Transition metal compounds for olefin polymerization catalysts, olefin polymerization catalysts containing the same, and polyolefins 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 olefin polymerization catalysts, 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 olefin polymerization catalysts in which a cyclopentadienyl group and a cyclopentadienyl group into which a silane-substituted product has been introduced are linked by a bridge, an olefin polymerization catalyst containing the same, and a polyolefin polymerized using the same. [Background technology]

[0002] Metallocene catalysts, one type of catalyst used for polymerizing olefins, are compounds in which ligands such as cyclopentadienyl, indenyl, or cycloheptadienyl are coordinately bonded to a transition metal or a transition metal halogen compound, and they have a sandwich structure as their basic form.

[0003] Unlike the Ziegler-Natta catalyst, another catalyst used for polymerizing olefins, in which the active sites (metal components) are dispersed on the surface of an inert solid and the properties of the active sites are not uniform, metallocene catalysts are known as single-site catalysts because they are a single compound with a fixed structure, and all of their active sites have the same polymerization properties. Polymers polymerized with such metallocene catalysts have a narrow molecular weight distribution and a uniform distribution of comonomers, and exhibit higher copolymerization activity compared to Ziegler-Natta catalysts.

[0004] However, there is still a need for olefin polymerization catalysts that can produce polyolefin resins with excellent processability. [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a transition metal compound for an olefin polymerization catalyst having a novel structure, an olefin polymerization catalyst containing the same, and a polyolefin polymerized using the same, which can produce a polyolefin-based resin excellent in processability.

Means for Solving the Problems

[0006] [[ID=...]] According to one embodiment of the present invention for achieving such an object, a transition metal compound represented by the following Chemical Formula 1 is provided.

Chemical Formula

[0007] In a specific example of the present invention, in the chemical formula 1, n is 1 or 2, M is zirconium or hafnium, and X is a halogen or substituted or unsubstituted C, respectively. 1-20 It is an alkyl group, Q is silicon, R1-R3 are each hydrogen, and R4-R7 are each hydrogen or substituted or unsubstituted C. 1-20 It is an alkyl group, and R8 and R9 are substituted or unsubstituted C, respectively. 1-20 It is alkyl, R 10 ~R 12 These are, respectively, substituted or non-substituted C. 1-20 Alkyl, or substituted or unsubstituted C 6-20 It could also be Aryl.

[0008] In a preferred example of the present invention, the compound represented by chemical formula 1 may be any one of the compounds represented by the following chemical formulas 1-1 to 1-16. [ka] JPEG0007860255000003.jpg186170 JPEG0007860255000004.jpg120170 In the above chemical formulas 1-1 to 1-16, M is zirconium or hafnium, and X is a halogen, or substituted or unsubstituted C, respectively. 1-20 It is an alkyl group, Me is a methyl group, and Ph is a phenyl group.

[0009] In a more preferred example of the present invention, the compound represented by chemical formula 1 may be a compound represented by the following chemical formulas 1-17 or 1-18. [ka] In the chemical formulas 1-17 and 1-18, Me is a methyl group.

[0010] Another embodiment of the present invention provides a catalyst for olefin polymerization comprising the transition metal compound and a co-catalyst compound.

[0011] In a specific example of the present invention, the co-catalyst compound may be one or more selected from the group consisting of the compound represented by chemical formula 2, the compound represented by chemical formula 3, and the compound represented by chemical 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 C is a halogen atom. 1-20 C substituted with hydrocarbon groups or halogens 1-20 It is a hydrocarbon group, In the above chemical formula 3, D is aluminum (Al) or boron (B), and R b , R c and R d Each of these is independently a halogen atom, C 1-20 C substituted with hydrocarbon groups and halogens 1-20 hydrocarbon group or C 1-20 It is an alkoxy group, In the above chemical formula 4, L is a neutral or cationic Lewis base, and [LH] + and [L] + is a Brønsted acid, Z is a group 13 element, and A is, independently, a substituted or unsubstituted C. 6-20 It is an aryl group, or a substituted or unsubstituted C 1-20 It is an alkyl group.

[0012] In a preferred example 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 example 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, trimethylborone, triethylborone, triisobutylborone, tripropylborone, and tributylborone.

[0014] In preferred examples of the present invention, the compound represented by chemical formula 4 is triethylammonium tetraphenylborone, tributylammonium tetraphenylborone, trimethylammonium tetraphenylborone, tripropylammonium tetraphenylborone, trimethylammonium tetra(p-tolyl)borone, trimethylammonium tetra(o,p-dimethylphenyl)borone, tributylammonium tetra(p-trifluoromethylphenyl)borone, trimethylammonium tetra(p-trifluoromethylphenyl)borone, tributylammonium tetrapentafluorophenylborone, N,N-diethylanilinium tetraphenylborone, N,N-diethylanilinium tetrapentafluorophenylborone, diethylammonium tetrapentafluorophenylborone, triphenylphosphonium tetraphenylborone, trimethylphosphonium tetraphenylborone, triethylammonium tetraphenylaluminum, tributylammonium tetraphenyl Phenyl 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,It is at least one selected from the group consisting of p-dimethylphenyl)borone, tributylammonium tetra(p-trifluoromethylphenyl)borone, triphenylcarbonium tetra(p-trifluoromethylphenyl)borone, and triphenylcarbonium tetrapentafluorophenylborone.

[0015] In specific examples of the present invention, the catalyst for olefin polymerization may further include a carrier supporting a transition metal compound. In preferred examples of the present invention, the carrier may support both the transition metal compound and a co-catalyst compound. In even more preferred examples of the present invention, the carrier may include 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 carrier may be 0.001 to 1 mmol per gram of carrier, and the amount of the co-catalyst compound supported on the carrier may be 2 to 15 mmol per gram of carrier.

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

[0018] In a specific example of the present invention, the olefin monomer is C 2-20 Alpha-olefin (α-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 example of the present invention, the polyolefin may be obtained by copolymerizing ethylene and 1-hexene. [Effects of the Invention]

[0020] The transition metal compound for an olefin polymerization catalyst and the olefin polymerization catalyst containing the same according to an embodiment of the present invention have a specific steric structure, so that the physical properties of the polymer can be adjusted. In particular, a polyolefin-based resin excellent in processability can be produced.

Mode for Carrying Out the Invention

[0021] Hereinafter, the present invention will be described in more detail.

[0022] [Transition Metal Compound for Olefin Polymerization Catalyst] According to one specific example of the present invention, a transition metal compound represented by the following Chemical Formula 1 is provided.

Chem.

[0023] In the 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 of each other, 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 arylamide. Specifically, X may be, respectively, halogen, or substituted or unsubstituted C 1-20 alkyl. More specifically, X may be, respectively, 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, a substituted or unsubstituted C 1-20 alkyl, a substituted or unsubstituted C 2-20 alkenyl, a substituted or unsubstituted C 6-20 aryl, a substituted or unsubstituted C 1-20 alkyl C 6-20 aryl, a substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, a substituted or unsubstituted C 1-20 heteroalkyl, a substituted or unsubstituted C 3-20 heteroaryl, a substituted or unsubstituted C 1-20 alkylamide, a substituted or unsubstituted C 6-20 arylamide, or a substituted or unsubstituted C 1-20 silyl. Specifically, R1 to R3 are each hydrogen, and R4 to R7 are each hydrogen, or a substituted or unsubstituted C 1-20 alkyl. Also, R1 to R7 are each independently such that adjacent groups are linked to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring.

[0028] R8 and R9 are each independently a substituted or unsubstituted C 1-20 alkyl, a substituted or unsubstituted C 2-20 alkenyl, a substituted or unsubstituted C 6-20 aryl, a substituted or unsubstituted C 1-20 alkyl C 6-20 aryl, a substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, a substituted or unsubstituted C 1-20 heteroalkyl, a substituted or unsubstituted C 3-20 heteroaryl, a substituted or unsubstituted C 1-20 alkylamide, a substituted or unsubstituted C 6-20 arylamide, or a substituted or unsubstituted C 1-20It is a silyl. Specifically, R8 and R9 are substituted or unsubstituted C, respectively. 1-20 They may be alkyl groups. More specifically, R8 and R9 may each be methyl groups. Also, R8 and R9 may be linked to each other and be substituted or unsubstituted saturated or unsaturated C 2-20 They may form a ring.

[0029] R 10 ~R 12 These are, independently, substitute or non-substitute 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 Arylamides, or substituted or unsubstituted C 1-20 It is a cyril. Specifically, R 10 ~R 12 These are, respectively, substituted or non-substituted C. 1-20 Alkyl, or substituted or unsubstituted C 6-20 It could also be aryl. More specifically, R 10 ~R 12 These may be methyl or phenyl, respectively.

[0030] In a preferred example of the present invention, the compound represented by chemical formula 1 may be any one of the compounds represented by the following chemical formulas 1-1 to 1-16.

[0031] [ka] JPEG0007860255000009.jpg186170 JPEG0007860255000010.jpg120170

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

[0033] In a more preferred example of the present invention, the compound represented by chemical formula 1 may be a compound represented by the following chemical formulas 1-17 or 1-18.

[0034] [ka]

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

[0036] [Catalyst for olefin polymerization] Another embodiment of the present invention provides a catalyst for olefin polymerization comprising a transition metal compound represented by the following chemical formula 1 and a co-catalyst compound.

[0037] [ka]

[0038] In the above chemical formula 1, n, M, X, Q, R1 to R 12 This 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 the following chemical formulas 1-1 to 1-16.

[0040] [ka] JPEG0007860255000014.jpg186170 JPEG0007860255000015.jpg120170

[0041] In the above chemical formulas 1-1 to 1-16, M, X, Me, and Ph are as described in the section on transition metal compounds.

[0042] In a preferred example of the present invention, the compound represented by chemical formula 1 may be a compound represented by the following chemical formulas 1-17 or 1-18.

[0043] [ka]

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

[0045] In a specific example of the present invention, the co-catalyst compound may include one or more of the compounds represented by the following chemical formulas: chemical formula 2, chemical formula 3, and chemical formula 4.

[0046] [ka]

[0047] In the above chemical formula 2, n is an integer of 2 or more, and R a C is a halogen atom. 1-20 C substituted with hydrocarbons or halogens 1-20 Hydrocarbons are also acceptable. Specifically, R a This may be methyl, ethyl, n-butyl, or isobutyl.

[0048] [ka]

[0049] In the above chemical formula 3, D is aluminum (Al) or boron (B), and R b , R c and R d Each of these is independently a halogen atom, C 1-20 C substituted with hydrocarbon groups and halogens 1-20 hydrocarbon group or C 1-20 It is an alkoxy group. Specifically, when D is aluminum (Al), R b , R c and R d Each of these may independently be methyl or isobutyl, and when D is boron (B), R b , R c and R d Each of these may be pentafluorophenyl.

[0050] [ka]

[0051] In the above chemical formula 4, L is a neutral or cationic Lewis base, and [LH] + and [L] + is a Brønsted acid, Z is a group 13 element, and A is, independently, a substituted or unsubstituted C. 6-20 It is an aryl group, or a substituted or unsubstituted C 1-20 It is an alkyl group. Specifically, [LH] + This may also be a dimethylanilinium cation, [Z(A)4] - is [B(C6F5)4] - It may be [L] + is [(C6H5)3C] + That's fine.

[0052] Specifically, examples of compounds represented by the chemical formula 2 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, with methylaluminoxane being preferred, but the compound is not limited to these.

[0053] Examples of compounds represented by the above 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, trimethylborone, triethylborone, triisobutylborone, tripropylborone, and tributylborone. Trimethylaluminum, triethylaluminum, and triisobutylaluminum are preferred, but the compound is not limited to these.

[0054] Examples of compounds represented by the aforementioned chemical formula 4 include triethylammonium tetraphenylborone, tributylammonium tetraphenylborone, trimethylammonium tetraphenylborone, tripropylammonium tetraphenylborone, trimethylammonium tetra(p-tolyl)borone, trimethylammonium tetra(o,p-dimethylphenyl)borone, tributylammonium tetra(p-trifluoromethylphenyl)borone, trimethylammonium tetra(p-trifluoromethylphenyl)borone, tributylammonium tetrapentafluorophenylborone, N,N-diethylanilinium tetraphenylborone, N,N-diethylanilinium tetrapentafluorophenylborone, diethylammonium tetrapentafluorophenylborone, triphenylphosphonium tetraphenylborone, trimethylphosphonium tetraphenylborone, triethylammonium tetraphenylaluminum, and tributylammonium tetraphenylaluminum. Nium, 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,Examples include p-dimethylphenyl)borone, tributylammonium tetra(p-trifluoromethylphenyl)borone, triphenylcarbonium tetra(p-trifluoromethylphenyl)borone, and triphenylcarbonium tetrapentafluorophenylborone.

[0055] In specific examples of the present invention, the catalyst for olefin polymerization may further include a carrier supporting a transition metal compound. In preferred examples of the present invention, the carrier may support both the transition metal compound and the co-catalyst compound.

[0056] Here, the support may include a substance containing hydroxyl groups on its surface, preferably a substance having highly reactive hydroxyl and siloxane groups that has been dried and had moisture removed from its surface. 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 dried at high temperatures can be used as supports, and these may usually contain oxides, carbonates, sulfates, and nitrate components 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 is not particularly limited as long as it can support the transition metal compound and the co-catalyst compound.

[0057] Physical adsorption or chemical adsorption methods can be used to support transition metal compounds and / or co-catalyst compounds that can be used as catalysts for olefin polymerization.

[0058] For example, the physical adsorption method may be a method in which a solution containing a transition metal compound is brought into contact with a support and then dried, a method in which a solution containing both a transition metal compound and a co-catalyst compound is brought into contact with a support and then dried, or a method in which a solution containing a transition metal compound is brought into contact with a support and then dried to produce a support on which a transition metal compound is supported, and separately a method in which a solution containing a co-catalyst compound is brought into contact with a support and then dried to produce a support on which a co-catalyst compound is supported, and then these are mixed.

[0059] The chemical adsorption method may involve first supporting a co-catalyst compound on the surface of a support, and then supporting a transition metal compound on the co-catalyst compound, or covalently bonding the catalyst compound to the functional groups on the surface of the support (for example, in the case of silica, the hydroxyl groups (-OH) on the silica surface).

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

[0061] The amount of co-catalyst compound supported on the carrier may be 2 to 15 mmol per gram of carrier. When the ratio of co-catalyst compound to carrier satisfies the above range, it is advantageous in terms of maintaining catalyst activity 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 type of carrier, or the transition metal compound and the co-catalyst compound may be supported on two or more types of carriers, respectively. Alternatively, only one of the transition metal compound or the co-catalyst compound may be supported on the carrier.

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

[0064] Here, the olefin polymer may be a homopolymer of olefin monomers or a copolymer of olefin monomers and copolymers of olefin monomers and copolymers.

[0065] Olefin monomers are C 2-20 Alpha-olefin (α-olefin), C 1-20 Diolefin, C 3-20 Cycloolefin and C 3-20 It is 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 exemplified olefin monomers above, or a copolymer containing two or more.

[0067] In exemplary embodiments, the olefin polymer is composed of ethylene and C 3-20 The copolymer may be a copolymer of alpha-olefins, and a copolymer of ethylene and 1-hexene is preferred, but is not limited to these.

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

[0069] The olefin polymers according to specific examples of the present invention may be polymerized by polymerization reactions such as free radical, cationic, coordination, condensation, and addition, but are not limited to these.

[0070] In preferred embodiments, the olefin polymer may be produced by gas-phase polymerization, solution polymerization, or slurry polymerization. When the olefin polymer is produced by solution polymerization or slurry polymerization, examples of usable solvents include pentane, hexane, heptane, nonane, decane, and their isomers. 5-12 Examples include, but are not limited to, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents such as toluene and benzene, chlorine-substituted hydrocarbon solvents such as dichloromethane and chlorobenzene, and mixtures thereof.

[0071] [Examples] The present invention will be described more specifically below with reference to examples. However, the following examples are for illustrative purposes only and the scope of the present invention is not limited thereto.

[0072] Manufacturing Example 1: Preparation of Dimethylsilane[(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (Chemical Formulas 1-17) [(2-(cyclopentadienylmethyl)allyl)trimethylsilane] To a solution of 2-(trimethylsilylmethyl)allyl chloride (2g, 12.3 mmol) diluted in tetrahydrofuran (40 ml), sodium cyclopentadienide (6.92 g, 14.7 mmol, 2.4 M tetrahydrofuran solution) was gradually added dropwise at -30°C, and the temperature was gradually raised to room temperature while stirring for 12 hours. After terminating the reaction by adding distilled water at 0°C, the organic layer was separated by extraction with diethyl ether. After removing the remaining water with magnesium sulfate (MgSO4), the mixture was separated by column chromatography (hexane) to obtain 2.01 g (85%) of a pale rice-colored 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-trimethylsilylmethylally)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)silane] (2-(cyclopentadienylmethyl)allyl)trimethylsilane (1 g, 5.19 mmol) was diluted in tetrahydrofuran (20 ml), and n-BuLi (2.43 g, 5.72 mmol, 1.6 M hexane solution) was gradually added at -30°C. The temperature was then gradually raised to room temperature and the mixture was stirred for 12 hours. The solvent of the reaction solution was dried under vacuum to obtain a pale yellow solid compound. To a solution of this solid compound diluted in tetrahydrofuran (20 ml), dimethylsilyl(2,3,4,5-tetramethylcyclopentadienyl) chloride (1.12 g, 5.19 mmol) was gradually added dropwise at -30°C, and the temperature was gradually raised to room temperature while stirring for 12 hours. After removing the solvent under vacuum, the solution was extracted with hexane and filtered. After removing the solvent under vacuum, 1.93 g (100%) of the yellow liquid compound was obtained.

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

[0075] [Dimethylsilane[(2-trimethylsilylmethylally)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride] Dimethylsilane[(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)lithium ((dimethylsilane[(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)lithium) (1 g, 2.61 mmol) was diluted in toluene (20 ml) and zirconium tetrachloride (ZrCl4) (610 mg, 2.61 mmol) was gradually added at -30°C. The temperature was then gradually raised to room temperature and the mixture was stirred for 12 hours. After the reaction was complete, the reaction solution was filtered, and the solvent of the filtrate was dried under vacuum. The resulting solid was dried to obtain 540 mg (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] Manufacturing Example 2: Preparation of Dimethylsilane[(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)hafnium dichloride (Chemical Formulas 1-18) Dimethylsilane [(2-trimethylsilylmethylallyl)cyclopentadienyl](2,3,4,5-tetramethylcyclopentadienyl)lithium (1 g, 2.61 mmol) obtained by the method described in Preparation Example 1 was diluted in toluene (20 ml) and hafnium tetrachloride (HfCl4) (840 mg, 2.61 mmol) was gradually added at -30°C. The temperature was then gradually raised to room temperature and the mixture was stirred for 12 hours. After the reaction was complete, the reaction solution was filtered, and the solvent of the filtrate was dried under vacuum. The resulting solid 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] Manufacturing Example 3: Manufacturing of [(2-trimethylsilylmethylallyl)cyclopentadienyl](cyclopentadienyl)zirconium dichloride (chemical formula A-1 below) [ka]

[0078] 2-[2-(trimethylsilylmethyl)allyl]cyclopentadienyllithium (30 mg, 0.15 mmol) was diluted in toluene / tetrahydrofuran (1.5 ml) and cyclopentadienyl zirconium trichloride (CpZrCl3) (40 mg, 0.15 mmol) was gradually added at -30°C. The temperature was then gradually raised to room temperature and the mixture was stirred for 12 hours. After the reaction was complete, the reaction solution was filtered, and the solvent of the filtrate was dried under vacuum. The resulting solid was washed with hexane and dried to obtain 27 mg (43%) of a pale rice-colored 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] Manufacturing Example 4: Production of [(2-trimethylsilylmethylallyl)cyclopentadienyl](pentamethylcyclopentadienyl)zirconium dichloride (chemical formula A-2) [ka]

[0080] A solution of 2-[2-(trimethylsilylmethyl)allyl]cyclopentadienyl lithium (100 mg, 0.50 mmol) obtained by the method described in Production Example 3 was diluted in toluene / tetrahydrofuran (3.0 ml) and then mixed with pentamethylcyclopentadienyl zirconium trichloride (Cp * ZrCl3) (168 mg, 0.50 mmol) was gradually added at -30°C, and the temperature was gradually raised to room temperature while stirring for 12 hours. After the reaction was complete, the reaction solution was filtered, and the solvent of the filtrate was dried under vacuum. The resulting solid was washed with hexane and dried to obtain 180 mg (73%) of a pale rice-colored 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 Polyolefins were polymerized using the transition metal compounds (compounds 1-17) obtained in Production Example 1. Specifically, a 2-liter autoclave reactor was used for polymerization. All reagents used were handled under inert conditions using a glove box or Schlenk technique.

[0082] After removing foreign matter such as moisture and oxygen under vacuum at 100°C for approximately 20 minutes, 1 liter of hexane was injected into the reactor and stirred at 200 rpm to raise the temperature to 80°C, the polymerization temperature. Subsequently, compound 1-17 and methyl aluminoxane (MAO) as a co-catalyst were mixed in an Al / Zr ratio of 2,000, and the pre-prepared catalyst was added to the reactor. Here, the amount of catalyst was adjusted from 0.8 to 3.2 mg depending on the activity.

[0083] Subsequently, including the hexane vapor pressure, it reaches 1 kgf / cm². 2 After injecting nitrogen to achieve this state, ethylene is added at 4 kgf / cm³. 2 Inject with a total pressure of 5 kgf / cm². 2 The reactor was adjusted to the specified temperature. 1-hexene was added while stirring the reactor at 1,000 rpm, and polymerization was carried out for 15 minutes. After polymerization was complete, the reaction gas was vented, and the reactor was opened to obtain the resulting resin. After drying the resin for more than 24 hours, 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 Olefin polymerization was carried out in the same manner as in Example 1, except that compound A-1 was used as the transition metal compound. 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 Olefin polymerization was carried out in the same manner as in Example 1, except that compound A-2 was used as the transition metal compound. 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] JPEG0007860255000023.jpg250170 JPEG0007860255000024.jpg31170*MW: weight-average molecular weight, PDI: polydispersity index, Tm: melting point

[0088] According to embodiments of the present invention, a transition metal compound for olefin polymerization catalysts and a catalyst for olefin polymerization containing the same can be provided, which have a unique three-dimensional structure that allows for adjustment of the physical properties of the polymer, and in particular can produce polyolefin resins with excellent processability.

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 from 1 to 20. M is titanium (Ti), zirconium (Zr), or hafnium (Hf). X is, independently of each other, 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 arylamide, and Q is carbon (C), silicon (Si), germanium (Ge), or tin (Sn). R １ ~R ３ These are, 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 Arylamides, or substituted or unsubstituted C １－２０ Cyril, R １ ~R ３ Each of these groups is independently linked to an adjacent group, resulting in substituted or unsubstituted saturated or unsaturated C ４－２０ They may form a ring, R ４ ~R ７ Each of these is independently hydrogen, or substituted or unsubstituted C. １－２０ It is alkyl, R ８ and R ９ These are, independently, substitutional or non-substitutional 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 Arylamides, or substituted or unsubstituted C １－２０ Cyril, R ８ and R ９ These are linked together, resulting in substituted or unsubstituted saturated or unsaturated C ２－２０ They may form a ring, R １０ ~R １２ These are, independently, substitutional or non-substitutional 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 Arylamides, or substituted or unsubstituted C １－２０ It's Cyril.

2. In the above chemical formula 1, n is 1 or 2, M is zirconium or hafnium, and X is a halogen or substituted or unsubstituted C, respectively. １－２０ It is alkyl, Q is silicon, R １ ~R ３ These are hydrogen atoms, and R ４ ~R ７ These are, respectively, hydrogen, or substituted or unsubstituted C. １－２０ It is alkyl, R ８ and R ９ These are, respectively, substituted or non-substituted C. １－２０ It is alkyl, R １０ ~R １２ These are, respectively, substituted or non-substituted C. １－２０ Alkyl, or substituted or unsubstituted C ６－２０ The transition metal compound according to claim 1, wherein it is an aryl compound.

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

4. The transition metal compound according to claim 1, wherein the compound represented by chemical formula 1 is a compound represented by the following chemical formula 1-17 or 1-18. 【Transformation 3】 In the chemical formulas 1-17 and 1-18, Me is a methyl group.

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

6. The catalyst for olefin polymerization according to claim 5, wherein the co-catalyst compound is one or more selected from the group consisting of the compound represented by chemical formula 2, the compound represented by chemical formula 3, and the compound represented by chemical formula 4 below. 【Chemistry 4】 【change】 [Chemical formula 4] [L-H] ＋ [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 C is a halogen atom. １－２０ C substituted with hydrocarbon groups or halogens １－２０ It is a hydrocarbon group, In the above chemical formula 3, D is aluminum (Al) or boron (B), and R ｂ , R ｃ and R ｄ are each independently a halogen atom, a C １－２０ hydrocarbon group, a C １－２０ hydrocarbon group substituted with halogen, or a C １－２０ alkoxy group. In the above chemical formula 4, L is a neutral or cationic Lewis base, and [L-H] ＋ and [L] ＋ is a Brønsted acid, Z is a group 13 element, and A is, independently, a substituted or unsubstituted C. ６－２０ It is an aryl group, or a substituted or unsubstituted C １－２０ It is an alkyl group.

7. The catalyst for olefin polymerization 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 catalyst for olefin polymerization 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 compounds represented by the aforementioned chemical formula 4 are triethylammonium tetraphenylborone, tributylammonium tetraphenylborone, trimethylammonium tetraphenylborone, tripropylammonium tetraphenylborone, trimethylammonium tetra(p-tolyl)borone, trimethylammonium tetra(o,p-dimethylphenyl)borone, tributylammonium tetra(p-trifluoromethylphenyl)borone, trimethylammonium tetra(p-trifluoromethylphenyl)borone, tributylammonium tetrapentafluorophenylborone, N,N-diethylanilinium tetraphenylborone, N,N-diethylanilinium tetrapentafluorophenylborone, diethylammonium tetrapentafluorophenylborone, triphenylphosphonium tetraphenylborone, trimethylphosphonium tetraphenylborone, triethylammonium tetraphenylaluminum, and 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,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammonium tetra(o,The catalyst for olefin polymerization according to claim 6, which is at least one selected from the group consisting of p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarbonium tetra(p-trifluoromethylphenyl)boron, and triphenylcarbonium tetrapentafluorophenylboron.

10. The catalyst for olefin polymerization according to claim 5, further comprising a transition metal compound, a co-catalyst compound, or a carrier supporting both thereof.

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

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

13. A method for producing polyolefins, characterized by polymerizing an olefin monomer in the presence of the olefin polymerization catalyst described in claim 5.

14. The olefin monomer is C ２－２０ α-olefin, C １－２０ diolefin, C ３－２０ cycloolefin and C ３－２０ The method for producing a polyolefin according to claim 13, wherein the olefin monomer is at least one selected from the group consisting of cyclodiolefin.

15. A method for producing a polyolefin according to claim 14, comprising copolymerizing ethylene and 1-hexene.

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