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 same. When the catalyst composition comprising the transition metal compound of the present invention is used, an olefin polymer can be prepared with high productivity.

Description

Transition metal compounds and catalyst compositions containing the same

[0001] Cross-citation with related applications

[0002] The present application claims the benefit of priority based on Korean patent applications No. 10-2024-0152103, No. 10-2024-0152105 and No. 10-2024-0152104 filed on October 31, 2024, and all contents disclosed in the documents of said Korean patent applications are incorporated herein as part of the specification.

[0003] Technology field

[0004] The present invention relates to a transition metal compound of a novel structure and a catalyst composition containing the same.

[0005]

[0006] Generally, olefin polymers such as ethylene copolymers are useful polymer materials used as materials for blow molded products, extruded products, films, sheets, etc., and have been manufactured in the presence of a Ziegler-Natta catalyst system.

[0007] The above-mentioned Ziegler-Natta catalyst is a heterogeneous catalyst used in systems where the phase of the reactant and the phase of the catalyst are not identical, such as liquid-phase reactant-solid catalyst systems. Such a Ziegler-Natta catalyst is composed of two components, typically consisting of transition metals such as titanium (Ti), vanadium (V), chromium (Cr), molybdenum (Mo), zirconium (Zr), halogen compounds (e.g., TiCl4), alkyllithium, and alkylaluminum.

[0008] However, the above-mentioned Ziegler-Natta catalyst has a disadvantage in that it fails to overcome the limitations of a heterogeneous catalyst, as the concentration of active species relative to transition metal atoms is only a few percent to several tens of percent, and most transition metal atoms do not perform their functions.

[0009] Recently, metallocene compounds have been attracting attention as next-generation catalysts capable of overcoming these disadvantages. The metallocene compounds are known to exhibit desirable polymerization activity in olefin polymerization as homogeneous catalysts containing group 4 metals.

[0010] Most metallocene catalysts used in polymerization have group 4 metal elements such as titanium, zirconium, and hafnium (Hf) and supporting ligands as precursors, and consist of two aromatic pentatomic rings and two halogen compounds acting as leaving groups. Among these, the supporting ligands coordinating to the central metal are typically aromatic cyclopentadienyl groups.

[0011] Although these metallocene catalysts are applied in various ways, such as in olefin polymerization processes, they have shown some limitations in catalytic activity (particularly in solution processes at temperatures above 100°C). For example, due to relatively fast end-terminating reactions (or chain-linking reactions) such as the beta-hydride elimination reaction, it is generally known that low molecular weight olefin polymers with a molecular weight (Mn) of 20,000 or less can be produced at temperatures above 100°C. Furthermore, it is known that the active species of metallocene catalysts tend to become deactivated at temperatures above 100°C. Therefore, in order to increase the applicability of metallocene catalysts, it is necessary to find a way to overcome the aforementioned limitations.

[0012]

[0013] The present invention aims to provide a novel transition metal compound and a catalyst composition containing the same, which exhibit excellent copolymerization and high productivity.

[0014]

[0015] (1) The present invention provides a transition metal compound represented by the following chemical formula 1.

[0016] [Chemical Formula 1]

[0017]

[0018] In the above chemical formula 1,

[0019] M is Hf or Zr, and

[0020] L is an alkyl group having 1 to 20 carbon atoms, and

[0021] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0022] R1 and R2 are each independently N(R 31 )(R 32 ) or an alkoxy group having 1 to 20 carbon atoms, and

[0023] R3 and R4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, N(R 33 )(R 34 ) or is a halogen,

[0024] R5 to R 30 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and

[0025] R 31 to R 34 Each is independently an alkyl group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a silylalkyl group having 1 to 20 carbon atoms.

[0026] (2) In the present invention as in (1) above, R1 and R2 are N(R 31 )(R 32 ) and provides transition metal compounds in which R3 and R4 are halogens.

[0027] (3) The present invention provides a transition metal compound in which the transition metal compound represented by the above formula 1 is represented by any one of the following formulas 1-1 to 1-4.

[0028] [Chemical Formula 1-1]

[0029]

[0030] [Chemical Formula 1-2]

[0031]

[0032] [Chemical Formula 1-3]

[0033]

[0034] [Chemical Formula 1-4]

[0035]

[0036] In the above chemical formulas 1-1 to 1-4, hexyl, dodecyl, and C 12 H 25 It is a straight hydrocarbon chain without branches.

[0037] (4) In the present invention as in (1) above, R1 and R2 are N(R 31 )(R 32 ) and R3 and R4 are N(R 33 )(R 34 Provides a transition metal compound that is ).

[0038] (5) The present invention provides a transition metal compound in which the transition metal compound represented by the above formula 1 is represented by the following formula 1-5 or formula 1-6.

[0039] [Chemical Formula 1-5]

[0040]

[0041] [Chemical Formula 1-6]

[0042]

[0043] In the above chemical formulas 1-5 and 1-6, hexyl, dodecyl, and C12 H 25 It is a straight hydrocarbon chain without branches.

[0044] (6) The present invention provides a transition metal compound according to (1) above, wherein M is Hf and R1 and R2 are alkoxy groups having 1 to 20 carbon atoms.

[0045] (7) The present invention provides a transition metal compound in which the transition metal compound represented by the above formula 1 is represented by any one of the following formulas 1-7 to 1-12.

[0046] [Chemical Formula 1-7]

[0047]

[0048] [Chemical Formula 1-8]

[0049]

[0050] [Chemical Formula 1-9]

[0051]

[0052] [Chemical Formula 1-10]

[0053]

[0054] [Chemical Formula 1-11]

[0055]

[0056] [Chemical Formula 1-12]

[0057]

[0058] (8) The present invention provides a catalyst composition comprising any one of (1) to (7) a transition metal compound and a co-catalyst.

[0059] (9) The present invention provides a catalyst composition according to (8), wherein the co-catalyst comprises one or more selected from the group consisting of compounds represented by the following chemical formulas 2 to 5.

[0060] [Chemical Formula 2]

[0061] -[Al(R 35 )-O] a -

[0062] In the above chemical formula 2,

[0063] R 35 Each is independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and

[0064] a is an integer greater than or equal to 2, and

[0065] [Chemical Formula 3]

[0066] E(R 36 ) 3

[0067] In the above chemical formula 3,

[0068] E is aluminum or boron, and

[0069] R 36 Each is independently hydrogen, a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and

[0070] [Chemical Formula 4]

[0071] [Le-H] + [G(A)4] -

[0072] [Chemical Formula 5]

[0073] [Le] + [G(A)4] -

[0074] In the above chemical formulas 4 and 5,

[0075] Le is a neutral or cationic Lewis acid, and

[0076] [Le-H] + is Mount Brønsted, and

[0077] G is a Group 13 element, and

[0078] A is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein, when the alkyl group or aryl group is substituted, the substituent is a halogen group, a hydrocarbyl 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.

[0079] (10) 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 of (8) or (9) above.

[0080] (11) The present invention provides a method for manufacturing an olefin polymer, wherein the olefin polymer is an ethylene / alpha-olefin copolymer, in accordance with (10) above.

[0081] (12) The present invention provides a method for producing an olefin polymer according to (11), wherein the alpha-olefin comprises one or more selected from the group consisting of 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, 1-eicocene, norbornene, norvonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

[0082]

[0083] By using a catalyst containing the transition metal compound of the present invention, olefin polymers can be manufactured with high productivity.

[0084]

[0085] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0086]

[0087] Terms and words used in the description and claims of the present invention shall not be interpreted as being limited to their ordinary or dictionary meanings, and shall be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0088] The term “alkyl” as used herein means a straight-chain, cyclic, or branched hydrocarbon residue unless otherwise noted, and includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, and hexyl.

[0089] As used herein, the term “cycloalkyl” refers to a non-aromatic cyclic hydrocarbon radical composed of carbon atoms unless otherwise noted. “Cycloalkyl” includes, by non-limiting example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

[0090] As used herein, the term “aryl” refers, unless otherwise noted, to an optionally substituted benzene ring or to a ring system that may be formed by fusing one or more optional substituents. Exemplary optional substituents include a substituted C1-3 alkyl, substituted C2-3 alkenyl, substituted C2-3 alkynyl, heteroaryl, heterocyclic, aryl, alkoxy, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonylamino, carboxyamide, aminocarbonyl, carboxy, oxo, hydroxy, mercapto, amino, nitro, cyano, halogen, or ureido. Such rings or ring systems may optionally be fused to aryl rings (e.g., benzene rings), carbon ring rings, or heterocyclic rings having one or more optional substituents. Examples of 'aryl' groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl, or phenanthyl, and their substituted derivatives.

[0091] In the present invention, “alkylaryl” means an aryl group substituted by the alkyl group.

[0092] In the present invention, “arylalkyl” means an alkyl group substituted by the aryl group.

[0093] In the present invention, “hydrocarbyl” means a monovalent hydrocarbon group having 1 to 20 carbon atoms, consisting only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl, or arylalkyl, unless otherwise noted.

[0094] In the present invention, “alkylene group” may refer to divalent aliphatic saturated hydrocarbons such as methylene, ethylene, propylene, and butylene.

[0095] In the present invention, the term “alkoxy group” may include all functional groups, atomic groups, or compounds in which the hydrogen at the terminal end of an alkyl group is substituted with an oxygen atom, such as methoxy, ethoxy, propoxy, and butoxy.

[0096] In this specification, the term “substitution” means that a hydrogen atom bonded to a carbon atom of a compound is replaced by another substituent (e.g., hydrogen, halogen, amine group, nitrile group, alkyl group, cycloalkyl group, alkoxy group, aryloxy group, aryl group, heterocyclic group, etc.), and the substitution site is not limited to the site where the hydrogen atom is substituted, that is, as long as the substituent is a site where the hydrogen atom can be substituted, and in the case of two or more substitutions, the two or more substituents may be the same or different from each other.

[0097] Unless otherwise stated, the term “substituted or unsubstituted” in this specification means that it is substituted or unsubstituted with one or more substituents selected from the group including hydrogen, halogen, amine group, nitrile group, alkyl group, cycloalkyl group, alkoxy group, aryloxy group, aryl group, and heterocyclic group, or is substituted or unsubstituted with a substituent in which two or more of the exemplified substituents are connected.

[0098] In this specification, where the terms “substituted” or “substituted or unsubstituted” are not modified before a functional group, unless otherwise noted, it means an unsubstituted functional group.

[0099]

[0100] The present invention relates to a transition metal compound represented by the following chemical formula 1.

[0101] [Chemical Formula 1]

[0102]

[0103] In the above chemical formula 1,

[0104] M is Hf or Zr, and

[0105] L is an alkyl group having 1 to 20 carbon atoms, and

[0106] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0107] R1 and R2 are each independently N(R 31 )(R 32 ) or an alkoxy group having 1 to 20 carbon atoms, and

[0108] R3 and R4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, N(R 33 )(R 34 ) or is a halogen,

[0109] R5 to R 30 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and

[0110] R 31 to R 34 Each is independently an alkyl group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a silylalkyl group having 1 to 20 carbon atoms.

[0111]

[0112] The transition metal compound of the present invention has a structure in which a divalent amine group or an alkoxy group is bonded to the upper phenolate and a divalent amine group or a halogen is bonded to the lower phenolate, as shown in the structure of Formula 1, and exhibits catalytic activity equivalent to or higher than that of conventional compounds and can show improved solubility. When using the transition metal compound of the present invention, an olefin polymer with high crystallinity and improved mechanical properties can be prepared due to the high melting temperature (Tm). This is a unique feature that can be achieved by the novel structure of the compound newly developed in the present invention.

[0113]

[0114] In the above chemical formula 1, M is Hf or Zr. Specifically, M can be Hf.

[0115] In the above chemical formula 1, L is an alkyl group having 1 to 20 carbon atoms. Specifically, L may be an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms, and may be, for example, a methyl group or a butyl group.

[0116] In the above chemical formula 1, Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms. Specifically, it may be an alkylene group having 2 to 40 carbon atoms, an alkylene group having 2 to 30 carbon atoms, an alkylene group having 2 to 10 carbon atoms, an alkylene group having 2 to 6 carbon atoms, and, for example, a propylene group.

[0117] In the above Chemical Formula 1, R1 and R2 are each independently N(R 31 )(R 32 ) or an alkoxy group having 1 to 20 carbon atoms. Specifically, N(R 31 )(R 32 It may be an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

[0118] In the above Chemical Formula 1, R3 and R4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, N(R 33 )(R 34 ) or is a halogen. Specifically, N(R 33 )(R 34 It can be ) or halogen (e.g., F).

[0119] At this time, R 31 to R 34 Each is independently an alkyl group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a silylalkyl group having 1 to 20 carbon atoms. Specifically, R 31 to R34 Each can independently be an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms, or an alkyl group having 1 to 12 carbon atoms, and, for example, can be a hexyl group or a dodecyl group.

[0120] In the above Chemical Formula 1, R5 to R 30 Each is independently hydrogen, a halogen, a cyano group, an amine group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Specifically, it may be hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and, for example, may be hydrogen or a tert-butyl group. More specifically, R5 to R 16, R 18 to R 24 and R 26 to R 30 is hydrogen, and R 17 and R 25 It may be hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and, for example, may be hydrogen or a tert-butyl group.

[0121]

[0122] As a specific example, in the transition metal compound represented by the above Chemical Formula 1, R1 and R2 in Chemical Formula 1 are N(R 31 )(R 32 ) and R3 and R4 can be halogens (e.g., F).

[0123] For example, the transition metal compound represented by the above chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-4.

[0124] [Chemical Formula 1-1]

[0125]

[0126] [Chemical Formula 1-2]

[0127]

[0128] [Chemical Formula 1-3]

[0129]

[0130] [Chemical Formula 1-4]

[0131]

[0132] In the above chemical formulas 1-1 to 1-4, hexyl, dodecyl, and C 12 H 25 It is a straight hydrocarbon chain without branches.

[0133]

[0134] In addition, as a specific example, in the transition metal compound represented by the above Chemical Formula 1, R1 and R2 in Chemical Formula 1 are N(R 31 )(R 32 ) and R3 and R4 are N(R 33 )(R 34 It can be.

[0135] For example, the transition metal compound represented by the above chemical formula 1 may be represented by the following chemical formula 1-5 or chemical formula 1-6.

[0136] [Chemical Formula 1-5]

[0137]

[0138] [Chemical Formula 1-6]

[0139]

[0140] In the above chemical formulas 1-5 and 1-6, hexyl, dodecyl, and C 12 H 25 It is a straight hydrocarbon chain without branches.

[0141]

[0142] In addition, as a specific example, the transition metal compound represented by the above chemical formula 1 may have M as Hf and R1 and R2 as alkoxy groups having 1 to 20 carbon atoms. More specifically, R3 and R4 may be halogens (e.g., F).

[0143] For example, the transition metal compound represented by the above chemical formula 1 may be represented by any one of the following chemical formulas 1-7 to 1-12.

[0144] [Chemical Formula 1-7]

[0145]

[0146] [Chemical Formula 1-8]

[0147]

[0148] [Chemical Formula 1-9]

[0149]

[0150] [Chemical Formula 1-10]

[0151]

[0152] [Chemical Formula 1-11]

[0153]

[0154] [Chemical Formula 1-12]

[0155]

[0156]

[0157] In addition, the present invention relates to a catalyst composition comprising the aforementioned transition metal compound.

[0158] In the present invention, the “composition” includes reaction products and decomposition products formed from the materials of the composition, as well as a mixture of materials comprising the composition.

[0159] The catalyst composition of the present invention may further include a co-catalyst.

[0160] The above co-catalyst may be one known in the relevant technical field, and for example, the co-catalyst may include one or more selected from the group consisting of compounds represented by the following chemical formulas 2 to 5.

[0161] [Chemical Formula 2]

[0162] -[Al(R 35 )-O] a -

[0163] In the above chemical formula 2,

[0164] R 35 Each is independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and

[0165] a is an integer greater than or equal to 2, and

[0166] [Chemical Formula 3]

[0167] E(R 36 ) 3

[0168] In the above chemical formula 3,

[0169] E is aluminum or boron, and

[0170] R 36 Each is independently hydrogen, a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and

[0171] [Chemical Formula 4]

[0172] [Le-H] + [G(A)4] -

[0173] [Chemical Formula 5]

[0174] [Le] + [G(A)4] -

[0175] In the above chemical formulas 4 and 5,

[0176] Le is a neutral or cationic Lewis acid, and

[0177] [Le-H]+ is Mount Brønsted, and

[0178] G is a Group 13 element, and

[0179] A is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein, when the alkyl group or aryl group is substituted, the substituent is a halogen group, a hydrocarbyl 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.

[0180] The compound represented by the above chemical formula 2 is not particularly limited as long as it is an alkylaluminoxan. Preferred examples include methylaluminoxan, ethylaluminoxan, isobutylaluminoxan, butylaluminoxan, etc., and a particularly preferred compound is methylaluminoxan.

[0181] The compound represented by the above chemical formula 3 is not particularly limited, but preferred examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc., and particularly preferred compounds are selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[0182] Examples of compounds represented by the above chemical formula 4 or 5 include, when G is boron, for example, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] -, Dioctadecylmethylammonium tetrakis(phenyl)borate, Dioctadecylmethylammonium tetrakis[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, Tributylammonium tetrapentafluorophenylborate, N,N-Diethylanilinium tetrapentylborate, N,N-Diethylanilinium tetrapentafluorophenylborate, Diethylammonium tetrapentafluorophenylborate, Triphenylphosphonium tetraphenylborate, It may be trimethylphosphonium tetraphenylborate, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, triphenylcarbonium tetra(p-trifluoromethylphenyl)borate, triphenylcarbonium tetrapentafluorophenylborate, or a combination thereof, and where Z is aluminum, e.g., triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, It may be trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentafluorophenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, or a combination thereof, but is not limited thereto.

[0183] In particular, the co-catalyst used in the present invention may be a compound represented by the above chemical formula 4 or 5, and specifically may be dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate.

[0184] In addition, the transition metal compound represented by Chemical Formula 1 and the co-catalyst can also be used in a form supported on a carrier. A person skilled in the art can appropriately select and use a carrier, and for example, silica or alumina can be used.

[0185]

[0186] The present invention relates to a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the aforementioned catalyst composition.

[0187] In the present invention, the term “polymer” refers to a polymer compound produced by polymerizing monomers of the same or different types. Thus, the general term “polymer” encompasses “homopolymer,” a term commonly used to refer to a polymer produced from only one type of monomer, and “interpolymer,” a term defined below.

[0188] In the present invention, the term “copolymer” refers to a polymer produced by the polymerization of at least two different monomers. Thus, the general term “copolymer” includes “copolymer,” which is a term commonly used to refer to a polymer produced from two different monomers, and a polymer produced from two or more different monomers.

[0189] The olefin polymer of the present invention may be an olefin homopolymer or an olefin / alpha-olefin copolymer depending on the type of olefin monomer, and preferably an ethylene / alpha-olefin copolymer. In this case, the content of the alpha-olefin monomer, which is the comonomer, can be appropriately selected by a person skilled in the art according to the use, purpose, etc. of the olefin polymer, and may be, for example, about 1 mol% or more and 99 mol% or less.

[0190] The above alpha-olefin monomer may include one or more selected from the group consisting of 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, 1-eicocene, norbornene, norvonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

[0191] In the method for producing an olefin polymer according to the present invention, the catalyst composition may be dissolved or diluted and injected in an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of an olefin monomer, such as pentane, hexane, heptane, nonane, decane, and their isomers, an aromatic hydrocarbon solvent such as toluene and benzene, or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene. It is preferable to use a solvent in which a small amount of water or air, which acts as a poison to the catalyst, is removed by treating it with a small amount of alkylaluminum, and it is also possible to carry out the process by further using a co-catalyst.

[0192] In the method for manufacturing an olefin polymer according to the present invention, the most preferred manufacturing process using the catalyst composition is a solution process, and the composition can also be applied to a slurry or gas phase process when used with an inorganic carrier such as silica.

[0193] The above polymerization can be carried out by homopolymerizing with one olefin monomer or copolymerizing with two or more olefin monomers using a single continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

[0194] In addition, during the above polymerization reaction, an organoaluminum compound is further added to remove moisture within the reactor, and the polymerization reaction can proceed in its presence. Specific examples of such organoaluminum compounds include trialkylaluminum, dialkyl aluminum halides, alkyl aluminum dihalides, aluminum dialkyl hydrides, or alkyl aluminum sesquihalides, and more specific examples include Al(C2H5)3, Al(C2H5)2H, Al(C3H7)3, Al(C3H7)2H, Al(i-C4H9)2H, and Al(C8H 17 )3, Al(C 12 H 25 )3, Al(C2H5)(C 12 H 25 )2, Al(i-C4H9)(C 12 H 25 Examples include )2, Al(i-C4H9)2H, Al(i-C4H9)3, (C2H5)2AlCl, (i-C3H9)2AlCl, or (C2H5)3Al2Cl3. These organoaluminum compounds can be continuously fed into the reactor and can be fed at a ratio of about 0.1 to 10 moles per 1 kg of reaction medium fed into the reactor for proper moisture removal.

[0195] According to one embodiment of the present invention, the polymerization of the olefin polymer can be carried out by reacting for about 4 minutes to 2 hours, specifically about 4 minutes to 1 hour, or about 4 minutes to 30 minutes, under conditions of a temperature of about 80 to 200°C, specifically about 90 to 200°C, about 130 to 200°C, or about 150 to 170°C, and a pressure of about 20 to 100 bar, specifically about 20 to 50 bar, or about 20 to 40 bar.

[0196]

[0197] Examples

[0198] The present invention will be explained in more detail below through examples. However, the following examples are intended to illustrate the present invention and do not limit the scope of the present invention.

[0199]

[0200] Preparation of Transition Metal Compounds

[0201] Preparation Example 1

[0202] [Chemical Formula 1-1]

[0203]

[0204] The above compound was prepared as follows.

[0205] 2 g (10.64 mmol) of 4-amino-2-bromophenol reagent, 3.51 g (21.28 mmol) of 1-bromohexane, 7.24 mL (42.56 mmol) of DiPEA, and 27 mL of DMF were weighed into a 250 mL two-neck flask and refluxed overnight at 150 °C. After confirming the NMR, the mixture was worked up with water, EA, and magnesium sulfate, and the organic layer was concentrated to obtain a red liquid product of 2.33 g with a yield of 61.5%.

[0206] 1H-NMR (in CDCl3500 MHz): 6.90-6.50 (m, 3H), 3.23-2.99 (m, 4H), 1.52 (s, 4H), 1.31 (s, 12H), 0.91 (s, 6H)

[0207] 1.62 g (4.55 mmol) of the product obtained above was weighed into a 50 mL vial, and 9.1 mL of DMF was added. 218.2 mg (5.46 mmol) of NaH was added gradually at RT and reacted for 30 minutes, after which 410.83 μl (5.46 mmol) of chloromethylmethylether was added and reacted overnight. After confirming the NMR, workup was performed with water and EA / magnesium sulfate. 1.78 g of red liquid was obtained with a yield of 97.7%.

[0208] 1 H-NMR (in CDCl3500 MHz): 7.00(d, 1H), 6.80(d, 1H), 6.51(d,1H), 5.10(s, 2H), 3.54(s, 3H), 3.17(t, 4H), 1.54-1.51(m, 4H), 1.34-1.27(m, 12H), 0.9(t, 6H)

[0209] After quantifying 860 mg (2.15 mmol) of the product obtained above, 396 mg (2.37 mmol), 82 mg (0.43 mmol) of CuI, 69.3 µl (0.65 mmol) of DMEDA, and 913 mg (4.3 mmol) of K3PO4 into a 100 mL two-neck container, 4.3 mL of toluene was added, and the mixture was refluxed overnight at 130°C. Workup was performed with water and EA to obtain 790 mg of a white solid product with a yield of 75.5%.

[0210] 1H-NMR (in CDCl3500 MHz): 8.13(d, 2H), 7.39(t, 2H), 7.26(m, 4H), 6.72(d, 1H), 6.69(d, 1H), 4.70(s, 2H), 3.21(t, 4H), 3.02(s, 3H), 1.58-1.55(m, 4H), 1.28(s, 12H), 0.89(t, 6H)

[0211] 300 mg (0.616 mmol) of the product obtained above and 3.08 mL of THF were weighed into a 50 mL vial, and 271 µl (0.678 mmol) of 2.5 M n-BuLi in hexane was added dropwise and reacted overnight at RT. 314.2 µl (1.54 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise and reacted overnight at RT; after workup with EA and water, a white solid product was obtained.

[0212] 1 H-NMR (in CDCl3500 MHz): 8.10(d, 2H), 7.39(t, 2H), 7.31(d, 2H), 7.24(t, 2H), 7.19(d, 1H), 6.73(d, 1H), 4.59(s, 2H), 3.23(t, 4H), 2.24(s, 3H), 1.57-1.55(m, 4H), 1.36(s, 18H), 1.28-1.26(m, 12H), 1.87(t, 6H)

[0213] 640 mg (1.05 mmol) of 3-(9H-carbazol-9-yl)-N,N-dihexyl-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline, 176.4 mg (0.42 mmol) of 2-bromo-4-fluoro-1-(3-((4-fluoro-6-methylcyclohexa-1,5-dien-1-yl)oxy)propoxy)benzene--methane (1 / 1), 4.2 mL of dioxane, and 462.2 mg of K2CO3 in 6.7 mL of H2O were quantified and heated to 100°C. 24.2 mg of Tetrakix(triphenylphosphine)palladium was added and heated overnight. After working up with water and EA, 20 ml of MeOH + 5 ml of HCl concentrate was added and heated at 70°C for 4 hours to obtain 300 mg of white solid.

[0214] 1 H-NMR (in CDCl3500 MHz): 8.17(d, 4H), 7.33(t, 4H), 7.26(t, 4H), 7.19(d, 4H), 7.04(d,2H), 6.74(s, 2H), 6.62(m, 2H), 5.23(s, 2H), 3.88(t, 4H), 3.19-3.18(m, 8H), 2.07-2.03(m, 2H), 1.58-1.55(m, 8H), 1.26(s, 24H), 0.89(t, 12H)

[0215] After quantifying HfCl4 in a 10 mL vial, toluene was added, and MMB was added dropwise. After reacting for 5 minutes, 100 mg (0.087 mmol) of the ligand obtained above was dissolved in toluene and added dropwise to the reaction solution. After reacting overnight at RT, the toluene was completely evaporated, and the mixture was extracted with hexane to obtain 83 mg of a bright yellow solid product with a yield of 70.3%.

[0216] 1 H-NMR (in CDCl3500 MHz): 8.32(d, 2H), 8.11(d, 2H), 7.52(d, 2H), 7.41-7.31(m, 8H), 7.19-7.31(m, 4H), 6.97(d, 2H), 6.92(d, 2H), 6.56(d, 2H), 6.34-6.30(m, 2H), 4.39(m, 2H), 3.90-3.86(m, 2H), 3.47-3.43(m, 2H), 3.18(t, 8H), 1.63-1.49(m, 2H), 1.31-1.26(m, 24H), 0.89(t, 12H), -1.83(s, 6H)

[0217]

[0218] Preparation Example 2

[0219] [Chemical Formula 1-2]

[0220]

[0221] The above compound was prepared as follows.

[0222] 12 g (63.82 mmol) of 4-amino-2-bromophenol reagent, 31.813 g (127.64 mmol) of 1-bromododecane, 43.35 mL (255.28 mmol) of DiPEA, and 160 mL of DMF were weighed into a 250 mL two-neck flask, and the mixture was refluxed overnight at 150 °C. After confirming the NMR, the mixture was worked up with water, EA, and magnesium sulfate, and the organic layer was concentrated to obtain a red liquid product of 18 g with a yield of 53.8%.

[0223] 1 H-NMR (in CDCl3500 MHz): 6.88 (d, 1H), 6.74 (d, 1H), 6.57 (d, 1H), 4.88 (s, 1H), 3.14 (t, 4H), 1.50-1.52 (m, 4H), 1.32-1.27 (m, 40H), 0.88 (s, 6H)

[0224] 5 g (9.53 mmol) of the product obtained above was weighed into a 100 mL one-neck container, and 19.06 mL of DMF was added. 457.4 mg (11.406 mmol) of NaH was added gradually at RT and reacted for 30 minutes, after which 860.5 μl (11.436 mmol) of chloromethylmethylether was added and reacted overnight. After confirming the NMR, workup was performed with water and EA / magnesium sulfate. 5.3 g of red liquid was obtained with a yield of 97.8%.

[0225] 1H-NMR (in CDCl3 500 MHz): 6.99(d, 1H), 6.79(d, 1H), 6.51(d,1H), 5.10(s, 2H), 3.54(s, 3H), 3.17(t, 4H), 1.54-1.51(m, 4H), 1.30-1.26(m, 40H), 0.88(t, 6H)

[0226] 4.66 mg (8.2 mmol) of the product obtained above, 1.25 mg (7.45 mmol), 1.42 g (7.45 mmol) of CuI, 1.78 mL (22.35 mmol) of methylimidazole, and 6 g (28.31 mmol) of K3PO4 were weighed into a 250 mL two-neck container, 37.25 mL of toluene was added, and the mixture was refluxed overnight at 120°C. Workup was performed with water and EA to obtain 4.81 g of a white solid product with a yield of 94%.

[0227] 1 H-NMR (in CDCl3500 MHz): 8.13(d, 2H), 7.40(t, 2H), 7.29-7.24(m, 4H), 6.72(d, 1H), 6.69(d, 1H), 4.71(s, 2H), 3.21(t, 4H), 3.02(s, 3H), 1.60-1.56(m, 4H), 1.30-1.25(m, 40H), 0.89(t, 6H)

[0228] 4.81 g (7.34 mmol) of the product obtained above and 9.6 mL of THF were weighed into a 100 mL one-neck container, followed by the dropwise addition of 5.87 mL (14.67 mmol) of 2.5 M n-BuLi in hexane and an overnight reaction at RT. 3.74 mL (18.35 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise and an overnight reaction was performed at RT; after workup with EA and water, a yellow liquid product was obtained.

[0229] 1 H-NMR (in CDCl3500 MHz): 8.10(d, 2H), 7.39(t, 2H), 7.31(d, 2H), 7.23(t, 2H), 7.19(s, 1H), 6.73(d, 1H), 4.59(s, 2H), 3.23(t, 4H), 2.25(s, 3H), 1.56(s, 4H), 1.36(s, 12H), 1.25(m, 12H), 1.88(t, 6H)

[0230] In a 50 mL vial, 1.34 g (1.72 mmol) of the product obtained above, 299.2 mg (0.68 mmol) of 1,3-bis(2-bromo-4-fluorophenoxy)propane, 6.9 mL of dioxane, and 758.5 ​​mg of K3PO4 in 11 mL of H2O were quantified and heated to 100 °C. 40 mg of Tetrakix (triphenylphosphine) palladium was added and heated overnight. After working up with water and EA, 20 mL of MeOH + 5 mL of concentrated HCl was added, and the mixture was heated to 70 °C for 4 hours to obtain a yellow liquid.

[0231] 1H-NMR (in CDCl3500 MHz): 8.17(d, 4H), 7.33(t, 4H), 7.26(t, 4H), 7.19(d, 4H), 7.04(d,2H), 6.70(s, 2H), 6.61(m, 2H), 6.57(s, 2H), 6.17-6.15(m, 2H), 5.19(s, 1H), 3.87(t, 4H), 3.18(t, 8H), 2.05-2.02(m, 2H), 1.55(m, 8H), 1.23(s, 80H), 0.89(t, 12H)

[0232] After quantifying HfCl4 in a 10 mL vial, toluene was added, and MMB was added dropwise. After reacting for 5 minutes, 204 mg (0.138 mmol) of the ligand obtained above was dissolved in toluene and added dropwise to the reaction solution. After reacting overnight at RT, the toluene was completely evaporated, and the mixture was extracted with hexane to obtain 216 mg of a bright yellow solid product with a yield of 92.7%.

[0233] 1 H-NMR (in CDCl3500 MHz): 8.32(d, 2H), 8.11(d, 2H), 7.52(d, 2H), 7.40-7.32(m, 8H), 7.18(t, 2H), 6.97(d, 2H), 6.92(d, 2H), 6.56(s, 2H), 6.32(t, 2H), 4.40-4.37(m, 2H), 3.90-3.86(m, 2H), 3.46-3.43(m, 2H), 3.28(t, 8H), 1.59-1.54(m, 8H), 1.22(s, 80H), 0.88(t, 12H), -1.83(s, 6H)

[0234]

[0235] Preparation Example 3

[0236] [Chemical Formula 1-3]

[0237]

[0238] The above compound was prepared as follows.

[0239] 4.5g (11.24 mmol) of 3-bromo-N,N-dihexyl-4-(methoxymethoxy)aniline, 2.83g (10.12 mmol) of t-butyl carbazole, 2.14g (11.24 mmol) of CuI, 2.69g (33.72 mmol) of methylimidazole, and 9.07g (42.71 mmol) of K3PO4 were quantified into a 250 mL two-neck container, 56.2 mL of toluene was added, and the mixture was refluxed overnight at 120°C. Workup was performed with water and EA to obtain 5.56 g of a yellow liquid product with a yield of 82.6%.

[0240] 1 H-NMR (in CDCl3500 MHz): 8.12(d, 2H), 7.43(d, 2H), 7.24(d, 1H), 6.70(d, 1H), 6.67(d, 1H), 4.70(s, 2H), 3.20(t, 4H), 3.09(s, 3H), 1.58-1.55(m, 4H), 1.47(s, 18H), 1.28(s, 12H), 0.87(t, 6H)

[0241] 2.74 g (4.58 mmol) of the product obtained above and 22.9 mL of THF were weighed into a 100 mL Schlenk, and 2.56 mL (6.4 mmol) of 2.5 M n-BuLi in hexane was added dropwise at room temperature, followed by an overnight reaction at RT. 2.33 mL (11.44 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise, followed by an overnight reaction at RT; after workup with EA and water, 3.51 g of a beige solid product was obtained.

[0242] 1H-NMR (in CDCl3500 MHz): 8.08(d, 2H), 7.43(d, 2H), 7.20(d, 2H), 7.17(d, 1H), 6.73(d, 1H), 4.56(s, 2H), 3.22(t, 4H), 2.34(s, 3H), 1.55(s, 4H), 1.36(s, 18H), 1.27(s, 12H) 0.87(t, 6H)

[0243] 1.64 g (2.26 mmol) of the product obtained above, 382 mg (0.9 mmol) of 1,3-bis(2-bromo-4-fluorophenoxy)propane, 9 mL of dioxane, and 995 mg of K2CO3 in 14.4 mL of H2O were added to a 100 mL two-neck container and heated to 100 °C. 52 mg of Tetrakix(triphenylphosphine)palladium was added and heated overnight. After working up with water and EA, 20 mL of MeOH + 5 mL of concentrated HCl was added, and the mixture was heated to 70 °C for 4 hours to obtain a white solid.

[0244] 1 H-NMR (in CDCl3 500 MHz): 8.19(d, 4H), 7.40(t, 4H), 7.12(t, 4H), 6.98(d, 2H), 6.69(s,2H), 6.54(s, 2H), 6.50(d, 2H), 6.00-5.98(m, 2H), 5.04(s, 2H) 3.82(S, 4H), 3.15(t, 8H), 2.02-2.00(m, 2H), 1.53(s, 8H), 1.46(s, 36H), 1.26(s, 24H), 0.84(t, 12H)

[0245] After quantifying HfCl4 in a 10 mL vial, toluene was added, and MMB was added dropwise. After reacting for 5 minutes, 190 mg (0.14 mmol) of the ligand obtained above was dissolved in toluene and added dropwise to the reaction solution. After reacting overnight at RT, the toluene was completely evaporated, and the mixture was extracted with hexane to obtain 180 mg of a bright yellow solid product with a yield of 93.8%.

[0246] 1 H-NMR (in CDCl3 500 MHz): 8.29(s, 2H), 8.05(s, 2H), 7.41(s, 4H), 7.36(d, 2H), 7.28(d, 2H), 7.18(d, 2H), 6.96(d, 2H), 6.94(s, 2H), 6.54(s, 2H), 6.27(t, 2H), 4.58-4.55(m, 2H), 3.88-3.86(m, 2H), 3.45-3.40(m, 2H), 3.16(t, 8H), 1.52(s, 8H), 1.37(s, 18H), 1.26(s, 24H), 0.88(t, 12H), -1.81(s, 6H)

[0247]

[0248] Preparation Example 4

[0249] [Chemical Formula 1-4]

[0250]

[0251] The above compound was prepared as follows.

[0252] 4.9g (8.61 mmol) of 3-bromo-N,N-didodecyl-4-(methoxymethoxy)aniline, 2.17g (7.75 mmol) of t-butyl carbazole, 1.64g (8.61 mmol) of CuI, 2.06g (25.83 mmol) of methylimidazole, and 6.95g (32.72 mmol) of K3PO4 were quantified into a 250 mL two-neck container, 28.7 mL of toluene was added, and the mixture was refluxed overnight at 120°C. Workup was performed with water and EA to obtain 5.21 g of a yellow liquid product with a yield of 78.9%.

[0253] 1 H-NMR (in CDCl3 500 MHz): 8.11(d, 2H), 7.42(d, 2H), 7.21(d, 1H), 6.70(d, 1H), 6.67(t, 1H), 4.69(s, 2H), 3.19(t, 4H), 3.08(s, 3H), 1.58-1.54(m, 4H), 1.46(s, 18H), 1.25(s, 40H), 0.88(t, 6H)

[0254] 2.45 g (3.19 mmol) of the product obtained above and 16 mL of THF were weighed into a 100 mL one-neck container. Then, 1.79 mL (4.47 mmol) of 2.5 M n-BuLi in hexane was added dropwise at room temperature, followed by an overnight reaction at RT. 1.58 mL (7.98 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise, followed by an overnight reaction at RT. After workup with EA and water, 3.31 g of a yellow liquid product was obtained.

[0255] 1H-NMR (in CDCl3 500 MHz): 8.08(d, 2H), 7.42(d, 2H), 7.20(d, 2H), 7.16(d, 1H), 6.73(d, 1H), 4.55(s, 2H), 3.21(t, 4H), 2.34(s, 3H), 1.55(s, 4H), 1.45(s, 18H), 1.36(s, 12H), 1.25(s, 40H), 0.88(t, 6H)

[0256] 1.56 g (1.75 mmol) of the product obtained above, 295 mg (0.7 mmol) of 1,3-bis(2-bromo-4-fluorophenoxy)propane, 7 mL of dioxane, and 774 mg (5.6 mmol) of K2CO3 in 11.2 mL of H2O were added to a 100 mL two-neck container and heated to 100 °C. 40.5 mg (0.04 mmol) of Tetrakix (triphenylphosphine) palladium was added and heated overnight. After working up with water and EA, 20 mL of MeOH + 5 mL of concentrated HCl was added, and the mixture was heated at 70 °C for 4 hours to obtain 282 mg of a clear solid.

[0257] 1 H-NMR (in CDCl3 500 MHz): 8.18(d, 4H), 7.40(d, 4H), 7.11(d, 4H), 6.97(s, 2H), 6.69(s,2H), 6.53(s, 2H), 6.49(t, 2H), 5.95-5.94(m, 2H), 5.08(s, 2H) 3.81(t, 4H), 3.15(t, 8H), 2.01-1.98(m, 2H), 1.53(s, 8H), 1.45(s, 36H), 1.26(s, 80H), 0.88(t, 12H)

[0258] After quantifying HfCl4 in a 10 mL vial, toluene was added, and MMB was added dropwise. After reacting for 5 minutes, 190 mg (0.14 mmol) of the ligand obtained above was dissolved in toluene and added dropwise to the reaction solution. After reacting overnight at RT, the toluene was completely evaporated, and the mixture was extracted with hexane to obtain 180 mg of a bright yellow solid product with a yield of 93.8%.

[0259] 1 H-NMR (in CDCl3 500 MHz): 8.29(s, 2H), 8.05(s, 2H), 7.41(s, 4H), 7.36(d, 2H), 7.27(d, 4H), 6.96(d, 2H), 6.91(s, 2H), 6.54(s, 2H), 6.27(t, 2H), 4.58-4.56(m, 2H), 3.88-3.86(m, 2H), 3.45-3.39(m, 2H), 3.16(t, 8H), 1.52(s, 8H), 1.37(s, 18H), 1.25(s, 80H), 0.88(t, 12H), -1.81(s, 6H)

[0260]

[0261] Preparation Example 5

[0262] [Chemical Formula 1-5]

[0263]

[0264] The above compound was prepared as follows.

[0265] 2 g (10.64 mmol) of 4-amino-2-bromophenol reagent, 3.51 g (21.28 mmol) of 1-bromohexane, 7.24 mL (42.56 mmol) of DiPEA, and 27 mL of DMF were weighed into a 250 mL two-neck flask and refluxed overnight at 150 °C. After confirming the NMR, the mixture was worked up with water, EA, and magnesium sulfate, and the organic layer was concentrated to obtain a red liquid product of 2.33 g with a yield of 61.5%.

[0266] 1 H-NMR (in CDCl3500 MHz): 6.90-6.50 (m, 3H), 3.23-2.99 (m, 4H), 1.52 (s, 4H), 1.31 (s, 12H), 0.91 (s, 6H)

[0267] 1.62 g (4.55 mmol) of the product obtained above was weighed into a 50 mL vial, and 9.1 mL of DMF was added. 218.2 mg (5.46 mmol) of NaH was added gradually at RT and reacted for 30 minutes, after which 410.83 μl (5.46 mmol) of chloromethylmethylether was added and reacted overnight. After confirming the NMR, workup was performed with water and EA / magnesium sulfate. 1.78 g of red liquid was obtained with a yield of 97.7%.

[0268] 1 H-NMR (in CDCl3500 MHz): 7.00(d, 1H), 6.80(d, 1H), 6.51(d,1H), 5.10(s, 2H), 3.54(s, 3H), 3.17(t, 4H), 1.54-1.51(m, 4H), 1.34-1.27(m, 12H), 0.9(t, 6H)

[0269] After quantifying 860 mg (2.15 mmol) of the product obtained above, 396 mg (2.37 mmol), 82 mg (0.43 mmol) of CuI, 69.3 µl (0.65 mmol) of DMEDA, and 913 mg (4.3 mmol) of K3PO4 into a 100 mL two-neck container, 4.3 mL of toluene was added, and the mixture was refluxed overnight at 130°C. Workup was performed with water and EA to obtain 790 mg of a white solid product with a yield of 75.5%.

[0270] 1H-NMR (in CDCl3500 MHz): 8.13(d, 2H), 7.39(t, 2H), 7.26(m, 4H), 6.72(d, 1H), 6.69(d, 1H), 4.70(s, 2H), 3.21(t, 4H), 3.02(s, 3H), 1.58-1.55(m, 4H), 1.28(s, 12H), 0.89(t, 6H)

[0271] 300 mg (0.616 mmol) of the product obtained above and 3.08 mL of THF were weighed into a 50 mL vial, and 271 µl (0.678 mmol) of 2.5 M n-BuLi in hexane was added dropwise and reacted overnight at RT. 314.2 µl (1.54 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise and reacted overnight at RT; after workup with EA and water, a white solid product was obtained.

[0272] 1 H-NMR (in CDCl3500 MHz): 8.10(d, 2H), 7.39(t, 2H), 7.31(d, 2H), 7.24(t, 2H), 7.19(d, 1H), 6.73(d, 1H), 4.59(s, 2H), 3.23(t, 4H), 2.24(s, 3H), 1.57-1.55(m, 4H), 1.36(s, 18H), 1.28-1.26(m, 12H), 1.87(t, 6H)

[0273] 466 mg (0.78 mmol) of 4,4'-(propane-1,3-diylbis(oxy))bis(N,N-dihexylaniline), 1.2 g (1.96 mmol) of 3-(9H-carbazol-9-yl)-N,N-dihexyl-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline, 6 eq of K2CO3in 0.5 M H2O, and 0.1 M dioxane were added to a 100 mL two-neck container and heated to 100°C. 0.05 eq of Tetrakix(triphenylphosphine)palladium was added and heated overnight. After working up with water and EA, 20 ml of MeOH + 5 ml of HCl concentrate was added and heated at 70°C for 4 hours, then the salt was filtered and basified with an aqueous solution of Na2CO3 to obtain 850 mg of sticky solid.

[0274] 1 H-NMR (in CDCl3500 MHz): 8.18(d, 4H), 7.31(t, 4H), 7.25(t, 4H), 7.18(d, 4H), 7.04(d,2H), 6.74(s, 2H), 6.62(m, 2H), 5.23(s, 2H), 3.86(t, 4H), 3.20-3.17(m, 16H), 2.05-2.03(m, 2H), 1.59-1.54(m, 16H), 1.25(s, 40H), 0.88(t, 24H).

[0275] After quantifying 1 eq of HfCl4 into a 10 ml vial, toluene was added and cooled in the refrigerator for 30 minutes, after which 4.1 eq of MMB was added dropwise. After reacting for 5 minutes, 100 mg (0.068 mmol) of the ligand obtained above was dissolved in toluene and added dropwise to the reaction mixture. After reacting overnight at RT, the toluene was completely evaporated, and the mixture was extracted with hexane to obtain 86 mg of product.

[0276] 1H-NMR (in CDCl3500 MHz): 8.34(d, 2H), 8.10(d, 2H), 7.52(d, 2H), 7.41-7.32(m, 8H), 7.19-7.30(m, 4H), 6.98(d, 2H), 6.93(d, 2H), 6.56(d, 2H), 6.34-6.30(m, 2H), 4.38(m, 2H), 3.90-3.86(m, 2H), 3.47-3.43(m, 2H), 3.19(t, 16H), 1.61-1.48(m, 8H), 1.32-1.25(m, 48H), 0.88(t, 24H), -1.79(s, 6H).

[0277]

[0278] Preparation Example 6

[0279] [Chemical Formula 1-6]

[0280]

[0281] The above compound was prepared as follows.

[0282] 12 g (63.82 mmol) of 4-amino-2-bromophenol reagent, 31.813 g (127.64 mmol) of 1-bromododecane, 43.35 mL (255.28 mmol) of DiPEA, and 160 mL of DMF were weighed into a 250 mL two-neck flask, and the mixture was refluxed overnight at 150 °C. After confirming the NMR, the mixture was worked up with water, EA, and magnesium sulfate, and the organic layer was concentrated to obtain a red liquid product of 18 g with a yield of 53.8%.

[0283] 1 H-NMR (in CDCl3500 MHz): 6.88 (d, 1H), 6.74 (d, 1H), 6.57 (d, 1H), 4.88 (s, 1H), 3.14 (t, 4H), 1.50-1.52 (m, 4H), 1.32-1.27 (m, 40H), 0.88 (s, 6H)

[0284] 5 g (9.53 mmol) of the product obtained above was weighed into a 100 mL one-neck container, and 19.06 mL of DMF was added. 457.4 mg (11.406 mmol) of NaH was added gradually at RT and reacted for 30 minutes, after which 860.5 μl (11.436 mmol) of chloromethylmethylether was added and reacted overnight. After confirming the NMR, workup was performed with water and EA / magnesium sulfate. 5.3 g of red liquid was obtained with a yield of 97.8%.

[0285] 1H-NMR (in CDCl3500 MHz): 6.99(d, 1H), 6.79(d, 1H), 6.51(d,1H), 5.10(s, 2H), 3.54(s, 3H), 3.17(t, 4H), 1.54-1.51(m, 4H), 1.30-1.26(m, 40H), 0.88(t, 6H)

[0286] 4.66 mg (8.2 mmol) of the product obtained above, 1.25 mg (7.45 mmol), 1.42 g (7.45 mmol) of CuI, 1.78 mL (22.35 mmol) of methylimidazole, and 6 g (28.31 mmol) of K3PO4 were weighed into a 250 mL two-neck container, 37.25 mL of toluene was added, and the mixture was refluxed overnight at 120°C. Workup was performed with water and EA to obtain 4.81 g of a white solid product with a yield of 94%.

[0287] 1 H-NMR (in CDCl3500 MHz): 8.13(d, 2H), 7.40(t, 2H), 7.29-7.24(m, 4H), 6.72(d, 1H), 6.69(d, 1H), 4.71(s, 2H), 3.21(t, 4H), 3.02(s, 3H), 1.60-1.56(m, 4H), 1.30-1.25(m, 40H), 0.89(t, 6H)

[0288] 4.81 g (7.34 mmol) of the product obtained above and 9.6 mL of THF were weighed into a 100 mL one-neck container, followed by the dropwise addition of 5.87 mL (14.67 mmol) of 2.5 M n-BuLi in hexane and an overnight reaction at RT. 3.74 mL (18.35 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise and an overnight reaction was performed at RT; after workup with EA and water, a yellow liquid product was obtained.

[0289] 1 H-NMR (in CDCl3500 MHz): 8.10(d, 2H), 7.39(t, 2H), 7.31(d, 2H), 7.23(t, 2H), 7.19(s, 1H), 6.73(d, 1H), 4.59(s, 2H), 3.23(t, 4H), 2.25(s, 3H), 1.56(s, 4H), 1.36(s, 12H), 1.25(m, 12H), 1.88(t, 6H)

[0290] 1.22 g (1.62 mmol) of 4,4'-(propane-1,3-diylbis(oxy))bis(3-bromo-N,N-dihexylaniline), 2.5 eq of 3-(9H-carbazol-9-yl)-N,N-di(dodeca-1,3,5,7,9,11-hexayn-1-yl)-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline--dihydrogen (1 / 22), 6 eq of K2CO3in 0.5 M H2O, and 0.1 M dioxane were added to a 50 mL vial and heated to 100°C. 0.05 eq of Tetrakix(triphenylphosphine)palladium was added and heated overnight. After working up with water and EA, 20 ml of MeOH + 5 ml of HCl concentrate was added and heated at 70°C for 4 hours, then the salt was filtered and basified with an aqueous solution of Na2CO3 to obtain a sticky solid.

[0291] 1 H-NMR (in CDCl3500 MHz): 8.17(d, 4H), 7.32(t, 4H), 7.26(t, 4H), 7.19(d, 4H), 7.04(d,2H), 6.72(s, 2H), 6.61(m, 2H), 6.56(s, 2H), 6.16(m, 2H), 5.18(s, 2H), 3.87(t, 4H), 3.18(t, 16H), 2.05-2.02(m, 2H), 1.56(m, 16H), 1.24(s, 96H), 0.89(t, 24H)

[0292] After quantifying HfCl4 in a 10 mL vial, toluene was added, and MMB was added dropwise. After reacting for 5 minutes, 200 mg (0.11 mmol) of the ligand obtained above was dissolved in toluene and added dropwise to the reaction solution. After reacting overnight at RT, the toluene was completely evaporated, and the product was extracted with hexane to obtain a bright yellow product.

[0293] 1 H-NMR (in CDCl3500 MHz): 8.33(d, 2H), 8.11(d, 2H), 7.52(d, 2H), 7.40-7.32(m, 8H), 7.19(t, 2H), 6.97(d, 2H), 6.92(d, 2H), 6.57(s, 2H), 6.33(t, 2H), 4.40-4.37(m, 2H), 3.90-3.86(m, 2H), 3.46-3.43(m, 2H), 3.29(t, 16H), 1.59-1.52(m, 16H), 1.23(s, 96H), 0.88(t, 24H), -1.82(s, 12H)

[0294]

[0295] Preparation Example 7

[0296] [Chemical Formula 1-7]

[0297]

[0298] The above compound was prepared as follows.

[0299]

[0300] 1 eq of 4-Hexyloxyphenol, 8 mol% of PPTS, and 2 eq of DHP were dissolved in 1 M dichloromethane and placed in a 100 ml round flask. The reaction was carried out overnight at 40°C. After the reaction was complete, the mixture was cooled to room temperature, extracted with distilled water and MC, and dried. The dried solid was slurried with hexane to obtain intermediate 1A (yield: 99.0%).

[0301]

[0302] 1 eq. of intermediate 1A was placed in 0.3 M THF in a 100 ml Schlenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of I2 was slowly added. After the addition was complete, the reaction was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, a sat. sodium thiosulfate solution was added and stirred for 10 minutes. After EA extraction, the mixture was vacuum dried. The resulting solid was dissolved in hexane and filtered using a celite filter. The remaining filtrate was dried to obtain intermediate 1B (yield: 90.0%).

[0303]

[0304] 1 eq. of intermediate 1B, 1.1 eq. of carbazole, 20 mol% of CuI, 3.8 eq. of K3PO4, and 50 mol% of N-methylimidazole were added to a 100 ml flask in 0.2 M toluene. The reaction was carried out overnight at 115°C. After the reaction was complete, the mixture was cooled to room temperature, extracted with EA, and vacuum dried. The resulting solid was dissolved in hexane and processed in a column (Hex:EA=100:1) to obtain intermediate 1C (yield: 80.0%).

[0305]

[0306] 1 eq. of intermediate 1C was placed in 0.2 M THF in a 100 ml Schlenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of methyl borate was slowly added. The reaction was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, EA was extracted and vacuum dried. The resulting solid was slurried with methanol and filtered. The filtered product was dried to obtain intermediate 1D (yield: 70.0%).

[0307]

[0308] 1 eq. of 1,3-bis(2-bromo-4-fluorophenoxy)propane, 2.5 eq. of intermediate 1D, 6 eq. of K2CO3, and 5 mol% of Pd(PPh3)4 were placed in a 50 ml vial in 0.2 M 1,4-dioxane and 0.5 M H2O. The reaction was carried out overnight at 95°C. After the reaction was complete, the mixture was cooled to room temperature, extracted with EA, and vacuum dried. The resulting solid was dissolved in hexane and processed in a column (Hex:EA=50:1) to obtain intermediate 1E (yield: 60.0%).

[0309] 1 H-NMR (in CDCl3 500 MHz): 8.16(d, 4H), 7.35(t, 4H), 7.26(t, 4H), 7.14(d, 4H), 7.04(d, 1H), 7.02(d, 1H), 6.95(d, 2H), 6.86(d, 2H), 6.64-6.60(m, 2H), 6.18-6.15(m, 2H), 5.39(s, 2H), 3.89-3.85(m, 8H), 2.03-2.01(m, 2H), 1.76-1.72(m, 4H), 1.44-1.41(m, 4H), 1.33-1.26(m, 8H), 0.90-0.87(m, 6H)

[0310]

[0311] HfC l4 1 eq. of 0.05 M toluene was added, and 4.1 eq. of 2.0 M Butylmagnesium Chloride was added to the cold (-25°C) slurry. The mixture was stirred for 2 minutes, 1 eq. of intermediate 1E was added, and the mixture was washed with toluene. The temperature was gradually increased, and the reaction mixture was stirred overnight at room temperature. The black mixture was concentrated, and hexane was added to the dried solid and stirred for about 10 minutes. The solid was filtered and collected, and the colorless filtrate was concentrated to obtain a white product (yield: 70.0%).

[0312] 1 H-NMR (in CDCl3 500 MHz): 8.27-8.23(m, 2H), 7.99-7.97(m, 2H), 7.45(t, 2H), 7.38-7.30(m, 4H), 7.23-7.06(m, 10H), 6.92-6.90(m, 2H), 6.81-6.77(m, 2H), 6.27-6.21(m, 2H), 4.50-4.36(m, 2H), 3.89-3.73(m, 8H), 3.42-3.32(m, 2H), 1.71-1.68(m, 4H), 1.47-1.19(m, 16H), 0.82-0.80(m, 10H), 0.23-0.18(m, 4H), (-)0.85-(-)0.91(m, 1H), (-)1.33-(-)1.39(m, 1H), (-)1.52-(-)1.58(m, 1H), (-)1.76-(-)1.83(m, 1H)

[0313]

[0314] Preparation Example 8

[0315] [Chemical Formula 1-8]

[0316]

[0317] The above compound was prepared as follows.

[0318]

[0319] Intermediate 2A was obtained by the same method as in Preparation Example 7, except that the starting material was 4-Heptyloxyphenol instead of 4-Hexyloxyphenol (yield: 99.0%).

[0320]

[0321] Intermediate 2B was obtained in the same manner as in Preparation Example 7, except that intermediate 2A was used as the starting material instead of intermediate 1A (yield: 90.0%).

[0322]

[0323] Intermediate 2C was obtained by the same method as in Preparation Example 7, except that intermediate 2B was used instead of intermediate 1B and 3,6-Di-tert-butylcarbazole was used instead of carbazole (yield: 80.0%).

[0324]

[0325] Intermediate 2D was obtained in the same manner as in Preparation Example 7, except that intermediate 2C was used as the starting material instead of intermediate 1C (yield: 70.0%).

[0326]

[0327] Intermediate 2E was obtained in the same manner as in Preparation Example 7, except that intermediate 2D was used as the starting material instead of intermediate 1D (yield: 60.0%).

[0328] 1 H-NMR (in CDCl3 500 MHz):8.19(s, 4H), 7.42(d, 4H), 7.08(d, 4H), 7.01(d, 1H), 6.99(d, 1H), 6.94(d, 2H), 6.83(d, 2H), 6.57-6.52(m, 2H), 6.06-6.03(m, 2H), 5.24(s, 2H), 3.87-3.82(m, 8H), 2.03-2.00(m, 2H), 1.76-1.72(m, 4H), 1.48-1.44(m, 54H), 0.88(t, 6H)

[0329]

[0330] The product was obtained in the same manner as in Preparation Example 7, except that intermediate 2E was used as the starting material instead of intermediate 1E (yield: 70.0%).

[0331] 1H-NMR (in CDCl3 500 MHz): 8.25(d, 2H), 7.99(d, 2H), 7.36-7.34(m, 4H), 7.29-7.26(m, 4H), 7.14-7.04(m, 4H), 6.92-6.88(m, 2H), 6.75-6.74(m, 2H), 6.20-6.16(m, 2H), 4.66-4.51(m, 2H), 3.86-3.74(m, 8H), 3.40-3.32(m, 2H), 1.47-1.45(m, 32H), 1.31-1.18(m, 16H), 0.80-0.78(m, 24H), (-)0.68-(-)0.74(m, 1H), (-)1.22-(-)1.28(m, 1H), (-)1.37-(-)0.74(m, 1H), (-)0.68-(-)0.74(m, 1H)

[0332]

[0333] Preparation Example 9

[0334] [Chemical Formula 1-9]

[0335]

[0336] The above compound was prepared as follows.

[0337] The product was obtained in the same manner as in Preparation Example 8, except that the starting material was 4-Hexyloxyphenol instead of 4-Heptyloxyphenol (yield: 20.0%).

[0338]

[0339] Preparation Example 10

[0340] [Chemical Formula 1-10]

[0341]

[0342] The above compound was prepared as follows.

[0343] The product was obtained in the same manner as in Preparation Example 7, except that the starting material was 4-Heptyloxyphenol instead of 4-Hexyloxyphenol (yield: 20.0%).

[0344]

[0345] Preparation Example 11

[0346] [Chemical Formula 1-11]

[0347]

[0348] The above compound was prepared as follows.

[0349] The product was obtained in the same manner as in Preparation Example 8, except that 4-Octyloxyphenol was used as the starting material instead of 4-Heptyloxyphenol (yield: 20.0%).

[0350]

[0351] Preparation Example 12

[0352] [Chemical Formula 1-12]

[0353]

[0354] The above compound was prepared as follows.

[0355] The product was obtained in the same manner as in Preparation Example 7, except that 4-Octyloxyphenol was used as the starting material instead of 4-Hexyloxyphenol (yield: 20.0%).

[0356]

[0357] Comparative Manufacturing Example 1

[0358]

[0359] The above compound was prepared as follows.

[0360] Comparative Preparation Example 1 was obtained in the same manner as Preparation Example 8, except that p-Cresol was used instead of 4-Heptyloxyphenol and 3.0M Mtylmagnesium Bromide was used instead of 2.0M Butylmagnesium Chloride (Yield: 25.0%).

[0361]

[0362] Comparative Manufacturing Example 2

[0363]

[0364] The above compound was prepared as follows.

[0365] Comparative Preparation Example 2 was obtained in the same manner as Comparative Preparation Example 1, except that carbazole was used as the starting material instead of 3,6-Di-tert-butylcarbazole (yield: 25.0%).

[0366]

[0367] Comparative Manufacturing Example 3

[0368]

[0369] It was prepared by manufacturing according to the method disclosed in Patent Document WO 2012-027448 A1.

[0370]

[0371] Comparative Manufacturing Example 4

[0372]

[0373] The above compound was prepared as follows.

[0374] The product was obtained in the same manner as in Preparation Example 3, except that 1,3-bis(2-bromo-phenoxy)propane was used instead of 1,3-bis(2-bromo-4-fluorophenoxy)propane.

[0375]

[0376] Polymerization of Ethylene / Alpha-Olefin Copolymers

[0377] Example 1

[0378] 900 mL of n-hexane solvent and 300 mL of 1-octene were added to a 2L autoclave reactor (ZIPPERCLAVE-Autoclave Engineers, Parker Hannifin), and the reactor temperature was preheated to 160°C. At the same time, the reactor pressure was pre-filled with ethylene (35 bar). 1.0 μmol of the catalyst from Preparation Example 1, 10 μmol of dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (AB) at 10 equivalents relative to the catalyst, and 1.1 mmol of Tibal as a scavenger were sequentially introduced into the reactor under high argon pressure, and 400 mL of hydrogen (H2) was added to carry out the copolymerization reaction for 8 minutes. Next, the remaining ethylene gas was removed, and the polymer solution was added to an excess amount of ethanol to induce precipitation. The precipitated polymer was washed with ethanol 2 to 3 times and then dried in a vacuum oven at 90°C for at least 12 hours.

[0379]

[0380] Examples 2 to 12 and Comparative Examples 1 to 4

[0381] An ethylene / alpha-olefin copolymer was prepared in the same manner as in Example 1, except that the type of catalyst was changed according to Table 1 below.

[0382]

[0383] Classification Catalyst Type Example 1 Preparation Example 1 Example 2 Preparation Example 2 Example 3 Preparation Example 3 Example 4 Preparation Example 4 Example 5 Preparation Example 5 Example 6 Preparation Example 6 Example 7 Preparation Example 7 Example 8 Preparation Example 8 Example 9 Preparation Example 9 Example 10 Preparation Example 10 Example 11 Preparation Example 11 Example 12 Preparation Example 12 Comparative Example 1 Comparative Preparation Example 1 Comparative Example 2 Comparative Preparation Example 2 Comparative Example 3 Comparative Preparation Example 3 Comparative Example 4 Comparative Preparation Example 4

[0384]

[0385] <Analysis of Manufacturing Results for Ethylene / Alpha-Olefin Copolymers>

[0386] Experimental Example 1

[0387] The physical properties of each copolymer prepared in the above examples and comparative examples were compared and analyzed and are shown in Tables 2 and 3. The measurement conditions and methods are as follows.

[0388]

[0389] (1) Catalytic activity (kgPE / mmol)

[0390] The obtained polymer was vacuum-dried to measure the yield, and the value was calculated by dividing the polymer (kg) by the catalyst (mmol).

[0391]

[0392] (2) Density

[0393] According to ASTM D-792, a sheet with a thickness of 3 mm and a radius of 2 cm was prepared using a 180°C press mold and cooled at 10°C / min and measured on a Mettler balance.

[0394]

[0395] (3) Melt Index (MI) and Melt Flow Rate Ratio (MFRR)

[0396] MI according to ASTM D-1238 10 (Condition E, 190℃, 10Kg load) and MI 2.16 (Condition E, 190℃, 2.16Kg load) was measured, and MFRR is MI 10 / MI 2.16 It was calculated as.

[0397]

[0398] (4) Melting Temperature (Tm), Crystallization Temperature (Tc)

[0399] The melting temperature (Tm) and crystallization temperature (Tc) can be obtained using a Differential Scanning Calorimeter (DSC 6000) manufactured by PerkinElmer. Specifically, using DSC, the temperature of the copolymer was increased to 150°C and maintained for 5 minutes under a nitrogen atmosphere, then cooled to -100°C, and the temperature was increased again while observing the DSC curve. At this time, the heating rate and cooling rate were each set to 10°C / min.

[0400] In the measured DSC curve, the melting temperature was determined as the maximum point of the endothermic peak during the second heating increase, and the crystallization temperature was determined as the maximum point of the exothermic peak during cooling.

[0401]

[0402] Catalytic Activity (kgPE / mmol) Example 196.8 Example 297.2 Example 397.6 Example 498.5 Example 5116.2 Example 6121.4 Example 799 Example 8103 Example 9102 Example 10100 Example 11103 Example 1298 Comparative Example 177 Comparative Example 263.5 Comparative Example 390 Comparative Example 492

[0403]

[0404] Classification density (g / mL) MI 2.16 (g / 10min)MI 10 (g / 10min)MFRRTm(°C)Tc(°C) Example 10.86420.302.387.950.830.9 Example 20.86740.2601.9247.448.528.2 Example 30.86850.0620.58.149.731.5 Example 40.86350.241.767.344.826.2 Example 50.89050.212.411.4287.3671.43 Example 60.89010.191.910.0986.4669.01 Comparative Example 20.85720.6769.98414.7636.416.0 Comparative Example 30.8660.523.6717.06--Comparative Example 40.8820.030.3913--

[0405]

[0406] Referring to Tables 2 and 3 above, it can be confirmed that when a transition metal compound according to the present invention is used as a catalyst as in the embodiments of the present invention, olefin copolymers can be produced with excellent yield due to high catalytic activity.

[0407] Specifically, the transition metal compound according to the present invention has a structure in which a divalent amine group is bonded to the top phenolate and a divalent amine group or a halogen is bonded to the bottom phenolate, or an alkoxy group is bonded to the top phenolate, and it can be confirmed that the catalytic activity is further enhanced compared to the transition metal compound having a structure in which an alkyl group is bonded to the top phenolate or a hydrogen or alkyl group is bonded to the bottom phenolate, even if a divalent amine group is bonded to the top phenolate, which is the catalyst used in the comparative example.

[0408] In addition, it can be confirmed that the copolymers of Examples 1 to 5 have a higher melting temperature (Tm) compared to the copolymer of Comparative Example 2, indicating high crystallinity, which indicates high ethylene efficiency.

Claims

1. Transition metal compounds represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, M is Hf or Zr, and L is an alkyl group having 1 to 20 carbon atoms, and Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R1 and R2 are each independently N(R 31 )(R 32 ) or an alkoxy group having 1 to 20 carbon atoms, and R3 and R4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, N(R 33 )(R 34 ) or is a halogen, R5 to R 30 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and R 31 to R 34 Each is independently an alkyl group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a silylalkyl group having 1 to 20 carbon atoms.

2. In Claim 1, R1 and R2 are N(R 31 )(R 32 ) and, R3 and R4 are transition metal compounds that are halogens.

3. In Claim 2, A transition metal compound represented by the above chemical formula 1 is a transition metal compound represented by any one of 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 the above chemical formulas 1-1 to 1-4, hexyl, dodecyl, and C 12 H 25 It is a straight hydrocarbon chain without branches.

4. In Claim 1, R1 and R2 are N(R 31 )(R 32 ) and, R3 and R4 are N(R 33 )(R 34 ) transition metal compound.

5. In Claim 4, The transition metal compound represented by the above chemical formula 1 is a transition metal compound represented by the following chemical formula 1-5 or chemical formula 1-6: [Chemical Formula 1-5] [Chemical Formula 1-6] In the above chemical formulas 1-5 and 1-6, hexyl, dodecyl, and C 12 H 25 It is a straight hydrocarbon chain without branches.

6. In Claim 1, M is Hf, and R1 and R2 are transition metal compounds in which the alkoxy groups have 1 to 20 carbon atoms.

7. In Claim 6, A transition metal compound represented by the above chemical formula 1 is a transition metal compound represented by any one of the following chemical formulas 1-7 to 1-12: [Chemical Formula 1-7] [Chemical Formula 1-8] [Chemical Formula 1-9] [Chemical Formula 1-10] [Chemical Formula 1-11] [Chemical Formula 1-12] .

8. A catalyst composition comprising the transition metal compound of Claim 1 and a co-catalyst.

9. In Claim 8, A catalyst composition comprising one or more selected from the group consisting of compounds represented by the following chemical formulas 2 to 5, wherein the above co-catalyst: [Chemical Formula 2] -[Al(R 35 )-O] a - In the above chemical formula 2, R 35 Each is independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and a is an integer greater than or equal to 2, and [Chemical Formula 3] E(R 36 ) 3 In the above chemical formula 3, E is aluminum or boron, and R 36 Each is independently hydrogen, a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and [Chemical Formula 4] [Le-H] + [G(A)4] - [Chemical Formula 5] [And] + [G(A)4 - In the above chemical formulas 4 and 5, Le is a neutral or cationic Lewis acid, and [Le-H] + is Mount Brønsted, and G is a Group 13 element, and A is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein, when the alkyl group or aryl group is substituted, the substituent is a halogen group, a hydrocarbyl 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 producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition of claim 8 or 9.

11. In Claim 10, A method for manufacturing an olefin polymer, wherein the above olefin polymer is an ethylene / alpha-olefin copolymer.

12. In Claim 11, A method for preparing an olefin polymer, wherein the alpha-olefin comprises one or more selected from the group consisting of 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, 1-eicocene, norbornene, norvonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

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