Catalyst containing a mixed transition metal compound, olefin polymer prepared using the catalyst, and method for preparing the same

Abstract

The present invention relates to an olefin polymerization catalyst containing a mixed transition metal compound, which can be used to prepare various polyolefins having excellent processability and mechanical properties, an olefin polymer prepared using the same, and a method for preparing the same. The preparation method according to an embodiment of the present invention allows the easy preparation of an olefin polymerization catalyst containing a mixed transition metal compound by easily adjusting the ratio of the transition metal compound.

Description

[Technical Field]

[0001] The present invention relates to an olefin polymerization catalyst containing a mixed transition metal compound, which can prepare various polyolefins having excellent processability and mechanical properties, an olefin polymer prepared using the same, and a method for preparing the same. [Background technology]

[0002] Polyolefin polymers are widely used in everyday life as materials for shopping bags, greenhouses, fishing nets, cigarette wrappers, ramen packaging bags, yogurt bottles, battery cases, car bumpers, interior materials, shoe soles, washing machines, and more.

[0003] Traditionally, polyolefin polymers such as polyethylene, polypropylene, and ethylene-α-olefin copolymers and their copolymers have been prepared using heterogeneous catalysts such as Ziegler-Natta catalysts, which consist of titanium compounds and alkylaluminum compounds.

[0004] Recently, research has been conducted into the preparation of polyolefins using metallocene catalysts, which are homogeneous catalysts with extremely high catalytic activity. Metallocene catalysts are compounds in which ligands such as cyclopentadienyl, indenyl, or cycloheptadienyl are coordinated to a transition metal or transition metal halide, and have a basic sandwich structure. Various molecular structures are possible depending on the type of ligand and the type of central metal.

[0005] Ziegler-Natta catalysts are heterogeneous catalysts in which the metal components that act as active sites are dispersed on an inert solid surface, and the properties of the active sites are not uniform. In contrast, metallocene catalysts are single compounds with a fixed structure, and all active sites have the same polymerization properties, making them known as single-site catalysts.

[0006] Generally, metallocene catalysts are not active as polymerization catalysts by themselves, so they are used in conjunction with a co-catalyst such as methylaluminoxane. The co-catalyst activates the metallocene catalyst to a cation, and at the same time, the co-catalyst stabilizes the unsaturated cationic active species as anions that are not coordinated to the metallocene catalyst, forming a catalytic system active in the polymerization of various olefins.

[0007] Such metallocene catalysts are easy to copolymerize and can adjust the three-dimensional structure of the polymer depending on the symmetry of the catalyst. The polymers prepared using these catalysts have the advantages of narrow molecular weight distribution and uniform comonomer distribution.

[0008] On the other hand, polymers prepared using metallocene catalysts have excellent mechanical strength due to their narrow molecular weight distribution, but suffer from poor processability. To address this issue, various methods have been proposed, such as modifying the molecular structure of the polymer or broadening the molecular weight distribution. For example, Patent Document 1 improves polymer processability by using a catalyst that introduces long chain branches (LCBs) into the polymer main chain. However, supported catalysts suffer from low activity.

[0009] To overcome these shortcomings of single metallocene catalysts and develop catalysts that are simpler, more active, and have improved processability, methods for supporting heterogeneous metallocene catalysts with different properties have been proposed. For example, Patent Documents 2, 3, 4, 5, and 6 disclose methods for preparing polyolefins with bimodal molecular weight distributions using catalysts with different reactivities toward comonomers. While bimodal molecular weight distribution polyolefins prepared using these methods offer improved processability, they suffer from poor homogeneity due to the different molecular weight distributions. Consequently, it is difficult to obtain products with uniform physical properties after processing, and mechanical strength is reduced.

[0010] On the other hand, Patent Document 7 discloses a heterometallocene catalyst comprising a mixture of a first transition metal compound containing a cyclopentadienyl group and an indenyl group that are not connected by a bridge, and a second transition metal compound containing a substituted bisindenyl group that is connected by a silyl bridge.

[0011] Furthermore, to solve the problems of heterogeneous metallocene supported catalysts, a method using a binuclear metallocene catalyst with two active sites has been proposed. For example, Patent Document 8 proposes a method of controlling the molecular weight distribution and molecular weight by using a binuclear metallocene catalyst on a support, but the problem of low activity remains. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] U.S. Patent No. 5,272,236 [Patent Document 2] U.S. Patent No. 4,935,474 [Patent Document 3] U.S. Patent No. 6,828,394 [Patent Document 4] U.S. Patent No. 6,894,128 [Patent Document 5] Korean Patent No. 1437509 [Patent Document 6] U.S. Patent No. 6,841,631 [Patent Document 7] Korean Patent No. 1797890 [Patent Document 8] Korean Patent Publication No. 2004-0076965 Summary of the Invention [Problem to be solved by the invention]

[0013] An object of the present invention is to provide a method for preparing an olefin polymerization catalyst containing a mixed transition metal compound, by which the ratio of the transition metal compounds can be easily adjusted.

[0014] Another object of the present invention is to provide an olefin polymerization catalyst prepared by the above preparation method, which can prepare a variety of polyolefins having excellent processability and mechanical properties.

[0015] It is still another object of the present invention to provide a process for preparing an olefin polymer using the catalyst.

[0016] It is still another object of the present invention to provide an olefin polymer prepared using the catalyst. [Means for solving the problem]

[0017] According to one embodiment of the present invention, there is provided a method for preparing an olefin polymerization catalyst, comprising the steps of: (1) dissolving a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2 in a solvent; (2) adding a compound represented by the following chemical formula 3 to the solution obtained in step (1), followed by reacting them under stirring to obtain a mixture of transition metal compounds represented by the following chemical formulas 4 and 5; and (3) activating the mixture of transition metal compounds obtained in step (2) and a transition metal compound represented by the following chemical formula 6 with a co-catalyst compound.

[0018] [Chemical formula 1] JPEG0007727715000001.jpg31150[Chemical formula 2] JPEG0007727715000002.jpg33150[Chemical formula 3] MX4 [Chemical formula 4] JPEG0007727715000003.jpg66150[Chemical formula 5] JPEG0007727715000004.jpg66150[Chemical formula 6] JPEG0007727715000005.jpg47150

[0019] In the above chemical formulas 1 to 6, R1 to R5 and R6 to R 10 are each independently hydrogen, substituted or unsubstituted C1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamides, substituted or unsubstituted C 6-20 Arylamide, substituted or unsubstituted C 1-20 Alkylidene or substituted or unsubstituted C 1-20 silyl, and R1 to R5 and R6 to R 10 are each independently a substituted or unsubstituted saturated or unsaturated C 4-20 It may form a ring.

[0020] M is titanium (Ti), zirconium (Zr), or hafnium (Hf), respectively.

[0021] X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is an alkylidene.

[0022] Q are anionic leaving groups, each independently hydrogen, hydrocarbyl, heteroatom or halogen, a straight-chain or branched alkyl radical, or alkenyl radical, alkynyl radical, cycloalkyl radical or aryl radical, acyl radical, aroyl radical, alkoxy radical, aryloxy radical, alkylthio radical, dialkylamino radical, alkoxycarbonyl radical, aryloxycarbonyl radical, carbamoyl radical, alkyl- or dialkyl-carbamoyl radical, acyloxy radical, acylamino radical, aroylamino radical, straight-chain, branched, or cyclic alkylene radical, or combinations thereof.

[0023] m is the oxidation state of M and is +3, +4, or +5; o is the formal charge of the YZL ligand and is 0, -1, -2, or -3; L is a group 15 or 16 element, preferably nitrogen; Y is a Group 15 element, preferably nitrogen or phosphorus, more preferably nitrogen; Z is a Group 15 element, preferably nitrogen or phosphorus, more preferably nitrogen.

[0024] R 11 and R 12 are each independently C 1-20 a hydrocarbon group or a heteroatom-containing group, where the heteroatom is silicon, germanium, tin, lead, or phosphorus, or R 11 and R 12 can be combined with each other. R 13 is absent or hydrogen, C 1-20 R is an alkyl, halogen, or heteroatom-containing group. 14 and R 15 R is independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, or a polycyclic ring system. 16 and R 17are each independently absent, a hydrogen, an alkyl group, a halogen, a heteroatom, a hydrocarbyl group, or a heteroatom-containing group.

[0025] In one specific implementation example, R1 to R5 and R6 to R 10 are hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Alkenyl, or substituted or unsubstituted C 6-20 It is aryl.

[0026] In a specific implementation example, R1 to R5 and R6 to R 10 are halogens, C 1-20 Alkylsilyl, C 1-20 The alkenyloxy may be substituted with any one or more of the following.

[0027] In a more specific embodiment, the compound represented by Chemical Formula 1 is at least one of the compounds represented by Chemical Formulas 1-1 to 1-21 below, and the compound represented by Chemical Formula 2 is at least one of the compounds represented by Chemical Formulas 2-1 to 2-7 below.

[0028] [Chemical formula 1-1] JPEG0007727715000006.jpg20150[Chemical formula 1-2] JPEG0007727715000007.jpg20150[Chemical formula 1-3] JPEG0007727715000008.jpg19150[Chemical formula 1-4] JPEG0007727715000009.jpg19150[Chemical formula 1-5] JPEG0007727715000010.jpg19150[Chemical formula 1-6] JPEG0007727715000011.jpg19150[Chemical formula 1-7] JPEG0007727715000012.jpg19150[Chemical formula 1-8] JPEG0007727715000013.jpg19150[Chemical formula 1-9] JPEG0007727715000014.jpg19150[Chemical formula 1-10] JPEG0007727715000015.jpg19150[Chemical formula 1-11] JPEG0007727715000016.jpg19150[Chemical formula 1-12] JPEG0007727715000017.jpg19150[Chemical formula 1-13] JPEG0007727715000018.jpg20150[Chemical formula 1-14] JPEG0007727715000019.jpg20150[Chemical formula 1-15] JPEG0007727715000020.jpg22150[Chemical formula 1-16] JPEG0007727715000021.jpg18150[Chemical formula 1-17] JPEG0007727715000022.jpg20150[Chemical formula 1-18] JPEG0007727715000023.jpg20150[Chemical formula 1-19] JPEG0007727715000024.jpg20150[Chemical formula 1-20] JPEG0007727715000025.jpg18150[Chemical formula 1-21] JPEG0007727715000026.jpg22150[Chemical Formula 2-1] JPEG0007727715000027.jpg26150[Chemical formula 2-2] JPEG0007727715000028.jpg23150[Chemical formula 2-3] JPEG0007727715000029.jpg28150[Chemical formula 2-4] JPEG0007727715000030.jpg25150[Chemical formula 2-5] JPEG0007727715000031.jpg25150[Chemical Formula 2-6] JPEG0007727715000032.jpg28150[Chemical Formula 2-7] JPEG0007727715000033.jpg30150In the above chemical formula, Me is methyl and Ph is phenyl.

[0029] In one specific implementation, the solvent comprises at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate.

[0030] In a specific embodiment, in the step (1), the molar ratio of the compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 2 is in the range of 1:100 to 100:1.

[0031] In a specific embodiment, in the formula 3, M is zirconium or hafnium, and X is a halogen or a substituted or unsubstituted C 1-20 It is alkyl.

[0032] In a more specific embodiment, the compound represented by Chemical Formula 3 is ZrCl4 or HfCl4.

[0033] In a specific embodiment, in step (2), the reaction temperature is 0°C to 120°C, and the reaction time is 1 to 72 hours.

[0034] In one specific embodiment, the transition metal compound represented by the chemical formula 4 is at least one of the transition metal compounds represented by the following chemical formulas 4-1 to 4-21, and the transition metal compound represented by the chemical formula 5 is at least one of the transition metal compounds represented by the following chemical formulas 5-1 to 5-21.

[0035] [Chemical formula 4-1] JPEG0007727715000034.jpg38150[Chemical formula 4-2] JPEG0007727715000035.jpg38150[Chemical formula 4-3] JPEG0007727715000036.jpg38150[Chemical formula 4-4] JPEG0007727715000037.jpg37150[Chemical formula 4-5] JPEG0007727715000038.jpg42150[Chemical formula 4-6] JPEG0007727715000039.jpg39150[Chemical formula 4-7] JPEG0007727715000040.jpg43150[Chemical Formula 4-8] JPEG0007727715000041.jpg48150[Chemical formula 4-9] JPEG0007727715000042.jpg42150[Chemical formula 4-10] JPEG0007727715000043.jpg42150[Chemical Formula 4-11] JPEG0007727715000044.jpg48150[Chemical Formula 4-12] JPEG0007727715000045.jpg42150[Chemical formula 4-13] JPEG0007727715000046.jpg47150[Chemical formula 4-14] JPEG0007727715000047.jpg49150[Chemical formula 4-15] JPEG0007727715000048.jpg49150[Chemical formula 4-16] JPEG0007727715000049.jpg42150[Chemical Formula 4-17] JPEG0007727715000050.jpg47150[Chemical Formula 4-18] JPEG0007727715000051.jpg48150[Chemical Formula 4-19] JPEG0007727715000052.jpg47150[Chemical formula 4-20] JPEG0007727715000053.jpg40150[Chemical Formula 4-21] JPEG0007727715000054.jpg48150[Chemical Formula 5-1] JPEG0007727715000055.jpg32150[Chemical Formula 5-2] JPEG0007727715000056.jpg31150[Chemical Formula 5-3] JPEG0007727715000057.jpg31150[Chemical formula 5-4] JPEG0007727715000058.jpg31150[Chemical formula 5-5] JPEG0007727715000059.jpg41150[Chemical formula 5-6] JPEG0007727715000060.jpg35150[Chemical formula 5-7] JPEG0007727715000061.jpg35150[Chemical formula 5-8] JPEG0007727715000062.jpg41150[Chemical formula 5-9] JPEG0007727715000063.jpg31150[Chemical formula 5-10] JPEG0007727715000064.jpg30150[Chemical formula 5-11] JPEG0007727715000065.jpg42150[Chemical formula 5-12] JPEG0007727715000066.jpg32150[Chemical formula 5-13] JPEG0007727715000067.jpg41150[Chemical formula 5-14] JPEG0007727715000068.jpg42150[Chemical formula 5-15] JPEG0007727715000069.jpg43150[Chemical formula 5-16] JPEG0007727715000070.jpg34150[Chemical formula 5-17] JPEG0007727715000071.jpg41150[Chemical formula 5-18] JPEG0007727715000072.jpg42150[Chemical formula 5-19] JPEG0007727715000073.jpg43150[Chemical formula 5-20] JPEG0007727715000074.jpg31150[Chemical formula 5-21] JPEG0007727715000075.jpg47150In the above chemical formula, Me is methyl and Ph is phenyl.

[0036] In a specific embodiment, in the mixture of transition metal compounds obtained in step (2), the molar ratio of the transition metal compound represented by Chemical Formula 4 to the transition metal compound represented by Chemical Formula 5 is in the range of 1:100 to 100:1.

[0037] In a specific embodiment, the method for preparing the catalyst may further include a step (2') of drying the mixture of transition metal compounds obtained in the step (2).

[0038] In a specific embodiment, the method for preparing the catalyst may further include a step (2'') of dissolving the dried mixture of transition metal compounds obtained in step (2') in a solvent, and then removing unreacted materials and / or impurities using a filter.

[0039] In a specific embodiment, in Formula 6, M is zirconium or hafnium, each Q is independently hydrogen, halogen, or a hydrocarbyl group, and R 11 and R 12 are each independently C 1-6 is a hydrocarbon group, R 13 is hydrogen or methyl, and R 14 and R 15 are each independently a substituted aryl group.

[0040] In a more specific embodiment, the transition metal compound represented by the chemical formula 6 is a transition metal compound represented by the following chemical formula 6-1.

[0041] [Chemical formula 6-1] JPEG0007727715000076.jpg27150

[0042] In a specific embodiment, the co-catalyst compound may include one or more selected from the group consisting of a compound represented by the following chemical formula 7, a compound represented by the chemical formula 8, and a compound represented by the chemical formula 9:

[0043] [Chemical formula 7] JPEG0007727715000077.jpg22150[Chemical formula 8] JPEG0007727715000078.jpg25150[Chemical formula 9] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0044] In the above Chemical Formula 7, n is an integer of 2 or more, and R a is a halogen atom, C 1-20 C substituted with hydrocarbon or halogen groups 1-20 It is a hydrocarbon group.

[0045] In the above formula 8, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, C 1-20 Hydrocarbon groups, halogen-substituted C 1-20 Hydrocarbon group, or C 1-20 It is an alkoxy group.

[0046] In the formula 9, L is a neutral or cationic Lewis base, [LH] + and [L] + is a Bronsted acid, Z is a Group 13 element, and each A is independently a substituted or unsubstituted C 6-20 an aryl group or a substituted or unsubstituted C 1-20 It is an alkyl group.

[0047] In a more specific embodiment, the compound represented by Chemical Formula 7 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

[0048] The compound represented by Chemical Formula 8 is at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, and tributylboron.

[0049] Further, the compound represented by Chemical Formula 9 includes triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphine Phosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,At least one selected from the group consisting of N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate, triphenylcarbenium tetra(p-trifluoromethylphenyl)borate, and triphenylcarbenium tetrapentafluorophenylborate.

[0050] In a specific embodiment, the catalyst preparation method may further include (3') a step of supporting a part or all of the transition metal compounds represented by the chemical formulas 4 to 6 and the co-catalyst compound on a support before or after the step (3).

[0051] In one specific implementation, the support may include at least one selected from the group consisting of silica, alumina, and magnesium oxide (magnesia).

[0052] According to one embodiment of the present invention, there is provided an olefin polymerization catalyst prepared by the preparation method according to the embodiment of the present invention, the catalyst comprising a transition metal compound represented by any one of the chemical formulas 4 to 6 and a co-catalyst compound containing at least one selected from the group consisting of the compounds represented by the chemical formulas 7 to 9.

[0053] In a specific embodiment, the olefin polymerization catalyst may further include a support that supports a part or all of the transition metal compounds represented by the chemical formulas 4 to 6 and the co-catalyst compound including at least one selected from the group consisting of the compounds represented by the chemical formulas 7 to 9.

[0054] According to one embodiment of the present invention, there is provided a method for preparing an olefin polymer, comprising: (1) dissolving the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 in a solvent; (2) adding the compound represented by Chemical Formula 3 to the solution obtained in Step (1) and then reacting them under stirring to obtain a mixture of transition metal compounds represented by Chemical Formula 4 and Chemical Formula 5; (3) activating the mixture of transition metal compounds obtained in Step (2) and the transition metal compound represented by Chemical Formula 6 with a co-catalyst compound; (4) before or after Step (3), supporting a part or all of the transition metal compounds represented by Chemical Formulas 4 to 6 and the co-catalyst compound on a support; and (5) polymerizing an olefin in the presence of the catalyst obtained in Step (3) or Step (4).

[0055] In one specific implementation, the polymerization of olefins is copolymerization of an olefinic monomer and an olefinic comonomer, where the olefinic monomer is ethylene and the olefinic comonomer is 1-hexene.

[0056] According to one embodiment of the present invention, a cellulose ester having a density of 0.940 g / cm3 is prepared by the preparation method according to the embodiment of the present invention. 3 ~0.970g / cm 3 , (2) Melt Index Ratio (MI 21.6 / MI 2.16 (2) a weight average molecular weight (Mw) of 80,000 g / mol to 600,000 g / mol; and (3) a molecular weight distribution (MWD) as determined by a polydispersity index (Mw / Mn) of 10 to 50. [Effects of the Invention]

[0057] The preparation method according to the embodiment of the present invention can easily adjust the ratio of the transition metal compounds to easily prepare an olefin polymerization catalyst containing a mixed transition metal compound.

[0058] Furthermore, the olefin polymerization catalyst prepared by the preparation method according to the embodiment of the present invention can prepare various polyolefins having excellent processability and mechanical properties.

[0059] Furthermore, the method for preparing an olefin polymer according to the embodiment of the present invention allows for the preparation of various polyolefins having excellent processability and mechanical properties by a simple method.

[0060] In particular, the olefin polymers prepared by the catalysts according to the embodiments of the present invention can have bimodal or multi-modal molecular weight distributions, preventing phase separation of molecular structure. [Brief explanation of the drawings]

[0061] [Figure 1] FIG. 1 is a GPC (gel permeation chromatography)-FTIR (Fourier transform infrared spectroscopy) graph for measuring the BOCD index (Broad Orthogonal Comonomer Distribution index) of the olefin polymers prepared in the examples and comparative examples of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0062] The present invention will now be described in more detail.

[0063] [Method for preparing an olefin polymerization catalyst] The present invention provides a method for preparing an olefin polymerization catalyst, comprising the steps of: (1) dissolving a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2 in a solvent; (2) adding a compound represented by the following chemical formula 3 to the solution obtained in step (1), followed by reaction under stirring to obtain a mixture of transition metal compounds represented by the following chemical formulas 4 and 5; and (3) activating the mixture of transition metal compounds obtained in step (2) and a transition metal compound represented by the following chemical formula 6 with a co-catalyst compound.

[0064] <Step (1)> In the step (1), a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2 are dissolved in a solvent.

[0065] [Chemical formula 1] JPEG0007727715000079.jpg27150[Chemical formula 2] JPEG0007727715000080.jpg29150

[0066] In the above chemical formulas 1 and 2, R1 to R5 and R6 to R 10 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamides, substituted or unsubstituted C 6-20 Arylamide, substituted or unsubstituted C 1-20 Alkylidene or substituted or unsubstituted C 1-20 It should be noted that R1 to R5 and R6 to R 10 are each independently a substituted or unsubstituted saturated or unsaturated C 4-20 It may form a ring.

[0067] In one specific implementation example, R1 to R5 and R6 to R 10 are hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Alkenyl, or substituted or unsubstituted C 6-20 It may be aryl.

[0068] In one specific implementation example, R1 to R5 and R6 to R 10 are halogens, C 1-20 Alkylsilyl, C 1-20 It may be substituted with any one or more of the alkenyloxy.

[0069] In a more specific embodiment, the compound represented by Chemical Formula 1 is at least one of the compounds represented by Chemical Formulas 1-1 to 1-21 below, and the compound represented by Chemical Formula 2 is at least one of the compounds represented by Chemical Formulas 2-1 to 2-7 below.

[0070] [Chemical formula 1-1] JPEG0007727715000081.jpg19150[Chemical formula 1-2] JPEG0007727715000082.jpg18150[Chemical formula 1-3] JPEG0007727715000083.jpg18150[Chemical formula 1-4] JPEG0007727715000084.jpg18150[Chemical formula 1-5] JPEG0007727715000085.jpg21150[Chemical formula 1-6] JPEG0007727715000086.jpg19150[Chemical formula 1-7] JPEG0007727715000087.jpg18150[Chemical formula 1-8] JPEG0007727715000088.jpg20150[Chemical formula 1-9] JPEG0007727715000089.jpg19150[Chemical formula 1-10] JPEG0007727715000090.jpg19150[Chemical formula 1-11] JPEG0007727715000091.jpg19150[Chemical formula 1-12] JPEG0007727715000092.jpg19150[Chemical formula 1-13] JPEG0007727715000093.jpg20150[Chemical formula 1-14] JPEG0007727715000094.jpg20150[Chemical formula 1-15] JPEG0007727715000095.jpg20150[Chemical formula 1-16] JPEG0007727715000096.jpg19150[Chemical formula 1-17] JPEG0007727715000097.jpg20150[Chemical formula 1-18] JPEG0007727715000098.jpg20150[Chemical formula 1-19] JPEG0007727715000099.jpg20150[Chemical formula 1-20] JPEG0007727715000100.jpg19150[Chemical formula 1-21] JPEG0007727715000101.jpg22150[Chemical formula 2-1] JPEG0007727715000102.jpg26150[Chemical formula 2-2] JPEG0007727715000103.jpg23150[Chemical formula 2-3] JPEG0007727715000104.jpg29150[Chemical formula 2-4] JPEG0007727715000105.jpg27150[Chemical formula 2-5] JPEG0007727715000106.jpg26150[Chemical formula 2-6] JPEG0007727715000107.jpg27150[Chemical formula 2-7] JPEG0007727715000108.jpg29150In the above chemical formula, Me is methyl and Ph is phenyl.

[0071] In a specific embodiment, the solvent may include at least one selected from the group consisting of aliphatic hydrocarbon solvents such as hexane and pentane, aromatic hydrocarbon solvents such as toluene and benzene, chlorine-substituted hydrocarbon solvents such as dichloromethane, ether solvents such as diethyl ether and tetrahydrofuran, acetone, and ethyl acetate.Preferably, the solvent may be toluene, but is not particularly limited thereto.

[0072] When dissolving the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 in a solvent, the order of adding each compound is not particularly limited. That is, the compound represented by Chemical Formula 1 may be added to the solvent first and dissolved therein, and then the compound represented by Chemical Formula 2 may be added to the solvent and dissolved therein, or the dissolution order may be reversed. Alternatively, these two compounds may be added to the solvent at the same time and dissolved therein.

[0073] When dissolving the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 in a solvent, the temperature and dissolution time are not particularly limited. In a specific embodiment, the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are added to a solvent, either individually or simultaneously, at a temperature of −78° C. to 80° C., preferably −40° C. to 60° C., and more preferably at room temperature, and then stirred for 1 hour to 24 hours, preferably 5 hours to 20 hours, and more preferably about 15 hours to dissolve them.

[0074] In a specific embodiment, the molar ratio of the compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 2 dissolved in the solvent in step (1) is in the range of 1:100 to 100:1. Preferably, the molar ratio of the two compounds is 1:30 to 30:1. More preferably, the molar ratio of the two compounds is 1:20 to 20:1.

[0075] <Step (2)> The compound represented by the following Formula 3 is added to the solution obtained in step (1), and the mixture is reacted under stirring to obtain a mixture of transition metal compounds represented by the following Formulas 4 and 5.

[0076] [Chemical formula 3] MX4 [Chemical formula 4] JPEG0007727715000109.jpg57150[Chemical formula 5] JPEG0007727715000110.jpg57150

[0077] In the above Chemical Formulas 3 to 5, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). Specifically, M may be zirconium or hafnium.

[0078] X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 Specifically, X is a halogen or a substituted or unsubstituted C 1-20 More specifically, each X may be chlorine.

[0079] In the above Chemical Formula 4 and Chemical Formula 5, R1 to R5 and R6 to R 10 is as explained in step (1) above.

[0080] In a specific embodiment, the compound represented by Chemical Formula 3 is ZrCl4 or HfCl4.

[0081] In a specific embodiment, the temperature when the compound represented by Chemical Formula 3 is added to the solution obtained in step (1) may be −78° C. to 30° C. Preferably, the temperature when the compound represented by Chemical Formula 3 is added may be −40° C. to 10° C. More preferably, the temperature when the compound represented by Chemical Formula 3 is added may be about −30° C.

[0082] In a specific embodiment, after adding the compound represented by Chemical Formula 3, the temperature of the resulting reaction mixture is gradually increased to a range of 0°C to 120°C, preferably a range of 25°C to 100°C, more preferably about 70°C, and the reaction is carried out under stirring for 1 hour to 72 hours, preferably 5 hours to 48 hours, more preferably about 24 hours, to obtain a mixture of the transition metal compounds represented by Chemical Formula 4 and Chemical Formula 5.

[0083] In one specific embodiment, the transition metal compound represented by the chemical formula 4 is at least one of the transition metal compounds represented by the following chemical formulas 4-1 to 4-21, and the transition metal compound represented by the chemical formula 5 is at least one of the transition metal compounds represented by the following chemical formulas 5-1 to 5-21.

[0084] [Chemical formula 4-1] JPEG0007727715000111.jpg38150[Chemical formula 4-2] JPEG0007727715000112.jpg37150[Chemical formula 4-3] JPEG0007727715000113.jpg38150[Chemical formula 4-4] JPEG0007727715000114.jpg37150[Chemical formula 4-5] JPEG0007727715000115.jpg43150[Chemical formula 4-6] JPEG0007727715000116.jpg39150[Chemical formula 4-7] JPEG0007727715000117.jpg44150[Chemical formula 4-8] JPEG0007727715000118.jpg48150[Chemical formula 4-9] JPEG0007727715000119.jpg42150[Chemical formula 4-10] JPEG0007727715000120.jpg42150[Chemical formula 4-11] JPEG0007727715000121.jpg48150[Chemical formula 4-12] JPEG0007727715000122.jpg43150[Chemical formula 4-13] JPEG0007727715000123.jpg47150[Chemical formula 4-14] JPEG0007727715000124.jpg48150[Chemical formula 4-15] JPEG0007727715000125.jpg48150[Chemical formula 4-16] JPEG0007727715000126.jpg43150[Chemical Formula 4-17] JPEG0007727715000127.jpg47150[Chemical Formula 4-18] JPEG0007727715000128.jpg47150[Chemical Formula 4-19] JPEG0007727715000129.jpg46150[Chemical formula 4-20] JPEG0007727715000130.jpg41150[Chemical Formula 4-21] JPEG0007727715000131.jpg48150[Chemical Formula 5-1] JPEG0007727715000132.jpg32150[Chemical Formula 5-2] JPEG0007727715000133.jpg30150[Chemical Formula 5-3] JPEG0007727715000134.jpg32150[Chemical formula 5-4] JPEG0007727715000135.jpg30150[Chemical formula 5-5] JPEG0007727715000136.jpg42150[Chemical formula 5-6] JPEG0007727715000137.jpg34150[Chemical formula 5-7] JPEG0007727715000138.jpg34150[Chemical formula 5-8] JPEG0007727715000139.jpg41150[Chemical formula 5-9] JPEG0007727715000140.jpg31150[Chemical formula 5-10] JPEG0007727715000141.jpg31150[Chemical formula 5-11] JPEG0007727715000142.jpg41150[Chemical formula 5-12] JPEG0007727715000143.jpg31150[Chemical formula 5-13] JPEG0007727715000144.jpg41150[Chemical formula 5-14] JPEG0007727715000145.jpg43150[Chemical formula 5-15] JPEG0007727715000146.jpg42150[Chemical formula 5-16] JPEG0007727715000147.jpg35150[Chemical formula 5-17] JPEG0007727715000148.jpg41150[Chemical formula 5-18] JPEG0007727715000149.jpg41150[Chemical formula 5-19] JPEG0007727715000150.jpg42150[Chemical formula 5-20] JPEG0007727715000151.jpg30150[Chemical formula 5-21] JPEG0007727715000152.jpg47150In the above chemical formula, Me is methyl and Ph is phenyl.

[0085] In a specific embodiment, in the mixture of transition metal compounds obtained in step (2), the molar ratio of the transition metal compound represented by Chemical Formula 4 to the transition metal compound represented by Chemical Formula 5 is in the range of 1:100 to 100:1. Preferably, the molar ratio of the two compounds is 1:30 to 30:1. More preferably, the molar ratio of the two compounds is 1:20 to 20:1.

[0086] In a specific embodiment, the catalyst preparation method of the present invention may further include a step (2') of drying the mixture of transition metal compounds obtained in step (2). The drying conditions for the mixture are not particularly limited, but the drying may be carried out at a temperature ranging from 25°C to 80°C, preferably from 25°C to 50°C, and more preferably at about 25°C.

[0087] In a specific embodiment, the catalyst preparation method of the present invention may further include a step (2'') of dissolving the dried mixture of transition metal compounds obtained in step (2') in a solvent and then removing unreacted materials and / or impurities using a filter. The solvent may be substantially the same as the solvent used in step (1). Preferably, dichloromethane may be used, but is not limited thereto. The filter for removing unreacted materials and / or impurities is not particularly limited, but a Celite filter is preferably used.

[0088] <Step (3)> The mixture of transition metal compounds obtained in step (2) and a transition metal compound represented by the following formula 6 are activated with a co-catalyst compound. [Chemical formula 6] In Formula 6, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). Specifically, M may be zirconium or hafnium.

[0089] Q is an anionic leaving group, each independently hydrogen, hydrocarbyl, heteroatom or halogen, straight-chain or branched alkyl radical, or alkenyl radical, alkynyl radical, cycloalkyl radical or aryl radical, acyl radical, aroyl radical, alkoxy radical, aryloxy radical, alkylthio radical, dialkylamino radical, alkoxycarbonyl radical, aryloxycarbonyl radical, carbamoyl radical, alkyl- or dialkyl-carbamoyl radical, acyloxy radical, acylamino radical, aroylamino radical, straight-chain, branched-chain or cyclic alkylene radical, or a combination thereof. Specifically, each Q can independently be hydrogen, halogen, or hydrocarbyl group.

[0090] m is the oxidation state of M and is +3, +4 or +5. o is the formal charge of the YZL ligand and is 0, −1, −2, or −3. L is a Group 15 or 16 element, preferably nitrogen. Y is a Group 15 element, preferably nitrogen or phosphorus, more preferably nitrogen. Z is a Group 15 element, preferably nitrogen or phosphorus, more preferably nitrogen.

[0091] R 11 and R 12 are each independently C 1-20 a hydrocarbon group or a heteroatom-containing group, where the heteroatom is silicon, germanium, tin, lead, or phosphorus, or R 11 and R 12 can be bonded to each other. Specifically, R 11 and R 12 However, each independently C 1-6 It may be a hydrocarbon group.

[0092] R 13 is absent or hydrogen, C 1-20 alkyl, halogen, or heteroatom-containing groups. 13 can be hydrogen or methyl.

[0093] R 14 and R 15 are each independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, or a polycyclic ring system. 14 and R 15 may each independently be a substituted aryl group.

[0094] R 16 and R 17 may each independently be absent, a hydrogen, an alkyl group, a halogen, a heteroatom, a hydrocarbyl group, or a heteroatom-containing group.

[0095] In a specific embodiment, in Formula 6, M is zirconium or hafnium, each Q is independently hydrogen, halogen, or a hydrocarbyl group, and R 11 and R 12 However, each independently C 1-6 is a hydrocarbon group, R 13 is hydrogen or methyl, and R 14 and R 15 are each independently a substituted aryl group.

[0096] In a more specific embodiment, in the formula 6, R 14 and R 15 are each independently a group represented by the following chemical formula 6a.

[0097] [Chemical formula 6a] JPEG0007727715000154.jpg42150

[0098] In the above formula 6a, R 18 ~R 22 are each independently hydrogen, C 1-20 an alkyl group, a heteroatom, or a heteroatom-containing group having 40 or fewer carbon atoms; R 18 ~R 22 Two of the groups may be linked to form a cyclic or heterocyclic group.

[0099] In a more specific embodiment, the transition metal compound of Chemical Formula 6 is a compound represented by the following Chemical Formula 6-1. [Chemical formula 6-1] JPEG0007727715000155.jpg26150

[0100] In a specific embodiment, the co-catalyst compound may include one or more selected from the group consisting of a compound represented by the following chemical formula 7, a compound represented by the chemical formula 8, and a compound represented by the chemical formula 9:

[0101] [Chemical formula 7] JPEG0007727715000156.jpg22150In the above Chemical Formula 7, n is an integer of 2 or more, and R a is a halogen atom, C 1-20 Hydrocarbon or halogen-substituted C 1-20 It can be a hydrocarbon group. Specifically, R a can be methyl, ethyl, n-butyl, or isobutyl.

[0102] [Chemical formula 8] JPEG0007727715000157.jpg24150 In the above Chemical Formula 8, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, C 1-20 Hydrocarbon groups, halogen-substituted C 1-20 Hydrocarbon group, or C 1-20 Specifically, when D is aluminum (Al), R b , R c and R d are each independently methyl or isobutyl, and when D is boron (B), R b , R c and R d may each be pentafluorophenyl.

[0103] [Chemical formula 9] [LH] + [Z(A)4] - or [L] + [Z(A)4] - In the formula 9, L is a neutral or cationic Lewis base, [LH] + and [L] + is a Bronsted acid, Z is a Group 13 element, and each A is independently a substituted or unsubstituted C 6-20 an aryl group or a substituted or unsubstituted C 1-20 It is an alkyl group. Specifically, [LH] + is the dimethylanilinium cation, [Z(A)4] -is [B(C6F5)4] - and [L] + is [(C6H5)3C] + It could be.

[0104] In a more specific embodiment, examples of the compound represented by Chemical Formula 7 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., and methylaluminoxane is preferred, but is not limited thereto.

[0105] Examples of the compound represented by Chemical Formula 8 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, and tributylboron, of which trimethylaluminum, triethylaluminum, and triisobutylaluminum are preferred, but not limited to these.

[0106] Further, the compound represented by Chemical Formula 9 includes triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate, triphenylcarbenium tetra(p-trifluoromethylphenyl)borate, and triphenylcarbenium tetrapentafluorophenylborate.

[0107] In a specific embodiment, the catalyst preparation method of the present invention may further include a step (3') of supporting a part or all of the transition metal compounds represented by the chemical formulas 4 to 6 and the co-catalyst compound on a support before or after the step (3).

[0108] The support may include a substance containing hydroxyl groups on its surface. Preferably, a substance having highly reactive hydroxyl groups and siloxane groups that has been dried to remove moisture from its surface can be used. In a specific embodiment, the support may include at least one selected from the group consisting of silica, alumina, and magnesia. Specifically, silica, silica-alumina, silica-magnesia, etc., dried at high temperatures are used as the support. These typically contain oxides, carbonates, sulfates, and nitrates such as Na2O, K2CO3, BaSO4, and Mg(NO3)2. They may also contain carbon, zeolite, magnesium chloride, etc. However, the support is not limited to these and may be any material capable of supporting a transition metal compound and a promoter compound.

[0109] The carrier may have an average particle size of 10 μm to 250 μm, preferably 10 μm to 150 μm, and more preferably 20 μm to 100 μm.

[0110] The volume of the micropores in the support may be 0.1 cc / g to 10 cc / g, preferably 0.5 cc / g to 5 cc / g, and more preferably 1.0 cc / g to 3.0 cc / g.

[0111] The specific surface area of ​​the support is 1m 2 / g~1000m 2 / g, preferably 100m 2 / g~800m 2 / g, more preferably 200m 2 / g~600m 2 / g.

[0112] In a preferred embodiment, when the support is silica, the drying temperature for the silica may be room temperature to 900° C. The drying temperature may be preferably room temperature to 800° C., more preferably room temperature to 700° C. If the drying temperature is lower than room temperature, there may be too much moisture, which may cause a reaction between the moisture on the surface and the co-catalyst, and if the drying temperature exceeds 900° C., the structure of the support may be destroyed.

[0113] The hydroxyl group concentration in the dried silica may be 0.1 mmol / g to 5 mmol / g, preferably 0.7 mmol / g to 4 mmol / g, and more preferably 1.0 mmol / g to 2 mmol / g. If the hydroxyl group concentration is less than 0.1 mmol / g, the amount of the co-catalyst supported will be low, and if it exceeds 5 mmol / g, the catalyst component may become inactive.

[0114] In a specific embodiment, the support supports both the transition metal compounds represented by the above chemical formulas 4 to 6 and the promoter compound.

[0115] In this case, the total amount of the mixed transition metal compound supported on the support may be 0.001 mmol to 1 mmol per gram of support. When the ratio of the mixed transition metal compound to the support satisfies the above range, the supported catalyst exhibits appropriate activity, which is advantageous in terms of maintaining the catalyst activity and economy.

[0116] The total amount of promoter compounds supported on the carrier may be 2 mmol to 15 mmol per gram of carrier. If the ratio of promoter compounds to carrier satisfies the above range, it is advantageous in terms of maintaining catalyst activity and economy.

[0117] In a specific embodiment, one or more supports may be used. For example, both the mixed transition metal compound and the co-catalyst compound may be supported on one support, or the mixed transition metal compound and the co-catalyst compound may be supported on two or more supports, respectively. Alternatively, only one of the mixed transition metal compound and the co-catalyst compound may be supported on a support.

[0118] As a method for supporting the mixture of transition metal compounds and / or the promoter compound, a physical adsorption method or a chemical adsorption method can be used.

[0119] In a specific embodiment, the physical adsorption method may be a method in which a solution in which a mixed transition metal compound is dissolved is brought into contact with a support and then dried; a method in which a solution in which a mixed transition metal compound and a promoter compound are dissolved is brought into contact with a support and then dried; or a method in which a solution in which a mixed transition metal compound is dissolved is brought into contact with a support and then dried to prepare a support on which a mixed transition metal compound is supported, and separately a solution in which a promoter compound is dissolved is brought into contact with a support and then dried to prepare a support on which a promoter compound is supported, and then these are mixed together, etc.

[0120] In a specific embodiment, the chemical adsorption method may be a method in which a promoter compound is first supported on the surface of a support, and then a mixed transition metal compound is supported on the promoter compound, or a method in which a functional group on the surface of the support (e.g., in the case of silica, a hydroxy group (—OH) on the surface of silica) is covalently bonded to the mixed transition metal compound.

[0121] The solvent used when supporting the mixed transition metal compound and / or the co-catalyst compound is not particularly limited. For example, the solvent may include at least one selected from the group consisting of aliphatic hydrocarbon solvents such as hexane and pentane, aromatic hydrocarbon solvents such as toluene and benzene, chlorine-substituted hydrocarbon solvents such as dichloromethane, ether solvents such as diethyl ether and tetrahydrofuran, acetone, and ethyl acetate.

[0122] In a specific embodiment, the step (3') of supporting the mixed transition metal compound and / or the cocatalyst compound on the support may be carried out at a temperature of 0°C to 100°C, preferably at a temperature of room temperature to 90°C.

[0123] In step (3'), the process of supporting the mixed transition metal compound and / or the co-catalyst compound on the support can be carried out by thoroughly stirring the mixture of the mixed transition metal compound and / or the co-catalyst compound and the support for 1 minute to 24 hours, preferably 5 minutes to 15 hours.

[0124] [Olefin polymerization catalyst] According to one embodiment of the present invention, there is provided an olefin polymerization catalyst prepared by the preparation method according to the embodiment of the present invention, the catalyst comprising a transition metal compound represented by one of the following chemical formulas 4 to 6 and a co-catalyst compound containing at least one selected from the group consisting of compounds represented by the following chemical formulas 7 to 9:

[0125] [Chemical formula 4] JPEG0007727715000158.jpg65150[Chemical formula 5] JPEG0007727715000159.jpg65150[Chemical formula 6] JPEG0007727715000160.jpg48150

[0126] In the above chemical formulas 4 to 6, M, X, R1 to R5 and R6 to R 10 , R 11 ~R 17 , m, o, Q, Y, Z, and L are as explained in the section on the preparation method of the olefin polymerization catalyst.

[0127] [Chemical formula 7] JPEG0007727715000161.jpg23150[Chemical formula 8] JPEG0007727715000162.jpg25150[Chemical formula 9] [LH] + [Z(A)4] - or [L] + [Z(A)4] - In the above Chemical Formulas 7 to 9, n, D, L, Z, A and R a ~R d is as explained in the section on the preparation method of the olefin polymerization catalyst.

[0128] In a specific embodiment, the olefin polymerization catalyst may further include a support that supports a part or all of the transition metal compounds represented by the chemical formulas 4 to 6 and the co-catalyst compound including at least one selected from the group consisting of the compounds represented by the chemical formulas 7 to 9.

[0129] Specific details regarding the transition metal compounds represented by the chemical formulae 4 to 6, the co-catalyst compound containing at least one selected from the group consisting of the compounds represented by the chemical formulae 7 to 9, and the carrier are as explained in the section regarding the method for preparing an olefin polymerization catalyst.

[0130] [Method for preparing olefin polymer] According to one embodiment of the present invention, there is provided a method for preparing an olefin polymer, comprising: (1) dissolving the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 in a solvent; (2) adding the compound represented by Chemical Formula 3 to the solution obtained in Step (1) and then reacting them under stirring to obtain a mixture of transition metal compounds represented by Chemical Formula 4 and Chemical Formula 5; (3) activating the mixture of transition metal compounds obtained in Step (2) and the transition metal compound represented by Chemical Formula 6 with a co-catalyst compound; (4) before or after Step (3), supporting a part or all of the transition metal compounds represented by Chemical Formulas 4 to 6 and the co-catalyst compound on a support; and (5) polymerizing an olefin in the presence of the catalyst obtained in Step (3) or Step (4).

[0131] The specific contents of the steps (1) to (4) are substantially the same as the steps (1) to (3) and (3') in the method for preparing an olefin polymerization catalyst.

[0132] In a specific embodiment, the method for preparing an olefin polymer may further include (2') a step of drying the mixture of transition metal compounds in the step (2).

[0133] In a specific embodiment, the method for preparing an olefin polymer may further include a step (2'') of dissolving the dried mixture of transition metal compounds obtained in step (2') in a solvent, and then removing unreacted materials and / or impurities using a filter.

[0134] The specific contents of step (2') and step (2'') are substantially the same as step (2') and step (2'') in the above-mentioned method for preparing an olefin polymerization catalyst.

[0135] <Step (5)> Olefins are polymerized in the presence of the catalyst obtained in step (3) or step (4).

[0136] In a specific embodiment, the polymerization of olefins can be homopolymerization of an olefinic monomer or copolymerization of an olefinic monomer and an olefinic comonomer. Preferably, the polymerization of olefins is copolymerization of an olefinic monomer and an olefinic comonomer.

[0137] In one exemplary embodiment, the olefinic monomer and the olefinic comonomer are each at least one selected from the group consisting of α-olefins having 2 to 20 carbon atoms, diolefins having 1 to 20 carbon atoms, cycloolefins having 3 to 20 carbon atoms, and cyclodiolefins having 3 to 20 carbon atoms.

[0138] In one exemplary implementation, the olefinic monomer can be ethylene and the olefinic comonomer can be one or more selected from the group consisting of, but not limited to, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, and 1-hexadecene.

[0139] In a specific embodiment, the polymerization of olefins is copolymerization of an olefin-based monomer and an olefin-based comonomer, where the olefin-based monomer may be ethylene and the olefin-based comonomer may be, but is not limited to, 1-hexene.

[0140] In this case, the ethylene content is preferably 55 to 99.9% by weight, more preferably 90 to 99.9% by weight, and the α-olefin comonomer content is preferably 0.1 to 45% by weight, more preferably 0.1 to 10% by weight.

[0141] In a specific implementation, the polymerization of olefins can be, for example, but not limited to, free radical, cationic, coordination, condensation, addition, and the like polymerization reactions.

[0142] In an exemplary implementation, the polymerization of olefins can be carried out by, for example, but not limited to, a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method, etc. Preferably, the polymerization of olefins can be carried out by a gas phase polymerization method.

[0143] If the olefin polymerization is carried out by a solution polymerization method or a slurry polymerization method, examples of solvents that can be used include C 2 olefins such as pentane, hexane, heptane, nonane, decane, and their isomers. 5-12 Examples of suitable solvents include, but are not limited to, aliphatic hydrocarbon solvents; aromatic hydrocarbon solvents such as toluene and benzene; hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; and mixtures thereof.

[0144] [Olefin polymer] According to one embodiment of the present invention, a cellulose ester having a density of 0.940 g / cm3 is prepared by the preparation method according to the embodiment of the present invention. 3 ~0.970g / cm 3 , (2) Melt Index Ratio (MI 21.6 / MI 2.16 (2) a weight average molecular weight (Mw) of 80,000 g / mol to 600,000 g / mol; and (3) a molecular weight distribution (MWD) as determined by a polydispersity index (Mw / Mn) of 10 to 50.

[0145] In a specific embodiment, the olefin-based polymer may be a homopolymer of an olefin-based monomer or a copolymer of an olefin-based monomer and a comonomer.

[0146] In one exemplary embodiment, the olefin-based polymer may be a copolymer of an olefin-based monomer and an olefin-based comonomer. Specifically, the olefin-based polymer may be a copolymer of ethylene and an α-olefin-based comonomer having 3 to 20 carbon atoms. More specifically, the olefin-based monomer may be ethylene, and the α-olefin-based comonomer may be one or more selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, and 1-hexadecene.

[0147] In one exemplary implementation, the olefin-based polymer can be, but is not limited to, a high density polyethylene in which the olefin-based monomer is ethylene and the olefin-based comonomer is 1-hexene.

[0148] The olefin polymer according to one embodiment of the present invention has a density of 0.940 g / cm 3 ~0.970g / cm 3 Preferably, the density of the olefin polymer is 0.940 g / cm 3 ~0.965g / cm 3 and more preferably, the density of the olefin polymer is 0.945 g / cm 3 ~0.960g / cm 3 is.

[0149] In addition, the olefin polymer has a melt index ratio (MI21.6 / MI 2.16 ) is 30 to 200. Preferably, the melt index ratio of the olefin polymer is 50 to 200, and more preferably, the melt index ratio of the olefin polymer is 70 to 200.

[0150] The olefin polymer has a weight average molecular weight (Mw) of 80,000 g / mol to 600,000 g / mol, and preferably has a weight average molecular weight (Mw) of 200,000 g / mol to 500,000 g / mol.

[0151] The olefin polymer has a molecular weight distribution (MWD) based on a polydispersity index (Mw / Mn) of 10 to 50. Preferably, the olefin polymer has a molecular weight distribution based on a polydispersity index of 20 to 50.

[0152] The olefin polymers according to the present invention can have a bimodal or multimodal molecular weight distribution because phase separation of the molecular structure is prevented, and therefore can have excellent processability and mechanical properties.

[0153] (Example) The present invention will be described in more detail below with reference to examples. However, the following examples are intended to illustrate the present invention only, and the scope of the present invention is not limited to these examples.

[0154] (Preparation Example: Preparation of Mixed Transition Metal Compounds) (Preparation Example 1) 281 mg (2.46 mmol, 7 eq.) of lithium n-propylcyclopentadienide of formula 1-1 and 60 mg (0.42 mmol, 1.2 eq.) of lithium pentamethylcyclopentadienide of formula 2-1 were dissolved in 30 ml of toluene at 25°C. After cooling the solution to -30°C, 328 mg (1.41 mmol, 4 eq.) of zirconium chloride (ZrCl4) was gradually added. The temperature of the reaction mixture was gradually raised to room temperature and then to 70°C, followed by stirring for 24 hours. After completion of the reaction, lithium chloride (LiCl) was removed using a Celite filter, and the product was dried to obtain 459 mg of a mixture of transition metal compounds (yield: 86%).

[0155] 1 The structure of the mixed (1:3) transition metal compound of the compound of formula 4-1 ((pentamethylcyclopentadienyl)(n-propylcyclopentadienyl) zirconium dichloride) and the compound of formula 5-1 (bis(n-propylcyclopentadienyl) zirconium dichloride) was confirmed by H NMR. 1 H-NMR (CDCl3, 300 MHz) 6.28 (t, 12H), 6.19 (t, 12H), 6.02 (t, 2H), 5.94 (t, 2H), 2.60 (t, 14H), 2.02 (s, 15H), 1.64-1.52 (m, 14H), 0.93 (t, 20H).

[0156] (Preparation Example 2) 441 mg (3.87 mmol, 11 eq.) of lithium n-propylcyclopentadienide of the formula 1-1 and 60 mg (0.42 mmol, 1.2 eq.) of lithium pentamethylcyclopentadienide of the formula 2-1 were dissolved in 50 ml of toluene at 25°C. After cooling this solution to -30°C, 492 mg (2.11 mmol, 6 eq.) of zirconium chloride (ZrCl4) was gradually added. The temperature of the reaction mixture was gradually raised to room temperature and then to 70°C, followed by stirring for 24 hours. After completion of the reaction, lithium chloride (LiCl) was removed using a Celite filter, and the product was dried to obtain 675 mg of a mixture of transition metal compounds (yield: 84%).

[0157] 1 The structure of the mixed (1:5) transition metal compound of the compound of the formula 4-1 and the compound of the formula 5-1 was confirmed by 1 H NMR. 1 H-NMR (CDCl3, 300 MHz) 6.28 (t, 20H), 6.19 (t, 20H), 6.02 (t, 2H), 5.94 (t, 2H), 2.60 (t, 22H), 2.02 (s, 15H), 1.64-1.52 (m, 22H), 0.93 (t, 32H).

[0158] (Example: Preparation of olefin polymerization catalyst) Example 1 1.1 mg of the transition metal compound mixture obtained in Preparation Example 1 and 5.3 mg of the compound of Formula 6-1 ({[(2,4,6-Me3C6H2)NCH2CH2]2NH}Zr(CH2Ph)2) were mixed with 6.9 g of a 10 wt% toluene solution of methylaluminoxane (MAO) (Al / Zr = 120) in a glove box and stirred at room temperature for 1 hour. 2.0 g of silica (ES70) and 50 ml of purified toluene were added to a 100 ml flask. The mixed transition metal compound solution obtained above was poured into this silica slurry and stirred in an oil bath at 25°C for 3 hours. After the loading was complete and the solid / liquid phases were fully separated, the supernatant liquid was removed. The supported catalyst was washed three times with toluene and dried under vacuum at 25°C for 30 minutes to obtain 2.5 g of a free-flowing powder.

[0159] (Comparative Example 1) 1.1 mg of the compound of formula 5-1 (bis(n-propylcyclopentadienyl)zirconium dichloride) and 5.3 mg of the compound of formula 6-1 were mixed with 6.9 g of a 10 wt % toluene solution of methylaluminoxane (MAO) (Al / Zr = 120) in a glove box and stirred at room temperature for 1 hour. 2.0 g of silica (ES70) and 50 ml of purified toluene were added to a 100 ml flask. The mixed transition metal compound solution obtained above was poured into this silica slurry and stirred in an oil bath at 25 °C for 3 hours. After the loading was complete and the solid / liquid phases were fully separated, the supernatant liquid was removed. The supported catalyst was washed three times with toluene and dried under vacuum at 25 °C for 30 minutes to obtain 2.5 g of a free-flowing powder.

[0160] (Comparative Example 2) A free-flowing powder (2.5 g) was obtained in the same manner as in Preparation Example 2-3, except that 1.2 mg of the compound of formula 4-1 ((pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride) and 7.9 mg of the compound of formula 6-1 were used. The composition ratios of the reactants and products in the above examples are shown in Tables 1 and 2 below.

[0161] (Test example) Test Example Polyolefins were polymerized in a gas-phase fluidized bed reactor using each of the supported catalysts obtained in the Examples and Comparative Examples. Specifically, ethylene and 1-hexene were copolymerized for 1 hour in the presence of 50 mg of each of the supported catalysts obtained in the Examples and Comparative Examples and 0.6 ml of 1 M triisobutylaluminum (TIBAL) as a scavenger. The temperature in the reactor was maintained at approximately 85°C, and the ethylene pressure was 14 kgf / cm. 2 The initial amount of 1-hexene injected was 10 ml. Hydrogen was added to adjust the molecular weight of the polymer. The polymerization conditions are summarized in Table 1 below.

[0162] The physical properties of the olefin polymers prepared using the supported catalysts obtained in the Examples and Comparative Examples were measured as follows. The measurement results are shown in Table 2 below and FIG. (1) Density Measurement was performed according to ASTM D1505. (2) Melt index and melt flow ratio (MFR) Based on ASTM D 1238, the melt index was measured at 190°C with a load of 21.6 kg and a load of 2.16 kg, and the ratio (MI 21.6 / MI 2.16 ) was sought. (3) Molecular weight and molecular weight distribution Measurement was carried out using gel permeation chromatography-Fourier transform infrared spectroscopy (GPC-FTIR).

[0163] [Table 1]

[0164] [Table 2]

[0165] As can be seen from Table 2 and Figure 1, the olefin polymers obtained in the Examples, compared to the olefin polymers obtained in the Comparative Examples, showed a relatively large MFR, while the distribution of high molecular weight log Mw around 6 to 7 was similar. In particular, the olefin polymers of the Examples showed a larger MWD and a larger MI than the olefin polymers of the Comparative Examples. 21.6 Therefore, the processability can be improved even if the weight average molecular weight is similar. [Industrial Applicability]

[0166] The olefin polymer according to the embodiment of the present invention is prevented from undergoing phase separation in molecular structure, and is free from unevenness such as irregularities or cracks when formed into a film. Since the polymer has a bimodal or multimodal molecular weight distribution, the polymer exhibits excellent processability and mechanical properties.

Claims

1. The method includes the steps of: (1) dissolving at least one of compounds represented by the following chemical formulas 1-1 to 1-21 and at least one of compounds represented by the following chemical formulas 2-1 to 2-7 in a solvent; (2) adding a compound represented by the following chemical formula 3 to the solution obtained in the step (1), and then reacting them under stirring to obtain a mixture of at least one transition metal compound represented by the following chemical formulas 4-1 to 4-21 and at least one transition metal compound represented by the following chemical formulas 5-1 to 5-21; and (3) activating the mixture of transition metal compounds obtained in the step (2) and a transition metal compound represented by the following chemical formula 6 with a co-catalyst compound, A method for preparing an olefin polymerization catalyst, wherein the molar ratio of at least one of the compounds represented by the following chemical formulas 1-1 to 1-21 to at least one of the compounds represented by the following chemical formulas 2-1 to 2-7 is in the range of 1:30 to 30:1, but the molar ratio of at least one of the compounds represented by the following chemical formulas 1-1 to 1-21 is not the same as the molar ratio of at least one of the compounds represented by the following chemical formulas 2-1 to 2-7: [Chemical formula 1-1] [Chemical formula 1-2] [Chemical formula 1-3] [Chemical formula 1-4] [Chemical formula 1-5] [Chemical formula 1-6] [Chemical formula 1-7] [Chemical formula 1-8] [Chemical formula 1-9] [Chemical formula 1-10] [Chemical formula 1-11] [Chemical formula 1-12] [Chemical formula 1-13] [Chemical formula 1-14] [Chemical formula 1-15] [Chemical formula 1-16] [Chemical formula 1-17] [Chemical formula 1-18] [Chemical formula 1-19] [Chemical formula 1-20] [Chemical formula 1-21] [Chemical formula 2-1] [Chemical formula 2-2] [Chemical formula 2-3] [Chemical formula 2-4] [Chemical formula 2-5] [Chemical formula 2-6] [Chemical formula 2-7] [Chemical formula 3] MX ４ [Chemical formula 4-1] [Chemical formula 4-2] [Chemical formula 4-3] [Chemical formula 4-4] [Chemical formula 4-5] [Chemical formula 4-6] [Chemical formula 4-7] [Chemical formula 4-8] [Chemical formula 4-9] [Chemical formula 4-10] [Chemical formula 4-11] [Chemical formula 4-12] [Chemical formula 4-13] [Chemical formula 4-14] [Chemical formula 4-15] [Chemical formula 4-16] [Chemical formula 4-17] [Chemical formula 4-18] [Chemical formula 4-19] [Chemical formula 4-20] [Chemical formula 4-21] [Chemical formula 5-1] [Chemical formula 5-2] [Chemical formula 5-3] [Chemical formula 5-4] [Chemical formula 5-5] [Chemical formula 5-6] [Chemical formula 5-7] [Chemical formula 5-8] [Chemical formula 5-9] [Chemical formula 5-10] [Chemical formula 5-11] [Chemical formula 5-12] [Chemical formula 5-13] [Chemical formula 5-14] [Chemical formula 5-15] [Chemical formula 5-16] [Chemical formula 5-17] [Chemical formula 5-18] [Chemical formula 5-19] [Chemical formula 5-20] [Chemical formula 5-21] In the above formula, Me is methyl and Ph is phenyl. [Chemical formula 6] In the above chemical formulas 3 and 6, M is zirconium (Zr); X is Cl; Q are anionic leaving groups, each independently hydrogen, hydrocarbyl, heteroatom or halogen, a straight-chain or branched alkyl radical, alkenyl radical, alkynyl radical, cycloalkyl radical or aryl radical, acyl radical, aroyl radical, alkoxy radical, aryloxy radical, alkylthio radical, dialkylamino radical, alkoxycarbonyl radical, aryloxycarbonyl radical, carbamoyl radical, alkyl- or dialkyl-carbamoyl radical, acyloxy radical, acylamino radical, aroylamino radical, straight-chain, branched or cyclic alkylene radical, or combinations thereof; m is the oxidation state of M and is +3, +4 or +5; o is the formal charge of the Y, Z, and L ligands and is 0, −1, −2, or −3; L is nitrogen; Y is nitrogen or phosphorus; Z is nitrogen or phosphorus; R １１ and R １２ are each independently C １－２０ a hydrocarbon group or a heteroatom-containing group, where the heteroatom is silicon, germanium, tin, lead, or phosphorus, or R １１ and R １２ may be bonded to each other, R １３ is absent or hydrogen, C １－２０ alkyl, halogen or heteroatom-containing group; R １４ and R １５ are each independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, or a polycyclic ring system; R １６ and R １７ are each independently absent, a hydrogen, an alkyl group, a halogen, a heteroatom, a hydrocarbyl group, or a heteroatom-containing group.

2. 2. The method for preparing an olefin polymerization catalyst according to claim 1, wherein the solvent comprises at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate.

3. 2. The method for preparing an olefin polymerization catalyst according to claim 1, wherein in step (2), the reaction temperature is 0 to 120°C and the reaction time is 1 to 72 hours.

4. 2. The method for preparing an olefin polymerization catalyst according to claim 1, further comprising the step of: (2') drying the mixture of transition metal compounds obtained in step (2).

5. (2'') The method for preparing an olefin polymerization catalyst according to claim 4, further comprising the step of dissolving the dried mixture of transition metal compounds obtained in step (2') in a solvent, and then removing unreacted materials and / or impurities through a filter.

6. In Formula 6, M is zirconium, each Q is independently hydrogen, halogen, or a hydrocarbyl group, and R １１ and R １２ are each independently C １－６ is a hydrocarbon group, R １３ is hydrogen or methyl, and R １４ and R １５ 2. The method for preparing an olefin polymerization catalyst according to claim 1, wherein each of the groups is independently a substituted aryl group.

7. The method for preparing an olefin polymerization catalyst according to claim 6, wherein the transition metal compound represented by Chemical Formula 6 is a transition metal compound represented by the following Chemical Formula 6-1: [Chemical formula 6-1] 。

8. 2. The method for preparing an olefin polymerization catalyst according to claim 1, wherein the co-catalyst compound comprises one or more selected from the group consisting of a compound represented by the following chemical formula 7, a compound represented by the chemical formula 8, and a compound represented by the chemical formula 9: [Chemical formula 7] [Chemical formula 8] [Chemical formula 9] [L-H] ＋ [Z(A) ４ ] － or [L] ＋ [Z(A) ４ ] － In the above formula 7, n is an integer of 2 or more, and R ａ is a halogen atom, C １－２０ Hydrocarbon group or halogen-substituted C １－２０ is a hydrocarbon group, In Formula 8, D is aluminum (Al) or boron (B), and R ｂ , R ｃ and R ｄ are each independently a halogen atom, C １－２０ Hydrocarbon groups, halogen-substituted C １－２０ Hydrocarbon group, or C １－２０ is an alkoxy group, In Formula 9, L is a neutral or cationic Lewis base, and [L-H] ＋ and [L] ＋ is a Bronsted acid, Z is a Group 13 element, and each A is independently a substituted or unsubstituted C ６－２０ an aryl group or a substituted or unsubstituted C １－２０ It is an alkyl group.

9. 9. The method for preparing an olefin polymerization catalyst according to claim 8, wherein the compound represented by Chemical Formula 7 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

10. 9. The method for preparing an olefin polymerization catalyst according to claim 8, wherein the compound represented by Chemical Formula 8 is at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, and tributylboron.

11. The compound represented by Chemical Formula 9 is selected from the group consisting of triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium N,N-diethylanilinium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,The method for preparing an olefin polymerization catalyst according to claim 8, wherein the catalyst is at least one selected from the group consisting of N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate, triphenylcarbenium tetra(p-trifluoromethylphenyl)borate, and triphenylcarbenium tetrapentafluorophenylborate.

12. (3') before or after step (3), further comprising a step of supporting a part or all of the mixture of transition metal compounds, the transition metal compound represented by Chemical Formula 6, and the co-catalyst compound on a support.

13. 13. The method for preparing an olefin polymerization catalyst according to claim 12, wherein the support comprises at least one selected from the group consisting of silica, alumina, and magnesium oxide (magnesia).

14. An olefin polymerization catalyst prepared by the preparation method according to any one of claims 1 to 13.

15. (1) dissolving at least one compound represented by the following chemical formulas 1-1 to 1-21 and at least one compound represented by the following chemical formulas 2-1 to 2-7 in a solvent; (2) adding a compound represented by the following formula 3 to the solution obtained in step (1), and then reacting them under stirring to obtain a mixture of at least one transition metal compound represented by the following formulas 4-1 to 4-21 and at least one transition metal compound represented by the following formulas 5-1 to 5-21; (3) activating the mixture of transition metal compounds obtained in the step (2) and a transition metal compound represented by the following Chemical Formula 6 with a promoter compound; (4) before or after the step (3), a step of supporting a part or all of the mixture of the transition metal compounds, the transition metal compound represented by the following chemical formula 6, and the co-catalyst compound on a support; (5) polymerizing olefins in the presence of the catalyst obtained in step (3) or step (4), The molar ratio of at least one of the compounds represented by the following chemical formulas 1-1 to 1-21 to at least one of the compounds represented by the following chemical formulas 2-1 to 2-7 is in the range of 1:30 to 30:1, but the molar ratio of at least one of the compounds represented by the following chemical formulas 1-1 to 1-21 and the molar ratio of at least one of the compounds represented by the following chemical formulas 2-1 to 2-7 are not the same; Method for preparing olefin polymer: [Chemical formula 1-1] [Chemical formula 1-2] [Chemical formula 1-3] [Chemical formula 1-4] [Chemical formula 1-5] [Chemical formula 1-6] [Chemical formula 1-7] [Chemical formula 1-8] [Chemical formula 1-9] [Chemical formula 1-10] [Chemical formula 1-11] [Chemical formula 1-12] [Chemical formula 1-13] [Chemical formula 1-14] [Chemical formula 1-15] [Chemical formula 1-16] [Chemical formula 1-17] [Chemical formula 1-18] [Chemical formula 1-19] [Chemical formula 1-20] [Chemical formula 1-21] [Chemical formula 2-1] [Chemical formula 2-2] [Chemical formula 2-3] [Chemical formula 2-4] [Chemical formula 2-5] [Chemical formula 2-6] [Chemical formula 2-7] [Chemical formula 3] MX ４ [Chemical formula 4-1] [Chemical formula 4-2] [Chemical formula 4-3] [Chemical formula 4-4] [Chemical formula 4-5] [Chemical formula 4-6] [Chemical formula 4-7] [Chemical formula 4-8] [Chemical formula 4-9] [Chemical formula 4-10] [Chemical formula 4-11] [Chemical formula 4-12] [Chemical formula 4-13] [Chemical formula 4-14] [Chemical formula 4-15] [Chemical formula 4-16] [Chemical formula 4-17] [Chemical formula 4-18] [Chemical formula 4-19] [Chemical formula 4-20] [Chemical formula 4-21] [Chemical formula 5-1] [Chemical formula 5-2] [Chemical formula 5-3] [Chemical formula 5-4] [Chemical formula 5-5] [Chemical formula 5-6] [Chemical formula 5-7] [Chemical formula 5-8] [Chemical formula 5-9] [Chemical formula 5-10] [Chemical formula 5-11] [Chemical formula 5-12] [Chemical formula 5-13] [Chemical formula 5-14] [Chemical formula 5-15] [Chemical formula 5-16] [Chemical formula 5-17] [Chemical formula 5-18] [Chemical formula 5-19] [Chemical formula 5-20] [Chemical formula 5-21] In the above formula, Me is methyl and Ph is phenyl. [Chemical formula 6] In the above chemical formulas 3 and 6, M is zirconium (Zr); X is Cl; Q are anionic leaving groups, each independently hydrogen, hydrocarbyl, heteroatom or halogen, a straight-chain or branched alkyl radical, alkenyl radical, alkynyl radical, cycloalkyl radical or aryl radical, acyl radical, aroyl radical, alkoxy radical, aryloxy radical, alkylthio radical, dialkylamino radical, alkoxycarbonyl radical, aryloxycarbonyl radical, carbamoyl radical, alkyl- or dialkyl-carbamoyl radical, acyloxy radical, acylamino radical, aroylamino radical, straight-chain, branched or cyclic alkylene radical, or combinations thereof; m is the oxidation state of M and is +3, +4 or +5; o is the formal charge of the Y, Z, and L ligands and is 0, −1, −2, or −3; L is nitrogen; Y is nitrogen or phosphorus; Z is nitrogen or phosphorus; R １１ and R １２ are each independently C １－２０ a hydrocarbon group or a heteroatom-containing group, where the heteroatom is silicon, germanium, tin, lead, or phosphorus, or R １１ and R １２ may be bonded to each other, R １３ is absent or hydrogen, C １－２０ alkyl, halogen or heteroatom-containing group; R １４ and R １５ are each independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, or a polycyclic ring system; R １６ and R １７ are each independently absent, a hydrogen, an alkyl group, a halogen, a heteroatom, a hydrocarbyl group, or a heteroatom-containing group.

16. The method for preparing an olefin polymer according to claim 15, wherein the polymerization of the olefin is copolymerization of an olefin monomer and an olefin comonomer, the olefin monomer being ethylene and the olefin comonomer being 1-hexene.

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