl ligand, and a second metallocene compound, which is a bridged-metallocene compound including a low molecular weight, low crystallinity fluorenyl ligand and a cyclopentadienyl ligand.

[0096] 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.

[0097] 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.

[0098] 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.

[0099]

[0100] 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.

[0101]

[0102] Preferably, X 11 , X 12 can each independently be methyl or chloro, more preferably X 11 , X 12 can be all methyl or all chloro.

[0103]

[0104] 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.

[0105]

[0106] 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.

[0107]

[0108] Preferably, R1 to R5 are each independently hydrogen, methyl, isopropyl, n-butyl, phenyl, or -(CH2) n1 -OR 13 may be. More preferably, R1 to R5 may each independently be hydrogen, methyl, n-butyl, phenyl, or tertbutoxyhexyl.

[0109]

[0110] 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.

[0111]

[0112] 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.

[0113]

[0114] Preferably, R 13 It may be tert-butyl.

[0115]

[0116] 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.

[0117]

[0118] Preferably, the first metallocene compound represented by the above chemical formula 1 may be any one selected from the group consisting of:

[0119]

[0120] .

[0121]

[0122] 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.

[0123] 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.

[0124]

[0125] Accordingly, according to one embodiment of the present invention, the compound represented by the chemical formula 1 is

[0126] 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

[0127] 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:

[0128] [Reaction Formula 1]

[0129]

[0130] In the above reaction formula 1,

[0131] M1, X 11 , X 12 and R1 to R 12 is as defined in the above chemical formula 1,

[0132] X' is each independently a halogen.

[0133]

[0134] 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.

[0135]

[0136] Preferably, X 21 , X 22 can each independently be methyl or chloro, more preferably X 21 , X 22 Each can be chloro.

[0137]

[0138] Preferably, T2 may be C (carbon).

[0139]

[0140] 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 Q22 One or both of them are -(CH2) n2 -OR 32 It can be. Most preferably, R 20 Inland R 25 , Q 21 and Q 22 Either one or both may be tert-butoxyhexyl.

[0141]

[0142] 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.

[0143]

[0144] 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 23One 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.

[0145]

[0146] 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.

[0147]

[0148] Preferably, R 32 may be tertbutyl.

[0149]

[0150] 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.

[0151]

[0152] Preferably, the metallocene compound represented by the above chemical formula 2 may be any one selected from the group consisting of:

[0153]

[0154] .

[0155]

[0156] 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.

[0157] 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.

[0158]

[0159] Accordingly, according to one embodiment of the present invention, the compound represented by the chemical formula 2 is

[0160] 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;

[0161] 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

[0162] 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:

[0163] [Reaction Formula 2]

[0164]

[0165] In the above reaction formula 2,

[0166] 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,

[0167] X" is each independently a halogen.

[0168]

[0169] 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.

[0170]

[0171] 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.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177]

[0178] In addition, the above hybrid metallocene catalyst may further include a cocatalyst in order to improve high activity and process stability.

[0179] Specifically, the cocatalyst may include at least one compound represented by the following chemical formula 3.

[0180] [Chemical Formula 3]

[0181] -[Al(R 41 )-O]a-

[0182] In the above chemical formula 3,

[0183] R 41 is a halogen; or C substituted or unsubstituted with a halogen 1-20 It is hydrocarbyl;

[0184] a is an integer greater than or equal to 2.

[0185] 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.

[0186] Examples of compounds represented by the above chemical formula 3 include alkylaluminoxane compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane, and any one of these or a mixture of two or more thereof may be used.

[0187] Among the above compounds, the cocatalyst may be, more specifically, an alkylaluminoxane cocatalyst such as methylaluminoxane.

[0188] The above alkylaluminoxane cocatalyst can further enhance catalytic activity by including a metal element that stabilizes the first and second metallocene 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 metallocene compounds.

[0189] 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.

[0190] The hybrid metallocene catalyst according to the present invention having the above-described configuration can be produced by a production method including a step of supporting a promoter compound on a support, and a step of supporting the first and second transition metal compounds on the support. At this time, the supporting order of the promoter and the first and second transition metal compounds can be changed as needed, and the supporting order of the first and second transition metal compounds can also be changed as needed. The first and second transition metal 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 promoter on the support and then sequentially supporting the first and second transition metal compounds can enable the produced supported catalyst to realize high catalytic activity and better process stability in the production process of a polyethylene copolymer.

[0191] 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.

[0192]

[0193] 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.

[0194] 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.

[0195] 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.

[0196]

[0197] The above polymerization reaction is carried out under the condition of hydrogen input.

[0198] 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.

[0199] When injected within the above range, it is easier to implement the properties of the polyethylene copolymer described above.

[0200]

[0201] The above polymerization reaction can be carried out as a gas phase polymerization reaction or a slurry polymerization reaction.

[0202] Accordingly, it can be performed using a single gas phase polymerization reactor, a continuous slurry polymerization reactor, or a loop slurry reactor.

[0203]

[0204] In addition, the 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 use it by further using a cocatalyst.

[0205]

[0206] 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.

[0207]

[0208] 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.

[0209]

[0210] Accordingly, the present invention provides a biaxially oriented film comprising the polyethylene copolymer; or a biaxially oriented film comprising a composition comprising the polyethylene copolymer.

[0211] The present invention also provides a biaxially oriented film manufactured using the polyethylene copolymer or the composition.

[0212]

[0213] The biaxially stretched film according to the present invention can be manufactured according to a conventional film manufacturing method, except that the polyethylene copolymer is used.

[0214] For example, a biaxially stretched film according to the present invention can be manufactured according to the following stretching conditions, and more specific film manufacturing methods and conditions are as described in Examples 3 to 5 described below.

[0215] - Using Bruckner Lab extruder line Using Lab extruder line (L / D ratio: 42, Screw diameter: 25 mm, Melt / T-Die temperature: 220 ℃) ​​to manufacture 0.75 mm thick polyethylene copolymer sheet

[0216] - 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.

[0217] - Sequential stretching (MD→TD) is performed after preheating at 120 to 127 ℃ for 90 seconds each.

[0218]

[0219] In addition, the polyethylene biaxially oriented film according to the present invention may further include additives well known in the art in addition to the polyethylene copolymer described above. Specifically, such additives include solvents, heat stabilizers, antioxidants, UV absorbers, light stabilizers, metal deactivators, fillers, reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, optical bleaching agents, flame retardants, antistatic agents, foaming agents, and the like. The types of the additives are not particularly limited, and general additives known in the art can be used.

[0220]

[0221] In addition, the above biaxially stretched film can exhibit excellent heat resistance and mechanical properties by including the above polyethylene copolymer.

[0222]

[0223] The above biaxially stretched film may have an MD stretch ratio of 4 or more and a TD stretch ratio of 5 or more. Preferably, the stretched film may satisfy an MD stretch ratio of 5 or more and a TD stretch ratio of 5 or more.

[0224]

[0225] The above biaxially stretched film may have a 1% modulus in the MD direction measured according to ASTM D 882 of 360 MPa or more, 370 MPa or more, or 378 MPa or more, and 1000 MPa or less, and a 1% modulus in the TD direction of 400 MPa or more, 420 MPa or more, or 424 MPa or more, and 1000 MPa or less, under the conditions of satisfying an MD stretch ratio of 4 or more and a TD stretch ratio of 5 or more.

[0226]

[0227] The above biaxially stretched film may have a sum of 1% modulus in the MD and TD directions of 800 MPa or more, measured in accordance with ASTM D 882, under the condition that the MD stretch ratio is 4 or more and the TD stretch ratio is 5 or more. Preferably, the sum of 1% modulus may be 850 MPa or more, or 900 MPa or more, and 1500 MPa or less.

[0228]

[0229] The above biaxially stretched film may have a MD direction tensile elongation measured according to ASTM D 882 of 50% or more, 70% or more, 90% or more, or 91% or more, and 250% or less, 240% or less, or 233% or less, and a TD direction tensile elongation of 50% or more, 70% or more, 90% or more, or 93% or more, and 200% or less, 190% or less, 180% or less, or 178% or less.

[0230]

[0231] The above biaxially stretched film may have a sum of tensile elongation in the MD and TD directions measured in accordance with ASTM D 882 of 100% or more, 150% or more, 170% or more, 180% or more, or 184% or more, and 400% or less, 380% or less, 370% or less, or 363% or less, under the condition that the MD stretch ratio is 4 or more and the TD stretch ratio is 5 or more.

[0232]

[0233] The above biaxially stretched film may have a MD tear strength of 0.05 g / μm or more, 0.07 g / μm or more, 0.09 g / μm or more, 0.1 g / μm or more, 0.11 g / μm or more, 0.21 g / μm or more, 0.26 g / μm or more, or 0.29 g / μm or more, and 1 g / μm or less, 0.8 g / μm or less, 0.6 g / μm or less, or 0.52 g / μm or less, under the condition of satisfying an MD draw ratio of 4 or more and a TD draw ratio of 5 or more, according to ASTM 1922, and a TD tear strength of 0.2 g / μm or more, 0.23 g / μm or more, or 0.25 g / μm or more, and 0.9 g / μm or less, 0.8 g / μm or less, or It may be less than 0.78 g / μm.

[0234]

[0235] The above biaxially stretched film may have a sum of MD and TD tear strengths of 0.3 g / μm or more, 0.4 g / μm or more, or 0.46 g / μm or more, and 1.0 g / μm or less, 0.9 g / μm or less, or 0.86 g / μm or less, according to ASTM 1922, under the condition that the MD stretch ratio is 4 or more and the TD stretch ratio is 5 or more.

[0236]

[0237] The above biaxially stretched film, when measured for length change after shrinkage at 120°C for 7 minutes (shrinkage (%); measured as '[1 - (length after shrinkage) / (length before shrinkage)] * 100') under the conditions of satisfying an MD stretch ratio of 4 or more and a TD stretch ratio of 5 or more according to ASTM D 1204, may have an MD shrinkage ratio of 3% or more, or 4.9% or more, and 15% or less, 12% or less, or 10.1% or less, and a TD shrinkage ratio of 5% or more, or 7.5% or more, and 15% or less, 13% or less, 10% or less, or 12.5% ​​or less.

[0238]

[0239] The above biaxially oriented film may have a sum of shrinkage in the MD and TD directions of 25.0% or less, according to ASTM 1922, under the condition that the MD stretch ratio is 4 or more and the TD stretch ratio is 5 or more. Preferably, the sum of shrinkage in the MD and TD directions may be 10% or more, 12% or more, or 12.4% or more, and 24% or less, 23% or less, or 22.3% or less.

[0240]

[0241] In the present invention, the physical properties of a biaxially stretched film can be measured according to the above-described standard, and the specific method is as described in Experimental Example 2 described below.

[0242]

[0243] The polyethylene copolymer according to the present invention can be produced in a single reactor using a metallocene catalyst that hybridly supports a metallocene compound exhibiting high molecular weight and high crystallinity and a metallocene compound exhibiting low molecular weight and low crystallinity, and has an excellent effect of producing a biaxially oriented film with improved heat resistance by improving the main chain average molecular weight of the high crystallinity fraction.

[0244]

[0245] Hereinafter, embodiments of the present invention will be described in more detail in the following examples. However, the following examples are merely illustrative of embodiments of the present invention, and the content of the present invention is not limited by the following examples.

[0246]

[0247] <Preparation of metallocene compounds>

[0248] Synthesis Example 1-1: Preparation of Metallocene Compound A1

[0249]

[0250] (1) Synthesis of ligands

[0251] 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.

[0252] 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).

[0253]

[0254] (2) Synthesis of metallocene compounds

[0255] ​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.

[0256] 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).

[0257]

[0258] Synthesis Example 1-2: Preparation of Metallocene Compound A2

[0259]

[0260] (1) Synthesis of ligands

[0261] 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.

[0262] 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).

[0263]

[0264] (2) Synthesis of metallocene compounds

[0265] ​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.

[0266] 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).

[0267]

[0268] Synthesis Example 1-3: Preparation of Metallocene Compound A3

[0269]

[0270] (1) Synthesis of ligands

[0271] 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.

[0272] 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).

[0273] (2) Synthesis of metallocene compounds

[0274] 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.

[0275] 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).

[0276]

[0277] Synthesis Example 1-4: Preparation of Metallocene Compound A4

[0278]

[0279] (1) Synthesis of ligands

[0280] 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.

[0281] 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).

[0282] (2) Synthesis of metallocene compounds

[0283] 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.

[0284] 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).

[0285]

[0286] Synthesis Example 1-5: Preparation of Metallocene Compound A5

[0287]

[0288] (1) Synthesis of ligands

[0289] 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.

[0290] 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).

[0291] (2) Synthesis of metallocene compounds

[0292] 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.

[0293] 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).

[0294]

[0295] Synthesis Example 1-6: Preparation of Metallocene Compound A6

[0296]

[0297] (1) Synthesis of ligands

[0298] 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.

[0299] 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).

[0300] (2) Synthesis of metallocene compounds

[0301] 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.

[0302] 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).

[0303]

[0304] Synthesis Example 1-7: Preparation of Metallocene Compound A7

[0305]

[0306] 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.

[0307] 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).

[0308]

[0309] Synthesis Example 1-8: Preparation of Metallocene Compound A8

[0310]

[0311] 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.

[0312] 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).

[0313]

[0314] Synthesis Example 1-9: Preparation of Metallocene Compound A9

[0315]

[0316] (1) Synthesis of ligands

[0317] 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.

[0318] 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).

[0319]

[0320] (2) Synthesis of metallocene compounds

[0321] ​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.

[0322] 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).

[0323]

[0324] Synthesis Example 1-10: Preparation of Metallocene Compound A10

[0325]

[0326] 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.

[0327] 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).

[0328]

[0329] Synthesis Example 1-11: Preparation of Metallocene Compound A11

[0330]

[0331] 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.

[0332] 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).

[0333]

[0334] Synthesis Example 1-12: Preparation of Metallocene Compound A12

[0335]

[0336] 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.

[0337] 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).

[0338]

[0339] Synthesis Example 1-13: Preparation of Metallocene Compound A13

[0340]

[0341] 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.

[0342] 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).

[0343]

[0344] Synthesis Example 2-1: Preparation of Metallocene Compound B1

[0345]

[0346] (1) Synthesis of ligands

[0347] 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.

[0348] 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.

[0349] 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).

[0350]

[0351] (2) Synthesis of metallocene compounds

[0352] ​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.

[0353] 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).

[0354]

[0355] Synthesis Example 2-2: Preparation of Metallocene Compound B2

[0356]

[0357] (1) Synthesis of ligands

[0358] 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.

[0359] 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.

[0360] 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).

[0361]

[0362] (2) Synthesis of metallocene compounds

[0363] 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 a solid metallocene compound B2.

[0364] 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).

[0365]

[0366] Synthesis Example 2-3: Preparation of Metallocene Compound B3

[0367]

[0368] (1) Synthesis of ligands

[0369] 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.

[0370] 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).

[0371]

[0372] (2) Synthesis of metallocene compounds

[0373] 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.

[0374] 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).

[0375]

[0376] Synthesis Example 2-4: Preparation of Metallocene Compound B4

[0377]

[0378] (1) Synthesis of ligands

[0379] 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.

[0380] 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).

[0381]

[0382] (2) Synthesis of metallocene compounds

[0383] 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 a solid metallocene compound B4.

[0384] 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).

[0385]

[0386] Synthesis Example 2-5: Preparation of Metallocene Compound B5

[0387]

[0388] (1) Synthesis of ligands

[0389] 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.

[0390] 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.

[0391] 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).

[0392]

[0393] (2) Synthesis of metallocene compounds

[0394] ​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.

[0395] 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).

[0396]

[0397] Synthesis Example 2-6: Preparation of Metallocene Compound B6

[0398]

[0399] (1) Synthesis of ligands

[0400] 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.

[0401] 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.

[0402] 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).

[0403]

[0404] (2) Synthesis of metallocene compounds

[0405] 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.

[0406] 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).

[0407]

[0408] Synthesis Example 2-7: Preparation of Metallocene Compound B7

[0409]

[0410] (1) Synthesis of ligands

[0411] 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.

[0412] 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.

[0413] 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).

[0414]

[0415] (2) Synthesis of metallocene compounds

[0416] ​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. 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 6.25 g (7.19 mmol, 52.5% yield) of a solid metallocene compound B7.

[0417] 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).

[0418]

[0419] Synthesis Example 2-8: Preparation of Metallocene Compound B8

[0420]

[0421] (1) Synthesis of ligands

[0422] 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.

[0423] 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).

[0424]

[0425] (2) Synthesis of metallocene compounds

[0426] ​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.

[0427] 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).

[0428]

[0429] Synthesis Example 2-9: Preparation of Metallocene Compound B9

[0430]

[0431] (1) Synthesis of ligands

[0432] 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.

[0433] 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.

[0434] 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).

[0435]

[0436] (2) Synthesis of metallocene compounds

[0437] ​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.

[0438] 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).

[0439]

[0440] Synthesis Example 2-10: Preparation of Metallocene Compound B10

[0441]

[0442] (1) Synthesis of ligands

[0443] 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.

[0444] 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.

[0445] 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).

[0446]

[0447] (2) Synthesis of metallocene compounds

[0448] ​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.

[0449] 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).

[0450]

[0451] Synthesis Example 2-11: Preparation of Metallocene Compound B11

[0452]

[0453] (1) Synthesis of ligands

[0454] 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.

[0455] 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.

[0456] 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).

[0457]

[0458] (2) Synthesis of metallocene compounds

[0459] ​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.

[0460] 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).

[0461]

[0462] Synthesis Example 2-12: Preparation of Metallocene Compound B12

[0463]

[0464] (1) Synthesis of ligands

[0465] 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.

[0466] 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.

[0467] 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).

[0468]

[0469] (2) Synthesis of metallocene compounds

[0470] ​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.

[0471] 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).

[0472]

[0473] Synthesis Example 2-13: Preparation of Metallocene Compound B13

[0474]

[0475] (1) Synthesis of ligands

[0476] 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.

[0477] 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).

[0478]

[0479] (2) Synthesis of metallocene compounds

[0480] ​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.

[0481] 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).

[0482]

[0483] <Manufacture of supported catalysts>

[0484] Manufacturing Example 1: Manufacturing of Catalyst 1

[0485] Silica (SP 952, manufactured by Grace Davision) was dehydrated and dried under vacuum at 200°C for 12 hours.

[0486] 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.

[0487]

[0488] Manufacturing Examples 2 to 25: Manufacturing of Catalysts 2 to 25

[0489] 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.

[0490]

[0491] Manufacturing Examples 26 and 27: Manufacturing of catalysts 2 to 25

[0492] 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. The structures of metallocene compounds A14, A15, B14, and B15 used in Preparation Examples 26 and 27 are as follows.

[0493]

[0494]

[0495] 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 20A3B8 1227.13.0 Manufacturing Example 21 Catalyst 21A3B9 6 25.14.0 Manufacturing Example 22 Catalyst 22A3B10 7 25.7 4.3 Manufacturing Example 23 Catalyst 23A3B11 5 24.4 5.6 Manufacturing Example 24 Catalyst 24A3B12 13 27.21.8 Manufacturing Example 25 Catalyst 25A3B13 6 25.12.9 Manufacturing Example 26 Catalyst 26A14B14 3 14.6 6.1 Manufacturing Example 27 Catalyst 27A15B15 2 13.4 6.8

[0496] (The 'ratio' in Table 1 above means 'number of moles of metallocene compound 1 / number of moles of metallocene compound 2'.)

[0497] <Manufacture of polyethylene copolymer>

[0498] Examples 1-1 to 1-25 and Comparative Examples 1-1 to 1-4

[0499] 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.

[0500] 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.

[0501]

[0502] 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 325308.545 Comparative Example 1-2 Catalyst 2625.1301023 Comparative Example 1-3 Catalyst 2725.0195.554 Comparative Example 1-4 Catalyst 725.1256.869

[0503] <Experimental Example 1: Evaluation of Physical Properties of Polyethylene Copolymer>

[0504] 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.

[0505]

[0506] (1) MI 2.16 and MFRR(MFR 21.6 / MFR 2.16 )

[0507] Melt Index (MI2.16 ) 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.

[0508]

[0509] (2) Density (g / cm) 3 )

[0510] Density (g / cm) according to ASTM D 792, American Society for Testing and Materials 3 ) was measured.

[0511]

[0512] (3) Molecular structure analysis: Cross Fractionation Chromatography (CFC) analysis

[0513] - Analysis equipment: Polymer Char CFC (Detector: Integrated Detector IR5 MCT)

[0514] - 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.

[0515] - Crystallization: Cool the sample loaded on the TREF column from 100 ℃ to 35 ℃ at a rate of 0.5 ℃ / min.

[0516] - 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)

[0517] - 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.

[0518]

[0519] 1) Method for measuring high-crystallinity, medium-crystallinity, low-crystallinity content and soluble fraction

[0520] 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%).

[0521] <fraction temperature>

[0522] 35℃ / 40℃ / 43℃ / 46℃ / 49℃ / 52℃ / 55℃ / 58℃ / 61℃ / 64℃ / 67℃ / 70℃ / 73℃ / 76℃ / 79℃ / 82℃ / 85℃ / 88℃ / 91℃ / 94℃ / 97℃ / 100℃ / 105℃ / 120℃

[0523]

[0524] 2) The main chain average molecular weight (Mw) of the high-crystalline fraction T>90℃ ) calculate

[0525] 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.

[0526] [Mathematical Formula 1]

[0527] Main chain Mw of high crystallinity fraction =

[0528] In the above mathematical formula 1,

[0529] M T,i and C T,i : Molecular weight and concentration of each molecule eluted at different temperatures

[0530] n scb T,i : Number of scb in each molecule

[0531] M scb : scb molecular weight

[0532]

[0533] 3) Main chain average molecular weight (Mw) of low crystallinity fraction ,35<T≤70℃ ) calculate

[0534] : 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.

[0535] [Equation 2]

[0536] Main chain Mw of low crystallinity fraction =

[0537] In the above mathematical expression 2,

[0538] M T,i and C T,i : Molecular weight and concentration of each molecule eluted at different temperatures

[0539] n scb T,i : Number of scb in each molecule

[0540] M scb : scb molecular weight

[0541]

[0542] 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 1-1Catalyst33.5721.60.9284.32843.342k78kComparative Example 1-2Catalyst260.9318.80.9167.716.911.3160k101kComparative Example 1-3 Catalyst 270.3164.40.9270.52.63.114k103k Comparative example 1-4 Catalyst 73.3225.00.9342.723.455.642k84k.

[0543] (The 'k' in the low-crystal Mw and high-crystal Mw in Table 3 above means 1000 times.)

[0544] 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 had a structure having a high crystalline high molecular weight and a low crystalline low molecular weight, in which the main chain molecular weight of the high crystalline fraction was high and the main chain molecular weight of the low crystalline fraction was low. Meanwhile, although Example 1-3 and Comparative Example 1-1 used the same catalyst, it was confirmed that the content of the high crystalline fraction in Comparative Example 1-1 was lower than 45.0 wt% and the main chain molecular weight of the high crystalline fraction was also lower than that of the Examples, depending on the process conditions. Although Example 1-7 and Comparative Example 1-4 also used the same catalyst, it was confirmed that the main chain molecular weight of the high crystalline fraction in Comparative Example 1-4 was lower than that of the Examples, depending on the process conditions.

[0545] Comparative Examples 1-2 and 1-3, 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 Example 1-2 has a structure in which the main chain molecular weight of the low-crystalline fraction is higher than that of the high-crystalline fraction.

[0546]

[0547] <Manufacturing of Stretch Film>

[0548] Examples 2-1 to 2-10 and Comparative Examples 2-1 to 2-4

[0549] 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 2-2 and 2-3 could not be preheated and stretched under the conditions of 120 to 127°C.

[0550] - 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 ℃)

[0551] - 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.

[0552] - After preheating for 90 seconds each, sequential stretching (MD→TD) is performed under the conditions in Table 4 below.

[0553]

[0554] 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 3 Catalyst 26 Catalyst 27 Catalyst 7 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 (℃) 125 125 125 124 124 125 124 124 124 124 124 124 124 124 124 124 124 125 ...

[0555] <Experimental Example 2: Evaluation of Physical Properties of Biaxially Stretched Film>

[0556] 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.

[0557]

[0558] (1) Haze: Measured according to ASTM 1003

[0559] (2) Tensile properties (tensile modulus (1% modulus), elongation): Measured in each MD / TD direction according to ASTM D 882

[0560] (3) Tear strength: Measured in each MD / TD direction according to ASTM 1922

[0561] (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".

[0562]

[0563] 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

[0564] Comparative Example 2-1 Comparative Example 2-2 Comparative Example 2-3 Comparative Example 2-4 Catalyst Catalyst 3 Catalyst 26 Catalyst 27 Catalyst 7 PE used Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 Comparative Example 1-4 Thickness (μm) 16 ~ 28--17 ~ 27 Haze (%)7.9--9.31%Modulus(MPa)MD357--372TD367--384MD+TD724--756Tensile Elongation(%)MD508--532TD643--577MD+TD1151--1109Tear Strength(g / μm)MD1.34--2.11TD0.48--1.33MD+TD1.82--3.44Shrinkage(%,@120˚C)MD5.5--3.3TD2.9--3.0MD+TD8.4--6.6

[0565] According to the above table, it can be confirmed that the biaxially stretched 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.

[0566] In particular, the polyethylene copolymers of Example 1-3 and Comparative Example 1-1 and Example 1-7 and 1-4, despite using the same catalyst, had inferior high crystal content and main chain molecular weight of the high crystallinity fraction of Comparative Example 1-1 compared to Example 1-3, and inferior high crystallinity fraction main chain molecular weight of the high crystallinity fraction of Comparative Example 1-4 compared to Example 1-7, so that although stretching of Comparative Example 2-1 and Comparative Example 2-4 was possible, it was confirmed that stretching was not successful from the results of low 1% modulus and very high elongation. Since the stretched film is already in a stretched state, if the elongation for evaluating additional stretching is high, it can be seen that the crystal orientation has not occurred as much, so the stretchability can be seen to be inferior.

Claims

1. The main chain average molecular weight (Mw) of the highly crystalline fraction eluted at an elution temperature exceeding 90 ℃ during cross fractionation chromatography (CFC) analysis ,T>90℃ ) is 90,000 g / mol or more, The content ratio of highly crystalline fractions eluted at an elution temperature exceeding 90 ℃ during cross fractionation chromatography (CFC) analysis (TREF) T>90℃ ) is more than 45.0 wt% of the total elution fraction, Polyethylene copolymer.

2. In paragraph 1, Density measured according to ASTM D 792 is 0.920 g / cm 3 Above 0.940 g / cm 3 Lee Ha-in, Polyethylene copolymer.

3. In paragraph 1, Melt index (MI) measured according to ASTM D 1238 2.16 ) is 0.5 g / 10 min or more and 5.0 g / 10 min or less, Polyethylene copolymer.

4. In paragraph 1, MFRR(MFR 21.6 / MFR 2.16 ) is 15 or more and 40 or less, The above MFR 21.6 is measured at 190 ℃ and under a load of 21.6 kg according to ISO 1133. The above MFR 2.16 is measured at 190 ℃ and under a load of 2.16 kg according to ISO 1133. Polyethylene copolymer.

5. In paragraph 1, The above polyethylene copolymer is an ethylene / 1-hexene copolymer, Polyethylene copolymer.

6. A biaxially oriented film comprising the polyethylene copolymer of paragraph 1.

7. In paragraph 6, The above film has an MD stretch ratio of 4 or more and a TD stretch ratio of 5 or more. Biaxially oriented film.

8. In paragraph 6, The above film satisfies the conditions of MD stretch ratio 4 or more and TD stretch ratio 5 or more, The sum of the tensile modulus (1% modulus) in the MD and TD directions measured according to ASTM D 882 is 800 MPa or more. Biaxially oriented film.

9. In paragraph 6, The above film satisfies the conditions of MD stretch ratio 4 or more and TD stretch ratio 5 or more, The sum of the shrinkage in the MD and TD directions is 25.0% or less when shrinking for 7 minutes at 120°C as measured according to ASTM D 1204. Biaxially oriented film.

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