Dinuclear metallocene compound, supported dinuclear metallocene catalyst comprising same, and method for producing supported second nuclear metallocene

Abstract

The present invention relates to a dinuclear metallocene compound, a supported dinuclear metallocene catalyst prepared including the same, and a method for preparing the supported dinuclear metallocene catalyst.

Description

Technology Field

[0001] The present invention relates to a dinuclear metallocene compound, a supported dinuclear metallocene catalyst prepared including the same, and a method for preparing the supported dinuclear metallocene catalyst. Background Technology

[0002] More than 100 million tons of polyolefins, including polyethylene and polypropylene, are manufactured worldwide every year.

[0003] Although heterogeneous Ziegler-Natta catalysts are primarily used in the polymerization reactions of these polyolefins, active efforts are underway in the industry to replace them with homogeneous metallocene catalysts.

[0004] The manufacturing processes of polyolefins can be broadly classified into high-pressure radical processes, solution processes, slurry processes, and gas-phase processes, and currently, a large portion of polyolefins are manufactured using slurry and gas-phase processes, which are advantageous in terms of energy consumption.

[0005] However, in slurry and gas-phase processes, polymers must be produced from catalyst particles in the form of particles of a specific shape and size. Therefore, morphology control is very important for the stable operation of the process.

[0006] Typically, when homogeneous metallocene catalysts are introduced into polyolefin polymerization processes in solution form or in a form with uncontrolled particle shape, stable process operation is impossible due to the non-uniform shape and size of the resulting polymer particles. For this reason, to apply metallocene catalysts to slurry and gas-phase processes, supported catalysts are used, which are prepared by chemically and physically adsorbing the metallocene catalyst onto an inorganic support such as silica, with uniformly controlled particle shape and size.

[0007] Therefore, various methods for manufacturing supported catalysts suitable for use in polyolefin manufacturing processes are being researched and developed. In other words, there is a need for research on supported catalysts that maximize catalytic activity while allowing for easy control of particle shape to prevent problems arising from the introduction of the catalyst into the polyolefin manufacturing process. Prior art literature

[0008] Journal of Molecular Catalysis A: Chemical 2003, 195, 11;Inorganica Chimica Acta 2003, 350, 1 The problem to be solved

[0009] The present invention provides a novel dinuclear metallocene compound capable of producing a supported metallocene catalyst having an enhanced functional effect.

[0010] In addition, the present invention provides a supported dinuclear metallocene catalyst having excellent particle size control and high activity, and a method for manufacturing the same.

[0011] In addition, the present invention provides a method for producing polyolefins using the supported dinuclear metallocene catalyst of the present invention, which has excellent particle size control and high activity. means of solving the problem

[0012] To achieve the above objective, the present invention provides a novel dinuclear metallocene compound capable of producing a supported dinuclear metallocene catalyst with excellent particle size control and high activity, wherein the dinuclear metallocene compound of the present invention is represented by the following chemical formula 1.

[0013] [Chemical Formula 1]

[0014]

[0015] (In the above chemical formula 1,

[0016] M1 and M2 are independently group 4, group 5, or group 6 transition metals;

[0017] A is a C1-C30 alkylene, a C6-C30 arylene, or a C3-C30 heteroarylene;

[0018] Cp1 and Cp2 are independently cyclopentadienyl; or cyclopentadienyl with an aromatic ring or an aliphatic ring fused thereto; and

[0019] R1 to R8 are independently hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C2-C30 alkenyl, C6-C30 aryl, C6-C30 aryloxy, C1-C30 alkyl C6-C30 aryl, C6-C30 aryl C1-C30 alkyl, mono C1-C30 alkylamino, di C1-C30 alkylamino, tri C1-C30 alkylamino, mono C6-C30 arylamino, di C6-C30 arylamino, or tri C6-C30 arylamino;

[0020] R a and R b are independently hydrogen, C1-C30 alkyl, C6-C30 aryloxy C1-C30 alkyl, or C1-C30 alkoxy C1-C30 alkyl;

[0021] X1 to X4 are independently halogen, C1-C30 alkyl, C2-C30 alkenyl, arylalkyl, triC1-C30 alkylsilyl, or triC6-C30 arylsilyl;

[0022] The above cyclopentadienyl; or cyclopentadienyl fused with an aromatic ring or an aliphatic ring; may be further substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 aryl C1-C20 alkyl, C1-C20 alkyl C6-C20 aryl, C1-C20 alkylsilyl, silyl C1-C20 alkyl, C6-C20 arylsilyl, C6-C20 silylaryl, C1-C20 alkoxy, C1-C20 alkylsiloxy, C6-C20 aryloxy, halogen, and amino.)

[0023] Preferably, in Formula 1 according to one embodiment of the present invention, M1 and M2 may independently be titanium, hafnium, or zirconium, and

[0024] Cp1 and Cp2 are independently cyclopentadienyl, indenyl, or fluorenyl, and the cyclopentadienyl, indenyl, and fluorenyl may be further substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, C1-C20 alkyl C6-C20 aryl, halogen, and amino.

[0025] More preferably, in Formula 1 according to one embodiment of the present invention, M1 and M2 are zirconium; A is a C1-C20 alkylene; Cp1 and Cp2 are independently cyclopentadienyl, indenyl, or fluorenyl; R1 to R8 are independently hydrogen, a C1-C20 alkyl, or a C1-C20 alkoxy; R a and R b are independently C1-C20 alkyl, C6-C20 aryloxy C1-C20 alkyl, or C1-C20 alkoxy C1-C20 alkyl; X1 to X4 are independently halogen or C1-C20 alkyl; and the cyclopentadienyl, indenyl, and fluorenyl may be further substituted with one or more substituents selected from hydrogen and C1-C10 alkyl.

[0026] Preferably, Formula 1 according to one embodiment of the present invention can be represented by the following Formula 2.

[0027] [Chemical Formula 2]

[0028]

[0029] (In the above chemical formula 2,

[0030] M1 and M2 are independently titanium, hafnium, or zirconium;

[0031] R1 to R8 are independently hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C2-C30 alkenyl, C6-C30 aryl, C6-C30 aryloxy, C1-C30 alkyl, C6-C30 aryl, C6-C30 aryl, C1-C30 alkyl, mono-C1-C30 alkylamino, di-C1-C30 alkylamino, tri-C1-C30 alkylamino, mono-C6-C arylamino, di-C6-C30 arylamino, or tri-C6-C30 arylamino;

[0032] R 11 to R 18 are independently hydrogen, C1-C30 alkyl, C1-C30 alkoxy, or C2-C30 alkenyl;

[0033] R a and R b are independently C1-C30 alkyl, C6-C30 aryloxy C1-C30 alkyl, or C1-C30 alkoxy C1-C30 alkyl;

[0034] X1 to X4 are independently halogen, C1-C30 alkyl, C2-C30 alkenyl, arylalkyl, triC1-C30 alkylsilyl, or triC6-C30 arylsilyl;

[0035] n is an integer from 1 to 20.

[0036] In Formula 2 according to one embodiment of the present invention, M1 and M2 are zirconium; R1 to R8 and R 11 to R 18 are independently hydrogen or C1-C30 alkyl; R a and R b are independently C1-C30 alkyls; X1 to X4 are independently C1-C30 alkyls; and n can be an integer from 1 to 15.

[0037] Preferably, in Formula 2 according to one embodiment of the present invention, M1 and M2 are zirconium; R1 to R2 and R5 to R6 are independently C1-C10 alkyls; R3 to R4, R7 to R8 are and R 11 to R 18are independently hydrogen or C1-C10 alkyl; R a and R b are independently C1-C7 alkyls; X1 to X4 are independently C1-C7 alkyls; and n can be an integer from 1 to 10.

[0038] In addition, the present invention provides a supported dinuclear metallocene catalyst supported with the dinuclear metallocene compound of the present invention, wherein the supported dinuclear metallocene catalyst of the present invention is,

[0039] Aluminum compound-carrier complex and

[0040] The dinuclear metallocene compound represented by the above chemical formula 1 is characterized by being supported on the above aluminum compound-carrier complex.

[0041] Preferably, the aluminum compound-carrier composite of the present invention may be a composite formed by an aluminum compound on one or more carriers selected from silica, alumina, magnesium chloride, calcium chloride, bauxite, zeolite, magnesium oxide, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide, and thorium oxide.

[0042] Preferably, the ratio of the metal of the dinuclear metallocene catalyst of the present invention to the aluminum of the aluminum compound-carrier composite may be 1:20 to 70.

[0043] In addition, the present invention provides a method for manufacturing a supported dinuclear metallocene catalyst of the present invention, wherein the method for manufacturing a supported dinuclear metallocene catalyst of the present invention comprises:

[0044] A step of preparing an aluminum compound-carrier composite by reacting an aluminum compound and a carrier; and

[0045] The method includes the step of preparing a supported dinuclear metallocene catalyst by reacting the above aluminum compound-carrier complex with the dinuclear metallocene compound represented by the above chemical formula 1.

[0046] According to one embodiment of the present invention, the aluminum compound may be used in an amount of 0.4 to 0.5 parts by weight per 100 parts by weight of the carrier, and the dinuclear metallocene compound represented by Formula 1 may be used in a ratio of 110 to 140 μmol-Metal / g-(silica-aluminoxane complex) with respect to the aluminum compound-carrier complex.

[0047] In addition, the present invention provides a method for producing a polyolefin comprising the step of polymerizing one or more olefin monomers in the presence of the supported dinuclear metallocene catalyst of the present invention.

[0048] Preferably, in one embodiment of the method for producing a polyolefin of the present invention, the olefin monomer may be one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, and mixtures thereof. Effects of the invention

[0049] The dinuclear metallocene compound of the present invention can be used as a polyolefin catalyst by introducing cyclopentathiophene and including two transition metals to produce a polyolefin having high activity and a uniform composition.

[0050] Furthermore, the dinuclear metallocene compound of the present invention can easily produce a supported catalyst with uniformly controlled particle shape and size.

[0051] In addition, the supported dinuclear metallocene catalyst supported with the dinuclear metallocene compound of the present invention exhibits excellent catalytic activity, suppresses the formation of polymers with large particle sizes, and can produce polyolefins with uniform particle shape and size.

[0052] Accordingly, the supported dinuclear metallocene catalyst of the present invention can be easily applied to slurry processes and gas phase processes where energy consumption is reduced.

[0053] Furthermore, the supported catalyst of the present invention does not cause problems during input into the polyolefin manufacturing process, and the method for manufacturing polyolefins using the supported catalyst of the present invention enables a stable process by facilitating the control of the particle shape and size of the polymer being manufactured. Brief explanation of the drawing

[0054] FIG. 1 shows a dinuclear metallocene compound represented by Formula 1-1 prepared in Example 1 of the present invention and a formula prepared in Comparative Example 1. 2 (R 6 = Me; R 7 = H)'s 1 This is a diagram comparing H NMR spectra. Specific details for implementing the invention

[0055] The present invention will be described in more detail below. Unless otherwise defined, technical and scientific terms used herein have the meanings commonly understood by those skilled in the art to which this invention pertains. Furthermore, descriptions of known functions and configurations that could unnecessarily obscure the essence of the invention are omitted in the following description.

[0056] As used herein, the term “alkyl” means a saturated straight-chain or branched non-cyclic hydrocarbon having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in one embodiment preferably 1 to 15 carbon atoms, in one embodiment preferably 1 to 10 carbon atoms, or in one embodiment preferably 1 to 7 carbon atoms (where the number of carbon atoms is not particularly limited). “Lower alkyl” means a straight-chain or branched alkyl having 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms in one embodiment. Representative saturated straight-chain alkyls include -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl, and -n-decyl, while saturated branched alkyls include -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,3-dimethylhexyl, It includes 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethylpentyl, 2,2-dimethylhexyl, 3,3-dimethylpentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-diethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-diethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.

[0057] In this specification, when described as "C1-C10," it means that the number of carbon atoms is 1 to 10. For example, C1-C10 alkyl means an alkyl having 1 to 10 carbon atoms.

[0058] As used herein, the term “alkenyl” means a saturated straight-chain or branched non-cyclic hydrocarbon comprising 2 to 30, in one embodiment, preferably 2 to 20, preferably 2 to 15, preferably 2 to 10, and preferably 2 to 7 carbon atoms and at least one carbon-carbon double bond. Representative straight-chain and branched (C2-C10) alkenyls include -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutylenyl, -1-pentenyl, -2-pentenyl, -3-methyl-1-butenyl, -2-methyl-2-butenic, -2,3-dimethyl-2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1-heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2-octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3-nonenyl, -1-disenyl, -2-disenyl, and -3-disenyl. These alkenyl groups may be optionally substituted.

[0059] The terms “halogen” and “halo” as used in this specification mean fluorine, chlorine, bromine, or iodine.

[0060] As used herein, the terms “haloalkyl,” “haloalkoxy,” “haloalkenyl,” or “haloalkynyl” each mean an alkyl, alkoxy, alkenyl, or alkynyl group in which one or more hydrogen atoms are substituted with halogen atoms. For example, haloalkyls include -CF3, -CHF2, -CH2F, -CBr3, -CHBr2, -CH2Br, -CC13, -CHC12, -CH2CI, -CI3, -CHI2, -CH2I, -CH2-CF3, -CH2-CHF2, -CH2-CH2F, -CH2-CBr3, -CH2-CHBr2, -CH2-CH2Br, -CH2-CC13, -CH2-CHC12, -CH2-CH2CI, -CH2-CI3, -CH2-CHI2, -CH2-CH2I, and similar ones. Herein, alkyl and halogen are as defined above.

[0061] As used in this specification, the term “alkoxy” means -O-(alkyl), including -OCH3, -OCH2CH3, -O(CH2)2CH3, -O(CH2)3CH3, -O(CH2)4CH3, -O(CH2)5CH3, and similar ones, wherein alkyl is as defined above.

[0062] The term “lower alkoxy” as used in this specification means -O-(lower alkyl), where lower alkyl is the same as defined above.

[0063] As used herein, the term "aryl" means a carbon-ring aromatic group containing 5 to 10 ring atoms. Representative examples include, but are not limited to, phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, etc. The carbon-ring aromatic group may be optionally substituted.

[0064] As used herein, the term "aryloxy" is RO-, where R is the aryl defined above. "aryltio" is RS-, where R is the aryl defined above.

[0065] As used herein, the term "cycloalkyl" means a monocyclic or polycyclic saturated ring having carbon and hydrogen atoms and not having carbon-carbon multiple bonds. Examples of cycloalkyl groups include, but are not limited to, (C3-C10)cycloalkyls (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl). Cycloalkyl groups may be optionally substituted. In one embodiment, the cycloalkyl group is a monocyclic or bicyclic ring.

[0066] The term “cyclopentadienyl fused with an aromatic ring or an aliphatic ring” as used in this specification means that one or more rings selected from an aromatic ring and an aliphatic ring are fused to cyclopentadienyl, and examples include indenyl, fluorenyl, etc., and also include 5,10-dihydro-5-methylindeno[1,2,-b]indole and cyclopentadiopene.

[0067] As used herein, the term “mono-alkylamino” means -NH(alkyl), including -NHCH3, -NHCH2CH3, -NH(CH2)2CH3, -NH(CH2)3CH3, -NH(CH2)4CH3, -NH(CH2)5CH3, and similar ones, wherein alkyl is as defined above.

[0068] As used herein, the term “di-alkylamino” means -N(alkyl)(alkyl), including -N(CH3)2, -N(CH2CH3)2, -N((CH2)2CH3)2, -N(CH3)(CH2CH3), and similar ones, wherein each alkyl is an alkyl defined above independently of each other.

[0069] The term "alkylamino" as used in this specification is a concept including mono-alkylamino and di-alkylamino as defined above.

[0070] As used in this specification, the terms "carboxyl" and "carboxy" mean -COOH.

[0071] As used herein, “heteroaryl” is an aromatic heterocycle ring of 5 to 10 members comprising at least one carbon atom selected from the group consisting of nitrogen, oxygen and sulfur, and having at least one heteroatom selected from the group consisting of mono- and bicyclic ring systems. Representative heteroaryls are triazoleyl, tetrazolyl, oxadiazoleyl, pyridyl, furyl, benzofuranyl, thiophenyl, benzothiophenyl, quinolinyl, pyrrolyl, indoleyl, oxazolyl, benzoxazolyl, imidazoleyl, benzimidazoleyl, thiazolyl, benzothiazoleyl, isoxazolyl, pyrazolyl, isothiazoleyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, cinnolinyl, phthalazinyl, quinazolinyl, pyrimidyl, oxetanil, azefinil, piperazinyl, morpholinyl, dioxanil, tiethanil, and oxazolyl. The heteroaryl group can be monocyclic or bicyclic. Heteroaryl may be used interchangeably with the terms heteroaryl ring, heteroaryl group, or heteroaromatic, all of which may include an arbitrarily substituted ring.

[0072] As used herein, the term "substituted" means that a hydrogen atom of the substituted portion (e.g., alkyl, aryl, heteroaryl, heterocyclic, or cycloalkyl) is replaced by a substituent. In one embodiment, each carbon atom of the substituted group is not substituted by two or more substituents. In another embodiment, each carbon atom of the substituted group is not substituted by one or more substituents. In the case of a keto substituent, two hydrogen atoms are replaced by oxygen attached to the carbon by a double bond. Unless otherwise specified with respect to substituents, optionally substituted substituents of the present invention include C1-C20 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl group, C6-C20 aryl, C6-C20 aryl C1-C20 alkyl, C1-C20 alkyl C6-C20 aryl, C1-C20 alkylsilyl, silyl C1-C20 alkyl, C6-C20 arylsilyl, C6-C20 silylaryl, C1-C20 alkoxy, C1-C20 alkylsiloxy, C6-C20 aryloxy, halogen, hydroxyl, -NO2, -NR a1 R b1 , -NR a1 C(=O) R b1 , -NR a1 C(=O)NR a1 R b1 , -NR a1 C(=O)OR b1 , -NR a1 SO2R b1 , -OR a1 , -CN, -C(=O)R a1 , -C(=O)OR a1 , -C(=O)NR a1 R b1 , -OC(=O)R a1 , -OC(=O)OR a1 , -OC(=O)NR a1 R b1 , -NR a1 SO2R b1 , -PO3R a1 , -PO(OR a1 )(OR b1 ), -SO2R a1 , -S(O)R a1, -SO(NR a1 )R b1 (e.g., sulfoximine), -S(NR a1 )R b1 (e.g., sulfilimine) and -SR a1 can be used, and here R a1 and R b1 may be the same or different, and independently are hydrogen, halogen, amino, alkyl, alkoxyalkyl, haloalkyl, aryl, or heterocyclic, or R such as an attached nitrogen atom a1 and R b1 can take the form of a heterocycle. Here, R a1 and R b1 There may be multiple atoms depending on the bonded atoms, and preferably, the alkyl may be C1-C6 alkyl, the aryl may be C6-C12, and the heterocycle may be C3-C12.

[0073] Hereinafter, a dinuclear metallocene compound, a supported dinuclear metallocene compound, a method for manufacturing the same, and a method for manufacturing a polyolefin using the same will be described in detail according to one embodiment of the present invention.

[0074] The present invention provides a novel dinuclear metallocene compound that enables the production of a supported metallocene catalyst having high activity and very easy particle size control.

[0075] The dinuclear metallocene compound of the present invention is represented by the following chemical formula 1.

[0076] [Chemical Formula 1]

[0077]

[0078] (In the above chemical formula 1,

[0079] M1 and M2 are independently group 4, group 5, or group 6 transition metals;

[0080] A is a C1-C30 alkylene, a C6-C30 arylene, or a C3-C30 heteroarylene;

[0081] Cp1 and Cp2 are independently cyclopentadienyl; or cyclopentadienyl with an aromatic ring or an aliphatic ring fused thereto; and

[0082] R1 to R8 are independently hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C2-C30 alkenyl, C6-C30 aryl, C6-C30 aryloxy, C1-C30 alkyl C6-C30 aryl, C6-C30 aryl C1-C30 alkyl, mono C1-C30 alkylamino, di C1-C30 alkylamino, tri C1-C30 alkylamino, mono C6-C30 arylamino, di C6-C30 arylamino, or tri C6-C30 arylamino;

[0083] R a and R b are independently hydrogen, C1-C30 alkyl, C6-C30 aryloxy C1-C30 alkyl, or C1-C30 alkoxy C1-C30 alkyl;

[0084] X1 to X4 are independently halogen, C1-C30 alkyl, C2-C30 alkenyl, arylalkyl, triC1-C30 alkylsilyl, or triC6-C30 arylsilyl;

[0085] The above cyclopentadienyl; or cyclopentadienyl fused with an aromatic ring or an aliphatic ring; may be further substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 aryl C1-C20 alkyl, C1-C20 alkyl C6-C20 aryl, C1-C20 alkylsilyl, silyl C1-C20 alkyl, C6-C20 arylsilyl, C6-C20 silylaryl, C1-C20 alkoxy, C1-C20 alkylsiloxy, C6-C20 aryloxy, halogen, and amino.)

[0086] The novel dinuclear metallocene catalyst of the present invention is very useful for producing supported catalysts with improved properties that can be easily applied to slurry processes and gas phase processes in polyolefin processes.

[0087] In addition, the novel dinuclear metallocene catalyst of the present invention can support a large amount of dinuclear metallocene catalyst on a support by introducing a specific functional group, cyclopentathiophenyl (cyclopentadienyl fused with thiophene), into the dinuclear metallocene, thereby enabling the production of a highly active catalyst.

[0088] When a supported catalyst is prepared using a compound in which a cyclopentadienyl ligand fused with a thiophene ring is introduced, the novel dinuclear metallocene compound of the present invention allows for superior particle size control and high activity compared to when a mononuclear metallocene catalyst is used.

[0089] Preferably, in Formula 1 according to one embodiment of the present invention, M1 and M2 may independently be titanium, hafnium, or zirconium, and more preferably titanium or zirconium in terms of having excellent catalytic activity, and even better zirconium.

[0090] More preferably, in Formula 1 according to one embodiment of the present invention, Cp1 and Cp2 are independently substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, or substituted or unsubstituted fluorenyl, preferably independently substituted or unsubstituted cyclopentadienyl or substituted or unsubstituted indenyl, and even more preferably cyclopentadienyl.

[0091] In Formula 1 according to one embodiment of the present invention, cyclopentadienyl, indenyl, and fluorenyl may be further substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, C1-C20 alkyl C6-C20 aryl, halogen, and amino, and preferably may be further substituted with one or more substituents selected from halogen, C1-C20 alkyl, C6-C20 aryl, and C1-C20 alkyl C6-C20 aryl, more preferably may be further substituted with one or more substituents selected from C1-C10 alkyl, C6-C12 aryl, and C1-C10 alkyl C6-C12 aryl, even more preferably may be further substituted with one or more substituents selected from C1-C5 alkyl, C6-C10 aryl, and C1-C5 alkyl C6-C10 aryl, and even better may be substituted with C1-C5 alkyl.

[0092] In terms of preparing a supported catalyst having superior catalytic activity, preferably in Formula 1 according to one embodiment of the present invention, M1 and M2 are zirconium; A is a C1-C20 alkylene; Cp1 and Cp2 are independently cyclopentadienyl, indenyl, or fluorenyl; R1 to R8 are independently hydrogen, a C1-C20 alkyl, or a C1-C20 alkoxy; R a and R b are independently C1-C20 alkyl, C6-C20 aryloxy C1-C20 alkyl, or C1-C20 alkoxy C1-C20 alkyl; X1 to X4 are independently halogen or C1-C20 alkyl; the cyclopentadienyl, indenyl, and fluorenyl may be further substituted with one or more substituents selected from hydrogen and C1-C10 alkyl, more preferably M1 and M2 are zirconium; A is C1-C10 alkylene; Cp1 and Cp2 are independently cyclopentadienyl or indenyl; R1 to R8 are independently hydrogen, C1-C10 alkyl, or C1-C10 alkoxy; R a and R bare independently C1-C10 alkyl, C6-C12 aryloxy C1-C10 alkyl, or C1-C10 alkoxy C1-C10 alkyl; X1 to X4 are independently halogen or C1-C10 alkyl; and the cyclopentadienyl and indenyl may be further substituted with one or more substituents selected from hydrogen and C1-C10 alkyl.

[0093] Formula 1 according to one embodiment of the present invention can be represented by the following Formula 2.

[0094] [Chemical Formula 2]

[0095]

[0096] (In the above chemical formula 2,

[0097] M1 and M2 are independently titanium, hafnium, or zirconium;

[0098] R1 to R8 are independently hydrogen, C1-C30 alkyl, C1-C30 alkoxy, C2-C30 alkenyl, C6-C30 aryl, C6-C30 aryloxy, C1-C30 alkyl, C6-C30 aryl, C6-C30 aryl, C1-C30 alkyl, mono-C1-C30 alkylamino, di-C1-C30 alkylamino, tri-C1-C30 alkylamino, mono-C6-C arylamino, di-C6-C30 arylamino, or tri-C6-C30 arylamino;

[0099] R 11 to R 18 are independently hydrogen, C1-C30 alkyl, C1-C30 alkoxy, or C2-C30 alkenyl;

[0100] R a and R b are independently C1-C30 alkyl, C6-C30 aryloxy C1-C30 alkyl, or C1-C30 alkoxy C1-C30 alkyl;

[0101] X1 to X4 are independently halogen, C1-C30 alkyl, C2-C30 alkenyl, arylalkyl, triC1-C30 alkylsilyl, or triC6-C30 arylsilyl;

[0102] n is an integer from 1 to 20.

[0103] Preferably, in Formula 2 according to one embodiment of the present invention, M1 and M2 are zirconium; R1 to R8 and R 11 to R 18 are independently hydrogen or C1-C30 alkyl; R a and R b are independently C1-C30 alkyls; X1 to X4 are independently C1-C30 alkyls; n may be an integer from 1 to 15, more preferably M1 and M2 are zirconium; R1 to R2 and R5 to R6 are independently C1-C10 alkyls; R3 to R4, R7 to R8 are and R 11 to R 18 are independently hydrogen or C1-C10 alkyl; R a and R b are independently C1-C7 alkyls; X1 to X4 are independently C1-C7 alkyls; n may be an integer from 1 to 10, more preferably M1 and M2 are zirconium; R1 to R2 and R5 to R6 are independently C1-C7 alkyls; R3 to R4, R7 to R8 are and R 11 to R 18 are independently hydrogen or C1-C7 alkyl; R a and R b are independently C1-C5 alkyls; X1 to X4 are independently C1-C7 alkyls; and n can be an integer from 1 to 10.

[0104] A novel dinuclear metallocene compound represented by Formula 1 according to one embodiment of the present invention can be prepared without limitation by conventional organic synthesis methods well known in the art, and, for example, can be prepared as shown in Reaction Scheme 1 below.

[0105] [Reaction Equation 1]

[0106]

[0107] (In Equation 1, M is a Group 4, Group 5, or Group 6 transition metal, and

[0108] R1 to R4, R 11 to R 14 , R a , R b and X1 to X4 are identical to the definitions in claims 1 and 2.)

[0109] Starting material R in Reaction Scheme 1 according to one embodiment of the present invention a SiCl2-(CH2) n -(R b )SiCl2 is R of various structures a SiCl2-CH=CH2, R a SiCl2-CH=CH2, R a SiCl2-CH2CH=CH2, or CH2=CH-(CH2) n-4 R with various structures in -CH=CH2 a It can be prepared by reacting Si(H)Cl2 under a platinum catalyst. The reaction carried out under the platinum catalyst is commonly known as a hydrosililation reaction and is a mature synthesis technique. R a Since this methyl phosphide reactive material (i.e., MeSiCl2-CH=CH2, MeSiCl2-CH2CH=CH2, MeSi(H)Cl2) is readily available on the market, R a It is easy to prepare the dinuclear metallocene compound of Chemical Formula 1 above, which is this methyl.

[0110] R a SiCl2-(CH2) n -(R b By reacting cyclochloropentadienyl, indenyl, and fluorenyl lithium compounds having various substituents with )SiCl2, in the above reaction scheme 1 2 Compounds represented by can be prepared. Tetramethylcyclopentadienyl lithium (i.e., R 11 to R 14Since compounds (methyl ga) are widely used in the preparation of metallocene or half-metallocene catalysts, they are readily available, and because they possess symmetry, they do not induce stereoisomer formation in the final compound of Formula 1, R 11 to R 14 It is easy to prepare a dinuclear metallocene compound of the above chemical formula 1 in which methyl is present.

[0111] of Reaction Scheme 1 below 2 Cyclopentadienyl lithium having a thiophene ring with various substituents fused to a compound represented by 3 By reacting a compound represented by 4 Compounds represented by can be prepared. The cyclopentadienyl lithium compound with a fused thiophene ring is 5 By reacting NaBH4 with a cyclopentane compound in which a thiophene ring represented by is fused, and treating with acid 6 A cyclopentine compound with a fused thiophene ring represented by can be prepared and reacted with n-BuLi. 5 From the compound represented by 3 The method of manufacturing compounds represented by is a mature synthesis technique. 5 The compound represented by can be prepared in a single step by reacting a thiophene compound having various substituents (i.e., R3 and R4) at the 2,3-position with an acrylic acid having various substituents (i.e., R5 and R6) at the 2,3-position. Chemical formula in which R3 and R4 are hydrogen or methyl, and R5 and R6 are methyl. 5 Synthesis of the compound represented by [formula] is advantageous in terms of raw material supply and yield, so it is easy to manufacture the dinuclear metallocene compound of the above chemical formula 1, in which R3 and R4 are hydrogen or methyl and R5 and R6 are methyl.

[0112] 4A compound represented by Formula 1, which is the object of the present invention, can be prepared by attaching a Group 4 transition metal (i.e., Ti, Zr, Hf) to a compound represented by [formula]. The methods and conditions for attaching the Group 4 metal are already developed and known mature techniques. Typically, 4 A compound represented by [formula] can be treated with an equivalent amount of n-BuLi and subsequently reacted with MCl4 to prepare a compound of Formula 1 in which X1 and X2 are Cl, which can be used for the preparation of a supported catalyst. Additionally, a compound of Formula 1 in which X1 and X2 are Cl can be reacted with MeLi or MeMgCl to prepare a compound of Formula 1 in which X1 and X2 are methyl, which can be used for the preparation of a supported catalyst. Since the compound in which X1 and X2 are methyl is soluble in hexane, it can be easily separated and purified from other by-products and by-products through a hexane extraction process after the reaction. 4 Most by-products and by-products generated during the process of attaching a metal to the compound represented by are insoluble in hexane. On the other hand, the compound represented by Chemical Formula 1, in which X1 and X2 are Cl, and the mononuclear compound in which X1 and X2 are methyl have low solubility in hexane and cannot be separated and purified through simple processes such as hexane extraction. Furthermore, regarding the compound of Chemical Formula 1 in which X1 and X2 are methyl, along with the ease of separation and purification, 4 A compound represented by can be easily produced in a single step with high yield by successively introducing equivalent amounts of n-BuLi, MeMgCl, and MCl4 into a reactor.

[0113] Compounds where M is Zr are desirable because they exhibit high activity in olefin polymerization compared to compounds where M is Ti and Hf.

[0114] It is desirable that a supported catalyst is prepared using a compound in which n is 1 to 10, preferably n is 2 to 8, and exhibits high activity.

[0115] The dinuclear metallocene compound represented by Chemical Formula 1, prepared by the method described above, has a novel structure and consists of two mononuclear metallocene compounds, each containing a cyclopentadienyl or derivative backbone and a transition metal serving as an active site, connected at regular intervals around a silicon linker. The silicon linker between the mononuclear metallocene compounds reduces unnecessary interactions between metals while maintaining the stable characteristics of a dinuclear metallocene, making it easy to modify the ligand structure and providing good accessibility to alpha-olefins. Consequently, when supported on a carrier, it exhibits superior activity and allows for easy particle control, making it highly useful for polymerizing polyolefins.

[0116] In addition, the present invention provides a supported dinuclear metallocene catalyst in which a novel dinuclear metallocene compound of the present invention is supported on a support.

[0117] The supported dinuclear metallocene catalyst of the present invention is,

[0118] Aluminum compound-carrier complex and

[0119] The dinuclear metallocene compound represented by the above chemical formula 1 is characterized by being supported on the above aluminum compound-supported complex.

[0120] The supported dinuclear metallocene catalyst of the present invention has two transition metals and, by using the novel dinuclear metallocene compound of the present invention which introduces a specific functional group, cyclopentathiophenyl, it exhibits higher catalytic activity compared to conventional supported catalysts, and allows for easier control of particle shape and size, thereby enabling the production of more uniform polyolefins during polyolefin polymerization.

[0121] A supported dinuclear metallocene catalyst supported with a dinuclear metallocene compound according to one embodiment of the present invention exhibits high activity compared to conventional supported catalysts prepared using mononuclear metallocene compounds and is advantageous for application in production processes by suppressing the formation of large particles in polymerization reactions.

[0122] In other words, preparing a supported catalyst using a dinuclear metallocene compound allows a larger amount of the metallocene compound to be attached to the support compared to preparing it using a mononuclear metallocene compound, which is advantageous for achieving high activity.

[0123] In other words, when preparing a supported catalyst using a mononuclear metallocene compound, there is a limit of 90 μmol-Metal / g-(aluminum compound-support complex) for the amount of metallocene that can be attached to the aluminum compound-support complex; if more than this amount is added and reacted, attachment does not occur and the metallocene is eluted, and the activity does not increase. On the other hand, when preparing a supported catalyst using a dinuclear metallocene compound represented by Chemical Formula 1 of the present invention, up to 150 μmol-Metal / g-(silica-aluminoxane complex) all the added metallocene compounds are attached to the support without any eluting. Furthermore, even in the case of a supported catalyst composed of silica, methylaluminoxane, and a metallocene compound of the same composition (e.g., 90 μmol-Metal / g-(silica-aluminoxane complex)), the one prepared using the dinuclear metallocene catalyst has the advantage of showing higher activity compared to the supported catalyst prepared using a mononuclear metallocene.

[0124] An aluminum compound-carrier composite according to one embodiment of the present invention may be formed by an aluminum compound on one or more carriers selected from silica, alumina, magnesium chloride, calcium chloride, bauxite, zeolite, magnesium oxide, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide, and thorium oxide.

[0125] An aluminum compound according to one embodiment of the present invention may be one or more aluminum compounds selected from organic aluminum compounds represented by the following Chemical Formula 11 or the following Chemical Formula 12. [Chemical Formula 11]

[0126] -[Al(R 21 )-O] c -

[0127] [Chemical Formula 12]

[0128] D(R 22 )3

[0129] (In the above chemical formulas 11 and 12,

[0130] R 21 is a halogen, a C1-C30 hydrocarbyl, or a C1-C20 hydrocarbyl substituted with a halogen, and c is an integer greater than or equal to 2, and

[0131] D is aluminum or boron, and R 22 is a C1-C20 hydrocarbyl or a halogen-substituted C1-C20 hydrocarbyl.

[0132] Specific examples of the compound of Formula 11 of the present invention include methylaluminoxane (methylaluminoxane), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, and decylaluminoxane, and preferably methylaluminoxane. Specific examples of the compound of Formula 12 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, and trioctylaluminum. There are ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, and tributylboron, as well as dimethylaluminum methoxide, diethylaluminum methoxide, dibutylaluminum methoxide, methylaluminum dimethoxide, ethylaluminum dimethoxide, butylaluminum dimethoxide, dimethylaluminum chloride, and diethylaluminum chloride, Examples include dibutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, and butylaluminum dichloride.Preferably, trimethylaluminum, triethylaluminum, or triisobutylaluminum may be used.

[0133] The ratio of the metal of the dinuclear metallocene catalyst according to one embodiment of the present invention to the aluminum of the aluminum compound-support composite (Zr:Al ratio) may be 1:20 to 70, preferably 1:30 to 50, and more preferably 1:35 to 45.

[0134] In addition, the present invention provides a method for manufacturing a supported dinuclear metallocene catalyst of the present invention, wherein the method for manufacturing a supported dinuclear metallocene catalyst of the present invention comprises:

[0135] A step of preparing an aluminum compound-carrier composite by reacting an aluminum compound and a carrier; and

[0136] The method includes the step of preparing a supported dinuclear metallocene catalyst by reacting the above aluminum compound-carrier complex with the dinuclear metallocene compound represented by the above chemical formula 1.

[0137] The supported dinuclear metallocene catalyst of the present invention exhibits excellent catalytic activity by supporting a novel dinuclear metallocene compound of the present invention, into which two transition metals and a specific functional group, cyclopentathiophenyl, are introduced, thereby allowing a large amount of the dinuclear metallocene compound to be easily supported.

[0138] An aluminum compound-carrier composite according to one embodiment of the present invention may be prepared in a hydrocarbon solvent, but preferably in a toluene solvent at 30 to 130 o It can be manufactured by reacting at C for about 30 minutes to 5 hours, but is not limited thereto.

[0139] An aluminum compound according to one embodiment of the present invention may be used in an amount of 30 to 60 parts by weight per 100 parts by weight of a carrier, preferably in an amount of 40 to 50 parts by weight.

[0140] When an aluminum compound-support composite is prepared with the above-mentioned content, the supported catalyst activity can be maximized, and most of the added aluminum compound is attached to the silica surface, making the manufacturing process easier and advantageous for ensuring economic feasibility.

[0141] Preferably, if the aluminum compound is added in an amount of 0.4 parts by weight or less, the activity is low, and if it is added in an amount of 0.5 parts by weight or more, a significant amount of the added aluminum compound does not adhere to the silica surface, and the amount that adheres is smaller than when added in an amount of 0.4 to 0.5 parts by weight, which may cause problems in achieving high activity. Various forms of carriers may be used, but are not limited thereto.

[0142] The step of preparing a supported dinuclear metallocene catalyst by supporting a dinuclear metallocene compound of Formula 1 according to one embodiment of the present invention on an aluminum compound-support composite of the present invention may also utilize various types of hydrocarbon solvents, but it is preferable to use toluene solvent. Although there are no particular limitations on the reaction temperature and time, 20 to 130 o A supported catalyst can be prepared by reacting at C for about 30 minutes to 5 hours.

[0143] According to one embodiment of the present invention, the aluminum compound represented by the following chemical formula 1, a dinuclear metallocene compound, can be used as 110 to 140 μmol-Metal / g-(aluminum compound-carrier complex) with respect to the aluminum compound-carrier complex.

[0144] In one embodiment of the present invention, a dinuclear metallocene compound represented by Formula 1 can be added to an aluminum compound-carrier complex at a ratio of 110 to 140 μmol-Metal / g-(aluminum compound-carrier complex) to maximize activity (the number of g of polymer produced by adding unit g of supported catalyst). To prevent adverse effects such as reduced reaction or lowered activity caused by the added dinuclear metallocene compound adhering to the surface of the aluminum compound-carrier complex, the dinuclear metallocene compound can preferably be used at a ratio of 125 to 135 μmol-Metal / g-(aluminum compound-carrier complex).

[0145] The activity of the supported catalyst may vary depending on the value of n in Chemical Formula 2 used in the preparation of the supported catalyst, and in Chemical Formula 2 of one embodiment of the present invention, excellent activity may be achieved when the value of n is 1 to 20, preferably 1 to 15, and more preferably 1 to 10.

[0146] In addition, the present invention provides a method for producing polyolefin comprising the step of polymerizing one or more olefin monomers in the presence of the supported dinuclear metallocene catalyst of the present invention.

[0147] A method for manufacturing polyolefin according to one embodiment of the present invention can produce polyolefin by introducing the supported dinuclear metallocene catalyst of the present invention into an existing commercial gas-phase process or slurry process as is or with some modification, or by developing a new process and introducing it. In the gas-phase process, the polymerization reaction can be carried out by contacting only the supported dinuclear metallocene catalyst and the olefin monomer without introducing a solvent, and the reaction temperature and pressure are operated according to conventional gas-phase process conditions. In the slurry process, the reaction can be carried out under a hydrocarbon solvent, but typically, aliphatic hydrocarbon solvents such as hexane and isobutane are mainly used, and the reaction temperature and pressure are operated according to conventional slurry process conditions.

[0148] An olefin monomer according to one embodiment of the present invention may be one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, and mixtures thereof.

[0150] Examples and comparative examples of the present invention are described below. However, the following examples are merely preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[0151] <Reagents and Experimental Conditions>

[0152] All experiments were performed in an inert atmosphere using a standard glove box and Schlenk technology. THF, hexane, and toluene were distilled from benzophenone ketyl. 1,5-hexadiene, 1,7-octadiene, and 1,9-decadiene were purchased from TCI and purified into Na / K alloys. Dichloromethylsilane, dichlorodimethylsilane, allyl(dichloro)methylsilane, dichloromethylvinylsilane, thiophene, n-BuLi (2.5 M hexane solution), methyl magnesium bromide (3.0 M diethyl ether solution), and zirconium chloride (IV) were purchased from Sigma Aldrich Korea, 1,2,3,4-tetramethyl-1,3-cyclopentadiene, 2-methylthiophene, and 2,3-dimethylthiophene were purchased from Alpha-A, and tiglic acid was purchased from TCI and used without purification. The hexane (anhydrous grade) used in the polymerization reaction was purchased from Fisher Scientific Korea and purified into a Na / K alloy. 1 1H NMR (600 MHz) and 13 13C NMR (150 MHz) analysis was performed on a JEOL ECZ 600 instrument.

[0154] [Example 1] Chemical formula 1-1 (n = 6; R 3 = HR 4 = Me;) manufacturing

[0155] [Chemical Formula 1-1]

[0156]

[0157] Preparation of MeSiCl2-(CH2)6-(Me)SiCl2

[0158] After quantitatively adding 1,5-hexadiene (3.00 g, 36.5 mmol), dichloromethylsilane (12.6 g, 110 mmol), 1 drop of Karlsted catalyst solution, and toluene (20 mL) to a Schlenk flask inside a glove box, 40-45 o The reaction was allowed overnight under reflux at C. 50-60 o Remove reactants, solvent, and byproducts using a vacuum line at C, and 100-110 o A clear liquid compound was obtained by vacuum distillation at C (5.23 g, 46%).

[0159] Compound 2(n = 6; R 11 inside R 14 = Me) manufacturing

[0160] TMCP (1,2,3,4-tetramethyl-1,3-cyclopentadiene) was prepared as the TMCP-Li salt by lithiating with n-BuLi (1 equivalent) in hexane (0.3 M) and then filtering. THF was -30 o The mixture was pre-cooled in a refrigerator at C before use. In a glove box, TMCP-Li salt (0.500 g, 3.90 mmol) and THF (3.8 mL) were weighed and added to a vial, followed by the addition of MeSiCl2-(CH2)6-(Me)SiCl2 (0.609 g, 1.95 mmol) and THF (2.0 mL) under stirring. The reaction was carried out overnight while raising the temperature to room temperature. After removing the solvent using a vacuum line, the byproduct lithium chloride was removed through filtration using Celite while washing several times with hexane. A white solid compound was obtained by removing the solvent using a vacuum line (0.837 g, 89%).

[0161] Preparation of Compound 3 (R1, R2, R4 = Me; R3 = H)

[0162] In Reaction Scheme 1, referring to the method disclosed in J. Organomet. Chem., 2011, 696, 2451-2456 5 A compound represented by was synthesized. In a two-necked round-bottom flask inside a glove box 5 After quantitatively adding the compound represented by (16.1 g, 89.3 mmol), THF (80 mL), and methanol (40 mL), 0 o The temperature was lowered to C, and sodium borohydride (4.70 g, 124 mmol) was added. The temperature was maintained at 0 for 1 hour. o After maintaining the temperature at C, the temperature was raised to room temperature and the reaction was carried out overnight. Cold water (160 mL) was added to terminate the reaction, and the solution was transferred to a separatory funnel to extract the organic layer, while the aqueous layer was extracted with diethyl ether (2 × 50 mL). The extracts were collected, water was removed with anhydrous magnesium sulfate, and filtered; the filtrate was then taken and the solvent removed. To the obtained compound (15.9 g, 87.5 mmol): p - After adding toluenesulfonic acid (82.7 mg, 0.480 mmol) and toluene (250 mL), the reaction was carried out under reflux for 15 minutes. 0 o After lowering the temperature by immersion in a C low-temperature bath, the solution was passed through a short silica gel column, and the column was additionally washed with hexane to remove the solvent from the filtrate. 6 A compound represented by was obtained (12.6 g, 88%). In a 1-neck round-bottom flask inside a glove box 6 After quantitatively adding the compound represented by (12.6 g, 76.8 mmol) and hexane (250 mL), -78 o The temperature was lowered to C, and n-BuLi (21.5 g, 2.48 M, 76.8 mmol) was slowly added. The reaction was allowed to proceed overnight while raising the temperature to room temperature. The white solid compound was filtered while washing several times with hexane. 311.8 g, 90% was obtained.

[0163] Compound 4(n = 6; R a , R b , R 11 -R 14 , R1, R 2, Manufacture of R4= Me; R3= H)

[0164] THF is -30 o It was used after being pre-chilled in refrigerator C. The product prepared by the above method in a vial inside a glove box 2 Compound represented by (0.350 g, 0.724 mmol), 3 Compound represented by (0.246 g, 1.45 mmol), copper cyanide (0.600 mg, 7.24 μmol), and THF (6.9 mL) were quantitatively added, and the reaction was carried out overnight while raising the temperature to room temperature. After removing the solvent using a vacuum line, the byproduct lithium chloride was removed through a filtration process using Celite while washing several times with hexane. By removing the solvent through a vacuum line, a viscous, dark brown compound 4 was obtained (0.459 g, 86%).

[0165] Chemical formula 1-1(n = 6; R3= H, R4 = Me) manufacturing

[0166] The above-prepared in a single-neck round flask inside a glove box 4 After adding the compound represented by (0.284 g, 0.385 mmol) and THF (2.0 mL), -30 o The temperature was lowered to C, and n-BuLi (98.6 mg, 1.54 mmol) and hexane (0.62 mL) were slowly added under stirring. The reaction was carried out for 1 hour while raising the temperature to room temperature. Afterwards, again -30 oThe temperature was lowered to C, and methyl magnesium bromide solution (0.510 g, 3.28 M, 1.62 mmol), zirconium chloride (IV) (0.284 g, 0.754 mmol), and THF (2.0 mL) were added. The reaction was allowed to proceed overnight while raising the temperature to room temperature. After removing the solvent using a vacuum line, 60-70 o By-products and by-products were removed through a filtration process using Celite while washing several times with hexane heated to C. The solvent was removed using a vacuum line to obtain a light brown solid compound (0.317 g, 86%).

[0167] 1 H NMR (C6D6): δ 6.50-6.48 (m, 2H), 2.28-2.25 (m, 6H, CH3), 2.23-2.20 (m, 6H, CH3), 2.03-1.99 (m, 12H, CH3), 1.97, 1.96, 1.95 (s, 6H, CH3), 1.83-1.78 (m, 12H, CH3), 1.75-1.13 (m, 12H, CH2), 0.85, 0.83, 0.70 and 0.68 (s, 6H, SiCH3), -0.29 - -0.32 (m, 6H, ZrCH3), -0.83 - -0.86 (m, 6H, ZrCH3) ppm.

[0168] 13 C{ 1H} NMR (C6D6): δ 144.29, 144.24, 141.69, 141.63, 127.61, 127.51, 127.40, 127.33, 126.63, 126.07, 124.91, 124.31, 123.29, 122.78, 122.69, 117.94, 116.55, 116.46, 87.79, 87.72, 87.66, 78.44, 78.38, 78.27, 36.64, 36.57, 35.64, 35.61, 35.57, 33.65, 33.43, 33.35, 23.52, 23.41, 17.46, 17.18, 16.27, 15.41, 15.38, 15.33, 15.22, 14.79, 14.75, 12.40, 12.01, -0.78, -0.89, -0.91 ppm.

[0170] [Example 2] Chemical formula 1-1 (n = 8; R 3 = H; R 4 = Me) manufacturing

[0171] It was prepared using the same method as in [Example 1], except that 1,7-octadiene was used instead of 1,5-hexadiene, and the yield in the final step, the metallization reaction, was 72%.

[0172] 1 H NMR (C6D6): δ 6.50-6.48 (m, 2H), 2.26 (s, 6H, CH3), 2.23-2.20 (m, 6H, CH3), 2.05-1.99 (m, 12H, CH3), 1.97 and 1.96 (s, 6H, CH3), 1.86-1.82 (m, 6H, CH3), 1.80 and 1.79 (s, 6H, CH3), 1.73-1.12 (m, 16H, CH2), 0.85, 0.84, 0.70 and 0.69 (s, 6H, SiCH3), -0.31 (s, 6H, ZrCH3), -0.85 (s, 6H, ZrCH3) ppm.

[0173] 13 C{ 1H} NMR (C6D6): δ144.24, 144.21, 141.58, 141.56, 141.47, 127.53, 127.49, 127.42, 127.38, 127.33, 127.30, 126.56, 126.05, 126.01, 124.89, 124.26, 124.23, 123.26, 122.68, 122.63, 117.95, 117.90, 117.85, 116.54, 116.49, 116.46, 87.68, 87.64, 87.54, 87.49, 78.29, 78.22, 78.15, 78.09, 36.69, 36.65, 36.61, 35.66, 35.62, 35.60, 35.55, 34.16, 33.96, 33.94, 29.85, 29.80, 29.70, 23.60, 23.58, 23.49, 23.46, 17.54, 17.49, 17.21, 17.18, 16.36, 16.34, 15.41, 15.39, 15.35, 15.25, 14.76, 12.45, 12.07, -0.77, -0.86 ppm.

[0175] [Example 3] Chemical formula 1-1 (n = 10; R 3 = H; R 4 = Me) manufacturing

[0176] It was prepared using the same method as in [Example 1], except that 1,9-decadien was used instead of 1,5-hexadiene, and the yield in the final step, the metallization reaction, was 90%.

[0177] 1H NMR (C6D6): δ 6.50-6.48 (m, 2H), 2.26, 2.22 and 2.21 (s, 12H, CH3), 2.04 and 2.03 (s, 3H, CH3), 2.01 and 2.00 (s, 9H, CH3), 1.96 and 1.95 (s, 6H, CH3), 1.84 and 1.83 (s, 6H, CH3), 1.79 (s, 6H, CH3), 1.74-1.13 (m, 16H, CH2), 0.85, 0.84, 0.70 and 0.69 (s, 6H, SiCH3), -0.31 (s, 6H, ZrCH3), -0.86 (s, 6H, ZrCH3) ppm.

[0178] 13 C{ 1 H} NMR (C6D6): δ144.24, 141.58, 141.49, 127.61, 127.57, 127.51, 127.42, 127.40, 127.33, 126.58, 126.05, 124.91, 124.28, 124.25, 123.28, 122.68, 122.65, 117.97, 117.94, 117.91, 117.89, 116.50, 116.46, 87.70, 87.66, 87.55, 87.52, 78.30, 78.26, 78.16, 78.13, 36.63, 36.59, 35.61, 35.59, 35.54, 35.51, 34.16, 34.13, 33.96, 30.10, 30.04, 30.02, 29.96, 29.92, 29.86, 23.61, 23.54, 17.52, 17.18, 16.34, 16.31, 15.41, 15.38, 15.34, 15.24, 14.74, 14.72, 12.44, 12.06, -0.79, -0.87 ppm.

[0180] [Example 4] Chemical formula 1-1(n = 2; R 3 = H; R 4 = Me) manufacturing

[0181] It was prepared using the same method as in [Example 1], except that dichloromethylvinylsilane was used instead of 1,5-hexadiene and 1.5 equivalents of dichloromethylsilane were used instead of 3 equivalents, and the yield in the final step, the metallization reaction, was 49%.

[0182] 1 H NMR (C6D6): δ 6.51-6.47 (m, 2H), 2.28-1.80 (m, 42H, CH3), 1.68-1.28 (m, 4H, CH2), 1.11, 1.09, 0.93, 0.92, 0.79 and 0.78 (s, 6H, SiCH3), -0.29 (s, 6H, ZrCH3), -0.82 and -0.83 (s, 6H, ZrCH3) ppm.

[0183] 13 C{ 1 H} NMR (C6D6): δ144.34, 144.31, 144.29, 141.65, 141.60, 127.57, 127.45, 127.35, 126.69, 126.64, 125.81, 125.11, 124.98, 124.12, 123.36, 122.63, 122.53, 122.51, 118.10, 118.02, 118.00, 116.54, 116.49, 116.46, 87.46, 87.34, 87.22, 78.36, 78.25, 78.14, 77.90, 77.82, 36.81, 36.72, 35.78, 35.70, 35.65, 16.32, 15.60, 15.52, 15.36, 15.28, 14.94, 14.86, 14.80, 12.44, 12.08, 9.32, 9.30, 9.01, 8.85, -1.02, -1.05, -1.12, -1.19, -1.25 ppm.

[0185] [Example 5] Chemical formula 1-1(n = 3; R 3 = H; R 4 = Me) manufacturing

[0186] It was prepared using the same method as in [Example 4], except that allyl(dichloro)methylsilane was used instead of dichloromethylvinylsilane, and the yield in the final step, the metallization reaction, was 81%.

[0187] 1 H NMR (C6D6): δ 6.50-6.47 (m, 2H), 2.27-2.19 (m, 12H, CH3), 2.10-1.86 (m, 24H, CH3), 1.79-1.76 (m, 6H, CH3), 1.74-1.33 (m, 6H, CH2), 0.88, 0.86, 0.72 and 0.70 (s, 6H, SiCH3), -0.28--0.32 (m, 6H, ZrCH3), -0.84 and -0.85 (s, 6H, ZrCH3) ppm.

[0188] 13 C{ 1H} NMR (C6D6): δ144.32, 144.25, 144.23, 144.20, 144.14, 141.60, 141.56, 141.53, 127.51, 127.44, 127.38, 126.57, 126.09, 126.06, 125.94, 125.90, 124.97, 124.94, 124.88, 124.29, 124.18, 124.12, 123.32, 123.27, 122.69, 122.63, 122.51, 122.48, 118.05, 117.98, 117.93, 117.84, 116.56, 116.46, 87.42, 87.35, 87.32, 87.30, 87.25, 87.20, 87.18, 78.05, 77.90, 77.87, 77.81, 36.77, 36.76, 36.67, 35.73, 35.68, 35.66, 35.58, 22.25, 22.19, 22.15, 21.72, 21.68, 17.66, 17.63, 17.58, 16.39, 16.36, 16.33, 15.65, 15.58, 15.55, 15.52, 15.49, 15.33, 15.25, 14.93, 14.90, 14.84, 14.74, 12.45, 12.07, -0.65, -0.70, -0.73, -0.77, -0.81 ppm.

[0190] [Example 6] Formula 1-1 (n = 6; R 3 = H; R 4 = H) Manufacturing

[0191] It was prepared using the same method as in [Example 1], except that thiophene was used instead of 2-methylthiophene, and the yield in the final step, the metallization reaction, was 89%.

[0192] 1H NMR (C6D6): δ 6.90-6.85 (m, 2H), 6.80-6.75 (m, 2H), 2.26-2.22 (m, 6H, CH3), 2.02-1.91 (m, 18H, CH3), 1.83-1.77 (m, 12H, CH3), 1.73-1.13 (m, 12H, CH2), 0.84, 0.83, 0.69 and 0.68 (s, 6H, SiCH3), -0.31 and -0.32 (s, 6H, ZrCH3), -0.94 and -0.95 (s, 6H, ZrCH3) ppm.

[0193] 13 C{ 1 H} NMR (C6D6): δ 140.99, 140.96, 140.90, 140.86, 129.63, 129.33, 129.09, 129.06, 129.02, 128.56, 128.50, 128.45, 128.35, 127.56, 127.51, 127.46, 127.41, 127.34, 126.85, 126.77, 125.69, 125.08, 124.50, 124.44, 123.46, 122.92, 122.83, 118.86, 118.78, 118.36, 118.31, 118.26, 87.90, 87.83, 87.77, 87.69, 78.16, 78.08, 78.03, 77.98, 37.71, 37.69, 37.65, 35.81, 35.77, 35.75, 35.69, 33.58, 33.51, 33.42, 33.39, 23.49, 23.46, 17.50, 17.12, 15.49, 15.42, 15.32, 15.28, 14.81, 14.77, 12.32, 12.00, -0.77, -0.92 ppm.

[0195] [Example 7] Chemical formula 1-1 (n = 6; R 3 = Me; R 4 = Me) manufacturing

[0196] It was prepared using the same method as in [Example 1], except that 2,3-dimethylthiophene was used instead of 2-methylthiophene, and the yield in the final step, the metallization reaction, was 80%.

[0197] 1 H NMR (C6D6): δ 2.39-2.31 (m, 6H, CH3), 2.18-2.08 (m, 12H, CH3), 2.05-1.95 (m, 18H, CH3), 1.85-1.73 (m, 12H, CH3), 1.72-1.12 (m, 12H, CH2), 0.87, 0.84, 0.71 and 0.68 (s, 6H, SiCH3), -0.29, -0.30 and -0.31 (s, 6H, ZrCH3), -0.88 and -0.89 (s, 6H, ZrCH3) ppm.

[0198] 13 C{ 1 H} NMR (C6D6): δ 141.45, 141.42, 141.36, 141.33, 136.09, 136.04, 136.01, 127.51, 127.45, 127.42, 127.40, 127.33, 124.96, 124.85, 124.81, 124.42, 124.32, 124.23, 123.10, 122.69, 122.65, 122.58, 122.55, 118.44, 118.41, 118.38, 87.62, 87.53, 87.46, 87.43, 87.39, 77.76, 77.74, 77.69, 77.62, 36.04, 35.97, 35.70, 35.66, 35.59, 33.69, 33.41, 33.24, 23.60, 23.51, 23.27, 17.39, 17.33, 17.31, 16.98, 15.60, 15.58, 15.56, 15.45, 15.32, 15.26, 15.11, 14.74, 14.70, 13.67, 13.64, 12.80, 12.18, 12.11, 12.08, -0.69, -0.78, -0.98, -1.04 ppm.

[0200] [Comparative Example 1] Mononuclear compound Chemical formula 2 (R 3 = H; R 4 = Me) manufacturing

[0201] [Chemical Formula 2]

[0202]

[0203] TMCp-Li salt and 3 The compound represented by was prepared using the same method as the preparation method of [Example 1]. THF is -30 o It was used after being pre-chilled in C's refrigerator.

[0204] TMCp-Li salt (1.00 g, 7.80 mmol) and THF (7.5 mL) were weighed and added to a 1-neck round-bottom flask inside a glove box, and then dichlorodimethylsilane (1.51 g, 11.7 mmol) and THF (5.0 mL) were added under stirring. The reaction was carried out overnight while raising the temperature to room temperature. After removing the solvent using a vacuum line, the byproduct lithium chloride was removed by filtration with Celite while washing several times with hexane. A viscous compound was obtained by removing the solvent using a vacuum line (1.53 g, 91%).

[0205] The obtained viscous compound (0.400 g, 1.86 mmol) in a 1-neck round-bottom flask, 3 Compound represented by (0.317 g, 1.86 mmol), copper cyanide (1.70 mg, 18.6 μmol), and THF (8.5 mL) were quantitatively added, and the reaction was carried out overnight while raising the temperature to room temperature. After removing the solvent using a vacuum line, the byproduct lithium chloride was removed by filtration with Celite while washing several times with hexane. A viscous, dark brown compound was obtained by removing the solvent using a vacuum line (0.610 g, 96%).

[0206] After adding the above-obtained viscous dark brown compound (0.200 g, 0.584 mmol) and THF (2.0 mL) to a vial, -30 o The temperature was lowered to C, and n-BuLi (74.8 mg, 1.17 mmol) and hexane (0.47 mL) were slowly added under stirring. The reaction was carried out for 1 hour while raising the temperature to room temperature. Afterwards, again -30 o The temperature was lowered to C, and methyl magnesium bromide solution (0.408 g, 3.11 M, 1.23 mmol), zirconium chloride (IV) (0.216 g, 0.572 mmol), and THF (2.0 mL) were added. The reaction was carried out overnight while raising the temperature to room temperature. After removing the solvent using a vacuum line, by-products and by-products were removed by Celite filtration while washing several times with toluene. After removing the solvent using a vacuum line, the mixture was triturated under hexane and filtered to obtain a light brown solid compound (0.151 g, 57%).

[0207] 1 H NMR (C6D6): δ 6.49 (s, 1H), 2.26 (s, 3H, CH3), 2.21 (s, 3H, CH3), 2.00 (s, 3H, CH3), 1.98 (s, 3H, CH3), 1.95 (s, 3H, CH3), 1.76 (s, 6H, CH3), 0.73 (s, 3H, SiCH3), 0.57 (s, 3H, SiCH3), -0.31 (s, 3H, ZrCH3), -0.85 (s, 3H, ZrCH3) ppm.

[0208] 13 C{ 1 H} NMR (C6D6): δ 144.24, 141.59, 127.28, 126.34, 124.48, 122.86, 117.85, 116.43, 88.10, 78.65, 36.48, 35.45, 16.24, 15.29, 15.15, 14.66, 12.33, 11.94, 1.95, 1.67 ppm.

[0210] [Comparative Example 2] Mononuclear compound Chemical Formula 2 (R 3 = H;R 4 = H) manufacturing

[0211] It was prepared using the same method as [Comparative Example 1], except that thiophene was used instead of 2-methylthiophene, and the yield in the final step, the metallization reaction, was 89%.

[0212] 1 ¹H NMR (C6D6): δ 6.87 (d, J = 4.8 Hz, 1H), 6.76 (d, J = 4.8 Hz, 1H), 2.23 (s, 3H, CH3), 1.98 (s, 3H, CH3), 1.92 (s, 3H, CH3), 1.91 (s, 3H, CH3), 1.75 (s, 6H, CH3), 0.72 (s, 3H, SiCH3), 0.56 (s, 3H, SiCH3), -0.33 (s, 3H, ZrCH3), -0.95 (s, 3H, ZrCH3) ppm.

[0213] 13 C{ 1 H} NMR (C6D6): δ 140.83, 129.18, 129.01, 127.31, 127.01, 124.62, 123.01, 118.72, 118.18, 88.11, 78.36, 37.54, 35.64, 15.23, 14.67, 12.25, 11.93, 11.91, 1.96, 1.64 ppm.

[0215] [Comparative Example 3] Mononuclear compound Chemical Formula 2 (R 3 = Me;R 4 = Me) manufacturing

[0216] It was prepared using the same method as [Comparative Example 1], except that 2,3-dimethylthiophene was used instead of 2-methylthiophene, and the yield in the final step, the metallization reaction, was 85%.

[0217] 1H NMR (C6D6): δ 2.33 (s, 3H, CH3), 2.11 (s, 3H, CH3), 2.09 (s, 3H, CH3), 2.00 (s, 3H, CH3), 1.99 (s, 3H, CH3), 1.96 (s, 3H, CH3), 1.77 (s, 3H, CH3), 1.75 (s, 3H, CH3), 0.75 (s, 3H, SiCH3), 0.58 (s, 3H, SiCH3), -0.30 (s, 3H, ZrCH3), -0.90 (s, 3H, ZrCH3) ppm.

[0218] 13 C{ 1 H} NMR (C6D6): δ 141.44, 136.15, 127.38, 124.83, 124.68, 124.62, 122.73, 118.39, 88.03, 78.11, 35.88, 35.57, 15.41, 15.00, 14.63, 13.57, 12.71, 12.06, 11.96, 2.09, 1.62 ppm.

[0220] [Comparative Example 4] Preparation of a dinuclear metallocene compound (Chemical Formula 3) into which a ligand with an unfused thiophene ring is introduced

[0221] [Chemical Formula 3]

[0222]

[0223] It was prepared using the same method as in [Example 1], except that indene was used instead of 2-methylthiophene, and the yield in the final step, the metallization reaction, was 82%.

[0224] 1H NMR (C6D6): δ 7.75-7.70 (m, 2H), 7.51-7.41 (m, 2H), 7.30-7.24 (m, 2H), 7.17-7.13 (m, 2H), 7.04-6.98 (m, 2H), 5.73-5.69 (m, 2H), 1.98-1.74 (m, 24H, CH3), 1.73-1.13 (m, 12H, CH2), 0.86, 0.85, 0.69 and 0.68 (s, 6H, SiCH3), -0.07 and -0.08 (s, 6H, ZrCH3), -1.23 and -1.25 (s, 6H, ZrCH3) ppm.

[0225] 13 C{ 1 H} NMR (C6D6): δ 130.62, 130.27, 127.38, 127.31, 127.28, 126.48, 126.38, 126.23, 126.13, 125.99, 125.96, 125.28, 124.90, 124.60, 124.55, 122.02, 121.15, 118.39, 117.96, 113.32, 113.20, 91.00, 90.79, 83.38, 83.05, 37.65, 37.63, 37.50, 33.53, 33.49, 33.44, 33.39, 32.63, 32.28, 31.98, 23.72, 23.68, 23.22, 23.15, 23.07, 16.94, 16.79, 15.05, 14.88, 14.39, 14.33, 14.30, 14.27, 11.80, 11.73, 11.70, -1.09, -1.12, -1.14, -1.34 ppm.

[0227] [Comparative Example 5] Preparation of a mononuclear metallocene compound (Chemical Formula 4) into which a ligand with a thiophene ring fused has been introduced

[0228] [화학식 4]

[0229]

[0230] Compound of Formula 4 was prepared by carrying out the same procedure as Comparative Example 1, except that Indenyl was used instead of Compound 3 in Comparative Example 1, and the yield in the final step, the metallization reaction, was 84%.

[0231] 1 ¹H NMR (C6D6): δ 7.63 (d, J = 8.4 Hz, 1H), 7.31 (d, J = 8.4 Hz, 1H), 7.18 (t, J = 8.4 Hz, 1H), 7.05 (d, J = 3.6 Hz, 1H), 6.90 (t, J = 8.4 Hz, 1H), 5.57 (d, J = 3.6 Hz, 1H), 1.85 (s, 3H, CH3), 1.84 (s, 3H, CH3), 1.72 (s, 3H, CH3), 1.63 (s, 3H, CH3), 0.66 (s, 3H, SiCH3), 0.49 (s, 3H, SiCH3), -0.16 (s, 3H, ZrCH3), -1.32 (s, 3H, ZrCH3) ppm.

[0232] 13 C{ 1 H} NMR (C6D6): δ 130.59, 127.71, 126.56, 126.54, 126.37, 126.11, 125.93, 124.83, 124.47, 121.54, 118.10, 113.15, 91.48, 83.85, 37.54, 32.36, 14.88, 14.25, 11.68, 11.59, 1.50, 1.13 ppm.

[0234] [Example 8] Chemical formula 1-1 (n = 6; R 3 = H; R 4 = Me) to 90 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0235] Phase 1Dried silica (Grace, SYLOPOL 2410, 5.0 g) was placed in a round-necked flask inside a glove box, and methylaluminoxane (MAO, Grace, 10 wt% methylaluminoxane solution in toluene, 4.6 wt Al, 25 g, 42.6 mmol Al) was added and stirred at 70°C for 3 hours. Afterward, unreacted methylaluminoxane was removed by filtration while washing with toluene (20 mL × 3 times) and hexane (20 mL × 3 times). The solvent was removed using a vacuum line to obtain a silica-aluminoxane complex.

[0236] Phase 2 : The above silica-aluminoxane complex (0.25 g), the chemical formula 1-1 of Example 1 (11.0 mg, 11.3 μmol), and toluene (10 mL) were added to a round-necked flask and reacted at 70°C for 2 hours. Afterward, the mixture was filtered while washing with toluene (3 mL × 3 times) and hexane (3 mL × 3 times), and the solvent was removed using a vacuum line to obtain a supported dinuclear metallocene catalyst in the form of a solid powder.

[0237] Ethylene polymerization At room temperature, the interior of a high-pressure reactor (internal capacity: 125 mL, stainless steel) was purged with nitrogen. Triethylaluminum (5.7 mg, 50 μmol), hexane (70 mL), and the supported dinuclear metallocene catalyst (2 mg) prepared in the second step were introduced into the reactor. After raising the temperature to 70°C, the ethylene valve was opened to maintain the internal ethylene pressure at 20 bar. After polymerization was carried out for 1 hour, the ethylene supply was stopped, and the ethylene was vented once the temperature dropped to room temperature. The reaction mixture was filtered to remove the solvent, and an ethylene polymer was obtained.

[0239] [Example 9] Chemical formula 1-1 (n = 6; R 3 = H; R 4 = Me) to 105μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0240] In the second step, the compound of formula 1-1 (n = 6; R3= H; R4= Me) was prepared and polymerized in the same manner as in [Example 8], except that 12.8 mg (13.1 μmol) of the compound was used instead of 11.0 mg (11.3 μmol). After filtration in the second step, it was confirmed that all the added metallocenes were attached to the silica-aluminoxane complex, as the filtrate was clear.

[0242] [Example 10] Formula 1-1 (n = 6; R 3 = H; R 4 = Me) to 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0243] In the second step, the compound of formula 1-1 (n = 6; R3= H; R4= Me) was prepared and polymerized in the same manner as in [Example 8], except that 14.7 mg (15.0 μmol) of the compound was used instead of 11.0 mg (11.3 μmol). After filtration in the second step, it was confirmed that all the added metallocenes were attached to the silica-aluminoxane complex, as the filtrate was clear.

[0245] [Example 11] Formula 1-1 (n = 6; R 3 = H; R 4 = Me) 135 μ Preparation of supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0246] In the second step, the compound of formula 1-1 (n = 6; R3= H; R4= Me) was prepared and polymerized in the same manner as in [Example 8], except that 16.5 mg (16.9 μmol) of the compound was used instead of 11.0 mg (11.3 μmol). After filtration in the second step, it was confirmed that all the added metallocenes were attached to the silica-aluminoxane complex, as the filtrate was clear.

[0248] [Example 12] Formula 1-1 (n = 6; R 3 = H; R 4 = Me) to 150 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0249] In the second step, the compound of formula 1-1 (n = 6; R3= H; R4= Me) was prepared and polymerized in the same manner as in [Example 8], except that 18.3 mg (18.8 μmol) of the compound was used instead of 11.0 mg (11.3 μmol). After filtration in the second step, it was confirmed that all the added metallocenes were attached to the silica-aluminoxane complex, as the filtrate was clear.

[0251] [Example 13] Formula 1-1 (n = 8; R 3 = H; R 4 = Me) to 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0252] In the second step, the product was prepared and polymerized in the same manner as in [Example 8], except that Formula 1-1 (n = 8; R3= H; R4= Me) (15.1 mg, 15.0 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). After filtration in the second step, the filtrate was clear, confirming that all the added metallocenes were attached to the silica-aluminoxane complex.

[0254] [Example 14] Chemical formula 1-1 (n = 10; R 3 = H; R 4 = Me) to 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0255] In the second step, the product was prepared and polymerized in the same manner as in [Example 8], except that Formula 1-1 (n = 10; R3= H; R4= Me) (15.5 mg, 15.0 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). After filtration in the second step, the filtrate was clear, confirming that all the added metallocenes were attached to the silica-aluminoxane complex.

[0257] [Example 15] Chemical formula 1-1 (n = 2; R 3 = H; R 4 = Me) to 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0258] In the second step, the product was prepared and polymerized in the same manner as in [Example 8], except that Formula 1-1 (n = 2; R3= H; R4= Me) (13.8 mg, 15.0 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). After filtration in the second step, the filtrate was clear, confirming that all the added metallocenes were attached to the silica-aluminoxane complex.

[0260] [Example 16] Formula 1-1 (n = 3; R 3 = H; R 4 = Me) to 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0261] In the second step, the product was prepared and polymerized in the same manner as in [Example 8], except that Formula 1-1 (n = 3; R3= H; R4= Me) (14.0 mg, 15.0 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). After filtration in the second step, the filtrate was clear, confirming that all the added metallocenes were attached to the silica-aluminoxane complex.

[0263] [Example 17] Formula 1-1 (n = 6; R 3 = H; R 4 = H) to 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0264] In the second step, the product was prepared and polymerized in the same manner as in [Example 8], except that Formula 1-1 (n = 6; R3= H; R4= Me) (14.2 mg, 15.0 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). After filtration in the second step, the filtrate was clear, confirming that all the added metallocenes were attached to the silica-aluminoxane complex.

[0266] [Example 18] Formula 1-1 (n = 6; R 3 = Me; R 4 = Me) to 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0267] In the second step, the product was prepared and polymerized in the same manner as in [Example 8], except that Formula 1-1 (n = 6; R3= H; R4= Me) (15.1 mg, 15.0 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). After filtration in the second step, the filtrate was clear, confirming that all the added metallocenes were attached to the silica-aluminoxane complex.

[0269] [Comparative Example 5] Chemical Formula 2 (R 3 = H; R 4 = Me) to 90 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0270] In the second step, the product was prepared and polymerized in the same manner as in [Example 8], except that Formula 2 (R3= H; R4= Me) (10.4 mg, 22.5 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). After filtration in the second step, the filtrate was clear, confirming that all the added metallocenes were attached to the silica-aluminoxane complex.

[0272] [Comparative Example 6]: Chemical formula 2(R 3 = H; R 4 = Me) to 105 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0273] In the second step, preparation and polymerization were carried out in the same manner as in [Example 8], except that Formula 2 (R3= H; R4= Me) (12.1 mg, 26.3 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). Since the filtrate was yellow after filtration in the second step, it was inferred that not all of the added mononuclear metallocene compound was attached to the silica-aluminoxene complex, and ICP analysis confirmed that the amount attached was significantly small compared to the Zr dosage (105 μmol / g-(silica-aluminoxene complex)) (67 μmol / g-supported catalyst).

[0275] [Comparative Example 7] Chemical Formula 2(R 3 = H; R 4 = Me) to 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0276] In the second step, preparation and polymerization were carried out in the same manner as in [Example 8], except that Formula 2 (R3= H; R4= Me) (13.9 mg, 30.0 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). Since the filtrate was yellow after filtration in the second step, it was inferred that not all of the added mononuclear metallocene compound was attached to the silica-aluminoxene complex, and ICP analysis confirmed that the amount attached was significantly small compared to the Zr dosage (120 μmol / g-(silica-aluminoxene complex)) (68 μmol / g-supported catalyst).

[0278] [Comparative Example 8] Chemical Formula 2 (R 3 = H; R 4 = H) to 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0279] In the second step, the product was prepared and polymerized in the same manner as in [Example 8], except that Formula 2 (R3= H; R4= H) (10.1 mg, 30.0 μmol) was used instead of Formula 1-1 (n = 6; R2= H; R4= Me) (11.0 mg, 11.3 μmol). Since the filtrate was clear after filtration in the second step, it is inferred that all the added metallocenes were attached to the silica-aluminoxane complex.

[0281] [Comparative Example 9] Chemical Formula 2 (R 3 = Me; R 4 = Me) to 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0282] In the second step, the product was prepared and polymerized in the same manner as in [Example 8], except that Formula 2 (R3= Me; R4= Me) (10.7 mg, 30.0 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). Since the filtrate was clear after filtration in the second step, it is inferred that all the added metallocenes were attached to the silica-aluminoxane complex.

[0284] [Comparative Example 10] Formula 3 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0285] In the second step, the product was prepared and polymerized in the same manner as in [Example 8], except that Formula 3 (13.2 mg, 15.0 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). Since the filtrate was clear after filtration in the second step, it is inferred that all the added metallocene was attached to the silica-aluminoxane complex.

[0287] [Comparative Example 11] Formula 4 120 μ Preparation of a supported catalyst using mol-Zr / g-(silica-aluminoxane complex) and ethylene polymerization using the same

[0288] In the second step, the product was prepared and polymerized in the same manner as in [Example 8], except that Formula 4 (12.4 mg, 30 μmol) was used instead of Formula 1-1 (n = 6; R3= H; R4= Me) (11.0 mg, 11.3 μmol). Seeing that the filtrate was clear after filtration in the second step, it is inferred that all the added metallocene was attached to the silica-aluminoxane complex.

[0290] Table 1 below summarizes the details and results of Examples 8 to 18 and Comparative Examples 1 to 11. Table 2 shows the polymer particle size distribution obtained in Example 10, Comparative Example 5, and Comparative Example 10.

[0291] [Results of Supported Catalyst Preparation and Ethylene Polymerization] Example # chemical formula Zr dosage (Al / Zr dosage ratio) μmol / g-(silica-aluminoxane complex) Al and Zr content measured by ICP (Al / Zr ratio) μmol / g-supported catalyst Activity (kg-polymer / g-cat) M w (kDa) PDI Example 8 Chemical formula 1n = 6; R3 = H;R4 = Me; 90 (53) 4700, 83 (57) 10.6 308 3.1 Example 9 Chemical formula 1n = 6; R3 = H;R4 = Me; 105 (46) 4700, 100 (46) 10.9 312 3.1 Example 10 Chemical formula 1n = 6; R3 = H;R4 = Me; 120 (40) 4700, 110 (43) 13.7 323 3.2 Example 11 Chemical formula 1n = 6; R3 = H;R4 = Me; 135 (36) 4600, 120 (38) 13.2 309 3.1 Example 12 Chemical formula 1n = 6; R3 = H;R4 = Me; 150 (32) 4500, 130 (35) 10.8 309 3.2 Example 13 Chemical formula 1n = 8; R3 = H;R4 = Me; 120 (40) 4600, 100 (46) 12.6 306 3.2 Example 14 Chemical formula 1n = 10; R3 = H;R4 = Me; 120 (40) 4700, 110 (43) 10.8 285 2.9 Example 15 Chemical formula 1n = 2; R3 = H;R4= Me; 120 (40) 4500, 93 (48) 8.3 375 3.4 Example 16 Chemical formula 1n = 3 R3 = H; R4 = Me; 120 (40) 4500, 100 (45) 10.7 328 3.3 Example 17 Chemical formula 1n=6; R3= H; R4= H; 120 (40) 4600, 100 (42) 9.7 336 3.4 Example 18 Chemical formula 1n = 6; R3 = Me; R4 = Me 120 (40) 4600, 110 (42) 9.3 333 2.7 Comparative Example 5 Chemical formula 2 R3 = H; R4 = Me 90 (53) 4600, 52 (88) 6.2 374 3.4 Comparative Example 6 Chemical formula 2R3 = H;R4 = Me; 105 (46) 4500, 67 (67) 6.1 356 3.3 Comparative Example 7 Chemical formula 2R3 = H;R4 = Me; 120 (40) 4600, 68 (68) 6.3 331 3.4 Comparative Example 8 Chemical formula 2R3 = H;R4 = H; 120 (40) 4500, 67 (67) 4.9 359 3.4 Comparative Example 9 Chemical formula 2R3 = Me;R4 = Me; 120 (40) 4700, 73 (64) 4.8 393 2.9 Comparative Example 10 Chemical formula 3 120 (40) 4600, 88 52 10.8 248 2.9 Comparative Example 11 Chemical formula 4 120 40 4800,96 50 7.4 391 3.1

[0292] Distribution of generated polymer particles (weight%) Examples chemical formula 53 or less (μm) 53-100 (μm) 150-200 (μm) 200-300 (μm) 300-500 (μm) 500-600 (μm) 600-850 (μm) 850-1000 (μm) 1000 or more (μm) Example 10 Chemical formula 1-1n = 6; R3 = H;R4 = Me; 0 2 3 7 34 23 28 3 0 Comparative Example 5 Chemical formula 2R3 = H; R4 = Me; 0 0 0 3 31 21 36 7 1 Comparative Example 10 Chemical formula 3 0 0 1 2 25 20 36 13 3

[0293] Through the above examples and comparative examples, it was confirmed that when a supported dinuclear metallocene catalyst prepared using a dinuclear metallocene compound represented by Chemical Formula 1 is prepared, all administered dinuclear metallocene compounds are easily attached to the support, whereas when a supported catalyst is prepared using a mononuclear metallocene compound represented by Chemical Formula 2, not all mononuclear metallocene compounds are attached, and only a portion of the administered mononuclear metallocene compounds are attached. In other words, when a supported catalyst is prepared using a dinuclear metallocene compound, a larger amount of metallocene compounds are attached to the support compared to when prepared using a mononuclear metallocene compound, and the prepared supported dinuclear metallocene catalyst has high activity.

[0294] In addition, from Comparative Example 10 compared to Example 13 in Table 1, it can be seen that when a supported catalyst is prepared using the dinuclear metallocene catalyst of the present invention, which is composed of a ligand with a thiophene ring fused thereto, a supported catalyst having higher activity can be prepared.

[0295] In addition, as shown in Table 2, compared to cases where a mononuclear metallocene catalyst or a supported catalyst prepared using a dinuclear metallocene catalyst composed of a ligand that does not have a thiophene ring fused to it is used as a catalyst in the ethylene polymerization process, it can be seen that the case where a supported catalyst prepared using a dinuclear metallocene catalyst composed of a ligand that has a thiophene ring fused to it is used is very advantageous for commercial process input because it suppresses the formation of polymers with large particle sizes.

[0297] As described above, although embodiments of the present invention have been described in detail, a person skilled in the art to which the present invention pertains will be able to implement the present invention in various modified ways without departing from the spirit and scope of the present invention as defined in the appended claims. Therefore, future modifications to the embodiments of the present invention will not depart from the technology of the present invention.

Claims

Claim 1 A dinuclear metallocene compound represented by the following chemical formula 1. [Chemical Formula 1] In the above Chemical Formula 1, M1 and M2 are independently group 4 transition metals; A is a C1-C10 alkylene; Cp1 and Cp2 are independently cyclopentadienyl, said cyclopentadienyl may be substituted with one or more C1-C5 alkyl groups; R1 to R8 are independently hydrogen or C1-C5 alkyl groups; and R a and R b are independently C1-C5 alkyls; X1 to X4 are independently C1-C5 alkyls. Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 In claim 1, the above chemical formula 1 is a dinuclear metallocene compound represented by the following chemical formula 2. [Chemical Formula 2] In the above chemical formula 2, M1 and M2 are independently titanium, hafnium, or zirconium; R1 to R8 are independently hydrogen, or C1-C5 alkyl; R 11 to R 18 are independently hydrogen, or C1-C5 alkyl;R a and R b are independently C1-C5 alkyls; X1 to X4 are independently C1-C5 alkyls; and n is an integer from 1 to 10. Claim 6 delete Claim 7 In claim 5, in the above formula 2, M1 and M2 are zirconium; R1 to R2 and R5 to R6 are independently C1-C5 alkyl; R3 to R4, R7 to R8 are and R 11 to R 18 A dinuclear metallocene compound in which the hydrogen or C1-C5 alkyls are independently hydrogen or C1-C5 alkyls. Claim 8 An aluminum compound-support complex and a supported dinuclear metallocene catalyst characterized by a dinuclear metallocene compound represented by the following chemical formula 1 being supported on the aluminum compound-support complex. [Chemical Formula 1] In the above Chemical Formula 1, M1 and M2 are independently group 4 transition metals; A is a C1-C10 alkylene; Cp1 and Cp2 are independently cyclopentadienyl, said cyclopentadienyl may be substituted with one or more C1-C5 alkyl groups; R1 to R8 are independently hydrogen or C1-C5 alkyl groups; and R a and R b are independently C1-C5 alkyls; X1 to X4 are independently C1-C5 alkyls. Claim 9 In claim 8, the aluminum compound-carrier composite is a supported dinuclear metallocene catalyst in which an organoaluminum compound forms a composite on one or more carriers selected from silica, alumina, magnesium chloride, calcium chloride, bauxite, zeolite, magnesium oxide, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide, and thorium oxide. Claim 10 A supported dinuclear metallocene catalyst according to claim 8, wherein the molar ratio of the metal of the dinuclear metallocene catalyst to the aluminum of the aluminum compound-support complex is 1:2 to 70. Claim 11 A method for preparing a supported dinuclear metallocene catalyst, comprising: a step of preparing an aluminum compound-support complex by reacting an aluminum compound and a support; and a step of preparing a supported dinuclear metallocene catalyst by reacting the aluminum compound-support complex with a dinuclear metallocene compound represented by the following Chemical Formula 1. [Chemical Formula 1] In the above Chemical Formula 1, M1 and M2 are independently group 4 transition metals; A is a C1-C10 alkylene; Cp1 and Cp2 are independently cyclopentadienyl, said cyclopentadienyl may be substituted with one or more C1-C5 alkyl groups; R1 to R8 are independently hydrogen or C1-C5 alkyl groups; and R a and R b are independently C1-C5 alkyls; X1 to X4 are independently C1-C5 alkyls. Claim 12 A method for manufacturing a supported dinuclear metallocene catalyst according to claim 11, wherein the aluminum compound is used in an amount of 0.4 to 0.5 parts by weight per 100 parts by weight of a carrier. Claim 13 A method for preparing a supported dinuclear metallocene catalyst according to claim 11, wherein the dinuclear metallocene compound represented by the above chemical formula 1 is used in a ratio of 110 to 140 μmol-Metal / g-(silica-aluminoxane complex) with respect to the aluminum compound-carrier complex. Claim 14 A method for producing a polyolefin comprising the step of polymerizing one or more olefin monomers in the presence of a supported dinuclear metallocene catalyst selected from any one of claims 8 to 10. Claim 15 A method for producing a polyolefin according to claim 14, wherein the olefin monomer is one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, and mixtures thereof.

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