Transition metal compound for olefin polymerization catalyst, olefin polymerization catalyst containing the same, and polyolefin polymerized using the same

Abstract

The present invention relates to a transition metal compound for olefin polymerization catalyst in which a cyclopentadienyl group and a cyclopentadienyl group having a silane substituent are connected by a bridge, an olefin polymerization catalyst containing the same, and a polyolefin polymerized using the same. The transition metal compound for olefin polymerization catalyst and the olefin polymerization catalyst containing the same according to an embodiment of the present invention have a unique stereostructure, which makes it possible to adjust the physical properties of the polymer, and in particular, to produce a polyolefin resin with excellent processability.

Description

[Technical field]

[0001] The present invention relates to a transition metal compound for use as an olefin polymerization catalyst, an olefin polymerization catalyst containing the same, and a polyolefin polymerized using the same. Specifically, the present invention relates to a transition metal compound for use as an olefin polymerization catalyst in which a cyclopentadienyl group and a silane-substituted cyclopentadienyl group are connected by a bridge, an olefin polymerization catalyst containing the same, and a polyolefin polymerized using the same. [Background technology]

[0002] Metallocene catalysts, which are one of the catalysts used to polymerize olefins, are compounds in which ligands such as cyclopentadienyl, indenyl, and cycloheptadienyl are coordinated to a transition metal or a transition metal halide, and have a sandwich structure as their basic form.

[0003] Ziegler-Natta catalysts, another catalyst used to polymerize olefins, have metal components that act as active sites dispersed on the surface of an inert solid, and the properties of the active sites are not uniform. On the other hand, metallocene catalysts are known as single-site catalysts, in that all active sites have the same polymerization properties, since they are one compound with a fixed structure. Polymers polymerized with such metallocene catalysts have narrow molecular weight distributions, uniform comonomer distributions, and higher copolymerization activity than Ziegler-Natta catalysts.

[0004] However, there remains a demand for an olefin polymerization catalyst capable of producing polyolefin resins with excellent processability. Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a transition metal compound for use in an olefin polymerization catalyst, which has a novel structure and enables the production of polyolefin resins having excellent processability, an olefin polymerization catalyst containing the same, and a polyolefin polymerized using the same. [Means for solving the problem]

[0006] In order to achieve this object, one embodiment of the present invention provides a transition metal compound represented by the following chemical formula 1: [ka] In the above Chemical Formula 1, n is an integer of 1 to 20, M is titanium (Ti), zirconium (Zr) or hafnium (Hf); 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, or C 6-20 is an aryl amide, Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn); R1 to R7 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 6-20Arylamide or substituted or unsubstituted C 1-20 silyl, and R1 to R7 are each independently a substituted or unsubstituted saturated or unsaturated C 4-20 may form a ring, R8 and R9 are each independently a 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 or substituted or unsubstituted C 1-20 silyl, but R8 and R9 are linked together to form a substituted or unsubstituted saturated or unsaturated C 2-20 may form a ring, R 10 ~R 12 each independently represents a 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 or substituted or unsubstituted C 1-20 This is Cyril.

[0007] In a specific example of the present invention, in the above formula 1, n is 1 or 2, M is zirconium or hafnium, and X is a halogen or a substituted or unsubstituted C 1-20 Q is an alkyl group, R1 to R3 are each hydrogen, and R4 to R7 are each hydrogen or a substituted or unsubstituted C 1-20 alkyl, R and R are each a substituted or unsubstituted C 1-20 is alkyl, R 10 ~R 12 are substituted or unsubstituted C 1-20 Alkyl or substituted or unsubstituted C 6-20 It may be aryl.

[0008] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 1 may be any one of the compounds represented by Chemical Formulas 1-1 to 1-16 below. [ka] JPEG2025510579000003.jpg186170 In the above chemical formulas 1-1 to 1-16, M is zirconium or hafnium, and X is a halogen or a substituted or unsubstituted C 1-20 alkyl, Me is a methyl group, and Ph is a phenyl group.

[0009] In a more preferred embodiment of the present invention, the compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 1-17 or 1-18 below. [ka] In the above chemical formulas 1-17 and 1-18, Me is a methyl group.

[0010] Another embodiment of the present invention provides an olefin polymerization catalyst comprising the transition metal compound described above and a cocatalyst compound.

[0011] In an embodiment of the present invention, the co-catalyst compound may be one or more selected from the group consisting of a compound represented by the following formula 2, a compound represented by the following formula 3, and a compound represented by the following formula 4. [ka] [Chemical formula 4] [LH] + [Z(A)4] - or [L] + [Z(A)4] - In the above Chemical Formula 2, 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 is a hydrocarbon group, In the above formula 3, 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 radicals, halogen-substituted C 1-20 Hydrocarbon group or C 1-20 is an alkoxy group, In the above formula 4, 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 Aryl group or substituted or unsubstituted C 1-20 It is an alkyl group.

[0012] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 2 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

[0013] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 3 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.

[0014] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 4 is selected from the group consisting of triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraf phenylaluminum, 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,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammonium tetra(o,At least one selected from the group consisting of triphenylcarbonium tetra(p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarbonium tetra(p-trifluoromethylphenyl)boron, and triphenylcarbonium tetrapentafluorophenylboron.

[0015] In an embodiment of the present invention, the olefin polymerization catalyst may further comprise a carrier supporting a transition metal compound. In a preferred embodiment of the present invention, the carrier may support both the transition metal compound and the cocatalyst compound. In a further preferred embodiment of the present invention, the carrier may comprise at least one selected from the group consisting of silica, alumina and magnesia.

[0016] In a specific example of the present invention, the amount of the transition metal compound supported on the support may be 0.001 to 1 mmol per 1 g of the support, and the amount of the co-catalyst compound supported on the support may be 2 to 15 mmol per 1 g of the support.

[0017] According to still another embodiment of the present invention, there is provided a polyolefin obtained by polymerizing an olefin monomer in the presence of the olefin polymerization catalyst.

[0018] In an embodiment of the present invention, the olefinic monomer is 2-20 Alpha-olefin, C 1-20 Diolefin, C 3-20 Cycloolefin and C 3-20 It may be at least one selected from the group consisting of cyclodiolefins.

[0019] In a preferred embodiment of the present invention, the polyolefin may be obtained by copolymerizing ethylene and 1-hexene. Effect of the Invention

[0020] The transition metal compound for an olefin polymerization catalyst and the olefin polymerization catalyst containing the same according to the embodiment of the present invention have a unique three-dimensional structure, which makes it possible to adjust the physical properties of the polymer, and in particular, makes it possible to produce a polyolefin resin with excellent processability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The present invention will now be described in more detail.

[0022] [Transition metal compounds for olefin polymerization catalysts] According to one embodiment of the present invention, there is provided a transition metal compound represented by the following Chemical Formula 1: [ka]

[0023] In the above chemical formula 1, n is an integer of 1 to 20, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. Specifically, n may be 1 or 2.

[0024] M is titanium (Ti), zirconium (Zr) or hafnium (Hf). Specifically, M may be zirconium or hafnium.

[0025] 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, or C 6-20 Specifically, X is a halogen or a substituted or unsubstituted C 1-20 More specifically, each X may be chlorine.

[0026] Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn). Specifically, Q may be silicon.

[0027] R1 to R7 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 or substituted or unsubstituted C 1-20 Specifically, R1 to R3 are each hydrogen, and R4 to R7 are each hydrogen or a substituted or unsubstituted C 1-20 R1 to R7 may each independently be linked to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 A ring may be formed.

[0028] R8 and R9 are each independently a 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 or substituted or unsubstituted C 1-20Specifically, R and R are each a substituted or unsubstituted C 1-20 More specifically, R8 and R9 may each be methyl. R8 and R9 may also be linked together to form a substituted or unsubstituted saturated or unsaturated C 2-20 A ring may be formed.

[0029] R 10 ~R 12 each independently represents a 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 or substituted or unsubstituted C 1-20 Specifically, R 10 ~R 12 are substituted or unsubstituted C 1-20 Alkyl or substituted or unsubstituted C 6-20 More specifically, R 10 ~R 12 may each be methyl or phenyl.

[0030] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 1 may be any one of the compounds represented by Chemical Formulas 1-1 to 1-16 below.

[0031] [ka] JPEG2025510579000009.jpg186170 JPEG2025510579000010.jpg120170

[0032] In the above chemical formulas 1-1 to 1-16, M is zirconium or hafnium, and X is a halogen or a substituted or unsubstituted C 1-20 alkyl, Me is a methyl group, and Ph is a phenyl group.

[0033] In a more preferred embodiment of the present invention, the compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 1-17 or 1-18 below.

[0034] [ka]

[0035] In the above chemical formulas 1-17 and 1-18, Me is a methyl group.

[0036] [Olefin polymerization catalyst] According to another embodiment of the present invention, there is provided an olefin polymerization catalyst comprising a transition metal compound represented by the following Chemical Formula 1 and a cocatalyst compound:

[0037] [ka]

[0038] In the above Chemical Formula 1, n, M, X, Q, R1 to R 12 is as explained in the section on transition metal compounds.

[0039] In a specific example of the present invention, the compound represented by Chemical Formula 1 may be any one of the compounds represented by Chemical Formulas 1-1 to 1-16 below.

[0040] [ka] JPEG2025510579000014.jpg186170 JPEG2025510579000015.jpg120170

[0041] In the above Chemical Formulas 1-1 to 1-16, M, X, Me and Ph are as explained in the section on the transition metal compound.

[0042] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 1-17 or 1-18 below.

[0043] [ka]

[0044] In the above chemical formulas 1-17 and 1-18, Me is as explained in the section on the transition metal compound.

[0045] In an embodiment of the present invention, the co-catalyst compound may include one or more of a compound represented by the following Formula 2, a compound represented by the following Formula 3, and a compound represented by the following Formula 4.

[0046] [ka]

[0047] In the above Chemical Formula 2, 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 Specifically, R a may be methyl, ethyl, n-butyl or isobutyl.

[0048] [ka]

[0049] In the above formula 3, 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 radicals, halogen-substituted C 1-20 Hydrocarbon group or C 1-20 Specifically, when D is aluminum (Al), R b , R c and R d may each independently be methyl or isobutyl, and when D is boron (B), R b , R c and R d may each be pentafluorophenyl.

[0050] [ka]

[0051] In the above formula 4, 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 Aryl group or substituted or unsubstituted C 1-20 It is an alkyl group. Specifically, [LH] + may be a dimethylanilinium cation, [Z(A)4] - is [B(C6F5)4] - [L] + is [(C6H5)3C] + may be also possible.

[0052] Specifically, examples of the compound represented by Chemical Formula 2 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., and methylaluminoxane is preferred, but is not limited thereto.

[0053] Examples of the compound represented by Chemical Formula 3 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 these, trimethylaluminum, triethylaluminum, and triisobutylaluminum are preferred, but the invention is not limited thereto.

[0054] Examples of the compound represented by the chemical formula 4 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, and tributylammonium tetraphenylaluminum. ammonium, 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,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarbonium tetra(p-trifluoromethylphenyl)boron, triphenylcarbonium tetrapentafluorophenylboron, etc.

[0055] In an embodiment of the present invention, the olefin polymerization catalyst may further comprise a support supporting the transition metal compound. In a preferred embodiment of the present invention, the support may support both the transition metal compound and the cocatalyst compound.

[0056] Here, the support may include a substance containing a hydroxyl group on the surface, and preferably a substance having a highly reactive hydroxyl group and a siloxane group that has been dried to remove moisture from the surface can be used. For example, the support may include at least one selected from the group consisting of silica, alumina, and magnesia. Specifically, silica, silica-alumina, and silica-magnesia that have been dried at high temperatures can be used as the support, and these may usually contain oxide, carbonate, sulfate, and nitrate components such as Na2O, K2CO3, BaSO4, and Mg(NO3)2. These may also include carbon, zeolite, magnesium chloride, and the like. However, the support is not limited to these, and is not particularly limited as long as it can support a transition metal compound and a promoter compound.

[0057] As a method for supporting a transition metal compound and / or a cocatalyst compound that can be used in an olefin polymerization catalyst, a physical adsorption method or a chemical adsorption method can be used.

[0058] For example, the physical adsorption method may be a method in which a solution in which a transition metal compound is dissolved is brought into contact with a support and then dried; a method in which a solution in which a 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 transition metal compound is dissolved is brought into contact with a support and then dried to produce a support on which the 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 produce a support on which the promoter compound is supported, and then these are mixed together.

[0059] 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 transition metal compound is supported on the promoter compound, or a method in which a catalyst compound is covalently bonded to a functional group on the surface of the support (for example, in the case of silica, a hydroxy group (-OH) on the surface of the silica).

[0060] The amount of the transition metal compound supported on the carrier may be 0.001 to 1 mmol per 1 g of the carrier. When the ratio of the transition metal compound to the carrier satisfies the above range, appropriate supported catalytic activity is exhibited, which is advantageous in terms of maintaining the activity of the catalyst and in terms of economic efficiency.

[0061] The amount of the promoter compound supported on the carrier may be 2 to 15 mmol per 1 g of the carrier. If the ratio of the promoter compound to the carrier satisfies the above range, it is advantageous in terms of maintaining the activity of the catalyst and economic efficiency.

[0062] One or more types of carriers may be used. For example, both the transition metal compound and the co-catalyst compound may be supported on one carrier, or the transition metal compound and the co-catalyst compound may be supported on two or more carriers. Also, only one of the transition metal compound and the co-catalyst compound may be supported on a carrier.

[0063] [Olefin Polymerization] An olefin polymer may be produced by polymerizing an olefin monomer in the presence of an olefin polymerization catalyst according to an embodiment of the present invention.

[0064] Here, the olefin polymer may be a homopolymer of an olefin monomer or a copolymer of an olefin monomer and a comonomer.

[0065] The olefin monomer is C 2-20 Alpha-olefin, C 1-20 Diolefin, C 3-20 Cycloolefin and C 3-20 At least one selected from the group consisting of cyclodiolefins.

[0066] For example, the olefin monomer may be ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, or 1-hexadecene, and the olefin polymer may be a homopolymer containing only one of the olefin monomers exemplified above, or a copolymer containing two or more of them.

[0067] In an exemplary embodiment, the olefin polymer comprises ethylene and C 3-20 The copolymer may be an alpha-olefin copolymer, and is preferably an ethylene and 1-hexene copolymer, but is not limited thereto.

[0068] In this case, the content of ethylene is preferably 55 to 99.9% by weight, more preferably 90 to 99.9% by weight, and the content of the alpha-olefin comonomer is preferably 0.1 to 45% by weight, more preferably 0.1 to 10% by weight.

[0069] The olefin-based polymer according to the embodiment of the present invention may be polymerized by, for example, free radical, cationic, coordination, condensation, addition, and other polymerization reactions, but is not limited thereto.

[0070] In a preferred embodiment, the olefin polymer may be produced by a gas phase polymerization method, a solution polymerization method, a slurry polymerization method, or the like. When the olefin polymer is produced by a solution polymerization method or a slurry polymerization method, examples of the solvent that can be used include C hexane, such as pentane, hexane, heptane, nonane, decane, and isomers thereof. 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.

[0071] [Example] The present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrating the present invention and are not intended to limit the scope of the present invention.

[0072] Preparation Example 1: Preparation of dimethylsilane[(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (chemical formula 1-17) [(2-(cyclopentadienylmethyl)allyl)trimethylsilane] Sodium cyclopentadienide (6.92g, 14.7mmole, 2.4M tetrahydrofuran solution) was slowly added dropwise to a solution of 2-(trimethylsilylmethyl)allyl chloride (2g, 12.3mmole) diluted in tetrahydrofuran (40ml) at -30℃, and the temperature was gradually raised to room temperature and stirred for 12 hours. Distilled water was added at 0℃ to terminate the reaction, and the organic layer was separated by extraction with diethyl ether. The remaining water was removed with magnesium sulfate (MgSO4), and then separated by column chromatography (hexane) to obtain 2.01g (85%) of a light brown oil compound. 1 H-NMR (CDCl3, 300 MHz): δ 6.42-6.02 (m, 4H), 4.60-4.55 (m, 2H), 3.06-2.97 (m, 2H), 2.87-2.85 (m, 2H), 1.54 (s, 2H), 0.03 (d, 9H).

[0073] [Dimethyl[(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)silane] To a solution of (2-(cyclopentadienylmethyl)allyl)trimethylsilane (1g, 5.19mmole) diluted in tetrahydrofuran (20ml), n-BuLi (2.43g, 5.72mmole, 1.6M hexane solution) was slowly added at -30℃, and the temperature was gradually raised to room temperature and stirred for 12 hours. The solvent of the reaction solution was dried under vacuum to obtain a pale yellow solid compound. This solid compound was diluted in tetrahydrofuran (20 ml) and dimethylsilyl(2,3,4,5-tetramethylcyclopentadienyl) chloride (1.12 g, 5.19 mmole) was slowly added dropwise to the solution at -30°C, the temperature was gradually raised to room temperature and the mixture was stirred for 12 hours. After removing the solvent under vacuum, the mixture was extracted with hexane and filtered. The solvent was removed under vacuum to obtain 1.93 g (100%) of a yellow liquid compound.

[0074] [Dimethylsilane[(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)lithium] Dimethyl[(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)silane (1.93 g, 5.21 mmole) was diluted in diethyl ether (20 ml) and n-BuLi (4.67 g, 11.0 mmole, 1.6 M hexane solution) was added slowly at -30°C, and the temperature was gradually raised to room temperature and stirred for 12 hours. The solvent of the reaction solution was removed under vacuum, and the reactants were filtered with hexane. The solvent was removed under vacuum to obtain 2 g (100%) of a yellow solid compound.

[0075] [Dimethylsilane[(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride] Dimethylsilane[(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)lithium (1g, 2.61mmole) was diluted in toluene (20ml) and zirconium tetrachloride (ZrCl4) (610mg, 2.61mmole) was added slowly at -30℃, and the temperature was gradually raised to room temperature and stirred for 12 hours. When the reaction was completed, the reaction solution was filtered and the solvent of the filtrate was dried under vacuum. The solid produced was dried to obtain 540mg (39%) of a yellow solid compound. 1 H-NMR (CDCl3, 500 MHz): δ 6.68 (m, 1H), 5.67 (m, 1H), 5.31 (m, 1H), 4.56 (s, 1H), 4.48 (s, 1H), 3.34 (m, 1H), 2.08 (s, 3H), 2.04 (s, 3H), 1.95 (s, 3H), 1.88 (s, 3H), 1.53 (s, 3H), 0.84 (s, 3H), 0.81 (s, 3H), 0.04 (s, 9H).

[0076] Preparation Example 2: Preparation of dimethylsilane[(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)hafnium dichloride (chemical formula 1-18) Dimethylsilane [(2-trimethylsilylmethylallyl)cyclopentadienyl] (2,3,4,5-tetramethylcyclopentadienyl) lithium (1 g, 2.61 mmole) obtained by the method of Preparation Example 1 was diluted in toluene (20 ml) to which hafnium tetrachloride (HfCl4) (840 mg, 2.61 mmole) was slowly added at -30°C, and the temperature was gradually raised to room temperature and stirred for 12 hours. When the reaction was completed, the reaction solution was filtered and the solvent of the filtrate was dried under vacuum. The solid produced was dried to obtain 570 mg (35%) of a yellow solid compound. 1 H-NMR (CDCl3, 500 MHz): δ 6.59 (m, 1H), 5.63 (m, 1H), 5.27 (m, 1H), 4.55 (s, 1H), 4.47 (s, 1H), 3.35 (m, 1H), 2.10 (s, 3H), 2.07 (s, 3H), 2.03 (s, 3H), 1.95 (s, 3H), 1.53 (s, 3H), 0.83 (s, 3H), 0.80 (s, 3H), 0.04 (s, 9H).

[0077] Preparation Example 3: Preparation of [(2-trimethylsilylmethylallyl)cyclopentadienyl](cyclopentadienyl)zirconium dichloride (chemical formula A-1 below) [ka]

[0078] Cyclopentadienyl zirconium trichloride (CpZrCl3) (40mg, 0.15mmole) was slowly added to a solution of 2-[2-(trimethylsilylmethyl)allyl]cyclopentadienyllithium (30mg, 0.15mmole) diluted in toluene / tetrahydrofuran (1.5ml) at -30℃, and the temperature was gradually raised to room temperature and stirred for 12 hours. When the reaction was completed, the reaction solution was filtered and the filtrate solvent was dried under vacuum. The solid produced was washed with hexane and dried to obtain 27mg (43%) of a light brown solid compound. 1 H-NMR (CDCl3, 300 MHz): δ 6.46 (s, 5H), 6.33 (t, 2H), 6.23 (t, 2H), 4.55 (d, 1H), 4.44 (d, 1H), 3.27 (s, 2H), 1.52 (s, 2H), 0.05 (s, 9H).

[0079] Preparation Example 4: Preparation of [(2-trimethylsilylmethylallyl)cyclopentadienyl](pentamethylcyclopentadienyl)zirconium dichloride (chemical formula A-2) [ka]

[0080] 2-[2-(trimethylsilylmethyl)allyl]cyclopentadienyllithium (100 mg, 0.50 mmole) obtained by the method of Preparation 3 was diluted in toluene / tetrahydrofuran (3.0 ml) and the solution was treated with pentamethylcyclopentadienylzirconium trichloride (Cp * ZrCl3) (168 mg, 0.50 mmole) was slowly added at -30°C, and the temperature was gradually raised to room temperature and stirred for 12 hours. When the reaction was completed, the reaction solution was filtered and the filtrate solvent was dried under vacuum. The resulting solid was washed with hexane and dried to obtain 180 mg (73%) of a light beige solid compound. 1 H-NMR (CDCl3, 300 MHz): δ 6.05 (t, 2H), 5.97 (t, 2H), 4.53 (m, 1H), 4.43 (m, 1H), 3.24 (s, 2H), 2.03 (s, 15H), 0.04 (s, 9H).

[0081] Example 1: Synthesis of ethylene 1-hexene copolymer using compound 1-17 Polyolefin was polymerized using the transition metal compound (compound 1-17) obtained in Production Example 1. Specifically, a 2-liter autoclave reactor was used for the polymerization. All reagents used were subjected to inert conditions using a glove box or the Schlenk technique.

[0082] After removing foreign matter such as moisture and oxygen in a vacuum for about 20 minutes at 100°C, 1 liter of hexane was poured into the reactor and stirred at 200 rpm to raise the polymerization temperature to 80°C. Then, compound 1-17 was mixed with methylaluminoxane (MAO) as a cocatalyst in a ratio of Al / Zr=2,000, and the catalyst prepared in advance was poured into the reactor. Here, the amount of catalyst was adjusted to 0.8-3.2 mg depending on the activity.

[0083] Then, hexane vapor pressure is 1kgf / cm 2 After injecting nitrogen so that the pressure was 4 kgf / cm, ethylene was pumped 2 and the total pressure was 5kgf / cm 2 The temperature was adjusted to 100°C. 1-hexene was added while stirring the reactor at 1,000 rpm, and polymerization was carried out for 15 minutes. After polymerization was completed, the reaction gas was vented and the reactor was opened to obtain the resin produced. The resin was dried for 24 hours or more, and then its physical properties were measured. The amounts of catalyst and 1-hexene used are shown in Table 1 below.

[0084] Comparative Example 1: Synthesis of ethylene-1-hexene copolymer using compound A-1 Except for using Compound A-1 as the transition metal compound, olefin polymerization was carried out in the same manner as in Example 1. The amounts of catalyst and 1-hexene used are shown in Table 1 below.

[0085] Comparative Example 2: Synthesis of ethylene 1-hexene copolymer using compound A-2 Except for using Compound A-2 as the transition metal compound, olefin polymerization was carried out in the same manner as in Example 1. The amounts of catalyst and 1-hexene used are shown in Table 1 below.

[0086] The physical properties of the polyolefins obtained in Example 1 and Comparative Examples 1 and 2 were measured, and the results are shown in Table 1 below.

[0087] [Table 1] JPEG2025510579000023.jpg250170 JPEG2025510579000024.jpg31170*MW: weight average molecular weight, PDI: polydispersity index, Tm: melting point

[0088] According to an embodiment of the present invention, it is possible to provide a transition metal compound for an olefin polymerization catalyst, which has a unique stereostructure and thus allows adjustment of the physical properties of the polymer, and in particular, allows production of a polyolefin resin having excellent processability, and an olefin polymerization catalyst containing the same.

Claims

1. A transition metal compound represented by the following chemical formula 1. 【Chemistry 1】 In the above Chemical Formula 1, n is an integer of 1 to 20; M is titanium (Ti), zirconium (Zr) or hafnium (Hf); 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, or C ６－２０ is an aryl amide, Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn); R １ ~R ７ 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 Alkylamide, substituted or unsubstituted C ６－２０ Arylamide or substituted or unsubstituted C １－２０ Cyril, R １ ~R ７ each independently represents a substituted or unsubstituted saturated or unsaturated C ４－２０ may form a ring, R ８ and R ９ each independently represents a 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 Alkylamide, substituted or unsubstituted C ６－２０ Arylamide or substituted or unsubstituted C １－２０ Cyril, but R ８ and R ９ are linked to each other to form substituted or unsubstituted saturated or unsaturated C ２－２０ may form a ring, R １０ ~R １２ each independently represents a 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 Alkylamide, substituted or unsubstituted C ６－２０ Arylamide or substituted or unsubstituted C １－２０ This is Cyril.

2. In the formula 1, n is 1 or 2, M is zirconium or hafnium, and X is a halogen or a substituted or unsubstituted C. １－２０ is alkyl, Q is silicon, R １ ~R ３ are each hydrogen, R ４ ~R ７ Each represents hydrogen or a substituted or unsubstituted C １－２０ alkyl, R ８ and R ９ each represents a substituted or unsubstituted C １－２０ alkyl, R １０ ~R １２ each represents a substituted or unsubstituted C １－２０ Alkyl or substituted or unsubstituted C ６－２０ The transition metal compound of claim 1 which is aryl.

3. The compound represented by Chemical Formula 1 according to claim 1, wherein the compound represented by Chemical Formula 1 is any one of the compounds represented by the following Chemical Formulas 1-1 to 1-16. 【Chemistry 2】 【change】 【change】 In the above chemical formulas 1-1 to 1-16, M is zirconium or hafnium, and X is a halogen or a substituted or unsubstituted C １－２０ alkyl, Me is a methyl group, and Ph is a phenyl group.

4. The compound represented by Chemical Formula 1 is a compound represented by Chemical Formula 1-17 or 1-18 below. 【Chemistry 3】 In the above chemical formulas 1-17 and 1-18, Me is a methyl group.

5. A catalyst for olefin polymerization comprising the transition metal compound according to any one of claims 1 to 4 and a cocatalyst compound.

6. The catalyst for olefin polymerization according to claim 5, wherein the cocatalyst compound is at least one selected from the group consisting of a compound represented by the following formula 2, a compound represented by the following formula 3, and a compound represented by the following formula 4. 【Chemistry 4】 [Chemical formula 4] [L-H] ＋ [Z(A) ４ ] － Or [L] ＋ [Z(A) ４ ] － In the above formula 2, n is an integer of 2 or more, R ａ is a halogen atom, C １－２０ C substituted with a hydrocarbon group or halogen １－２０ is a hydrocarbon group, In the formula 3, D is aluminum (Al) or boron (B), 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 the above formula 4, L is a neutral or cationic Lewis base, [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.

7. The olefin polymerization catalyst according to claim 6, wherein the compound represented by Chemical Formula 2 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

8. The olefin polymerization catalyst according to claim 6, wherein the compound represented by Chemical Formula 3 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.

9. The compound represented by the chemical formula 4 includes triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, aluminum, 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,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammonium tetra(o,The olefin polymerization catalyst according to claim 6, which is at least one selected from the group consisting of triphenylcarbonium tetra(p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarbonium tetra(p-trifluoromethylphenyl)boron, and triphenylcarbonium tetrapentafluorophenylboron.

10. The olefin polymerization catalyst according to claim 5, further comprising a transition metal compound, a cocatalyst compound, or a support carrying both of them.

11. The olefin polymerization catalyst according to claim 10, wherein the support comprises at least one selected from the group consisting of silica, alumina and magnesia.

12. The olefin polymerization catalyst according to claim 10, wherein the amount of the transition metal compound supported on the support is 0.001 to 1 mmol per 1 g of the support, and the amount of the co-catalyst compound supported on the support is 2 to 15 mmol per 1 g of the support.

13. A polyolefin obtained by polymerizing an olefin monomer in the presence of the olefin polymerization catalyst according to claim 5.

14. The olefin monomer is C ２－２０ α-Olefin, C １－２０ Diolefin, C ３－２０ Cycloolefin and C ３－２０ 14. The polyolefin of claim 13, which is at least one selected from the group consisting of cyclodiolefins.

15. The polyolefin according to claim 14, which is obtained by copolymerizing ethylene and 1-hexene.

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