Transition metal compound and catalyst composition comprising the same

Abstract

The present invention relates to a transition metal compound having a novel structure represented by Formula 1, and a catalyst composition comprising the same: in Formula 1, M is Ti, Zr, or Hf, X1 and X2 are each independently C-R5, C-R6, or N, where R5 and R6 are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, or a cycloalkyl group of 5 to 20 carbon atoms, r1 to R4 are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, or a cycloalkyl group of 5 to 20 carbon atoms, R7 to R12 are each independently an alkyl group of 1 to 20 carbon atoms, L1 and L2 are each independently a single bond or an alkylene group of 1 to 20 carbon atoms, Cy1 and Cy2 are each independently a cycloalkyl group of 5 to 20 carbon atoms, and R7 to R12 are each independently a single bond or an alkylene group of 1 to 20 carbon atoms. And X1 and X2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms, or an aralkyl group of 7 to 20 carbon atoms.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 2022-0142694 filed on October 31, 2022, and Korean Patent Application No. 2022-0142695 filed on October 31, 2022, in the Korean Intellectual Property Office, the contents of which are incorporated herein by reference. Technical Field

[0004] The present invention relates to a transition metal compound having a novel structure and a catalyst composition comprising the transition metal compound. Background Art

[0005] In general, olefin polymers such as ethylene copolymers are useful polymer materials for use as materials for hollow molded products, extrusion molded products, films, sheets, etc., and have been produced in the presence of a Ziegler-Natta catalyst system.

[0006] Ziegler-Natta catalysts are heterogeneous catalysts and are catalysts used in systems where the phases of the reactants and the catalysts are not the same, such as liquid reactant-solid catalyst systems, etc. Such Ziegler-Natta catalysts consist of two components, usually halogen compounds of transition metals (such as TiCl4), alkyl lithium, alkyl aluminum, etc., and the transition metals include titanium (Ti), vanadium (V), chromium (Cr), molybdenum (Mo) and zirconium (Zr).

[0007] However, the concentration of active species of the Ziegler-Natta catalyst is several to several tens of percent relative to transition metal atoms, and most transition metal atoms cannot exhibit their functions and have the defect of not being able to overcome the limitation as a heterogeneous catalyst.

[0008] Recently, metallocene compounds have attracted attention as next-generation catalysts that can overcome these drawbacks. Metallocene compounds are homogeneous catalysts including a Group 4 metal and are known to show desirable polymerization activity in olefin polymerization.

[0009] Most metallocene catalysts used for polymerization include metal elements of Group 4 such as titanium, zirconium and hafnium (Hf) and a support ligand as a precursor, and are composed of two aromatic five-membered rings and two halogen compounds as leaving groups. Among them, an aromatic cyclopentadienyl group is generally used as a support ligand coordinated with respect to a central metal.

[0010] Such metallocene catalysts are used in various applications including olefin polymerization processes, but the catalyst activity shows some limitations (particularly in a solution process under a temperature condition of 100° C. or higher), and it is known that, for example, due to a relatively fast terminal termination reaction (or chain reaction) such as a β-hydride elimination reaction, an olefin polymer having a low molecular weight showing a molecular weight (Mn) of 20,000 or less at a temperature of 100° C. or higher can be prepared. In addition, it is known that active species of metallocene catalysts are deactivated at a temperature of 100° C. or higher. Therefore, in order to increase the applicability of metallocene catalysts, a method for overcoming the above limitations is required.

[0011] [Prior art literature]

[0012] [Patent document]

[0013] (Patent Document 1) U.S. Registered Patent No. 5,064,802 Summary of the invention

[0014] Technical issues

[0015] An object of the present invention is to provide a novel transition metal compound capable of preparing an olefin-based polymer having high heat resistance, and a catalyst composition comprising the same.

[0016] Technical Solution

[0017] In order to achieve the above-mentioned objects, the present invention provides a transition metal compound, a catalyst composition and a method for preparing an olefin polymer.

[0018] (1) The present invention provides a transition metal compound represented by the following formula 1:

[0019] [Formula 1]

[0020]

[0021] In formula 1,

[0022] M is Ti, Zr or Hf,

[0023] X1 and X2 are each independently C-R5, C-R6 or N, wherein R5 and R6 are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms or a cycloalkyl group of 5 to 20 carbon atoms,

[0024] R1 to R4 are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, or a cycloalkyl group of 5 to 20 carbon atoms,

[0025] R7 to R 12 are each independently an alkyl group having 1 to 20 carbon atoms,

[0026] L1 and L2 are each independently a single bond or an alkylene group of 1 to 20 carbon atoms,

[0027] Cy1 and Cy2 are each independently a cycloalkyl group of 5 to 20 carbon atoms, and

[0028] X1 and X2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

[0029] (2) The present invention provides a transition metal compound according to (1), wherein M is Hf, X1 and X2 are each independently CH or N, R1 to R4 are each independently hydrogen or an alkyl group of 1 to 10 carbon atoms, and R7 to R 12 Each is independently an alkyl group of 1 to 10 carbon atoms, L1 and L2 are each independently an alkylene group of 1 to 6 carbon atoms, Cy1 and Cy2 are each independently a cycloalkyl group of 5 to 10 carbon atoms, and X1 and X2 are each independently an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

[0030] (3) The present invention provides a transition metal compound according to (1) or (2), wherein the transition metal compound represented by Formula 1 is a compound represented by the following Formula 1A or Formula 1B:

[0031] [Formula 1A]

[0032]

[0033] [Formula 1B]

[0034]

[0035] In Formula 1A and Formula 1B,

[0036] M is Ti, Zr or Hf,

[0037] R7 to R 12 are each independently an alkyl group having 1 to 20 carbon atoms,

[0038] L1 and L2 are each independently a single bond or an alkylene group of 1 to 20 carbon atoms,

[0039] Cy1 and Cy2 are each independently a cycloalkyl group of 5 to 20 carbon atoms, and

[0040] X1 and X2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

[0041] (4) The present invention provides a transition metal compound according to any one of (1) to (3), wherein the transition metal compound represented by Formula 1 is one selected from the group consisting of Formula 1-1 to Formula 1-5:

[0042] [Formula 1-1]

[0043]

[0044] [Formula 1-2]

[0045]

[0046] [Formula 1-3]

[0047]

[0048] [Formula 1-4]

[0049]

[0050] [Formula 1-5]

[0051]

[0052] (5) A catalyst composition according to the present invention comprises the transition metal compound according to any one of (1) to (4) and a co-catalyst.

[0053] (6) The present invention provides a catalyst composition according to (5), wherein the catalyst composition further comprises a transition metal compound represented by Formula 2:

[0054] [Formula 2]

[0055]

[0056] In formula 2,

[0057] Q is Ti, Zr or Hf,

[0058] R 13 To R 16 are each independently hydrogen or an alkyl group of 1 to 20 carbon atoms, wherein adjacent two or more may be linked to each other to form a ring,

[0059] R 17 and R 18 are each independently hydrogen, or an aryl group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent is an alkyl group having 1 to 6 carbon atoms,

[0060] Each R 19 is independently an alkyl group of 3 to 20 carbon atoms, a cycloalkyl group of 4 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms,

[0061] n is 1 to 5, and

[0062] Y1 and Y2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

[0063] (7) The present invention provides a catalyst composition according to (6), wherein the transition metal compound represented by Formula 2 is a compound represented by the following Formula 2A:

[0064] [Formula 2A]

[0065]

[0066] In Formula 2A,

[0067] Q is Ti, Zr or Hf,

[0068] R 17 and R 18 are each independently hydrogen or an aryl group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent is an alkyl group having 1 to 6 carbon atoms,

[0069] Each R 19 are independently an alkyl group of 3 to 20 carbon atoms, a cycloalkyl group of 4 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms, and

[0070] Y1 and Y2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

[0071] (8) The present invention provides a catalyst composition according to any one of (5) to (7), wherein the co-catalyst comprises one or more selected from the group consisting of Formula 3 to Formula 5:

[0072] [Formula 3]

[0073] -[Al(R a )-O] m -

[0074] [Formula 4]

[0075] D(R a )3

[0076] [Formula 5]

[0077] [LH] + [Z(A)4] - or [L]+ [Z(A)4] -

[0078] In the above formulas,

[0079] Each R a are independently a halogen group, a hydrocarbon group of 1 to 20 carbon atoms, or a halogen-substituted hydrocarbon group of 1 to 20 carbon atoms,

[0080] m is an integer greater than 2,

[0081] D is aluminum or boron,

[0082] L is a neutral or cationic Lewis acid,

[0083] Z is an element in group 13,

[0084] Each A is independently an aryl group of 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, or an alkyl group of 1 to 20 carbon atoms, and

[0085] The substituent of A is halogen, a hydrocarbon group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms or an aryloxy group of 6 to 20 carbon atoms.

[0086] (9) The present invention provides a method for producing an olefin polymer, comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition according to any one of (5) to (8).

[0087] Beneficial Effects

[0088] An olefin-based polymer having high heat resistance can be prepared using the transition metal compound of the present invention as a catalyst. DETAILED DESCRIPTION

[0089] Hereinafter, the present invention will be described in more detail to help understanding of the present invention.

[0090] It should be understood that the words or terms used in the present disclosure and claims should not be interpreted as the meanings defined in commonly used dictionaries. It should also be understood that based on the inventors can appropriately define the meanings of words or terms to best explain the principles of the present invention, words or terms should be interpreted as having meanings consistent with their meanings in the technical ideas of the present invention.

[0091] In the present invention, unless otherwise specified, "alkyl" refers to a linear, cyclic or branched hydrocarbon residue, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and hexyl.

[0092] In the present invention, unless otherwise specified, "cycloalkyl" refers to a non-aromatic cyclic hydrocarbon group consisting of carbon atoms. Non-limiting examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

[0093] In the present invention, unless otherwise mentioned, " aryl " refers to the optionally substituted phenyl ring or the ring system formed by fusing one or more optional substituents. The example of optional substituent includes substituted C1-3 alkyl, substituted C2-3 alkenyl, substituted C2-3 alkynyl, heteroaryl, heterocyclic radical, aryl, alkoxy with optional one to three fluorine substituents, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonylamino, formamide, aminocarbonyl, carboxyl, oxo, hydroxyl, sulfydryl, amino, nitro, cyano, halogen or urea. The ring or ring system can be optionally fused with aryl ring (such as phenyl ring), carbocycle or heterocycle with optional one or more substituents. The non-limiting examples of " aryl " include phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indenyl, anthracenyl, phenanthrenyl or its substituted derivatives.

[0094] In the present invention, "alkylaryl" refers to an aryl group substituted by an alkyl group.

[0095] In the present invention, "arylalkyl" refers to an alkyl group substituted with an aryl group.

[0096] In the present invention, "alkylene" refers to a branched or unbranched divalent unsaturated hydrocarbon, and the alkylene may be substituted or unsubstituted. The alkylene may include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butylene, pentylene, 3-pentylene, etc.

[0097] In the present invention, unless otherwise mentioned, "hydrocarbon group" means a monovalent hydrocarbon group of 1 to 20 carbon atoms, regardless of its structure, consisting only of carbon and hydrogen, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl and arylalkyl.

[0098] The transition metal compound of the present invention is characterized by being represented by Formula 1.

[0099] [Formula 1]

[0100]

[0101] In formula 1,

[0102] M is Ti, Zr or Hf,

[0103] X1 and X2 are each independently C-R5, C-R6 or N, wherein R5 and R6 are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms or a cycloalkyl group of 5 to 20 carbon atoms,

[0104] R1 to R4 are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, or a cycloalkyl group of 5 to 20 carbon atoms,

[0105] R7 to R 12 are each independently an alkyl group having 1 to 20 carbon atoms,

[0106] L1 and L2 are each independently a single bond or an alkylene group of 1 to 20 carbon atoms,

[0107] Cy1 and Cy2 are each independently a cycloalkyl group of 5 to 20 carbon atoms, and

[0108] X1 and X2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

[0109] The transition metal compound of the present invention is characterized in that it contains a ring functional group at the Cy1 and Cy2 positions in Formula 1 and has a bulky structure. In this case, the solubility of the transition metal compound increases with the increase of the carbon number, and therefore, the preparation yield of the transition metal compound can be increased, and the activity as a catalyst may become excellent. In addition, if the transition metal compound is used as a catalyst in the copolymerization reaction of ethylene and α-olefins, the approach of α-olefins can be minimized due to the bulky structure of the catalyst, and ethylene / α-olefin copolymers with high melting temperatures (Tm) can be prepared.

[0110] As described above, the transition metal compound of the present invention can be usefully used as a catalyst for producing olefin polymers, and this is an inherent characteristic achieved by the new structure of the compound newly developed in the present invention.

[0111] In particular, in Formula 1, M may be Hf.

[0112] In particular, in Formula 1, X1 and X2 may each independently be CH or N.

[0113] Particularly, in Formula 1, R1 to R4 may each independently be hydrogen or an alkyl group of 1 to 10 carbon atoms, an alkyl group of 1 to 6 carbon atoms, an alkyl group of 1 to 3 carbon atoms, and particularly, hydrogen.

[0114] In particular, in Formula 1, R7 to R 12 Each of them independently may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 3 carbon atoms, in particular a methyl group, an ethyl group or a propyl group.

[0115] Particularly, in Formula 1, L1 and L2 may each independently be an alkylene group of 1 to 6 carbon atoms, an alkylene group of 1 to 3 carbon atoms, and particularly a methylene group.

[0116] Particularly, in Formula 1, Cy1 and Cy2 may each independently be a cycloalkyl group of 5 to 10 carbon atoms, a cycloalkyl group of 5 to 8 carbon atoms, a cycloalkyl group of 6 to 8 carbon atoms, and particularly a cyclohexyl group.

[0117] Specifically, in Formula 1, X1 and X2 can each independently be an alkyl group of 1 to 10 carbon atoms, an alkyl group of 1 to 6 carbon atoms, an alkyl group of 1 to 3 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aryl group of 6 to 10 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an aralkyl group of 11 to 20 carbon atoms, specifically, a methyl group, a phenyl group or a benzyl group.

[0118] Specifically, the transition metal compound represented by Formula 1 may be a compound represented by Formula 1A or Formula 1B.

[0119] [Formula 1A]

[0120]

[0121] [Formula 1B]

[0122]

[0123] In Formula 1A and Formula 1B,

[0124] M, R7 to R 12 , L1 and L2, Cy1 and Cy2, X1 and X2 are the same as defined above.

[0125] The transition metal compound represented by Formula 1 may be particularly one selected from the group consisting of Formula 1-1 to Formula 1-5, but all transition metal compounds corresponding to Formula 1 are included in the present invention without limitation.

[0126] [Formula 1-1]

[0127]

[0128] [Formula 1-2]

[0129]

[0130] [Formula 1-3]

[0131]

[0132] [Formula 1-4]

[0133]

[0134] [Formula 1-5]

[0135]

[0136] The catalyst composition of the present invention is characterized by including a transition metal compound represented by Formula 1 and a co-catalyst.

[0137] In the present invention, the "composition" includes a mixture of materials comprising the composition, and reaction products and decomposition products obtained from the materials of the composition.

[0138] In addition, the catalyst composition of the present invention may further include a co-catalyst.

[0139] The co-catalyst may be a co-catalyst known in the art. For example, one or more selected from Formula 4 to Formula 6 may be used as the co-catalyst.

[0140] [Formula 4]

[0141] -[Al(R a )-O] m -

[0142] [Formula 5]

[0143] D(R a )3

[0144] [Formula 6]

[0145] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0146] In the above formulas,

[0147] Each R a are independently a halogen group, a hydrocarbon group of 1 to 20 carbon atoms, or a halogen-substituted hydrocarbon group of 1 to 20 carbon atoms,

[0148] m is an integer greater than 2,

[0149] D is aluminum or boron,

[0150] L is a neutral or cationic Lewis acid,

[0151] Z is an element in group 13,

[0152] Each A is independently an aryl group of 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, or an alkyl group of 1 to 20 carbon atoms, and

[0153] The substituent of A is halogen, a hydrocarbon group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms or an aryloxy group of 6 to 20 carbon atoms.

[0154] The compound represented by Formula 4 is not particularly limited as long as it is an alkylaluminoxane. Preferred examples may include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and methylaluminoxane is particularly preferred.

[0155] The compound represented by Formula 5 is not particularly limited, and preferred examples thereof may include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and particularly preferably selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

[0156] If Z is boron, examples of the compound represented by Formula 6 may include, for example, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] -, dioctadecylmethylammonium tetra(phenyl)borate, dioctadecylmethylammonium tetra[3,5-bis(trifluoromethyl)phenyl]borate, triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, N,N-dimethyltetraphenylborate Ethylanilinium, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, diethylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphine tetraphenylborate, trimethylphosphine tetraphenylborate, tripropylammonium tetrakis(p-tolyl)borate, triethylammonium tetrakis(o-,p-xylyl)borate, trimethylammonium tetrakis(o-,p-xylyl)borate, trimethylammonium tetrakis(o-,p-xylyl)borate, triphenylcarbonium tetrakis(p-trifluoromethylphenyl)borate, or a combination thereof. If Z is aluminum, examples of the compound represented by Formula 5 may include, for example, triethyltetraphenylaluminum ammonium, tributyltetraphenylaluminum ammonium, trimethyltetraphenylaluminum ammonium, tripropyltetraphenylaluminum ammonium, trimethyltetra(p-toluene)aluminum ammonium, tripropyltetra(p-toluene)aluminum ammonium, triethyltetra(o-,p-xylyl)aluminum ammonium, tributyltetra(p-trifluoromethylphenyl)aluminum ammonium, tetra(p-trifluoromethylphenyl)trimethylammonium aluminum, tetra(p-trifluoromethylphenyl)aluminum tributylammonium, N,N-diethylanilinetetraphenylaluminum, N,N-diethylanilinetetrapentafluorophenylaluminum, diethyltetrapentaphenylaluminum ammonium, triphenylphosphinetetraphenylaluminum, trimethylphosphinetetraphenylaluminum, triethyltetraphenylaluminum ammonium, or a combination thereof, but are not limited thereto.

[0157] In particular, the co-catalyst used in the present invention may be a compound represented by Formula 6, particularly dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate.

[0158] In addition, the transition metal compound represented by Formula 1 and the co-catalyst may be used in a supported type through a carrier. Silica or alumina may be used as the carrier, but is not limited thereto.

[0159] In the present invention, the catalyst composition may further include a transition metal compound represented by Formula 2.

[0160] [Formula 2]

[0161]

[0162] In formula 2,

[0163] Q is Ti, Zr or Hf,

[0164] R 13 To R 16 are each independently hydrogen or an alkyl group of 1 to 20 carbon atoms, wherein adjacent two or more may be linked to each other to form a ring,

[0165] R 17 and R 18 are each independently hydrogen, or an aryl group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent is an alkyl group having 1 to 6 carbon atoms,

[0166] Each R 19 is independently an alkyl group of 3 to 20 carbon atoms, a cycloalkyl group of 4 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms,

[0167] n is 1 to 5, and

[0168] Y1 and Y2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

[0169] In the present invention, if the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 are used together, a catalyst imparting excellent elasticity and a catalyst imparting excellent heat resistance are mixed and used, and thus, a polymer simultaneously showing excellent levels of elasticity and heat resistance can be prepared.

[0170] In particular, in Formula 2, Q may be Hf.

[0171] In particular, in Formula 2, R 13 To R 16 may each independently be hydrogen or an alkyl group of 1 to 20 carbon atoms, wherein adjacent two or more may be linked to each other to form a ring, or R 13 and R 14 may each independently be an alkyl group of 1 to 20 carbon atoms and be linked to each other to form an aromatic ring of 5 to 20 carbon atoms, and R 15 and R 16 It may be hydrogen.

[0172] In particular, in Formula 2, R 17 and R 18 Each may independently be hydrogen or an aryl group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent may be an alkyl group having 1 to 6 carbon atoms.

[0173] Specifically, in Formula 2, each R 19 The group may independently be an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, specifically, an alkyl group having 3 to 6 carbon atoms.

[0174] Particularly, in Formula 2, n may be 1 to 5, 1 to 3, and particularly 2.

[0175] Particularly, in Formula 2, Y1 and Y2 can each independently be an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms, and particularly an alkyl group of 1 to 20 carbon atoms.

[0176] More specifically, the transition metal compound represented by Formula 2 may be a compound represented by Formula 2A.

[0177] [Formula 2A]

[0178]

[0179] In Formula 2A,

[0180] Q is Ti, Zr or Hf,

[0181] R17 and R18 are each independently hydrogen or an aryl group having 6 to 20 carbon atoms which may be substituted, wherein the substitution is an alkyl group having 1 to 6 carbon atoms,

[0182] Each R19 is independently an alkyl group of 3 to 20 carbon atoms, a cycloalkyl group of 4 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms.

[0183] Y1 and Y2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

[0184] In Formula 2A,

[0185] Q, R 17 To R 19 , Y1 and Y2 are the same as defined above.

[0186] The transition metal compound represented by Formula 2 may specifically be the following compounds, but all transition metal compounds corresponding to Formula 2 may be included in the present invention without limitation.

[0187]

[0188] In addition, the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 in the catalyst composition may be used in a ratio of 1:1 to 1:10, specifically 1:1 to 1:6, 1:1 to 1:4 or 1:2.

[0189] The method for preparing an olefin polymer of the present invention is characterized by comprising the step of polymerizing an olefin monomer in the presence of a catalyst composition.

[0190] In the present invention, "polymer" refers to a polymer compound prepared by polymerizing monomers of the same or different types. As such, the generic term polymer includes the term homopolymer used to refer to polymers prepared from only one type of monomer and the term interpolymer as described below.

[0191] In the present invention, the term "interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. As such, the general term for interpolymer refers to a polymer prepared from two different types of monomers, and includes commonly used copolymers and polymers prepared from two or more different types of monomers.

[0192] In the present invention, the olefin monomer may be one or more selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene, but is not limited thereto.

[0193] In particular, the olefin polymer of the present invention may be an olefin homopolymer or an olefin-α-olefin copolymer, preferably an ethylene / α-olefin copolymer, depending on the type of olefin monomer. In this case, the amount of the α-olefin monomer as a comonomer may be appropriately selected by those skilled in the art according to the use, purpose, etc. of the olefin polymer, and may be about 1 to 99 mol%.

[0194] The catalyst composition can be injected after being dissolved or diluted in an aliphatic hydrocarbon solvent of 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane, isomers thereof, an aromatic hydrocarbon solvent such as toluene and benzene, or a hydrocarbon solvent substituted with a chlorine atom such as methylene chloride and chlorobenzene, which are suitable for olefin polymerization methods. The solvent used herein can be preferably used after removing a small amount of water or air (which serves as a catalyst poison) by treating with a small amount of alkylaluminum, and can be treated by further using a co-catalyst.

[0195] The most preferred preparation method using the catalyst composition is a solution process, and if the composition is used with an inorganic support such as silica, it can be applied to a slurry process or a gas phase process.

[0196] The polymerization may be carried out by homopolymerizing one type of olefin monomer or copolymerizing two or more olefin monomers using one of a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

[0197] In addition, in order to remove moisture in the reactor during the polymerization reaction, an organic aluminum compound may be further injected, and the polymerization reaction may be carried out in the presence thereof. Specific examples of such organic aluminum compounds may include trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, dialkylaluminum hydride or alkylaluminum sesquihalide, and more specific examples thereof may include Al(C2H5)3, Al(C2H5)2H, Al(C3H7)3, Al(C3H7)2H, Al(i-C4H9)2H, Al(C8H 17 )3、Al(C 12 H 25 )3、Al(C2H5)(C 12 H 25 )2、Al(i-C4H9)(C 12 H 25 )2, Al(i-C4H9)2H, Al(i-C4H9)3, (C2H5)2AlCl, (i-C3H9)2AlCl or (C2H5)3Al2Cl3. Such an organoaluminum compound may be continuously injected into the reactor, or may be injected at a ratio of about 0.1-10 mol per 1 kg of the reaction medium injected into the reactor to appropriately remove moisture.

[0198] According to an embodiment of the present invention, the polymerization of olefin polymers may be carried out at a temperature of about 80 to 200° C., particularly about 90 to 200° C., or about 130 to 200° C., and a pressure of about 20 to 100 bar, particularly about 20 to 50 bar, or about 20 to 40 bar, for about 8 minutes to 2 hours.

[0199] Example

[0200] Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[0201] <Preparation of transition metal compound>

[0202] Preparation Example 1

[0203] (1) Preparation of ligand compound (N-(cyclohexylmethyl)-6-mesitylpyridin-2-amine)

[0204]

[0205] 6-Bromo-N-(cyclohexylmethyl)pyridin-2-amine (1 g, 3.71 mmol), K2CO3 aqueous solution (11 mL), H2O (10 mL) and 1,4-dioxane (40 mL) were added to a double-necked flask and heated at 100°C. Pd(PPh3)4 (51 mg, 0.044 mmol) and 2,4,6-trimethylphenylboronic acid (730.2 mg, 4.45 mmol) were further added thereto, and then reacted at 100°C overnight. The reaction product was dried in vacuo and treated with EA and water. The organic layer was separated, dried over MgSO4 and concentrated, and the resultant was separated by column using hexane:EA=20:1 to produce a white solid product (900 mg, yield 78.64%).

[0206] 1 H-NMR(in CDCl3 500MHz):7.48(t,2H),6.90(s,2H),6.47(d,1H),6.30(d,1H),4.67(t,1H),3.08(t,2H ),2.30(s,3H),2.08(s,6H),1.83-1.66(m,5H),1.32-1.21(m,4H),1.04-0.84(m,2H).

[0207] (2) Preparation of transition metal compounds

[0208]

[0209] Catalyst is prepared in a glove box. The ligand compound of N-(cyclohexylmethyl)-6-mesitylenepyridine-2-amine prepared above 50mg (0.6125mmol) is weighed in a vial and dissolved by adding 1.6mL toluene. In another vial, HfCl is weighed and dissolved in toluene. Two vials are cooled for 5 minutes, and 0.122mL MMB (3M toluene solution) is added dropwise to HfCl, then reacted for 2 minutes at room temperature.

[0210] The reaction solution was cooled again in a refrigerator for 5 minutes, and the ligand compound solution was added dropwise thereto, followed by reaction at room temperature overnight. After toluene was dried in vacuo, the resultant was extracted with hexane to give a yellow solid product (49 mg, yield 73.5%).

[0211] 1 H-NMR(in CDCl3 500MHz):7.38(t,2H),6.82(s,4H),6.09(d,2H),5.94(d,2H),2.30(s,12H),2.08(s,6H),1.92-1.69(m,22H),1.38(m,2H),1.28(m,2H).

[0212] Preparation Example 2

[0213] (1) Preparation of ligand compounds

[0214] N-(Cyclohexylmethyl)-6-mesitylpyridin-2-amine prepared in Preparation Example 1 was used.

[0215] (2) Preparation of transition metal compounds

[0216]

[0217] In two vials, weigh N-(cyclohexylmethyl)-6-mesitylpyridine-2-amine (50mg, 0.1625mmol) and Hf(Bn)4 (44.12mg, 0.081mmol) prepared in Preparation Example 1, and inject 1.6mL toluene respectively therein. Cool the two vials in a refrigerator for 5 minutes. Mix the two reactants and react overnight at room temperature, and dry in a vacuum to produce a yellow solid product (50mg, 63.3% yield).

[0218] 1 H-NMR(in CDCl3 500MHz):7.48(t,2H),7.02(t,4H),6.85(s,2H),6.79(s,2H),6.89-6.67(m,6H),6.19(d,2H),6.02(d,2H),2.28(s,6H),2.14 (s,6H),2.08-2.05(m,2H),1.75(d,2H),1.61(s,6H),1.56(m,4H),1.45-1.39(m,6H),1.16(d,2H),0.58(q,2H),0.49(q,2H).

[0219] Preparation Example 3

[0220] (1) Preparation of ligand compound (N-(cyclohexylmethyl)-6-(2,4,6-triisopropylphenyl)pyridin-2-amine)

[0221]

[0222] 6-Bromo-N-(cyclohexylmethyl)pyridin-2-amine (1 g, 3.71 mmol), K2CO3 aqueous solution (11 mL), H2O (10 mL) and 1,4-dioxane (40 mL) were added to a double-necked flask and heated at 100°C. Pd(PPh3)4 (51 mg, 0.044 mmol) and 2,4,6-triisopropylphenylboronic acid (1.105 mg, 4.45 mmol) were further added thereto, and then reacted at 100°C overnight. The reaction product was vacuum dried and treated with EA and water. The organic layer was separated, dried over MgSO4 and concentrated, and the resultant was separated by column using hexane:EA=50:1 to produce a lemon solid product (650 mg, yield 44.62%).

[0223] 1 H-NMR(in CDCl3 500MHz):7.46(t,1H),6.54(d,1H),6.31(d,1H),4.64(s,1H),3.08(t,2H),2.91(m,1H),2.66(m,2H),1.80(d, 2H),1.73(d,2H),1.67(d,1H),1.60(m,3H),1.27(d,6H),1.20(s,1H),1.15(d,6H),1.10(d,6H),0.99(q,2H).

[0224] (2) Preparation of transition metal compounds

[0225]

[0226] In two vials, weigh the above prepared N-(cyclohexylmethyl)-6-(2,4,6-triisopropylphenyl)pyridine-2-amine (100 mg, 0.255 mmol) and Hf(Bn)4 (69.13 mg, 0.127 mmol), and inject 2.5 mL of toluene into each. The two vials were cooled in a refrigerator for 5 minutes. The two reactants were mixed and reacted overnight at room temperature and dried in a vacuum to produce a yellow solid product (30 mg, yield 10.3%).

[0227] 1H-NMR(in CDCl3 500MHz):7.43(t,2H),7.01(m,6H),6.66(t,2H),6.59(d,4H),6.31(d, 2H),6.05(d,2H),3.49(m,2H),2.87(m,4H),2.54(m,2H),2.13-2.02(m, 4H),1.85(d,2H),1.73(s,3H),1.62-1.61(m,4H),1.21(d,6H),1.13(d, 6H),1.08(d,12H),0.97(d,6H),0.93(d,6H),0.51(q,2H),0.41(q,2H).

[0228] Preparation Example 4

[0229] (1) Preparation of ligand compound (N-(cyclohexylmethyl)-2-mesitylene-6-methylpyrimidin-4-amine)

[0230]

[0231] 2-Chloro-N-(cyclohexylmethyl)-6-methylpyrimidine-4-amine (500 mg, 2.22 mmol), K2CO3 aqueous solution (5 mL), H2O (5 mL) and 1,4-dioxane (20 mL) were added to a double-necked flask and heated at 100°C. Pd(PPh3)4 (128.3 mg, 0.111 mmol) and 2,4,6-trimethylphenylboronic acid (437 mg, 2.664 mmol) were further added thereto, and then reacted at 100°C overnight. The reaction product was dried in vacuo and treated with EA and water. The organic layer was separated, dried over MgSO4 and concentrated, and the resultant was separated by column using hexane:EA=10:1 to produce a white solid product (622 mg, yield 86.6%).

[0232] 1 H-NMR(in CDCl3 500MHz):6.90(s,2H),6.31(s,1H),5.09(t,1H),3,30(t,2H),2.36(s,3H),2.30(s,3H),2 .09(s,6H),1.78(d,2H),1.72(d,2H),1.57-1.50(m,1H),1.27-1.14(m,4H),0.98(q,2H).

[0233] (2) Preparation of transition metal compounds

[0234]

[0235] Catalyst was prepared in a glove box. 50 mg (0.155 mmol) of the ligand compound of N-(cyclohexylmethyl)-2-mesitylene-6-methylpyrimidine-4-amine prepared above was weighed in a vial and dissolved by adding 1.5 mL of toluene. In another vial, HfCl4 was weighed and dissolved in 1.5 mL of toluene. The reaction solutions in the two vials were mixed and reacted overnight at room temperature. After vacuum drying, a yellow solid (50 mg, 64.2% yield) was obtained.

[0236] 1 H-NMR(in CDCl3 500MHz):7.06(t,2H),6.92(d,2H),6.91(s,2H),6.71(t,1H),6.04(s,1H),2.32(s,3H),2.1 6(s,6H),1.94(s,3H),1.59(d,4H),1.52-1.46(m,1H),1.31-1.27(m,4H),1.10-1.07(m,2H).

[0237] Preparation Example 5

[0238] (1) Preparation of ligand compound (N-(cyclohexylmethyl)-6-methyl-2-(2,4,6-triisopropylphenyl)pyrimidin-4-amine)

[0239]

[0240] 2-Chloro-N-(cyclohexylmethyl)-6-methylpyrimidine-4-amine (400 mg, 2.22 mmol), K2CO3 aqueous solution (4 mL), H2O (4 mL) and 1,4-dioxane (16 mL) were added to a double-necked flask and heated at 100°C. (PPh3)4 (128.3 mg, 0.111 mmol) and 2,4,6-triisopropylphenylboronic acid (661.12 mg, 2.664 mmol) were further added thereto, followed by reaction at 100°C overnight. The reaction product was dried in vacuo and treated with EA and water. The organic layer was separated, dried over MgSO4 and concentrated, and the resultant was separated by column using hexane:EA=20:1 to produce a white solid product (400 mg, yield 44.2%).

[0241] 1H-NMR(in CDCl3 500MHz):7.04(s,2H),6.38(s,1H),5.07(t,1H),3.29(t,2H),2.94-2.89(m,1H),2.70-2.36(m,2H),1.78(d,2H),1.72(d,2H ),1.66(d,1H),1.57-1.50(m,1H),1.28(s,3H),1.27(d,6H),1.21-1.19(m,2H),1.15(d,6H),1.13(d,6H),1.01-0.96(m,2H).

[0242] (2) Preparation of transition metal compounds

[0243]

[0244] The catalyst was prepared in a glove box. 50 mg (0.1273 mmol) of the ligand compound of N-(cyclohexylmethyl)-6-methyl-2-(2,4,6-triisopropylphenyl)pyrimidine-4-amine prepared above was weighed in a vial and dissolved by adding 1.3 mL of toluene. In another vial, HfCl4 was weighed and dissolved in 1.3 mL of toluene. The reaction solutions in the two vials were mixed and reacted at room temperature overnight. After vacuum drying, a yellow solid (60 mg, yield 81.1%) was obtained.

[0245] 1H-NMR (in CDCl3500MHz): 7.08 (t, 2H), 7.06 (s, 2H), 6.95 (s, 2H), 6.73 (t, 1H), 6.08 (s, 1H), 3.32 (d, 2H), 2.96-2.89 (m, 1H), 2. 77-2.72 (m, 2H), 1.92 (s, 3H), 1.67-1.59 (m, 6H), 1.55-1.48 (m, 1H), 1.30 (d, 6H), 1.22 (d, 6H), 1.17 (d, 6H), 1.10-1.07 (m, 3H).

[0246] Reference example

[0247]

[0248] The compounds of Reference Examples were prepared according to the method disclosed in the document [Organometallics 2011, 30, 12, 3318-3329].

[0249] Comparative Preparation Example 1

[0250]

[0251] According to the method disclosed in US10968289B2, the compound of Comparative Preparation Example 1 was prepared.

[0252] Comparative Preparation Example 2

[0253] (1) Preparation of ligand compound (N-isobutyl-2-mesitylene-6-methylpyrimidin-4-amine)

[0254]

[0255] 2-Chloro-N-isobutyl-6-methylpyrimidine-4-amine (1 g, 5 mmol), K2CO3 (2.08 g, 15 mmol), H2O (17 mL), toluene (17 mL) and ethanol (8 mL) were added to a double-necked flask and heated at 100°C. Pd(PPh3)4 (0.116 g, 0.1 mmol) and 2,4,6-trimethylphenylboronic acid (0.86 g, 5.3 mmol) were further added thereto, and then reacted at 100°C overnight. The reaction product was vacuum dried and treated with EA and water. The organic layer was separated, dried over MgSO4 and concentrated, and the resultant was recrystallized in methanol to produce a white solid product (1.4 mg, yield 99%).

[0256] 1 H-NMR(in CDCl3 500MHz):6.90(s,2H),6.34(s,1H),5.50(broad,1H),3.30(t,2H),2.39(s,3H),2.30(s,3H),1.87(m,1H),0.97(d,6H).

[0257] (2) Preparation of transition metal compounds

[0258]

[0259] Catalyst was prepared in a glove box. 200 mg (0.71 mmol) of the ligand compound prepared above was weighed in a vial and dissolved by adding 7 mL of toluene. In another vial, HfCl4 (113 mg, 0.35 mmol) was weighed and dissolved. After being cooled to -30 ° C, MMB (3 M toluene solution) (0.53 mL, 1.59 mmol) was added dropwise thereto, and then the reaction was continued overnight at room temperature. After vacuum drying toluene, the product was extracted with hexane to obtain a yellow solid product (120 mg, 44% yield).

[0260] 1H-NMR(in Benzene 500MHz):6.67(s,4H),5.26(s,2H),3.04(t,4H),2.07(s,6H),2.04(s,6H),1.87(s,12H),1.70(s,6H),1.41(m,2H),0.81(d,12H).

[0261] Comparative Preparation Example 3

[0262] (1) Preparation of ligand compound (6-(dibenzo[b,d]furan-1-yl)-N-propylpyridin-2-amine

[0263]

[0264] 6-Bromo-N-propylpyridin-2-amine (1 g, 4.65 mmol), dibenzo[b,d]furan-1-ylboronic acid (1.18 g, 5.58 mmol), K2CO3 (4.23 g) and H2O (15 mL) (30.6 mmol, 2 M), 1,4-dioxane (40 mL) and methanol (20 mL) were added to a double-necked flask and heated at 100°C. Pd(PPh3)4 (38 mg, 0.033 mmol) was further added thereto and then reacted overnight. The reaction product was dried in vacuo and treated with EA and water. The organic layer was separated, dried over MgSO4 and concentrated, and hexane was added thereto to produce a slurry to give a white solid product (0.50 g, 35.56% yield).

[0265] 1 H-NMR(in CDCl3 500MHz):7.89(d,1H),7.63-7.55(m,3H),7.51-7.40(m,3H),7.19(t,1H),6. 97(d,1H),6.48(d,1H),4.73(s,1H),3.30(m,2H),1.69(m,2H),1.02(t,3H).

[0266] (2) Preparation of transition metal compounds

[0267]

[0268] The catalyst was prepared in a glove box. HfCl4 (0.106 g, 0.331 mmol) was weighed into a vial and dissolved by adding toluene, followed by lowering the temperature to -30 ° C. Then, MMB (3M ether solution, 0.5 mL) was added dropwise thereto, followed by reaction at -30 ° C for 5 minutes. Afterwards, 200 mg (0.661 mmol) of the ligand compound of 6-(dibenzo[b, d]furan-1-yl)-N-propylpyridine-2-amine prepared above was weighed and dissolved by adding 6.6 mL toluene. The resulting solution was added dropwise to the HfCl4&MMB solution and then reacted for 2 hours.

[0269] The reaction solution was dried in vacuo and extracted with hexane to obtain a light yellow solid product (121 mg, yield 45.1%).

[0270] 1 H-NMR(in CDCl3 500MHz):7.56(d,2H),7.54(d,2H),7.48(d,2H),7.40-7.36(m,4H),7.14-7.11(m,4H),7. 02(d,2H),6.33(d,2H),5.70(d,2H),2.59(t,4H),1.36(m,4H),0.83(t,6H),-0.23(s,6H).

[0271] <Polymerization of ethylene / α-olefin copolymer>

[0272] Example 1

[0273] Into a 2L autoclave reactor, hexane solvent (900mL) and 1-octene (600mL) were added, and the temperature of the reactor was preheated to 150°C. At the same time, the pressure of the reactor was pre-filled with ethylene (35 bar). 0.5 to 1 μmol of the catalyst obtained by mixing the compounds of Preparation Example 1 and Reference Example in 1:2, 10 equivalents of tetrakis (pentafluorophenyl) boric acid dimethylanilinium cocatalyst (AB) relative to the catalyst, and 1.0 mmol Tibal as a scavenger were added to the reactor by applying high pressure argon pressure, and copolymerization was carried out (Top T. (temperature at the top of the reactor): 131.2°C, Δt. (temperature difference of the reactor before and after the reaction): 10.3°C). Then, the remaining ethylene gas was discharged, and the polymer solution was added to an excess of ethanol to induce precipitation. The precipitated polymer was washed twice or three times with ethanol and dried in a vacuum oven at 90°C for 12 hours or more.

[0274] Examples 2 to 5 and Comparative Examples 1 to 3

[0275] An ethylene / α-olefin copolymer was prepared by the same method as in Example 1, except that the specific conditions were changed as shown in Table 1.

[0276] [Table 1]

[0277]

[0278] As shown in Table 1, it can be found that all Examples 1 to 5 obtained ethylene / α-olefin copolymers in high yields.

[0279] <Analysis of Preparation Results of Ethylene / α-Olefin Copolymer>

[0280] Experimental Example 1

[0281] The physical properties of the copolymers prepared in the examples and comparative examples were compared and analyzed. The measurement conditions and methods were as follows.

[0282] (1) Catalyst activity (kgPE / mmol)

[0283] The obtained polymer was vacuum dried, the yield was measured, and a value obtained by dividing the polymer (kg) by the catalyst (mmol) was calculated.

[0284] (2) Density (g / cc)

[0285] According to ASTM D-792, the sample was manufactured into a sheet having a thickness of 3 mm and a radius of 2 cm using a press mold at 180° C. and cooled at a rate of 10° C. / min. The measurement was performed using a Mettler balance.

[0286] (3) Melt index and melt flow rate ratio (MFRR, MI 10 / MI 2.16 )

[0287] Measure MI according to ASTM D-1238 10 (Condition E, 190°C, 10kg load) and MI 2.16 (Condition E, 190°C, 2.16 kg load), and calculate MI 10 / MI 2.16 .

[0288] (4) Melting temperature (Tm) and crystallization temperature (Tc)

[0289] The melting temperature (Tm) and the crystallization temperature (Tc) were obtained using a differential scanning calorimeter (DSC6000) manufactured by PerkinElmer Co. Specifically, regarding the copolymer, DSC was used in a nitrogen atmosphere, and the temperature was raised to 150° C., maintained for 5 minutes, cooled to −100° C., and raised again while observing the DSC curve. In this case, the heating rate and the cooling rate were each 10° C. / min.

[0290] On the measured DSC curve, the melting temperature is set as the maximum point of the endothermic peak during the second temperature increase, and the crystallization temperature is set as the maximum point of the exothermic peak during cooling.

[0291] [Table 2]

[0292]

[0293] As shown in Table 2, considering that the ethylene / α-olefin copolymers of Examples 1 to 5 showed higher Tm than the comparative example, it can be confirmed that ethylene / α-olefin copolymers having excellent heat resistance were prepared. The results are the effects shown by using the transition metal compound represented by Formula 1 developed in the present invention as a catalyst.

Claims

1. A transition metal compound represented by the following formula 1: [Formula 1] In formula 1, M is Ti, Zr or Hf, X1 and X2 are each independently C-R5, C-R6 or N, wherein R5 and R6 are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms or a cycloalkyl group of 5 to 20 carbon atoms, R1 to R4 are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, or a cycloalkyl group of 5 to 20 carbon atoms, R7 to R 12 are each independently an alkyl group having 1 to 20 carbon atoms, L1 and L2 are each independently a single bond or an alkylene group of 1 to 20 carbon atoms, Cy1 and Cy2 are each independently a cycloalkyl group of 5 to 20 carbon atoms, and X1 and X2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

2. The transition metal compound according to claim 1, wherein M is Hf, X1 and X2 are each independently CH or N, R1 to R4 are each independently hydrogen or an alkyl group of 1 to 10 carbon atoms, R7 to R 12 are each independently an alkyl group having 1 to 10 carbon atoms, L1 and L2 are each independently an alkylene group having 1 to 6 carbon atoms, Cy1 and Cy2 are each independently a cycloalkyl group of 5 to 10 carbon atoms, and X1 and X2 are each independently an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 20 carbon atoms, or an aralkyl group of 7 to 20 carbon atoms.

3. The transition metal compound according to claim 1, wherein the transition metal compound represented by Formula 1 is a compound represented by the following Formula 1A or Formula 1B: [Formula 1A] [Formula 1B] In Formula 1A and Formula 1B, M is Ti, Zr or Hf, R7 to R 12 are each independently an alkyl group having 1 to 20 carbon atoms, L1 and L2 are each independently a single bond or an alkylene group of 1 to 20 carbon atoms, Cy1 and Cy2 are each independently a cycloalkyl group of 5 to 20 carbon atoms, and X1 and X2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

4. The transition metal compound according to claim 1, wherein the transition metal compound represented by Formula 1 is one selected from the group consisting of the following Formulas 1-1 to 1-5: [Formula 1-1] [Formula 1-2] [Formula 1-3] [Formula 1-4] [Formula 1-5] 5. A catalyst composition comprising the transition metal compound according to claim 1 and a co-catalyst.

6. The catalyst composition according to claim 5, wherein the catalyst composition further comprises a transition metal compound represented by the following Formula 2: [Formula 2] In formula 2, Q is Ti, Zr or Hf, R 13 To R 16 are each independently hydrogen or an alkyl group of 1 to 20 carbon atoms, wherein adjacent two or more may be linked to each other to form a ring, R 17 and R 18 are each independently hydrogen, or an aryl group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent is an alkyl group having 1 to 6 carbon atoms, Each R 19 is independently an alkyl group of 3 to 20 carbon atoms, a cycloalkyl group of 4 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms, n is 1 to 5, and Y1 and Y2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

7. The catalyst composition according to claim 6, wherein the transition metal compound represented by Formula 2 is a compound represented by the following Formula 2A: [Formula 2A] In Formula 2A, Q is Ti, Zr or Hf, R 17 and R 18 are each independently hydrogen or an aryl group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent is an alkyl group having 1 to 6 carbon atoms, Each R 19 are independently an alkyl group of 3 to 20 carbon atoms, a cycloalkyl group of 4 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms, and Y1 and Y2 are each independently an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkaryl group of 7 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms.

8. The catalyst composition according to claim 5, wherein the co-catalyst comprises one or more selected from the group consisting of the following formulas 3 to 5: [Formula 3] <h2 style=";text-align:left;direction:ltr">-[Al(R<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> )-O]<h2 style=";text-align:left;direction:ltr"> m <h2 style=";text-align:left;direction:ltr"> - [Formula 4] D(R a )3 [Formula 5] [L-H] + [Z(A)4] - or [L] + [Z(A)4] - In the above formulas, Each R a are independently a halogen group, a hydrocarbon group of 1 to 20 carbon atoms, or a halogen-substituted hydrocarbon group of 1 to 20 carbon atoms, m is an integer greater than 2, D is aluminum or boron, L is a neutral or cationic Lewis acid, Z is an element in group 13, Each A is independently an aryl group of 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, or an alkyl group of 1 to 20 carbon atoms, and The substituent of A is halogen, a hydrocarbon group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms or an aryloxy group of 6 to 20 carbon atoms.

9. A method for preparing an olefin polymer, the method comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition according to any one of claims 5 to 8.

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