Transition metal compound and catalyst composition comprising same

Abstract

The present invention relates to a transition metal compound having a novel structure and a catalyst composition comprising the same.

Description

Technical Field

[0001] Cross-reference to Related Applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0022825, filed with the Korean Intellectual Property Office on February 21, 2023, the content of which is incorporated herein by reference.

[0003] The present invention relates to a transition metal compound having a novel structure and a catalyst composition including the transition metal compound. Background Art

[0004] Generally, olefin polymers such as ethylene copolymers are useful polymer materials for materials such as hollow molded articles, extruded molded articles, films, sheets, etc., and are prepared in the presence of a Ziegler-Natta catalyst system.

[0005] The Ziegler-Natta catalyst is a heterogeneous catalyst and is a catalyst used in a system where the reactant phase and the catalyst phase are different, for example, a system such as a liquid reactant - solid catalyst. This Ziegler-Natta catalyst consists of two components and is generally composed of a halogen compound (e.g., TiCl4) of a transition metal including titanium (Ti), vanadium (V), chromium (Cr), molybdenum (Mo), and zirconium (Zr), an alkyl lithium, an alkyl aluminum, etc.

[0006] However, the concentration of the active species of the Ziegler-Natta catalyst is several% to several tens% with respect to the transition metal atoms, and most of the transition metal atoms may not be able to exert their functions, and it has the defect of being unable to overcome the limitations as a heterogeneous catalyst.

[0007] Recently, as a next-generation catalyst that can overcome these defects, metallocene compounds have received attention. Metallocene compounds are homogeneous catalysts including Group 4 metals and are known to exhibit ideal polymerization activity in olefin polymerization.

[0008] Most metallocene catalysts for polymerization include Group 4 metal elements such as titanium, zirconium, and hafnium (Hf), and a supporting 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 the supporting ligand coordinated with the central metal.

[0009] This metallocene catalyst is used in various applications including olefin polymerization processes, but the catalyst activity exhibits some limitations (especially in solution processes at temperatures above 100 °C), and it is known that, for example, due to relatively rapid chain termination reactions (or chain transfer reactions) such as β-hydride elimination reactions, low molecular weight olefin polymers with a molecular weight (Mn) of less than 20,000 can be prepared at temperatures above 100 °C. In addition, it is known that the active species of metallocene catalysts are deactivated at temperatures above 100 °C. Therefore, in order to improve the applicability of metallocene catalysts, methods to overcome the above limitations are needed. Summary of the Invention

[0010] Technical Problem

[0011] An object of the present invention is to provide a novel transition metal compound and a catalyst composition containing the compound, the transition metal compound exhibiting excellent copolymerization performance and being capable of preparing olefin polymers, especially olefin polymers having a high melting temperature and a high molecular weight.

[0012] Technical Solution

[0013] To solve the above tasks, the present invention provides a transition metal compound, a catalyst composition, and a method for preparing an olefin polymer.

[0014] (1) The present invention provides a transition metal compound represented by Chemical Formula 1.

[0015] [Chemical Formula 1]

[0016]

[0017] In Chemical Formula 1,

[0018] M is Ti, Zr, or Hf,

[0019] R1 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms,

[0020] Ring A is wherein, R2 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, and if R2 is substituted, R2 is substituted by an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms,

[0021] m is 1 and n is 3, or m is 2 and n is 2,

[0022] Each X is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

[0023] (2) The present invention provides the transition metal compound according to (1), wherein M is Hf, R1 is an alkyl group having 1 to 15 carbon atoms, R2 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms, wherein if R2 is substituted, R2 is substituted by an alkyl group having 1 to 15 carbon atoms, m is 1, and n is 3.

[0024] (3) The present invention provides the transition metal compound according to (1) or (2), wherein M is Hf, R1 is an alkyl group having 1 to 15 carbon atoms, R2 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms, wherein if R2 is substituted, R2 is substituted by an alkyl group having 1 to 15 carbon atoms, m is 2, and n is 2.

[0025] (4) The present invention provides the transition metal compound according to any one of (1) to (3), wherein the transition metal compound represented by Chemical Formula 1 is one selected from the following Chemical Formula 1-1 to Chemical Formula 1-4.

[0026] [Chemical Formula 1-1]

[0027]

[0028] [Chemical Formula 1-2]

[0029]

[0030] [Chemical Formula 1-3]

[0031]

[0032] [Chemical Formula 1-4]

[0033]

[0034] In Chemical Formula 1-1 to Chemical Formula 1-4,

[0035] R1 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms,

[0036] R2 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms. If R2 is substituted, R2 is substituted by an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms.

[0037] Each X is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

[0038] (5) The present invention provides a transition metal compound according to any one of (1) to (4), wherein the transition metal compound represented by Chemical Formula 1 is one selected from the following compounds.

[0039]

[0040]

[0041]

[0042]

[0043] (6) The present invention provides a catalyst composition comprising the transition metal compound according to any one of (1) to (5) and a cocatalyst.

[0044] (7) The present invention provides the catalyst composition according to (6), wherein the catalyst composition further comprises a transition metal compound represented by the following Chemical Formula 2.

[0045] [Chemical Formula 2]

[0046]

[0047] In Chemical Formula 2,

[0048] Q is Ti, Zr or Hf,

[0049] R 13 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and two or more adjacent ones of the alkyl groups may be connected to each other to form a ring,

[0050] R 17 and R 18 are each independently hydrogen or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein the substitution is carried out by an alkyl group having 1 to 6 carbon atoms,

[0051] Each R 19 is independently 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,

[0052] n is 1 to 5,

[0053] Y1 and Y2 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

[0054] (8) The present invention provides the catalyst composition according to (6) or (7), wherein the transition metal compound represented by Chemical Formula 2 is a compound represented by the following Chemical Formula 2A.

[0055] [Chemical Formula 2A]

[0056]

[0057] In Chemical Formula 2A,

[0058] Q is Ti, Zr, or Hf,

[0059] R 17 and R 18 are each independently hydrogen or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein the substitution is carried out by an alkyl group having 1 to 6 carbon atoms,

[0060] each R 19 is independently 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,

[0061] Y1 and Y2 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

[0062] (9) The present invention provides the catalyst composition according to any one of (6) to (8), wherein the cocatalyst includes one or more selected from the following Chemical Formula 3 to Chemical Formula 5.

[0063] [Chemical Formula 3]

[0064] -[Al(R a )-O] m -

[0065] [Chemical Formula 4]

[0066] D(R a )3

[0067] [Chemical Formula 5]

[0068] [L-H] + [Z(A)4] - or [L] + [Z(A)4] -

[0069] In the above chemical formula,

[0070] each R a is independently a halogen radical, a hydrocarbon radical having 1 to 20 carbon atoms, or a halogen-substituted hydrocarbon radical having 1 to 20 carbon atoms,

[0071] m is an integer of 2 or more,

[0072] D is aluminum or boron,

[0073] L is a neutral or cationic Lewis acid,

[0074] Z is an element in Group 13,

[0075] each A is independently an aryl group having 6 to 20 carbon atoms, in which one or more hydrogen atoms may be substituted by substituents; or an alkyl group having 1 to 20 atoms,

[0076] The substituents of A are halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0077] (10) The present invention provides a method for preparing an olefin polymer, the method comprising the step of polymerizing an olefin monomer in the presence of a catalyst composition according to any one of (6) to (9).

[0078] (11) The present invention provides the method for preparing an olefin polymer according to (10), wherein the olefin polymer is an ethylene / α-olefin copolymer.

[0079] Advantageous effects

[0080] By using the transition metal compound according to the present invention as a catalyst, an olefin polymer having a high melting temperature and a high molecular weight can be easily prepared. Detailed embodiments

[0081] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0082] It should be understood that the words or terms used in the present disclosure and the claims should not be construed as having the meanings defined in a common dictionary. It will be further understood that, based on the principle that the inventor can appropriately define the meanings of the words or terms to best illustrate the invention, the words or terms should be understood as having meanings consistent with their meanings in the technical concept of the present invention.

[0083] Unless otherwise specified, the term "alkyl" as used in this specification refers to a straight-chain, cyclic, or branched hydrocarbon residue, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and hexyl, without limitation thereto.

[0084] Unless otherwise specified, the term "cycloalkyl" as used in this specification refers to a non-aromatic cyclic hydrocarbon radical composed of carbon atoms. Non-limiting examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

[0085] Unless otherwise specified, the term "aryl" as used in this specification refers to an optionally substituted benzene ring, or a ring system formed by fusing one or more optionally substituted groups. Examples of the optional substituents include: substituted C 1-3 alkyl, substituted C 2-3 alkenyl, substituted C 2-3 alkynyl, heteroaryl, heterocycle, aryl, alkoxy having one to three optional fluorine substituents, aryloxy, aralkyloxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonylamino, formamide, aminocarbonyl, carboxyl, oxy, hydroxy, mercapto, amino, nitro, cyano, halogen, or ureido. The ring or ring system may optionally be fused to an aryl ring (such as a benzene ring), a carbocyclic ring, or a heterocyclic ring having one or more optional substituents. Non-limiting examples of "aryl" include phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracenyl, phenanthryl, or their substituted derivatives.

[0086] In the present invention, "alkylaryl" refers to an aryl substituted by an alkyl.

[0087] In the present invention, "arylalkyl" refers to an alkyl substituted by an aryl.

[0088] In the present invention, unless otherwise specified, "hydrocarbyl" refers to a monovalent hydrocarbyl group consisting of 1 to 20 carbon atoms composed only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl, and arylalkyl.

[0089] The transition metal compound of the present invention is characterized by being represented by the following Chemical Formula 1.

[0090] [Chemical Formula 1]

[0091]

[0092] In Chemical Formula 1,

[0093] M is Ti, Zr, or Hf,

[0094] R1 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms,

[0095] Ring A is wherein, R2 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms. If R2 is substituted, then R2 is substituted by an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms,

[0096] m is 1 and n is 3, or m is 2 and n is 2,

[0097] each X is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.

[0098] The transition metal compound of the present invention is a fused-ring pyrimidine derivative containing a sulfur (S) atom with high electron density, wherein a secondary amine is substituted at positions 2 and 4, and according to the substitution position, a four-membered ring can be formed between the nitrogen atom at position 1 or 3 of pyrimidine and the transition metal. Due to the structural specificity, the copolymerization performance of the comonomer is lower compared with the monomer, and a copolymer with high crystallinity can be formed.

[0099] Thus, the transition metal compound of the present invention can be used as a catalyst for preparing an olefin polymer, and this is an inherent property that can be achieved due to the novel structure of the newly developed compound of the present invention.

[0100] Specifically, in Chemical Formula 1, M can be Hf.

[0101] Specifically, in Chemical Formula 1, R1 can be an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms. Specifically, it can be propyl.

[0102] Specifically, in Chemical Formula 1, Ring A is wherein, R2 can be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms. If R2 is substituted, then R2 can be substituted by an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, or an alkyl group having 1 to 15 carbon atoms. Specifically, in Chemical Formula 1, R2 can be phenyl, naphthyl, etc., and R2 can be substituted by an alkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, for example, methyl, and the number of substituents can be multiple.

[0103] Specifically, in Chemical Formula 1, m can be 1 and n can be 3, or m can be 2 and n can be 2.

[0104] Specifically, in Chemical Formula 1, each X can independently 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, an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 11 to 20 carbon atoms. Specifically, it can be a methyl group, a phenyl group, or a benzyl group.

[0105] Specifically, the transition metal compound represented by Chemical Formula 1 can be one transition metal compound selected from the following Chemical Formulas 1-1 to 1-4.

[0106] [Chemical Formula 1-1]

[0107]

[0108] [Chemical Formula 1-2]

[0109]

[0110] [Chemical Formula 1-3]

[0111]

[0112] [Chemical Formula 1-4]

[0113]

[0114] In Chemical Formulas 1-1 to 1-4,

[0115] R1 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms,

[0116] R2 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms. If R2 is substituted, R2 is substituted by an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms.

[0117] Each X independently is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

[0118] The transition metal compound represented by Chemical Formula 1 can be one selected from the following compounds, but the present invention includes all transition metal compounds corresponding to Chemical Formula 1 without limitation.

[0119]

[0120]

[0121]

[0122]

[0123] The transition metal compound of the present invention is characterized by comprising a transition metal compound represented by Chemical Formula 1 and a cocatalyst.

[0124] In the present invention, "composition" includes a mixture of the following materials, the materials including the composition, and reaction products and decomposition products obtained from the materials of the composition.

[0125] Furthermore, the catalyst composition of the present invention may further comprise a cocatalyst.

[0126] As the cocatalyst, a cocatalyst known in the art can be used. For example, one or more selected from Chemical Formulas 4 to 6 can be used as the cocatalyst.

[0127] [Chemical Formula 4]

[0128] -[Al(R a )-O] m -

[0129] [Chemical Formula 5]

[0130] D(R a )3

[0131] [Chemical Formula 6]

[0132] [L-H] + [Z(A)4] - or [L] + [Z(A)4] -

[0133] In the above chemical formulas,

[0134] each R a is independently a halogen radical, a hydrocarbon radical having 1 to 20 carbon atoms, or a halogen-substituted hydrocarbon radical having 1 to 20 carbon atoms,

[0135] m is an integer of 2 or more,

[0136] D is aluminum or boron,

[0137] L is a neutral or cationic Lewis acid,

[0138] Z is an element in Group 13,

[0139] Each A is independently an aryl group having 6 to 20 carbon atoms, where one or more hydrogen atoms may be substituted by substituents; or an alkyl group having 1 to 20 atoms,

[0140] The substituents of A are halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0141] There is no specific limitation on the compound represented by Chemical Formula 4, as long as it is an alkylaluminoxane. Preferred examples may include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., and particularly preferably, methylaluminoxane.

[0142] There is no specific limitation on the compound represented by Chemical Formula 5, and its preferred examples may include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylmethanolaluminum, dimethylethanolaluminum, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc., and particularly preferably, it may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[0143] If Z is boron, examples of the compound represented by Chemical Formula 6 may include, for example, bis(octadecylmethylammonium)tetrakis(pentafluorophenyl)borate [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] -, bis(octadecylmethyl)ammonium tetrakis(phenyl)borate, bis(octadecylmethyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis(o,m-dimethylphenyl)borate, tributylammonium tetrakis(p-trifluoromethylphenyl)borate, trimethylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, diethylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, tripropylammonium tetrakis(p-tolyl)borate, triethylammonium tetrakis(o,m-dimethylphenyl)borate, trimethylammonium tetrakis(o,m-dimethylphenyl)borate, triphenylcarbenium tetrakis(p-trifluoromethylphenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, or a combination thereof; if Z is aluminum, it may include, for example, triethylammonium tetraphenylaluminate, tributylammonium tetraphenylaluminate, trimethylammonium tetraphenylaluminate, tripropylammonium tetraphenylaluminate, trimethylammonium tetrakis(p-tolyl)aluminate, tripropylammonium tetrakis(p-tolyl)aluminate, triethylammonium tetrakis(o,m-dimethylphenyl)aluminate, tributylammonium tetrakis(p-trifluoromethylphenyl)aluminate, trimethylammonium tetrakis(p-trifluoromethylphenyl)aluminate, tributylammonium tetrakis(pentafluorophenyl)aluminate, N,N-diethylanilinium tetraphenylaluminate, N,N-diethylanilinium tetrakis(pentafluorophenyl)aluminate, diethylammonium tetrakis(pentafluorophenyl)aluminate, triphenylphosphonium tetraphenylaluminate, trimethylphosphonium tetraphenylaluminate, triethylammonium tetraphenylaluminate, tributylammonium tetraphenylaluminate, or a combination thereof, without limitation.

[0144] Specifically, the cocatalyst used in the present invention may be a compound represented by Chemical Formula 6, specifically, bis(octadecylmethyl)ammonium tetrakis(pentafluorophenyl)borate.

[0145] In addition, the transition metal compound represented by Chemical Formula 1 and the cocatalyst may be used in a supported form through a carrier. Silica or alumina may be used as the carrier without limitation.

[0146] In the present invention, the catalyst composition may further contain a transition metal compound represented by the following Chemical Formula 2.

[0147] [Chemical Formula 2]

[0148]

[0149] In Chemical Formula 2,

[0150] Q is Ti, Zr or Hf,

[0151] R 13 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and two or more adjacent ones of the alkyl groups may be connected to each other to form a ring.

[0152] R 17 and R 18 each independently is hydrogen or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein the substitution is carried out by an alkyl group having 1 to 6 carbon atoms.

[0153] Each R 19 independently is 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.

[0154] n is 1 to 5.

[0155] Y1 and Y2 each independently are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.

[0156] In the present invention, if a transition metal compound represented by Chemical Formula 1 and a transition metal compound represented by Chemical Formula 2 are used together, a catalyst having high elasticity and a catalyst having excellent heat resistance are mixed and used. Therefore, a polymer that simultaneously exhibits excellent elasticity and heat resistance can be prepared.

[0157] Specifically, in Chemical Formula 2, Q may be Hf.

[0158] Specifically, in Chemical Formula 2, R 13 to R 16 may each independently be hydrogen or an alkyl group having 1 to 20 carbon atoms, and two or more adjacent ones of the alkyl groups may be connected to each other to form a ring, or R 13 and R 14 may each independently be an alkyl group having 1 to 20 carbon atoms and may be connected to each other to form an aromatic ring having 5 to 20 carbon atoms, and R 15 and R 16 may be hydrogen.

[0159] Specifically, in Chemical Formula 2, R 17 and R 18 may each independently be hydrogen or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein the substitution may be carried out by an alkyl group having 1 to 6 carbon atoms.

[0160] Specifically, in Chemical Formula 2, each R 19 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.

[0161] Specifically, in Chemical Formula 2, n may be 1 to 5, 1 to 3, specifically 2.

[0162] Specifically, in Chemical Formula 2, Y1 and Y2 may each independently be an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, specifically, an alkyl group having 1 to 20 carbon atoms.

[0163] More specifically, the transition metal compound represented by Chemical Formula 2 may be a compound represented by the following Chemical Formula 2A.

[0164] [Chemical Formula 2A]

[0165]

[0166] In Chemical Formula 2A,

[0167] Q is Ti, Zr, or Hf,

[0168] R 17 and R 18 are each independently hydrogen or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein the substitution is carried out by an alkyl group having 1 to 6 carbon atoms.

[0169] Each R 19 is independently 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.

[0170] Y1 and Y2 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

[0171] In Chemical Formula 2A,

[0172] Q, R 17 to R 19 are the same as those defined above.

[0173] The transition metal compound represented by Chemical Formula 2 may specifically be the following compounds, but the present invention may include all transition metal compounds corresponding to Chemical Formula 2 without limitation.

[0174]

[0175] In addition, in the catalyst composition, the transition metal compound represented by Chemical Formula 1 and the transition metal compound represented by Chemical Formula 2 may be in a ratio of 10:1 to 1:10, specifically, 1:1 to 1:6, 1:1 to 1:5, or 1:3 to 1:4.

[0176] The method for preparing an olefin polymer according to the present invention is characterized by including a step of polymerizing an olefin monomer in the presence of the catalyst composition.

[0177] In the present invention, "polymer" refers to a polymer compound prepared by polymerizing the same or different types of monomers. Thus, the general term of polymer includes the homopolymer term used to refer to a polymer prepared from only one type of monomer and the interpolymer term as specified below.

[0178] In the present invention, the term "interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. Thus, the general term of interpolymer refers to a polymer prepared from two different types of monomers and includes the commonly used copolymer and polymers prepared from more than two different types of monomers.

[0179] 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, without limitation.

[0180] In particular, depending on the type of olefin monomer, the olefin polymer of the present invention may be an olefin homopolymer or an olefin-α-olefin copolymer, and preferably, it may be an ethylene / α-olefin copolymer. In this case, the content of the α-olefin monomer as a comonomer can 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%.

[0181] The catalyst composition may be injected after being dissolved or diluted in the following solvents suitable for the olefin polymerization process: aliphatic hydrocarbon solvents having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane, and their isomers; aromatic hydrocarbon solvents, such as toluene and benzene; or hydrocarbon solvents substituted with chlorine atoms, such as dichloromethane and chlorobenzene. The solvents used herein may preferably be used after being treated with a small amount of alkylaluminum to remove a small amount of water or air acting as a catalyst poison, and may be further treated by using a cocatalyst.

[0182] The most preferred preparation process using the catalyst composition is the solution process, and if the composition is used together with an inorganic carrier such as silica, it can also be applied to the slurry process or the gas phase process.

[0183] The polymerization can be carried out by homopolymerizing one type of olefin monomer or copolymerizing two or more olefin monomers by using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

[0184] In addition, in order to remove moisture in the reactor during the polymerization reaction, an organoaluminum compound can be further injected, and the polymerization reaction can be carried out in its presence. Specific examples of such organoaluminum compounds can include trialkylaluminum, dialkylaluminum halide, alkyldialuminum halide, dialkylaluminum hydride or sesquialkylaluminum halide, and more specific examples thereof can 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 organoaluminum compounds can be continuously injected into the reactor, or can be injected in a proportion of about 0.1 to 10 mol per 1 kg of the reaction medium. The organoaluminum compound is injected into the reactor to appropriately remove moisture.

[0185] According to one embodiment of the present invention, the polymerization of the olefin polymer can be carried out at a temperature of about 80 °C to 200 °C, specifically, at a temperature of about 90 °C to 200 °C, or about 130 °C to 200 °C, and at a pressure of about 20 bar to 100 bar, specifically, about 20 bar to 50 bar, or about 20 bar to 40 bar for about 8 minutes to 2 hours.

[0186] Examples

[0187] Hereinafter, the present invention will be described in more detail with reference to the examples. However, the examples are for illustrative purposes of the present invention, and the scope of the present invention is not limited thereto.

[0188] <Preparation of Transition Metal Compound>

[0189] Preparation Example 1

[0190]

[0191] The compound was prepared according to the following scheme.

[0192]

[0193] (1) Preparation of Compound S1-1

[0194] 2,4-Dichlorobenzo[4,5]thieno[3,2-d]pyrimidine (3.0 g, 11.8 mmol) and propan-1-amine (2.09 g, 35.3 mmol) were added to 30 mL of 1,4-dioxane. K2CO3 (4.9 g, 35.3 mmol) was added thereto, and the temperature was raised to 80 °C. After heating and stirring for about 12 hours, the temperature was cooled to room temperature, and 100 mL of water was added thereto. The precipitated solid was filtered, and the filtered solid was dissolved in chloroform again, washed once with water, separated, slurried with anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. A small amount of ethyl acetate was added to the concentrated compound, and then stirred at room temperature. The resulting solid was filtered to obtain the white target compound S1-1 (2.7 g, yield 82.7%).

[0195] (2) Preparation of Compound S1-2

[0196] Compound S1-1 (2.0 g, 7.2 mmol) and mesitylboronic acid (1.3 g, 7.9 mmol) were dissolved in 60 mL of 1,4-dioxane, and then 20 mL of an aqueous K3PO4 solution (3.06 g, 14.4 mmol) was added thereto, and the temperature was raised. Tricyclohexylphosphine (0.12 g, 0.4 mmol) and bis(dibenzylideneacetone)palladium(0) (0.12 g, 0.2 mmol) dissolved in 1,4-dioxane were added to the refluxing mixture, and then refluxed and stirred for 12 hours. After the reaction was completed, the temperature was lowered to room temperature, and 1,4-dioxane was removed under reduced pressure. Ethyl acetate was added to the concentrated mixture, and extraction was performed. The organic layer was separated, washed once with water, slurried with anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. The mixture was separated by column chromatography using a mixed solvent of hexane and ethyl acetate at 50 / 1 to obtain the pale yellow target compound S1-2 (0.75 g, yield 29%).

[0197] (3) Preparation of Compound S1

[0198] In the glove box, after dissolving compound S1-2 (0.1 g, 0.3 mmol) in 10 mL of toluene, n-butyllithium (2.5 M in hexane) (0.12 mL, 0.3 mmol) was added, and the resulting mixture was stirred at room temperature for 1 hour. In another flask, hafnium tetrachloride (0.09 g, 0.3 mmol) was diluted in 5 mL of toluene, and methylmagnesium bromide (3.0 M in diethyl ether) (0.41 mL, 1.2 mmol) was added thereto at low temperature. After stirring for about 5 minutes, the mixed solution of compound S1-2 and n-butyllithium was added. The mixture was stirred at room temperature for 4 hours. 15 mL of hexane was added to the mixture and stirred for 2 hours. The mixture was filtered, and the filtrate was concentrated under reduced pressure. 5 mL of methyl tert-butyl ether was added thereto to dissolve the obtained concentrate, and the resulting solution was concentrated to about 1 / 2 and recrystallized to obtain the target compound S1 (0.08 g, yield 49.5%).

[0199] 1 H NMR (500 MHz, CDCl3): 8.40 (d, 1H), 7.95 (d, 1H), 7.63 (t, 1H), 7.50 (t, 1H), 6.83 (s, 2H), 2.99 (t, 2H), 2.36 (s, 3H), 1.83 (s, 6H), 1.59 - 1.64 (q, 2H), 0.97 (t, 3H), 0.20 (s, 9H)

[0200] Preparation Example 2

[0201]

[0202] This compound was prepared according to the following method.

[0203] In the glove box, after dissolving compound S1-2 (0.1 g, 0.3 mmol) in 10 mL of toluene, n-butyllithium (2.5 M in hexane) (0.12 mL, 0.3 mmol) was added, and the resulting mixture was stirred at room temperature for 1 hour. In another flask, hafnium tetrachloride (0.04 g, 0.15 mmol) was diluted in 5 mL of toluene, and methylmagnesium bromide (3.0 M in diethyl ether) (0.21 mL, 0.6 mmol) was added thereto at low temperature. After stirring for about 5 minutes, the mixed solution of compound S1-2 and n-butyllithium was added. The mixture was stirred at room temperature for 4 hours. 15 mL of hexane was added to the mixture and stirred for 2 hours. The mixture was filtered through a pad of diatomaceous earth, and the filtrate was concentrated under reduced pressure to obtain the target compound S2 (0.05 g, yield 38.9%).

[0204] 11H NMR (500 MHz, CDCl3): δ 8.41 (d, 2H), 7.96 (d, 2H), 7.63 (t, 2H), 7.49 (t, 2H), 6.84 (s, 4H), 3.00 (br, 4H), 2.36 (s, 6H), 1.83 (s, 12H), 1.61 (m, 4H), 0.99 (t, 6H), 0.20 (s, 6H)

[0205] Preparation Example 3

[0206]

[0207] This compound was prepared according to the following scheme.

[0208]

[0209] (1) Preparation of Compound S3-1

[0210] 2,4-Dichlorobenzo[4,5]thieno[3,2-d]pyrimidine (3.0 g, 11.8 mmol) and mesitylboronic acid (2.12 g, 12.9 mmol) were dissolved in 40 mL of 1,4-dioxane, and 15 mL of an aqueous K2CO3 solution (4.88 g, 35.3 mmol) was added thereto, followed by heating. Tetrakis(triphenylphosphine)palladium(0) (0.14 g, 0.11 mmol) was added to the refluxing mixture, and refluxing and stirring were carried out for 12 hours. After completion of the reaction, the resulting product was cooled to room temperature, 1,4-dioxane was removed under reduced pressure, ethyl acetate was added to the concentrated mixture, and extraction was carried out. The organic layer was separated, washed once with water, slurried with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure. The mixture was slurried with an excess of hexane and a small amount of ethyl acetate to obtain the target compound S3-1 as a pale yellow solid (3.5 g, yield 87.8%).

[0211] (2) Preparation of Compound S3-2

[0212] Compound S3-1 (3.0 g, 11.8 mmol) and 2-methylpropan-1-amine (0.44 mL, 4.4 mmol) were dissolved in 10 mL of N,N-dimethylformamide, and potassium iodide (0.05 g, 0.3 mmol) and triethylamine (1.23 mL, 8.9 mmol) were added thereto, followed by heating to 60 °C. After stirring for 12 hours, the reaction mixture was added to 100 mL of water and extracted with ethyl acetate. The organic layer was separated, washed once with water, slurried with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure. The concentrate was solidified and slurried with a small amount of hexane and filtered to obtain the target compound S3-2 as a pale yellow solid (0.64 g, yield 60.0%).

[0213] (3) Preparation of Compound S3

[0214] In a glove box, after dissolving Compound S3-2 (0.1 g, 0.3 mmol) in 10 mL of toluene, hafnium tetrabenzyl (0.14 g, 0.3 mmol) was added, and the resulting mixture was stirred at room temperature for 12 hours. After the reaction was completed, the mixture was heated to 50 °C to remove the solvent under reduced pressure. The concentrated compound was concentrated by displacement with hexane to obtain the target compound S3 in the form of an orange foam (0.06 g, yield 27.3%).

[0215] 1 H NMR (500 MHz, CDCl3): 8.44 (d, 1H), 7.45 (d, 1H), 7.57 (t, 1H), 7.50 (t, 1H), 7.15 - 7.32 (m, 15H), 6.98 (s, 2H), 3.45 (t, 2H), 2.41 (s, 6H), 2.36 (s, 3H), 2.09 (s, 6H), 2.0 (m, 1H), 1.03 (d, 6H)

[0216] Preparation Example 4

[0217]

[0218] This compound was prepared according to the following scheme.

[0219]

[0220] (1) Preparation of Compound S4-1

[0221] Using 2,4-dichlorobenzo[4,5]thieno[3,2-d]pyrimidine (5.0 g, 19.6 mmol) and naphthalen-1-ylboronic acid (3.54 g, 20.6 mmol), the target compound S4-1 in the form of a pale yellow solid (5.8 g, yield 85.0%) was prepared in the same manner as in the preparation example of Compound S3-1.

[0222] (2) Preparation of Compound S4-2

[0223] Using Compound S4-1 (2.73 g, 7.9 mmol) and propan-1-amine (1.29 mL, 15.7 mmol), the target compound S4-2 in the form of a pale yellow solid (2.42 g, yield 83.2%) was prepared in the same manner as in the preparation example of Compound S3-2.

[0224] (3) Preparation of Compound S4

[0225] In a glove box, using compound S4-2 (0.32 g, 0.9 mmol), the target compound S4 (0.15 g, yield 31.2%) was prepared in the same manner as in the preparation example of compound S1, and the resulting compound was orange in color.

[0226] 1 H NMR (500 MHz, CDCl3): 8.49 (d, 1H), 8.06 (d, 1H), 8.01 (d, 1H), 7.95 (d, 1H), 7.82 (d, 1H), 7.74 (d, 1H), 7.62 (d, 1H), 7.47 - 7.59 (m, 4H), 3.62 (q, 2H), 1.76 (m, 2H), 1.07 (t, 3H), 0.9 (s, 9H).

[0227] Preparation Example 5

[0228]

[0229] This compound was prepared according to the following scheme.

[0230]

[0231] (1) Preparation of Compound S5-1

[0232] Using compound S3-1 (1.0 g, 3.0 mmol) and propan-1-amine (0.36 mL, 4.4 mmol), the target compound S5-1 (0.5 g, 46.9%) as a pale yellow solid was prepared in the same manner as in the preparation example of compound S3-2.

[0233] (2) Preparation of Compound S5

[0234] In a glove box, using compound S5-1 (0.50 g, 1.4 mmol), the target compound S5 (0.34 g, yield 42.1%) was prepared in the same manner as in the preparation example of compound S1, and the resulting compound was orange in color.

[0235] 1 H NMR (500 MHz, CDCl3):

[0236] 8.50 (d, 1H), 7.69 (d, 1H), 7.58 (t, 1H), 7.52 (t, 1H), 6.94 (s, 2H), 3.13 (t, 2H), 2.40 (s, 3H), 1.85 (s, 6H), 1.60 (m, 2H), 1.00 (m, 3H), 0.93 (s, 9H)

[0237] Preparation Example 6

[0238]

[0239] This compound was prepared according to the following scheme.

[0240]

[0241] In a glove box, using compound S5-1 (0.1 g, 0.3 mmol), the target compound S6 (0.05 g, yield 38.9%) with a pale yellow color was prepared in the same manner as in the preparation example of compound S2.

[0242] 1 H NMR (500 MHz, CDCl3):

[0243] 8.50 (d, 2H), 7.69 (d, 2H), 7.58 (t, 2H), 7.52 (t, 2H), 6.94 (s, 4H), 3.13 (t, 4H), 2.40 (s, 6H), 1.85 (s, 12H), 1.60 (m, 4H), 1.00 (m, 6H), 0.90 (s, 6H)

[0244] Preparation Example 7

[0245]

[0246] This compound was prepared according to the following scheme.

[0247]

[0248] In a glove box, compound S5-1 (0.1 g, 0.3 mmol) and hafnium tetrabenzyl (0.08 g, 0.15 mmol) were added to 5 mL of toluene and stirred at room temperature for 12 hours. After concentrating the mixture under reduced pressure, it was concentrated by displacement with hexane twice to obtain the target compound S7 (0.1 g, yield 65.1%) with a deep orange color.

[0249] 1 H NMR (500 MHz, C6D6):

[0250] 8.48 (d, 2H), 7.44 (d, 2H), 6.92 - 7.13 (m, 10H), 6.70 (s, 4H), 6.52 (d, 4H), 3.19 (m, 4H), 2.20 (s, 6H), 1.95 (s, 12H), 1.70 (m, 4H), 1.48 (s, 4H), 1.00 (t, 6H)

[0251] Preparation Example 8

[0252]

[0253] This compound was prepared according to the following scheme.

[0254]

[0255] (1) Preparation of Compound S8-1

[0256] Carbazole (3.44 g, 20.6 mmol) was dissolved in 65 ml of tetrahydrofuran and cooled to 0 °C. NaH (0.94 g, 23.5 mmol) was slowly added, and the resulting mixture was stirred for 10 minutes at the same temperature. Dichlorobenzo[4,5]thieno[3,2-d]pyrimidine (5.0 g, 19.6 mmol) was added to the mixture, and the resulting mixture was stirred at room temperature for 12 hours. The mixture was poured into 500 mL of water and extracted with dichloromethane. The organic layer was washed with water once more, separated, slurried with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. A small amount of ethyl acetate was added to the concentrated compound, slurried, and filtered to obtain the target compound S8-1 as a white solid (5.07 g, yield 67.0%).

[0257] (2) Preparation of Compound S8-2

[0258] Using compound S8-1 (2.0 g, 5.2 mmol) and propan-1-amine (0.64 mL, 7.8 mmol), the target compound S8-2 as a pale yellow solid (1.7 g, 80.3%) was prepared in the same manner as in the preparation example of compound S3-2.

[0259] (3) Preparation of Compound S8

[0260] In a glove box, using compound S8-2 (0.5 g, 1.2 mmol), the target compound S8 as a dark yellow solid (0.42 g, yield 67.0%) was prepared in the same manner as in the preparation example of compound S2.

[0261] 1 H NMR (500 MHz, CDCl3):

[0262] 8.47 (d, 2H), 8.16 (d, 4H), 7.75 (m, 6H), 7.60 (t, 2H), 7.52 (t, 2H), 7.46 (t, 4H), 7.38 (t, 4H), 3.62 (m, 4H), 1.78 (q, 4H), 1.07 (t, 6H), 0.90 (s, 6H)

[0263] Preparation Example 9

[0264]

[0265] This compound was prepared according to the following scheme.

[0266]

[0267] In a glove box, using compound S4-2 (0.2 g, 0.5 mmol), the target compound S9 (0.19 g, yield 78.8%) was prepared in the same manner as in the preparation example of compound S2 to obtain a yellow solid.

[0268] 1 H NMR (500 MHz, CDCl3):

[0269] 8.49 (d, 2H), 8.06 (d, 2H), 8.01 (d, 2H), 7.95 (d, 2H), 7.82 (d, 2H), 7.74 (d, 2H), 7.62 (d, 2H), 7.47 - 7.59 (m, 8H), 3.62 (q, 4H), 1.76 (m, 4H), 1.07 (t, 6H), 0.9 (s, 6H)

[0270] Comparative Preparation Example 1

[0271]

[0272] Comparative Preparation Example 1 was prepared according to the method known in the literature [Organometalics 2011, 30, 123318 - 3329].

[0273] Comparative Preparation Example 2

[0274]

[0275] This compound was prepared according to the following scheme.

[0276]

[0277] (1) Preparation of Compound C2-1

[0278] 2-Chloro-N-isobutyl-6-methylpyrimidin-4-amine (1.0 g, 5.0 mmol) and 2,4,6-trimethylphenylboronic acid (0.86 g, 5.3 mmol) were dissolved in 60 mL of tetrahydrofuran, and 20 mL of an aqueous K2CO3 solution (2.08 g, 15 mmol) was added thereto, followed by heating. Pd(PPh3)4 (0.12 g, 0.1 mmol) was added to the refluxing mixture, and the resulting mixture was stirred for 12 hours. The reaction mixture was cooled to room temperature, ethyl acetate and water were added thereto, and extraction was carried out. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure. The concentrated compound was recrystallized from MeOH to obtain a white solid product (1.4 g, yield 99%).

[0279] (2) Preparation of Compound C2

[0280] In a glove box, using Compound C2-1 (0.2 g, 0.71 mmol), the target yellow Compound C2 (0.12 g, yield 44%) was prepared in the same manner as in the preparation example of Compound S2.

[0281] 1 H-NMR (500 MHz, C6D6): 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)

[0282] <Polymerization of Ethylene / α-Olefin Copolymer>

[0283] Example 1

[0284] Hexane solvent (900 mL) and 1-octene (600 mL) were added to a 2 L autoclave reactor, and the temperature of the reactor was preheated to 120 °C. Meanwhile, the reactor was pre-pressurized with ethylene (35 bar). By applying high-pressure argon gas pressure, 3 μmol of a mixed catalyst prepared by mixing Preparation Example 1 and Preparation Example 2 in a ratio of 3:1, 15 μmol of dimethylanilinium tetrakis(pentafluorophenyl)borate cocatalyst (AB) which is 10 eq compared to the catalyst, and 0.6 mmol of triisobutylaluminum (Tibal) as a scavenger were sequentially added to the reactor, and the copolymerization reaction was carried out for 8 minutes. 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 with ethanol two or three times and dried in a vacuum oven at 90 °C for more than 12 hours.

[0285] [Table 1]

[0286] Catalyst Mixture Molar Ratio of Catalyst Mixture Example 1 Preparation Example 1: Comparative Preparation Example 1 1：3 Example 2 Preparation Example 2: Comparative Preparation Example 1 1：3 Example 3 Preparation Example 3: Comparative Preparation Example 1 1：3 Example 4 Preparation Example 4: Comparative Preparation Example 1 1：3 Example 5 Preparation Example 5: Comparative Preparation Example 1 1：3 Example 6 Preparation Example 6: Comparative Preparation Example 1 1：4 Example 7 Preparation Example 7: Comparative Preparation Example 1 1：4 Example 8 Preparation Example 8: Comparative Preparation Example 1 1：4 Example 9 Preparation Example 9: Comparative Preparation Example 1 1：4 Comparative Example 1 Comparative Preparation Example 2: Comparative Preparation Example 1 1：3 Comparative Example 2 Comparative Preparation Example 2: Comparative Preparation Example 1 1：4

[0287] <Analysis of Preparation Results of Ethylene / α-Olefin Copolymer>

[0288] Experimental Example 1

[0289] The physical properties of each copolymer prepared in the examples and comparative examples were compared and analyzed. The measurement conditions and methods are as follows.

[0290] (1) Catalyst Activity (k space PE / mmol)

[0291] The obtained polymer was dried in vacuo, the yield was measured, and the value obtained by dividing the polymer (kg) by the catalyst (mmol) was calculated.

[0292] (2) Melt Index

[0293] MI was measured according to ASTM D - 1238 216 (Condition E, 190 °C, 2.16 kg load).

[0294] (3) Melting Temperature (Tm)

[0295] The melting temperature (Tm) can be obtained using a differential scanning calorimeter (DSC6000) manufactured by PerkinElmer Co. Specifically, for the copolymer, in a nitrogen atmosphere using DSC, the temperature is raised to 150 °C, held for 5 minutes, cooled to - 100 °C, and then raised again while observing the DSC curve. In this case, the heating rate and the cooling rate are each 10 °C / min.

[0296] On the measured DSC curve, the melting temperature is set to the maximum point of the endothermic peak during the second heating process.

[0297] [Table 2]

[0298] Activity (kgPE / mmol) <![CDATA[MI 2.16 (g / 10min)]]> Tm (°C) Example 1 10.2 3.20 118 Example 2 11.5 5.11 118 Example 3 12.7 3.15 120 Example 4 12.2 3.06 121 Example 5 14.1 2.99 117 Example 6 12.5 4.41 116 Example 7 9.3 1.62 116 Example 8 13.9 4.54 117 Example 9 14.1 3.46 118 Comparative Example 1 9.6 3.89 88 Comparative Example 2 9.0 4.33 91

[0299] As shown in the results of Table 2, compared with Comparative Example 1, the ethylene / α - olefin copolymer in the examples exhibited a higher Tg, and it was confirmed that an ethylene / α - olefin copolymer with excellent heat resistance was prepared.

[0300] This is the effect exhibited by using the transition metal compound represented by Chemical Formula 1 developed in the present invention as a catalyst.

Claims

1. A transition metal compound represented by the following Chemical Formula 1: [Chemical Formula 1] In Chemical Formula 1, M is Ti, Zr or Hf, R1 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, Ring A is Wherein R2 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms. If R2 is substituted, R2 is substituted by an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, m is 1 and n is 3, or m is 2 and n is 2, Each X is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.

2. The transition metal compound according to claim 1, wherein M is Hf, R1 is an alkyl group having 1 to 15 carbon atoms, R2 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms. If R2 is substituted, R2 is substituted by an alkyl group having 1 to 15 carbon atoms, m is 1 and n is 3.

3. The transition metal compound according to claim 1, wherein M is Hf, R1 is an alkyl group having 1 to 15 carbon atoms, R2 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms. If R2 is substituted, R2 is substituted by an alkyl group having 1 to 15 carbon atoms, m is 2 and n is 2.

4. The transition metal compound according to claim 1, wherein The transition metal compound represented by Chemical Formula 1 is one selected from the following Chemical Formulas 1-1 to 1-4: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] In Chemical Formulas 1-1 to 1-4, R1 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, R2 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms. If R2 is substituted, R2 is substituted by an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, Each X is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.

5. The transition metal compound according to claim 1, wherein, The transition metal compound represented by Chemical Formula 1 is one selected from the following compounds:

6. A catalyst composition comprising the transition metal compound according to claim 1 and a cocatalyst.

7. The catalyst composition according to claim 6, wherein, The catalyst composition further comprises a transition metal compound represented by the following Chemical Formula 2: [Chemical Formula 2] In Chemical Formula 2, Q is Ti, Zr or Hf, R 13 to R 16 each independently is hydrogen or an alkyl group having 1 to 20 carbon atoms, and two or more adjacent ones of the alkyl groups may be connected to each other to form a ring R 17 and R 18 each independently is hydrogen or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein the substitution is carried out by an alkyl group having 1 to 6 carbon atoms, Each R 19 is independently 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, n is 1 to 5, Y1 and Y2 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.

8. The catalyst composition according to claim 6, wherein, The transition metal compound represented by Chemical Formula 2 is a compound represented by the following Chemical Formula 2A: [Chemical Formula 2A] In Chemical Formula 2A, Q is Ti, Zr or Hf, R 17 and R 18 each independently is hydrogen or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein the substitution is carried out by an alkyl group having 1 to 6 carbon atoms, Each R 19 is independently 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, Y1 and Y2 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.

9. The catalyst composition according to claim 6, wherein, The cocatalyst includes one or more selected from the following Chemical Formula 3 to Chemical Formula 5: [Chemical Formula 3] -[Al(R a )-O] m - [Chemical Formula 4] D(R a )3 [Chemical Formula 5] [L-H] + [Z(A)4] - or [L] + [Z(A)4] - In the above chemical formulas, Each R a is independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a halogen-substituted hydrocarbyl radical having 1 to 20 carbon atoms, m is an integer of 2 or more, 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 having 6 to 20 carbon atoms, in which one or more hydrogen atoms may be substituted by substituents; or an alkyl group having 1 to 20 atoms, The substituent of A is a halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.

10. A method for preparing an olefin polymer, the method comprising the step of polymerizing an olefin monomer in the presence of a catalyst composition according to any one of claims 6 to 9.

11. The method for preparing an olefin polymer according to claim 10, wherein, The olefin polymer is an ethylene / α-olefin copolymer.

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