Transition Metal Compound, Catalyst Comprising the Same, and Processes for Preparing the Same

Abstract

The present invention relates to transition metal compounds, catalysts for olefin polymerization containing the same, and methods for preparing the same. Specifically, the present invention relates to a transition metal compound having a 2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-indene](2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-indene]) backbone, a catalyst for olefin polymerization containing the same, and a method for preparing the said transition metal compound and catalyst. Because the transition metal compound and the catalyst for olefin polymerization containing the same according to a specific embodiment of the present invention have a unique stereochemical structure, it is possible to control the physical properties of the polymer.

Description

Technology Field

[0001] The present invention relates to transition metal compounds, catalysts for olefin polymerization containing the same, and methods for preparing the same. Specifically, the present invention relates to transition metal compounds having a 2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-indene](2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-indene]) backbone, catalysts for olefin polymerization containing the same, and methods for preparing said transition metal compounds and catalysts. Background Technology

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

[0003] Conventional polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-alphaolefin copolymers, and their copolymers, have been produced by heterogeneous catalysts such as Ziegler-Natta catalysts composed of titanium compounds and alkyl aluminum compounds.

[0004] Recently, methods for producing polyolefins using metallocene catalysts, which are homogeneous catalysts with very high catalytic activity, are being studied. Metallocene catalysts are compounds in which ligands such as cyclopentadienyl, indenyl, and cycloheptadienyl are coordinately bonded to transition metals or transition metal halogen compounds, and they have a sandwich structure as their basic form. In this case, they possess various molecular structures depending on the type of ligand and the type of central metal.

[0005] In contrast to heterogeneous catalysts such as Ziegler-Natta catalysts, where the active metal component is dispersed on an inert solid surface and the properties of the active site are non-uniform, metallocene catalysts are known as single-site catalysts because they are a single compound with a fixed structure, and all active sites possess identical polymerization characteristics.

[0006] Generally, metallocene catalysts are not active as polymerization catalysts on their own, so they are used together with co-catalysts such as methyl aluminoxane. Through the action of the co-catalyst, the metallocene catalyst is activated into a cation, and at the same time, the co-catalyst stabilizes an unsaturated cationic active species as an anion that is not coordinated to the metallocene catalyst, thereby forming a catalyst system that is active for various olefin polymerizations.

[0007] These metallocene catalysts facilitate copolymerization and allow for the control of the polymer's stereostructure based on the catalyst's symmetry; furthermore, polymers produced from them have the advantages of a narrow molecular weight distribution and a uniform distribution of comonomers.

[0008] However, there is still a demand for metallocene catalysts for olefin polymerization that can produce resins with high activity, further enhanced copolymerization, and improved physical properties. The problem to be solved

[0009] The objective of the present invention is to provide a transition metal compound for olefin polymerization catalyst having a novel structure and capable of producing a resin having high activity and excellent physical properties, and an olefin polymerization catalyst comprising the same.

[0010] Another objective of the present invention is to provide the above transition metal compound and a method for preparing an olefin polymerization catalyst containing the same. means of solving the problem

[0011] According to one embodiment for achieving the objective of the present invention, a transition metal compound represented by the following chemical formula 1 is provided.

[0012] [Chemical Formula 1]

[0013]

[0014] In the above chemical formula 1, l is an integer from 0 to 2, m is an integer from 0 to 3, and n is an integer from 0 to 5, and

[0015] M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and

[0016] X is independently a halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkinyl, C 6-20 Aril, C 1-20 Alkyl C 6-20 Aril, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamido or C 6-20 Arilamido,

[0017] R1 R3 are each independently 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 Alkylamido, substituted or unsubstituted C 6-20 Arylamido, or substituted or unsubstituted C 1-20 Silil, but R1 R3 are each independently connected adjacent groups to form saturated or unsaturated C that is substituted or unsubstituted. 4-20 It can form a ring,

[0018] R4 is substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C2-20 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 or substituted or unsubstituted C 2-20 It is alkinil.

[0019] Specifically, in Chemical Formula 1 above, l is 1 or 2, m and n are each 0 or 1, M is zirconium, and X is each a halogen or a substituted or unsubstituted C 1-20 It is alkyl, and R1 R3 are each substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 2-20 Alkenyl, or substituted or unsubstituted C 6-20 It is an aryl, and R4 is a substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl or substituted or unsubstituted C 2-20 It could be alkinyl.

[0020] Preferably, the transition metal compound represented by the above chemical formula 1 is at least one of the transition metal compounds represented by the following chemical formulas 1-1 to 1-21.

[0021] [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3]

[0022]

[0023] [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6]

[0024]

[0025] [Chemical Formula 1-7] [Chemical Formula 1-8] [Chemical Formula 1-9]

[0026]

[0027] [Chemical Formula 1-10] [Chemical Formula 1-11] [Chemical Formula 1-12]

[0028]

[0029] [Chemical Formula 1-13] [Chemical Formula 1-14] [Chemical Formula 1-15]

[0030]

[0031] [Chemical Formula 1-16] [Chemical Formula 1-17] [Chemical Formula 1-18]

[0032]

[0033] [Chemical Formula 1-19] [Chemical Formula 1-20] [Chemical Formula 1-21]

[0034]

[0035] According to one embodiment of the present invention, a method for preparing a transition metal compound is provided, comprising the steps of: (1) reacting a compound represented by the following chemical formula 2 with a compound represented by the following chemical formula 3 to obtain a compound represented by the following chemical formula 4; (2) reacting a compound represented by the following chemical formula 4 with a compound represented by the following chemical formula 5 to obtain a compound represented by the following chemical formula 6; (3) reacting a compound represented by the following chemical formula 6 with an organolithium compound to obtain a compound represented by the following chemical formula 7; and (4) reacting a compound represented by the following chemical formula 7 with a compound represented by the following chemical formula 8 to obtain a transition metal compound represented by the above chemical formula 1.

[0036] [Chemical Formula 2]

[0037]

[0038] [Chemical Formula 3]

[0039] Me2Si(X a )2

[0040] [Chemical Formula 4]

[0041]

[0042] [Chemical Formula 5]

[0043] R4NH2

[0044] [Chemical Formula 6]

[0045]

[0046] [Chemical Formula 7]

[0047]

[0048] [Chemical Formula 8]

[0049] MX4

[0050] In the above chemical formula, l, m, n, M, X, R1 R4 are as described in the above section on transition metal compounds, and Me is methyl, X a is a halogen.

[0051] Preferably, the compound represented by the above chemical formula 2 is at least one of the compounds represented by the following chemical formulas 2-1 to 2-16.

[0052] [Chemical Formula 2-1][Chemical Formula 2-2][Chemical Formula 2-3]

[0053]

[0054] [Chemical Formula 2-4][Chemical Formula 2-5][Chemical Formula 2-6]

[0055]

[0056] [Chemical Formula 2-7][Chemical Formula 2-8][Chemical Formula 2-9]

[0057]

[0058] [Chemical Formula 2-10][Chemical Formula 2-11][Chemical Formula 2-12]

[0059]

[0060] [Chemical Formula 2-13][Chemical Formula 2-14][Chemical Formula 2-15]

[0061]

[0062] [Chemical Formula 2-16]

[0063]

[0064] In a specific embodiment of the present invention, the reactions of steps (1) to (4) above may each be carried out independently in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate.

[0065] In a specific embodiment of the present invention, the reaction of step (4) may be carried out in the presence of an amine-based compound.

[0066] According to one embodiment for achieving another objective of the present invention, a catalyst for olefin polymerization is provided, comprising a transition metal compound represented by the above chemical formula 1; and a co-catalyst compound.

[0067] Here, the co-catalyst compound may be one or more selected from the group consisting of the compound represented by Chemical Formula 9 below, the compound represented by Chemical Formula 10 and the compound represented by Chemical Formula 11.

[0068] [Chemical Formula 9]

[0069]

[0070] [Chemical Formula 10]

[0071]

[0072] [Chemical Formula 11]

[0073] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0074] In the above chemical formula 9, n is an integer greater than or equal to 2, and R a is a halogen atom, C 1-20 C substituted with hydrocarbon groups or halogens 1-20 It is a hydrocarbon group, and

[0075] In the above chemical formula 10, D is aluminum (Al) or boron (B), and R b , R c and R d Each independently has a halogen atom, C 1-20 Hydrocarbon group, C substituted with a halogen 1-20 Hydrocarbon group or C 1-20 It is an alkoxy period, and

[0076] In the above chemical formula 11, 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 substituted or unsubstituted C 6-20 C that is an aryl group or is substituted or unsubstituted 1-20 It is an alkyl group.

[0077] Specifically, the compound represented by the above chemical formula 9 is at least one selected from the group consisting of methylaluminoxan, ethylaluminoxan, isobutylaluminoxan, and butylaluminoxan.

[0078] In addition, compounds represented by Chemical Formula 10 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, and tri- s -Butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p - At least one selected from the group consisting of tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, and tributyl boron.

[0079] In addition, the compound represented by the above chemical formula 11 is 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, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra( p -Tollil)Aluminum, Tripropylammonium Tetra( p -Tollil)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 -Tollil)Boron, Triethylammonium Tetra( o , p -Dimethylphenyl)boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarbonium tetra( p It is at least one selected from the group consisting of trifluoromethylphenyl)boron and triphenylcarbonium tetrapentafluorophenylboron.

[0080] In a specific embodiment of the present invention, the catalyst for olefin polymerization further comprises a carrier supporting a transition metal compound. Specifically, the carrier may support both a transition metal compound and a co-catalyst compound.

[0081] In a specific embodiment of the present invention, the above carrier may comprise at least one selected from the group consisting of silica, alumina, and magnesia.

[0082] Here, the total amount of transition metal compounds supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the total amount of co-catalyst compounds supported on the carrier is 2 to 15 mmole based on 1 g of the carrier.

[0083] According to another embodiment of the present invention, a method for preparing a catalyst for olefin polymerization is provided, comprising the steps of: (1) reacting a compound represented by Formula 2 above with a compound represented by Formula 3 above to obtain a compound represented by Formula 4 above; (2) reacting a compound represented by Formula 4 with a compound represented by Formula 5 above to obtain a compound represented by Formula 6 above; (3) reacting a compound represented by Formula 6 with an organolithium compound to obtain a compound represented by Formula 7 above; and (4) reacting a compound represented by Formula 7 with a compound represented by Formula 8 above to obtain a transition metal compound represented by Formula 1 above; and (5) supporting the transition metal compound, the co-catalyst compound, or both obtained in step (4) on a carrier. Effects of the invention

[0084] The transition metal compound and the olefin polymerization catalyst containing the same according to a specific embodiment of the present invention have a unique stereochemical structure, which enables the control of the physical properties of the polymer. Specific details for implementing the invention

[0085] The present invention will be described in more detail below.

[0086] Transition metal compounds

[0087] According to one embodiment of the present invention, a transition metal compound represented by the following chemical formula 1 is provided.

[0088] [Chemical Formula 1]

[0089]

[0090] In the above chemical formula 1, l is an integer from 0 to 2, m is an integer from 0 to 3, and n is an integer from 0 to 5. Specifically, l can be 1 or 2, and m and n can each be 0 or 1.

[0091] M is titanium (Ti), zirconium (Zr), or hafnium (Hf). Specifically, M may be hafnium or zirconium, and preferably zirconium.

[0092] X is independently a halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkinyl, C 6-20 Aril, C 1-20 Alkyl C 6-20 Aril, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamido or C 6-20 It is an arylamido. Specifically, X is each a halogen or a substituted or unsubstituted C 1-20 It may be an alkyl. More specifically, X may be a halogen, and preferably chlorine (Cl).

[0093] R1 R3 are each independently 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 Alkylamido, substituted or unsubstituted C 6-20 Arylamido, or substituted or unsubstituted C 1-20 It is silyl. Here, R1 R3 are each independently connected adjacent groups to form saturated or unsaturated C that is substituted or unsubstituted. 4-20 It can form a ring. Specifically, R1 R3 are each substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 2-20 Alkenyl, or substituted or unsubstituted C 6-20 It could be Aril.

[0094] R4 is 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 or substituted or unsubstituted C 2-20 It is an alkynyl. Specifically, R4 is a substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl or substituted or unsubstituted C 2-20 It could be alkinyl.

[0095] In a specific embodiment of the present invention, in the above Formula 1, l is 1 or 2, m and n are each 0 or 1, M is zirconium, and X is each a halogen or a substituted or unsubstituted C 1-20 It is alkyl, and R1 R3 are each substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 2-20 Alkenyl, or substituted or unsubstituted C 6-20 It is an aryl, and R4 is a substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 6-20 Aryl, substituted or unsubstituted C1-20 Alkyl C 6-20 Aryl or substituted or unsubstituted C 2-20 It could be alkinyl.

[0096] In a preferred embodiment of the present invention, the transition metal compound represented by the above chemical formula 1 may be at least one of the transition metal compounds represented by the following chemical formulas 1-1 to 1-21.

[0097] [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3]

[0098]

[0099] [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6]

[0100]

[0101] [Chemical Formula 1-7] [Chemical Formula 1-8] [Chemical Formula 1-9]

[0102]

[0103] [Chemical Formula 1-10] [Chemical Formula 1-11] [Chemical Formula 1-12]

[0104]

[0105] [Chemical Formula 1-13] [Chemical Formula 1-14] [Chemical Formula 1-15]

[0106]

[0107] [Chemical Formula 1-16] [Chemical Formula 1-17] [Chemical Formula 1-18]

[0108]

[0109] [Chemical Formula 1-19] [Chemical Formula 1-20] [Chemical Formula 1-21]

[0110]

[0111] Method for preparing transition metal compounds

[0112] According to another embodiment of the present invention, a method for preparing a transition metal compound is provided, comprising the steps of: (1) reacting a compound represented by the following chemical formula 2 with a compound represented by the following chemical formula 3 to obtain a compound represented by the following chemical formula 4; (2) reacting a compound represented by the following chemical formula 4 with a compound represented by the following chemical formula 5 to obtain a compound represented by the following chemical formula 6; (3) reacting a compound represented by the following chemical formula 6 with an organolithium compound to obtain a compound represented by the following chemical formula 7; and (4) reacting a compound represented by the following chemical formula 7 with a compound represented by the following chemical formula 8 to obtain a transition metal compound represented by the following chemical formula 1.

[0113] [Chemical Formula 1]

[0114]

[0115] [Chemical Formula 2]

[0116]

[0117] [Chemical Formula 3]

[0118] Me2Si(X a )2

[0119] [Chemical Formula 4]

[0120]

[0121] [Chemical Formula 5]

[0122] R4NH2

[0123] [Chemical Formula 6]

[0124]

[0125] [Chemical Formula 7]

[0126]

[0127] [Chemical Formula 8]

[0128] MX4

[0129] In the above chemical formula, l, m, n, M, X, R1 R4 are as described in the above section on transition metal compounds, and Me is methyl, X a is a halogen.

[0130] Preferably, the compound represented by the above chemical formula 2 may be at least one of the compounds represented by the following chemical formulas 2-1 to 2-16.

[0131] [Chemical Formula 2-1][Chemical Formula 2-2][Chemical Formula 2-3]

[0132]

[0133] [Chemical Formula 2-4][Chemical Formula 2-5][Chemical Formula 2-6]

[0134]

[0135] [Chemical Formula 2-7][Chemical Formula 2-8][Chemical Formula 2-9]

[0136]

[0137] [Chemical Formula 2-10][Chemical Formula 2-11][Chemical Formula 2-12]

[0138]

[0139] [Chemical Formula 2-13][Chemical Formula 2-14][Chemical Formula 2-15]

[0140]

[0141] [Chemical Formula 2-16]

[0142]

[0143] Preferably, the compound represented by the above chemical formula 8 may be ZrCl4.

[0144] In a specific embodiment of the present invention, the reactions of steps (1) to (4) above may each be carried out independently in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate, but the solvent is not particularly limited to these.

[0145] Step (1)

[0146] In step (1) above, a compound represented by chemical formula 2 is reacted with a compound represented by chemical formula 3 to obtain a compound represented by chemical formula 4. Preferably, the compound represented by chemical formula 3 may be Me2SiCl2.

[0147] The reaction of step (1) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate, but the solvent is not particularly limited to these. Preferably, the solvent may be toluene.

[0148] When dissolving the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3 in a solvent, the order of addition of each compound is not particularly restricted. That is, the compound represented by Chemical Formula 2 may be added to the solvent first and dissolved, and then the compound represented by Chemical Formula 3 may be added to the solvent and dissolved, or dissolved in the reverse order. In addition, the two compounds may be dissolved separately in the solvent and then slowly mixed.

[0149] When mixing the compound represented by Formula 2 and the compound represented by Formula 3, each dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Formula 2 and the compound represented by Formula 3, each dissolved in a solvent, can be slowly mixed at a temperature of -78 to 30°C, preferably -78 to -30°C, and more preferably about -30°C.

[0150] After mixing the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3, each dissolved in a solvent, the resulting solution is stirred to obtain the compound represented by Chemical Formula 4.

[0151] At this time, the temperature and time during stirring are not particularly limited. For example, the reaction can be carried out by stirring at a temperature of 25 to 150°C, preferably 80 to 110°C, more preferably about 90°C for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours.

[0152] After the reaction of step (1) is completed, the solvent is removed from the reaction solution under vacuum, a new solvent is added to extract the product, and then the solvent is removed again under vacuum to obtain the product. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.

[0153] Step (2)

[0154] In step (2) above, a compound represented by chemical formula 4 is reacted with a compound represented by chemical formula 5 to obtain a compound represented by chemical formula 6. Preferably, the compound represented by chemical formula 5 is t - It could be butylamine.

[0155] The reaction of step (2) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate, but the solvent is not particularly limited to these. Preferably, the solvent may be tetrahydrofuran.

[0156] When dissolving the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5 in a solvent, the order of addition of each compound is not particularly restricted. That is, the compound represented by Chemical Formula 4 may be added to the solvent first and dissolved, and then the compound represented by Chemical Formula 5 may be added to the solvent and dissolved, or dissolved in the reverse order. In addition, the two compounds may be dissolved separately in the solvent and then slowly mixed.

[0157] When mixing the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5, each dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5, each dissolved in a solvent, can be slowly mixed at a temperature of -78 to 30°C, preferably -78 to -30°C, and more preferably about -30°C.

[0158] After mixing the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5, each dissolved in a solvent, the resulting solution is stirred to obtain the compound represented by Chemical Formula 6.

[0159] At this time, the temperature and time during stirring are not particularly limited. For example, the reaction can be carried out by stirring at a temperature of -30 to 100°C, preferably 0 to 50°C, more preferably at room temperature for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours.

[0160] After the reaction of step (2) is completed, the solvent is removed from the reaction solution under vacuum, a new solvent is added to extract the product, and then the solvent is removed again under vacuum to obtain the product. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.

[0161] Step (3)

[0162] In step (3) above, the compound represented by Chemical Formula 6 is reacted with an organolithium compound to obtain a compound represented by Chemical Formula 7. Preferably, the organolithium compound is n - It could be butyl lithium.

[0163] The reaction of step (3) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate, but the solvent is not particularly limited to these. Preferably, the solvent may be hexane.

[0164] When dissolving the compound represented by Chemical Formula 6 and the organolithium compound in a solvent, the order of addition of each compound is not particularly restricted. That is, the compound represented by Chemical Formula 6 may be added to the solvent first and dissolved, followed by the addition and dissolution of the organolithium compound, or the order may be reversed. Additionally, the two compounds may be dissolved in the solvent separately and then slowly mixed. Specifically, it is preferable to slowly add the solution in which the organolithium compound is dissolved in the solvent to the solution in which the compound represented by Chemical Formula 6 is dissolved in the solvent.

[0165] When mixing the compound represented by Formula 6 and the organolithium compound, each dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Formula 6 and the organolithium compound, each dissolved in a solvent, can be slowly mixed at a temperature of -78 to 30°C, preferably -78 to -30°C, more preferably about -30°C.

[0166] After mixing the compound represented by Chemical Formula 6 and the lithium compound, each dissolved in a solvent, the resulting solution is stirred to obtain the compound represented by Chemical Formula 7.

[0167] At this time, the temperature and time during stirring are not particularly limited. For example, the reaction can be carried out by stirring at a temperature of -30 to 100°C, preferably 0 to 50°C, more preferably at room temperature for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours.

[0168] After the reaction of step (3) is completed, the solvent is removed from the reaction solution under vacuum, a new solvent is added to extract the product, and then the solvent is removed again under vacuum to obtain the product. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.

[0169] Step (4)

[0170] In step (4) above, a transition metal compound represented by chemical formula 1 is obtained by reacting a compound represented by chemical formula 7 with a compound represented by chemical formula 8. Preferably, the compound represented by chemical formula 8 may be zirconium chloride (ZrCl4).

[0171] The reaction of step (4) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate, but the solvent is not particularly limited to these. Preferably, the solvent may be toluene.

[0172] The reaction of step (4) can be carried out in the presence of an amine compound. The amine compound maintains the reaction environment in a basic state, thereby stabilizing the unstable compound represented by Formula 7 and preventing the compound from being protonated. Preferably, the amine compound may be trimethylamine, but is not particularly limited thereto.

[0173] When dissolving the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 in a solvent, the order of addition of each compound is not particularly restricted. That is, the compound represented by Chemical Formula 7 may be added to the solvent first and dissolved, and then the compound represented by Chemical Formula 8 may be added to the solvent and dissolved, or dissolved in the reverse order. In addition, the two compounds may be dissolved separately in the solvent and then slowly mixed.

[0174] Here, the order of addition of the amine compounds is not particularly limited. Preferably, the amine compounds can be dissolved by adding them to a solution in which the compound represented by Formula 7 is dissolved and then stirring sufficiently.

[0175] When mixing the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8, each dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8, each dissolved in a solvent, can be slowly mixed at a temperature of -78 to 30°C, preferably -78 to -30°C, and more preferably about -30°C.

[0176] A compound represented by Chemical Formula 7 and a compound represented by Chemical Formula 8, each dissolved in a solvent, are mixed, and the resulting solution is stirred to obtain a transition metal compound represented by Chemical Formula 1.

[0177] At this time, the temperature and time during stirring are not particularly limited. For example, the reaction can be carried out by stirring at a temperature of -30 to 100°C, preferably 0 to 50°C, more preferably at room temperature for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours.

[0178] After the reaction of step (4) is completed, the reaction solution is passed through a filter to remove impurities. The solvent is removed from the reaction solution under vacuum, a new solvent is added to extract the product, and then the solvent is removed again under vacuum to obtain the product. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.

[0179] Catalyst for olefin polymerization

[0180] According to another embodiment of the present invention, a catalyst for olefin polymerization is provided, comprising a transition metal compound represented by the following chemical formula 1; and a co-catalyst compound.

[0181] [Chemical Formula 1]

[0182]

[0183] In Chemical Formula 1 above, l, m, n, M, X, R1 R4 is as described in the above transition metal compound section.

[0184] In a preferred embodiment of the present invention, the transition metal compound represented by the above chemical formula 1 may be at least one of the transition metal compounds represented by the following chemical formulas 1-1 to 1-21.

[0185] [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3]

[0186]

[0187] [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6]

[0188]

[0189] [Chemical Formula 1-7] [Chemical Formula 1-8] [Chemical Formula 1-9]

[0190]

[0191] [Chemical Formula 1-10] [Chemical Formula 1-11] [Chemical Formula 1-12]

[0192]

[0193] [Chemical Formula 1-13] [Chemical Formula 1-14] [Chemical Formula 1-15]

[0194]

[0195] [Chemical Formula 1-16] [Chemical Formula 1-17] [Chemical Formula 1-18]

[0196]

[0197] [Chemical Formula 1-19] [Chemical Formula 1-20] [Chemical Formula 1-21]

[0198]

[0199] Meanwhile, the co-catalyst compound may include one or more of the compounds represented by Chemical Formula 9, Chemical Formula 10, and Chemical Formula 11 below.

[0200] [Chemical Formula 9]

[0201]

[0202] In the above chemical formula 9, n is an integer greater than or equal to 2, and R a is a halogen atom, C 1-20 C substituted with hydrocarbons or halogens 1-20 It can be a hydrocarbon. Specifically, R a is methyl, ethyl, n - It can be butyl or isobutyl.

[0203] [Chemical Formula 10]

[0204]

[0205] In the above chemical formula 10, D is aluminum (Al) or boron (B), and R b , R c and R d Each independently has a halogen atom, C 1-20 Hydrocarbon group, C substituted with a halogen 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 can independently be methyl or isobutyl, and when D is boron (B), R b , R c and R d Each can be a pentafluorophenyl.

[0206] [Chemical Formula 11]

[0207] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0208] In the above chemical formula 11, 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 substituted or unsubstituted C 6-20C that is an aryl group or is substituted or unsubstituted 1-20 It is an alkyl group. Specifically, [LH] + can be a dimethylanilinium cation, and [Z(A)4] - is [B(C6F5)4] - It could be, [L] + is [(C6H5)3C] + It could be.

[0209] Specifically, examples of compounds represented by the above chemical formula 9 include methylaluminoxan, ethylaluminoxan, isobutylaluminoxan, butylaluminoxan, etc., and methylaluminoxan is preferred, but is not limited to these.

[0210] Examples of compounds represented by the above chemical formula 10 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, and tri- s -Butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p Examples include tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc., and trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum are preferred, but are not limited to these.

[0211] Examples of compounds represented by the above chemical formula 11 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and 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, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra( p -Tollil)Aluminum, Tripropylammonium Tetra( p -Tollil)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 -Tollil)Boron, Triethylammonium Tetra( o , p -Dimethylphenyl)boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarbonium tetra( p Examples include trifluoromethylphenyl boron, triphenylcarbonium tetrapentafluorophenylboron, etc.

[0212] In a preferred embodiment of the present invention, the catalyst for olefin polymerization may further include a carrier supporting a transition metal compound. Specifically, the carrier may support both a transition metal compound and a co-catalyst compound.

[0213] At this time, the carrier may include a material containing hydroxyl groups on its surface, and preferably, a material having highly reactive hydroxyl groups and siloxane groups that has been dried to remove moisture from its surface may be used. For example, the carrier may include at least one selected from the group consisting of silica, alumina, and magnesia. Specifically, silica dried at high temperatures, silica-alumina, and silica-magnesia, etc., may be used as the carrier, and these may typically contain oxide, carbonate, sulfate, and nitrate components such as Na2O, K2CO3, BaSO4, and Mg(NO3)2. In addition, they may include carbon, zeolite, magnesium chloride, etc. However, the carrier is not limited to these, and is not particularly limited as long as it is capable of supporting transition metal compounds and co-catalyst compounds.

[0214] The carrier may have an average particle size of 10 to 250 μm, preferably an average particle size of 10 to 150 μm, and more preferably 20 to 100 μm.

[0215] The micropore volume of the carrier can be 0.1 to 10 cc / g, preferably 0.5 to 5 cc / g, and more preferably 1.0 to 3.0 cc / g.

[0216] The specific surface area of ​​the carrier can be 1 to 1,000 m² / g, preferably 100 to 800 m² / g, and more preferably 200 to 600 m² / g.

[0217] In a preferred embodiment, when the carrier is silica, the drying temperature of the silica may be room temperature to 900°C. The drying temperature may preferably be room temperature to 800°C, and more preferably room temperature to 700°C. If the drying temperature is lower than room temperature, there is too much moisture, causing the moisture on the surface to react with the co-catalyst, and if it exceeds 900°C, the structure of the carrier may collapse.

[0218] The concentration of hydroxyl groups in the dried silica may be 0.1 to 5 mmole / g, preferably 0.7 to 4 mmole / g, and more preferably 1.0 to 2 mmole / g. If the concentration of hydroxyl groups is less than 0.1 mmole / g, the loading amount of the co-catalyst is reduced, and if it exceeds 5 mmole / g, a problem may occur in which the catalyst component is inactivated.

[0219] The total amount of transition metal compounds supported on the support can be 0.001 to 1 mmole based on 1 g of the support. If the ratio of transition metal compounds to the support satisfies the above range, it exhibits appropriate supported catalyst activity, which is advantageous in terms of maintaining catalyst activity and economic feasibility.

[0220] The total amount of co-catalyst compound supported on the carrier can be 2 to 15 mmole based on 1 g of the carrier. If the ratio of the co-catalyst compound to the carrier satisfies the above range, it is advantageous in terms of maintaining catalyst activity and economic efficiency.

[0221] 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. Additionally, only one of the transition metal compound and the co-catalyst compound may be supported on the carrier.

[0222] Method for preparing a catalyst for olefin polymerization

[0223] According to another embodiment of the present invention, a method for preparing a catalyst for olefin polymerization is provided, comprising the steps of: (1) reacting a compound represented by the following chemical formula 2 with a compound represented by the following chemical formula 3 to obtain a compound represented by the following chemical formula 4; (2) reacting a compound represented by the following chemical formula 4 with a compound represented by the following chemical formula 5 to obtain a compound represented by the following chemical formula 6; (3) reacting a compound represented by the following chemical formula 6 with an organolithium compound to obtain a compound represented by the following chemical formula 7; and (4) reacting a compound represented by the following chemical formula 7 with a compound represented by the following chemical formula 8 to obtain a transition metal compound represented by the following chemical formula 1; and (5) supporting the transition metal compound, the co-catalyst compound, or both obtained in step (4) on a support.

[0224] [Chemical Formula 1]

[0225]

[0226] [Chemical Formula 2]

[0227]

[0228] [Chemical Formula 3]

[0229] Me2Si(X a )2

[0230] [Chemical Formula 4]

[0231]

[0232] [Chemical Formula 5]

[0233] R4NH2

[0234] [Chemical Formula 6]

[0235]

[0236] [Chemical Formula 7]

[0237]

[0238] [Chemical Formula 8]

[0239] MX4

[0240] In the above chemical formula, l, m, n, M, X, R1 R4 are as described in the above section on transition metal compounds, and Me is methyl, X a is a halogen.

[0241] The specific details of steps (1) to (4) above are substantially the same as steps (1) to (4) of the method for manufacturing the above transition metal compound.

[0242] Step (5)

[0243] In step (5) above, a transition metal compound, a co-catalyst compound, or both are supported on a carrier.

[0244] As a method for supporting transition metal compounds and / or co-catalyst compounds, a physical adsorption method or a chemical adsorption method may be used.

[0245] For example, the physical adsorption method may be a method of contacting a solution in which a transition metal compound is dissolved with a carrier and then drying it, a method of contacting a solution in which a transition metal compound and a co-catalyst compound are dissolved with a carrier and then drying it, or a method of preparing a carrier supported with a transition metal compound by contacting a solution in which a transition metal compound is dissolved with a carrier and then drying it, and separately preparing a carrier supported with a co-catalyst compound by contacting a solution in which a co-catalyst compound is dissolved with a carrier and then drying it, and then mixing the two.

[0246] The chemical adsorption method may be a method in which a co-catalyst compound is first supported on the surface of a support and then a transition metal compound is supported on the co-catalyst compound, or a method in which a transition metal compound is covalently bonded to a functional group on the surface of the support (e.g., in the case of silica, a hydroxyl group (-OH) on the silica surface).

[0247] Here, the solvent used when supporting the transition metal compound and / or 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, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, ether-based solvents such as diethyl ether and tetrahydrofuran, acetone, and ethyl acetate.

[0248] In a preferred embodiment, the process of supporting a transition metal compound and / or a co-catalyst compound on a carrier in step (5) above can be performed at a temperature of 0 to 100°C, preferably at room temperature to 90°C.

[0249] Additionally, the process of supporting the transition metal compound and / or co-catalyst compound on the carrier in step (5) can be performed by sufficiently stirring the mixture of the transition metal compound and / or co-catalyst compound and the carrier for 1 minute to 24 hours, preferably 5 minutes to 15 hours.

[0250] Polymerization of olefins

[0251] An olefin polymer can be produced by polymerizing an olefin monomer in the presence of an olefin polymerization catalyst according to an embodiment of the present invention.

[0252] Here, the olefin polymer may be a homopolymer of an olefin monomer or a copolymer of an olefin monomer and a comonomer.

[0253] 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.

[0254] 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.

[0255] In an exemplary embodiment, the olefinic polymer is ethylene and C 3-20 It may be a copolymer of alpha-olefins, and a copolymer of ethylene and 1-hexene is preferred, but is not limited to these.

[0256] In this case, the ethylene content is preferably 55 to 99.9 weight%, and more preferably 90 to 99.9 weight%. The alpha-olefin comonomer content is preferably 0.1 to 45 weight%, and more preferably 0.1 to 10 weight%.

[0257] In exemplary embodiments, the olefinic polymer may be polymerized by polymerization reactions such as free radical, cationic, coordination, condensation, and addition, but is not limited to these.

[0258] As a preferred embodiment, the olefinic polymer may be prepared by vapor phase polymerization, solution polymerization, or slurry polymerization, etc. When the olefinic polymer is prepared by solution polymerization or slurry polymerization, examples of solvents that may be used include C, such as pentane, hexane, heptane, nonane, decane, and isomers thereof. 5-12 Examples include 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, but are not limited to these.

[0259] Examples

[0260] The present invention will be explained in more detail below through examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited thereto.

[0261] Examples 1: N- tert -butyl-1,1-dimethyl-1-(2'- methyl -1',5',6',7'- Tetrahydrospiro [Cyclohexane-1,4'-indenyl])silanamine zirconium dichloride (N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine zirconium dichloride; Chemical formula 1- 1) of manufacturing

[0262] A transition metal compound of Chemical Formula 1-1 was prepared according to the synthesis procedure summarized in Reaction Scheme 1 below.

[0263] [Reaction Equation 1]

[0264]

[0265] Step 1: Spiro[5.5] Undecan -1-on( spiro[5.5]undecan -1-one; chemical formula b Synthesis of )

[0266] potassium t - In a solution of potassium tert-butoxide (11.43 g, 102 mmole) dispersed in toluene (80 ml), cyclohexanone (chemical formula) aA solution of ) (5.0 g, 51 mmole) diluted in toluene (50 mL) and a solution of 1,5-dibromopentane (11.71 g, 51 mmole) diluted in toluene (70 mL) were slowly added. Then, the mixture was stirred at 110°C for 12 hours. To terminate the reaction, 1 M hydrochloric acid was added at 0°C to neutralize the mixture, after which the organic layer was separated using a separatory funnel. The remaining water was removed with magnesium sulfate (MgSO4), and the solvent was removed under vacuum. The mixture was then separated by column chromatography (hexane:ethyl acetate = 20 / 1, v / v) to obtain 5.59 g (66%) of a white solid compound.

[0267] 1 H NMR (300 MHz, CDCl3): δ 2.40 (t, 2 H), 1.80-1.93 (m, 4 H), 1.66-1.75 (m, 4 H), 1.45-1.53 ​​(m, 4 H), 1.30-1.45 (m, 4 H).

[0268] step 2: 2 - Bromospiro[5,5]undecan -1-on(2- bromospiro[5,5]undecan -1-one; chemical formula c Synthesis of )

[0269] chemical formula b A solution of bromine (5.37 g, 34 mmole) diluted in diethyl ether (50 ml) was slowly added at 0°C to a solution of compound (5.59 g, 34 mmole) diluted in diethyl ether (50 ml), and then the temperature was slowly raised to room temperature and stirred for 12 hours. To terminate the reaction, a saturated solution of sodium thiosulfate (Na2S2O3) was added to remove the bromine remaining after the reaction, and the organic layer was separated using a separatory funnel. The remaining water was removed with magnesium sulfate, and after removing the solvent under vacuum, the mixture was separated by column chromatography (hexane:ethyl acetate = 20 / 1, v / v) to obtain 9.23 g of a yellow liquid compound (equivalent yield).

[0270] 1 H NMR (300 MHz, CDCl3): δ 4.94 (dd, 1 H), 2.57-2.66 (m, 1 H), 2.09 (dd, 1 H), 1.85-2.01 (m, 4 H), 1.64-1.78 (m, 4 H), 1.37-1.61 (m, 6 H), 1.20-1.34 (m, 2 H).

[0271] Step 3: Ethyl 3-oxo-2- (1-oxospiro[5,5]undeken-2-yl)butyrate(ethyl 3-oxo-2- (1-oxospiro[5.5]undecen-2-yl)butyrate; chemical formula d Synthesis of )

[0272] Chemical formula in a solution of ethyl acetoacetate sodium salt (11.45 g, 75 mmole) dispersed in toluene (70 ml) c A solution of compound (9.23 g, 38 mmole) diluted in toluene (30 ml) was added. The mixture was then stirred at 110°C for 12 hours. To terminate the reaction, 1 M hydrochloric acid was added at 0°C for neutralization, after which the organic layer was separated using a separatory funnel. Remaining water was removed with magnesium sulfate, and the solvent was removed under vacuum to obtain the chemical formula d 12.30 g (equivalent yield) of a yellow liquid mixture of the compound and ethyl acetoacetate was obtained.

[0273] step 4: 2 - (2-oxopropyl)spiro[5,5]undecan -1-on(2- (2-oxopropyl)spiro[5.5] undecan-1-one; chemical formula e Synthesis of )

[0274] chemical formula dA 3.0 M aqueous potassium hydroxide solution (120 mL) was added to a solution of a mixture of the compound and ethyl acetoacetate diluted in methanol (120 mL), and the mixture was stirred at 65°C for 12 hours. To terminate the reaction, 1 M hydrochloric acid was added at 0°C to neutralize the mixture, after which the organic layer was separated using a separatory funnel. The remaining water was removed with magnesium sulfate, and after removing the solvent under vacuum, the mixture was separated by column chromatography (hexane:ethyl acetate = 20 / 1, v / v) to obtain 3.46 g (31%) of the yellow liquid compound.

[0275] 1 H NMR (300 MHz, CDCl3): δ 3.25-3.36 (m, 1 H), 2.94 (dd, 1 H), 2.22 (s, 3 H), 2.12 (dd, 1 H), 1.85-2.04 (m, 4 H), 1.55-1.70 (m, 4 H), 1.24-1.52 (m, 7 H), 1.01-1.10 (m, 1 H).

[0276] step 5: 5 ',6',7',7a'- Tetrahydrospiro [ cyclohexane -1,4'- Inden ]2' (1'H)-one (5',6',7',7a'-tetrahydrospiro[cyclohexane-1,4'-inden]2' ( 1'H )-one; chemical formula f Synthesis of )

[0277] chemical formula e Potassium in a solution of the compound (3.46 g, 16 mmole) diluted in toluene (35 ml) tButoxide (2.10 g, 19 mmole) was added and stirred at room temperature for 4 hours. The reaction was terminated by adding distilled water, extracted with ethyl acetate, and the organic layer was separated using a separatory funnel. The remaining water was removed with magnesium sulfate, and after removing the solvent under vacuum, the mixture was separated by column chromatography (hexane:ethyl acetate = 20 / 1, v / v) to obtain 1.65 g (52%) of a compound consisting of a mixture of a yellow needle-shaped solid and a yellow liquid.

[0278] 1 H NMR (300 MHz, CDCl3): δ 5.90 and 5.81 (s, 1 H), 2.85-2.93 and 2.75-2,81 (m, 1 H), 2.59 and 2.75 (d, 1 H), 2.15-2.38 (m, 3 H), 0.92-2.02 (m, 14 H).

[0279] Step 6: 2'-methyl-1',2',5',6',7',7a'-hexahydrospiro[cyclohexane-1,4'-inden]-2'-ol (2'-methyl-1',2',5',6',7',7a'-hexahydrospiro[cyclohexane-1,4'-inden]-2'-ol; chemical formula g Synthesis of )

[0280] chemical formula f A solution of compound (1.0 g, 4.89 mmole) dissolved in tetrahydrofuran (20 mL) was cooled to -30°C, after which 1.6 M methyllithium solution (4.6 mL, 7.34 mmole) was slowly added, and the mixture was stirred at room temperature for 16 hours. The reaction was terminated by adding distilled water, extracted with ethyl acetate, and the organic layer was separated using a separatory funnel. Remaining water was removed with magnesium sulfate, and after removing the solvent under vacuum, the obtained chemical formula g The compound was used as is in the following reaction.

[0281] step 7: 2 '- methyl -5',6',7',7a'- Tetrahydrospiro [ cyclohexane -1,4'- Inden ](2'-methyl-5',6',7',7a'-tetrahydrospiro[cyclohexane-1,4'-indene; chemical formula h Synthesis of )

[0282] chemical formula g A solution of the compound dissolved in diethyl ether (10 mL) was cooled to 0°C, 1 M hydrochloric acid (6 mL) was added, and the mixture was stirred for 2 hours while maintaining the temperature. Subsequently, the solution was diluted with distilled water (10 mL), extracted with ethyl acetate, and the organic layer was separated using a separatory funnel. Remaining water was removed with magnesium sulfate, and after removing the solvent under vacuum, the solution was separated by column chromatography (hexane) to obtain a clear chemical formula as a colorless liquid. h 466 mg (47%) of the compound was obtained.

[0283] 1 H NMR (300 MHz, CDCl3): δ 6.10 and 5.85 (s, 1 H), 2.83 and 2.77 (s, 2 H), 2.23-2.10 (m, 2 H), 2.00 (s, 3 H), 1.71-1.54 (m, 4 H), 1.54-1.41 (m, 10 H).

[0284] step 8: 2 '- methyl -5',6',7',7a'- Tetrahydrospiro [ cyclohexane -1,4'- Indenil ] lithium(2'-methyl-5',6',7',7a'- tetrahydrospiro [ cyclohexane -1,4'- indenyl ] lithium; chemical formula i Synthesis of )

[0285] chemical formula h A solution of the compound (51 mg, 0.25 mmole) dissolved in tetrahydrofuran (5 mL) was cooled to -30°C, and then 1.6 M n- After slowly injecting a butyllithium solution (0.2 mL, 0.31 mmole), the mixture was stirred at room temperature for 16 hours. After removing the tetrahydrofuran solvent under vacuum, hexane was added to separate the lithium salt compound (chemical formula) formed in the separatory funnel.i After filtering, it was washed several times with hexane to purify it thoroughly, yielding 42 mg (79%).

[0286] Step 9: Chlorodimethyl(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silane; chemical formula j Synthesis of )

[0287] After cooling a solution of dimethyldichlorosilane (Me2SiCl2) (35 mg, 0.17 mmole) dissolved in toluene (1 ml) to -30°C, the chemical formula i A solution of the compound (35 mg, 0.17 mmole) dissolved in toluene (1 ml) was slowly injected, and the mixture was stirred at 90°C for 16 hours. After removing the toluene under vacuum, pentane was added to extract the product, and the pentane was removed under vacuum to obtain 39 mg (78%) of a white solid compound.

[0288] 1 H NMR (300 MHz, C6D6): δ 6.19 (s, 1H), 2.91 (s, 1H), 2.05 (s, 3H), 1.61-1.18 (m, 16H), 0.18-0.09 (m, 6H).

[0289] Step 10: N- tert -butyl-1,1-dimethyl-1-(2'- methyl -1',5',6',7'- tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine (N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine; chemical formula k Synthesis of )

[0290] chemical formula j After cooling a solution of the compound (39 mg, 0.13 mmole) dissolved in tetrahydrofuran (1 ml) to -30°C, t -butylamine( t A solution of (38 mg, 0.53 mmole) of (-butylamine) dissolved in tetrahydrofuran (1 ml) was slowly injected, and the mixture was stirred at room temperature for 16 hours. After removing the tetrahydrofuran under vacuum, pentane was added to extract the product, and the pentane was removed under vacuum to obtain 43 mg (97%) of a white solid compound.

[0291] 1H NMR (300 MHz, C6D6): δ 6.24 (s, 1H), 2.75 (s, 1H), 2.11 (s, 3H), 1.91 (m, 2H), 1.70-1.58 (m, 7H), 1.51-1.45 (m, 7H), 1.07 (s, 9H), 0.13 (d, 6H).

[0292] Step 11: N- tert -butyl-1,1-dimethyl-1-(2'- methyl -1',5',6',7'- Tetrahydrospiro [cyclohexane-1,4'-indene]-1'-yl)silanamine Dilithium Salt (N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine dilithium salt; chemical formula l Synthesis of )

[0293] chemical formula k After cooling a solution of the compound (43 mg, 0.13 mmole) dissolved in hexane (1 mL) to -30°C, 1.6 M t After slowly injecting a butyllithium (121 mg, 0.28 mmole) solution, the mixture was stirred at room temperature for 16 hours. After removing hexane under vacuum, the mixture was washed several times with pentane and dried for use in the next step.

[0294] Step 12: N- tert -butyl-1,1-dimethyl-1-(2'- methyl -1',5',6',7'- Tetrahydrospiro [cyclohexane-1,4'-inden]-1'-yl)silanamine zirconium dichloride (N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine zirconium dichloride; Chemical formula 1- 1) of synthesis

[0295] chemical formula lTrimethylamine (52 mg, 0.52 mmole) was added to a solution in which the compound was dissolved in toluene (2 ml) and stirred for 30 minutes, after which the solution was cooled to -30°C. Zirconium chloride (ZrCl4) (30 mg, 0.12 mmole) was added to this, and the mixture was stirred at room temperature for 16 hours. The reaction mixture was passed through a filter to remove impurities, and the toluene was removed under vacuum. Subsequently, pentane was added to extract the product, and the pentane was removed under vacuum to obtain 30 mg (47%) of the compound of Formula 1-1.

[0296] 1 H NMR (300 MHz, C6D6): δ 6.39 (s, 1H), 2.08 (s, 3H), 1.71-1.09 (m, 16H), 1.34 (s, 9H), 0.39 (s, 3H), 0.34 (s, 3H).

[0297] The transition metal compound and the olefin polymerization catalyst containing the same according to a specific embodiment of the present invention have a unique stereochemical structure, which enables the control of the physical properties of the polymer.

Claims

Claim 1 A transition metal compound, at least one of the transition metal compounds represented by the following chemical formulas 1-1 to 1-21: [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] . Claim 2 delete Claim 3 delete Claim 4 (1) a step of reacting a compound represented by Chemical Formula 2 below with a compound represented by Chemical Formula 3 below to obtain a compound represented by Chemical Formula 4 below; (2) a step of reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6 below; (3) a step of reacting a compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; and (4) a step of reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 below to obtain a transition metal compound represented by Chemical Formula 1 below, comprising a method for preparing a transition metal compound: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3]Me2Si(X a )2[Chemical Formula 4] [Chemical Formula 5]R4NH2[Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] In the above chemical formulas, l is an integer from 0 to 2, m is an integer from 0 to 3, n is an integer from 0 to 5, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and X is each independently a halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkinyl, C 6-20 Aril, C 1-20 Alkyl C 6-20 Aril, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamido or C 6-20 It is an arylamido, and R1 to R3 are each independently 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 Alkylamido, substituted or unsubstituted C 6-20 Arylamido, or substituted or unsubstituted C 1-20 It is a silyl, wherein R1 to R3 are each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 It can form a ring, and R4 is 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 or substituted or unsubstituted C 2-20 It is alkynyl, Me is methyl, X a is a halogen. Claim 5 In claim 4, a method for preparing a transition metal compound wherein the compound represented by Chemical Formula 2 above is at least one of the compounds represented by Chemical Formulas 2-1 to 2-16 below: [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 2-8][Chemical Formula 2-9] [Chemical Formula 2-10][Chemical Formula 2-11][Chemical Formula 2-12] [Chemical Formula 2-13][Chemical Formula 2-14][Chemical Formula 2-15] [Chemical Formula 2-16] . Claim 6 A method for preparing a transition metal compound according to claim 4, wherein the reactions of steps (1) to (4) are each independently carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate. Claim 7 A method for producing a transition metal compound according to claim 4, wherein the reaction of step (4) is carried out in the presence of an amine-based compound. Claim 8 A catalyst for olefin polymerization comprising the transition metal compound of claim 1; and a co-catalyst compound. Claim 9 In claim 8, the olefin polymerization catalyst wherein the co-catalyst compound is one or more selected from the group consisting of the compound represented by Chemical Formula 9, the compound represented by Chemical Formula 10, and the compound represented by Chemical Formula 11: [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11][LH] + [Z(A)4] - or [L] + [Z(A)4] - In the above chemical formula 9, n is an integer greater than or equal to 2, and R a is a halogen atom, C 1-20 C substituted with hydrocarbon groups or halogens 1-20 It is a hydrocarbon group, and in the above chemical formula 10, D is aluminum (Al) or boron (B), and R b , R c and R d Each independently has a halogen atom, C 1-20 Hydrocarbon group, C substituted with a halogen 1-20 Hydrocarbon group or C 1-20 It is an alkoxy group, and in the above chemical formula 11, 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 substituted or unsubstituted C 6-20 C that is an aryl group or is substituted or unsubstituted 1-20 It is an alkyl group. Claim 10 An olefin polymerization catalyst according to claim 9, wherein the compound represented by Chemical Formula 9 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane. Claim 11 In claim 9, the compound represented by Chemical Formula 10 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s -Butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p - An olefin polymerization catalyst selected from the group consisting of tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, and tributyl boron. Claim 12 In claim 9, the compound represented by Chemical Formula 11 is 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, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra( p -Tollil)Aluminum, Tripropylammonium Tetra( p -Tollil)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 -Tollil)Boron, Triethylammonium Tetra( o , p -Dimethylphenyl)boron, Triphenylcarbonium Tetra( p - An olefin polymerization catalyst selected from the group consisting of trifluoromethylphenyl)boron and triphenylcarbonium tetrapentafluorophenylboron. Claim 13 A catalyst for olefin polymerization according to claim 8, further comprising a carrier supporting a transition metal compound, a co-catalyst compound, or both. Claim 14 In claim 13, a catalyst for olefin polymerization comprising at least one carrier selected from the group consisting of silica, alumina, and magnesia. Claim 15 A catalyst for olefin polymerization according to claim 13, wherein the total amount of transition metal compounds supported on a carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the total amount of co-catalyst compounds supported on the carrier is 2 to 15 mmole based on 1 g of the carrier. Claim 16 (1) a step of reacting a compound represented by Chemical Formula 2 below with a compound represented by Chemical Formula 3 below to obtain a compound represented by Chemical Formula 4 below; (2) a step of reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6 below; (3) a step of reacting a compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; (4) a step of reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 below to obtain a transition metal compound represented by Chemical Formula 1 below; and (5) a step of supporting the transition metal compound, a co-catalyst compound, or both obtained in step (4) on a support [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3]Me2Si(X a )2[Chemical Formula 4] [Chemical Formula 5]R4NH2[Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] In the above chemical formulas, l is an integer from 0 to 2, m is an integer from 0 to 3, n is an integer from 0 to 5, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and X is each independently a halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkinyl, C 6-20 Aril, C 1-20 Alkyl C 6-20 Aril, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamido or C 6-20 It is an arylamido, and R1 to R3 are each independently 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 Alkylamido, substituted or unsubstituted C 6-20 Arylamido, or substituted or unsubstituted C 1-20 It is a silyl, wherein R1 to R3 are each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 It can form a ring, and R4 is 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 or substituted or unsubstituted C 2-20 It is alkynyl, Me is methyl, X a is a halogen.

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