Transition metal compound, catalyst composition containing the same, and method for producing olefin polymer using the same

Abstract

The present invention provides a transition metal compound, a catalyst composition containing the same, and a method for producing an olefin polymer using the same. The transition metal compound of the present invention, in which a specific functional group is introduced at a specific position, has high solubility and catalytic activity, and a method for producing an olefin polymer using the same can easily produce an olefin polymer having excellent physical properties through simple steps.

Description

[Technical field]

[0001] The present invention relates to a transition metal compound, a catalyst composition containing the same, and a method for producing an olefin polymer using the same, and more particularly to a transition metal compound having improved solubility by introducing a controlled specific functional group, a catalyst composition containing the same, and a method for producing an olefin polymer using the same. [Background technology]

[0002] Conventionally, the production of ethylene homopolymers or copolymers with α-olefins has generally used the so-called Ziegler-Natta catalyst system, which consists of a titanium or vanadium compound as the main catalyst component and an alkylaluminum compound as the cocatalyst component.

[0003] Although Ziegler-Natta catalyst systems exhibit high activity in ethylene polymerization, they have the disadvantage that the molecular weight distribution of the polymers produced is generally broad due to the heterogeneous catalytic active sites, and that the composition distribution is not uniform, particularly in copolymers of ethylene and α-olefins.

[0004] Recently, a so-called metallocene catalyst system has been developed, which consists of a metallocene compound of a transition metal in Group 4 of the periodic table, such as titanium, zirconium, or hafnium, and a co-catalyst, methylaluminoxane. The metallocene catalyst system is a homogeneous catalyst with a single type of catalytic active site, and is characterized by its ability to produce polyethylene with a narrower molecular weight distribution and more uniform composition distribution than the existing Ziegler-Natta catalyst system.

[0005] As a specific example, by activating metallocene compounds such as Cp2TiCl2, Cp2ZrCl2, Cp2ZrMeCl, Cp2ZrMe2, and ethylene (IndH4)2ZrCl2 with the co-catalyst methylaluminoxane, it has become possible to polymerize ethylene with high activity and produce polyethylene with a narrow molecular weight distribution (Mw / Mn).

[0006] However, it is difficult to obtain high molecular weight polymers using metallocene catalysts. In particular, when applied to solution polymerization methods carried out at high temperatures of 100°C or higher, the polymerization activity drops sharply and the β-hydrogen elimination reaction predominates, making it unsuitable for producing high molecular weight polymers with high weight average molecular weight (Mw).

[0007] Meanwhile, it has been disclosed that a so-called geometrically constrained ANSA-type metallocene catalyst in which transition metals are linked in a ring shape can be used as a catalyst capable of producing polymers with high catalytic activity and high molecular weight in ethylene homopolymerization or copolymerization of ethylene and α-olefins under solution polymerization conditions of 100°C or higher. ANSA-type metallocene catalysts have significantly improved octene injection and high temperature activity compared to metallocene catalysts. Nevertheless, most of the conventionally known ANSA-type metallocene catalysts contain Cl functional groups or methyl groups, etc., and therefore have problems that must be improved before they can be used in solution processes.

[0008] The Cl functional group substituted on the catalyst can cause corrosion depending on the material of the process equipment, and in order to avoid the problem of corrosion caused by Cl, ANSA-type metallocene catalysts substituted with dimethyl have been researched, but this also has poor solubility, making it difficult to inject the catalyst into the polymerization process. Toluene and xylene can be used to dissolve these catalysts with low solubility, but when producing products that may come into contact with food, the use of aromatic solvents such as toluene and xylene is problematic.

[0009] Therefore, there is a strong demand for research into competitive catalysts that have properties such as excellent solubility, high temperature activity, reactivity with higher α-olefins, and the ability to produce polymers with high molecular weights. Summary of the Invention [Problem to be solved by the invention]

[0010] An object of the present invention is to provide a transition metal compound having a specific, controlled functional group introduced therein in order to alleviate the above problems, and a catalyst composition containing the same.

[0011] Another object of the present invention is to provide a process for producing an olefin polymer using the transition metal compound of the present invention as a catalyst. [Means for solving the problem]

[0012] The present invention provides a transition metal compound having significantly improved solubility in non-aromatic hydrocarbons, and the transition metal compound of the present invention is represented by the following chemical formula 1. [ka] [In the above Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C20 alkyl; R5 to R12 are each independently hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkylC6-C20 aryl, triC1-C20 alkylsilyl, or triC6-C20 arylsilyl; or R5 to R12 may be linked to adjacent substituents by C3-C12 alkylene or C3-C12 alkenylene with or without a condensed ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring; R13 and R14 are each independently a C6-C20 aryl; X is a conjugated or non-conjugated C4-C20 diene; The diene may be further substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkylC6-C20 aryl, C1-C20 alkoxy, C6-C20 aryloxy, triC1-C20 alkylsilyl, and triC6-C20 arylsilyl; The diene forms a π-complex with a central metal M.]

[0013] Preferably, in the formula 1 according to an embodiment of the present invention, M is a transition metal of group 4 of the periodic table, A is carbon or silicon, R1 to R4 are each independently hydrogen or C1-C10 alkyl, and R5 to R12 are each independently hydrogen, C1-C10 alkyl, C1-C10 alkoxy, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 arylC1-C10 alkyl, C1-C10 alkylC6-C10 aryl, triC1-C10 alkylsilyl, or triC6-C10 arylsilyl, or R5 to R12 are each independently C3-C12 alkylene or C3-C12 alkenylene with or without a condensed ring with an adjacent substituent. R13 and R14 are each independently a C6-C10 aryl; X is a conjugated or non-conjugated C4-C10 diene; the diene may be further substituted with one or more substituents selected from the group consisting of C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 arylC1-C10 alkyl, C1-C10 alkylC6-C10 aryl, C1-C10 alkoxy, C6-C10 aryloxy, triC1-C10 alkylsilyl, and triC6-C10 arylsilyl; and the diene forms a π-complex with the central metal M.

[0014] More preferably, in the formula 1 according to an embodiment of the present invention, M is Ti, Zr or Hf, A is carbon or silicon, R1 to R4 are each independently hydrogen or C1-C4 alkyl, R5 to R12 are each independently hydrogen, C1-C4 alkyl or C1-C4 alkoxy, R13 and R14 are each independently C6-C10 aryl, and X is a conjugated or non-conjugated C4-C7 diene, the diene being: It may be further substituted with one or more substituents selected from the group consisting of C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 arylC1-C10 alkyl, C1-C10 alkylC6-C10 aryl, C1-C10 alkoxy, C6-C10 aryloxy, triC1-C10 alkylsilyl, and triC6-C10 arylsilyl, and the diene forms a π-complex with the central metal M.

[0015] In one embodiment of the present invention, the transition metal compound may be represented by the following Formula 2: [ka] [In the above Chemical Formula 2, M is Ti, Zr or Hf; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C4 alkyl; R13 and R14 are each independently a C6-C10 aryl; X is [ka] R21 to R27 are each independently hydrogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 arylC1-C10 alkyl, C1-C10 alkylC6-C10 aryl, C1-C10 alkoxy, C6-C10 aryloxy, triC1-C10 alkylsilyl, or triC6-C10 arylsilyl; m is an integer from 1 to 3; The X forms a π-complex with the central metal M.]

[0016] Specifically, in one embodiment of the present invention, the transition metal compound may be selected from the following compounds: [ka]

[0017] The transition metal compound according to one embodiment of the present invention may have a solubility in methylcyclohexane at 25° C. of 5% by weight or more.

[0018] The present invention also provides a transition metal catalyst composition for producing an ethylene homopolymer or an ethylene and an α-olefin copolymer, comprising the transition metal compound of the present invention. The transition metal catalyst composition of the present invention comprises a transition metal compound represented by the following Chemical Formula 1 and a cocatalyst: [ka] [In the above Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C20 alkyl; R5 to R12 are each independently hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkylC6-C20 aryl, triC1-C20 alkylsilyl, or triC6-C20 arylsilyl; or R5 to R12 may be linked to adjacent substituents by C3-C12 alkylene or C3-C12 alkenylene with or without a condensed ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring; R13 and R14 are each independently a C6-C20 aryl; X is a conjugated or non-conjugated C4-C20 diene; The diene may be further substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkylC6-C20 aryl, C1-C20 alkoxy, C6-C20 aryloxy, triC1-C20 alkylsilyl, and triC6-C20 arylsilyl; The diene forms a π-complex with a central metal M.]

[0019] The cocatalyst included in the transition metal catalyst composition may be an aluminum compound cocatalyst, a boron compound cocatalyst, or a mixture thereof.

[0020] The present invention also provides a process for producing an olefin polymer using the transition metal compound of the present invention.

[0021] The method for producing the olefin polymer includes a step of solution polymerizing one or more monomers selected from ethylene and an α-olefin in the presence of a transition metal compound represented by Chemical Formula 1, a cocatalyst, and a non-aromatic hydrocarbon solvent to obtain an olefin polymer.

[0022] The non-aromatic hydrocarbon solvent may be one or more selected from methylcyclohexane, cyclohexane, n-heptane, n-hexane, n-butane, isobutane, n-pentane, n-octane, isooctane, nonane, decane, and dodecane, and the solubility of the transition metal compound according to one embodiment of the present invention in the non-aromatic hydrocarbon solvent may be 5% by weight or more at 25° C.

[0023] Preferably, in the method for producing an olefin polymer according to one embodiment of the present invention, the cocatalyst may be an aluminum compound cocatalyst, a boron compound cocatalyst, or a mixture thereof. Specifically, the boron compound cocatalyst may be one or a mixture of two or more compounds selected from the compounds represented by the following chemical formulas 11 to 14, and the aluminum compound cocatalyst may be one or a mixture of two or more compounds selected from the compounds represented by the following chemical formulas 15 to 19. [ka] [ka] [ka] [ka] [In the above chemical formulas 11 to 14, B is a boron atom; R31 is phenyl, and the phenyl may be further substituted by 3 to 5 substituents selected from a fluorine atom, a C1-C20 alkyl, a C1-C20 alkyl substituted with a fluorine atom, a C1-C20 alkoxy, and a C1-C20 alkoxy substituted with a fluorine atom; R32 is a C5-C7 aromatic radical, a C1-C20 alkyl C6-C20 aryl radical or a C6-C20 aryl C1-C20 alkyl radical; Z is a nitrogen or phosphorus atom; R33 is a C1-C20 alkyl radical or an anilinium radical substituted with two C1-C10 alkyls along with the nitrogen atom; R34 is a C5-C20 alkyl; R35 is C5-C20 aryl or C1-C20 alkyl C6-C20 aryl; p is an integer of 2 or 3.

[0024] [ka] [ka] [ka] [ka] [ka] [In the above chemical formulas 15 to 19, R41 and R42 are each independently a C1-C20 alkyl group; r and s are each independently an integer from 5 to 20; R43 and R44 are each independently C1-C20 alkyl; E is hydrogen or halogen; t is an integer from 1 to 3; R45 is C1-C20 alkyl or C6-C30 aryl.

[0025] Preferably, in the production of an olefin polymer according to one embodiment of the present invention, the solution polymerization may be carried out at 100 to 220°C. Effect of the Invention

[0026] By introducing a controlled specific functional group into the transition metal compound of the present invention, the solubility in non-aromatic hydrocarbon solvents is significantly improved, the catalytic activity is high, and the catalytic activity can be maintained without being decreased during solution polymerization.

[0027] In addition, the transition metal compound of the present invention has a specific functional group introduced at a specific position, which makes it easy to inject and move the transition metal compound during solution processing, thereby significantly improving the polymerization process and being very advantageous for commercialization.

[0028] In addition, since the transition metal compound of the present invention has excellent solubility in non-aromatic hydrocarbon solvents and excellent reactivity with olefins, the polymerization of olefins is very easy and the yield of olefin polymers is high. Therefore, the catalyst composition containing the transition metal compound according to one embodiment of the present invention can be industrially and very effectively used in the production of olefin polymers having excellent physical properties.

[0029] The process for producing an olefin polymer of the present invention uses as a catalyst the transition metal compound of the present invention, which has excellent solubility in non-aromatic hydrocarbon solvents, making it easy to transport, inject, etc. the catalyst, and thus enabling the production of an olefin polymer more efficiently and environmentally friendly. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] The transition metal compound of the present invention, the catalyst composition containing the same, and the process for producing an olefin polymer using the same will be described in detail below.

[0031] As used herein, the singular forms "a," "an," and "the" can be intended to include the plural forms as well, unless the context indicates otherwise.

[0032] As used herein, "comprising" is an open-ended term having the same meaning as terms such as "comprising," "containing," "having," or "characterized by," and does not exclude further unrecited elements, materials, or steps.

[0033] As used herein, the terms "substituent," "radical," "group," "moiety," and "fragment" may be used interchangeably.

[0034] As used herein, the term "CA-CB" means "having a carbon number of A or more and B or less."

[0035] The term "alkyl" as used herein means a saturated linear or branched acyclic hydrocarbon having 1 to 20 carbon atoms, unless the number of carbon atoms is specifically limited. Representative saturated linear alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl, while saturated branched alkyls include isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, Includes 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethylpentyl, 2,2-dimethylhexyl, 3,3-dimethylpentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-decylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-diethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.

[0036] As used herein, "alkenyl" refers to a saturated, straight-chain or branched, non-cyclic hydrocarbon containing 2 to 10, preferably 2 to 10, carbon atoms, preferably 2 to 5 carbon atoms, and at least one carbon-carbon double bond. Representative straight chain and branched C2-C10 alkenyls include vinyl, allyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3 octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-disenyl, 2-disenyl, and 3-disenyl. Alkenyl includes radicals having cis and trans orientations, or alternatively, E and Z orientations.

[0037] As used herein, "alkoxy" means -O-alkyl, including -OCH, -OCHCH, -O(CH)CH, -O(CH)CH, -O(CH)CH, -O(CH)CH, -O(CH)CH, and the like, where alkyl is defined above.

[0038] As used herein, "alkylene" and "alkenylene" mean a divalent organic radical derived by removal of one hydrogen from an "alkyl" and "alkenyl", respectively, and follow the definitions of alkyl and alkenyl, respectively, above.

[0039] The term "cycloalkyl" as used herein means a monocyclic or polycyclic saturated ring having carbon and hydrogen atoms and no carbon-carbon multiple bonds. Examples of cycloalkyl groups are C3-C10 cycloalkyl, including, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. In one embodiment, the cycloalkyl group is a monocyclic or bicyclic ring.

[0040] As used herein, "aryl" refers to an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes single or fused ring systems, each ring suitably containing 4 to 7, preferably 5 or 6, ring atoms, including multiple aryls linked by a single bond. The fused ring system may include an aliphatic ring, such as a saturated or partially saturated ring, and must include at least one aromatic ring. The aliphatic ring may also include nitrogen, oxygen, sulfur, carbonyl, etc., within the ring. Specific examples of the aryl radical include, but are not limited to, phenyl, naphthyl, biphenyl, indenyl, fluorenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, krysenyl, naphthacenyl, 9,10-dihydroanthracenyl, etc.

[0041] The term "alkylaryl" as used herein means an aryl radical substituted with at least one alkyl, where "alkyl" and "aryl" are as defined above. Specific examples of the alkylaryl include, but are not limited to, tolyl, etc.

[0042] The term "arylalkyl" as used herein means an alkyl radical substituted with at least one aryl, where "alkyl" and "aryl" are as defined above. Specific examples of the arylalkyl include, but are not limited to, benzyl.

[0043] By "aryloxy" herein is meant an --O-aryl radical, where "aryl" is as previously defined.

[0044] Specific examples of "alkylsilyl" and "arylsilyl" used herein include, but are not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like.

[0045] As used herein, the term "diene" refers to a compound having two carbon-carbon double bonds and may be a compound selected from s-trans-1,3-butadiene, s-cis-1,3-butadiene, 2,4-pentadiene, cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, and bicyclo[2.2.1]hepta-1,3-diene, or a derivative thereof.For example, s-trans-n4-1,4-diphenyl-1,3-butadiene, s-trans-n4-3-methyl-1,3-pentadiene, s-trans-n4-1,4-dibenzyl-1,3-butadiene, s-trans-n4-1,3-pentadiene, s-trans-n4-2,4-hexadiene, s-trans-n4-1,4-ditolyl-1,3-butadiene, s-trans-n4-1,4-bis(trimethylsilyl)-1,3-butadiene ne), s-cis-n4-1,4-diphenyl-1,3-butadiene, s-cis-n4-3-methyl-1,3-pentadiene, s-cis-n4-1,4-dibenzyl-1,3-butadiene, s-cis-n4-1,3-pentadiene The aryl group may be, but is not limited to, s-cis-N4-2,4-hexadiene, s-cis-N4-1,4-ditolyl-1,3-butadiene, or s-cis-N4-1,4-bis(trimethylsilyl)-1,3-butadiene.

[0046] The term "olefin polymer" as used herein means a polymer prepared using an olefin within the range that can be recognized by those skilled in the art, specifically including all olefin homopolymers or copolymers of olefins, and meaning an olefin homopolymer or a copolymer of an olefin and an α-olefin.

[0047] The present invention provides a transition metal compound represented by the following chemical formula 1, which can be very effectively used in olefin polymerization because of its improved solubility and excellent thermal stability due to the introduction of a conjugated or non-conjugated diene functional group:

[0048] [ka]

[0049] [In the above Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C20 alkyl; R5 to R12 are each independently hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkylC6-C20 aryl, triC1-C20 alkylsilyl, or triC6-C20 arylsilyl; or R5 to R12 may be linked to adjacent substituents by C3-C12 alkylene or C3-C12 alkenylene with or without a condensed ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring; R13 and R14 are each independently a C6-C20 aryl; X is a conjugated or non-conjugated C4-C20 diene; The diene may be further substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkylC6-C20 aryl, C1-C20 alkoxy, C6-C20 aryloxy, triC1-C20 alkylsilyl, and triC6-C20 arylsilyl; The diene forms a π-complex with a central metal M.]

[0050] The transition metal compound according to one embodiment of the present invention is represented by Chemical Formula 1. In Chemical Formula 1, by introducing a conjugated or non-conjugated diene having 4 to 20 carbon atoms as X, the solubility in non-aromatic hydrocarbon solvents is significantly improved, the catalytic activity is very high, and an environmentally friendly olefin polymer can be produced through a simple process.

[0051] Specifically, the transition metal compound of the present invention, which is the ANSA-type catalyst of the present invention, has a diene functional group introduced at a specific position, thereby increasing the solubility in non-aromatic hydrocarbon solvents, maintaining catalytic activity, and enabling the easy production of olefin polymers in a solution process.

[0052] Preferably, in the formula 1 according to an embodiment of the present invention, M is a transition metal of group 4 of the periodic table, A is carbon or silicon, R1 to R4 are each independently hydrogen or C1-C10 alkyl, and R5 to R12 are each independently hydrogen, C1-C10 alkyl, C1-C10 alkoxy, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 arylC1-C10 alkyl, C1-C10 alkylC6-C10 aryl, triC1-C10 alkylsilyl, or triC6-C10 arylsilyl, or R5 to R12 are each independently C3-C12 alkylene or C3-C12 alkenylene with or without a condensed ring with an adjacent substituent. R13 and R14 are each independently a C6-C10 aryl; X is a conjugated or non-conjugated C4-C10 diene; the diene may be further substituted with one or more substituents selected from the group consisting of C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 arylC1-C10 alkyl, C1-C10 alkylC6-C10 aryl, C1-C10 alkoxy, C6-C10 aryloxy, triC1-C10 alkylsilyl, and triC6-C10 arylsilyl; and the diene forms a π-complex with the central metal M.

[0053] More preferably, in the formula 1 according to an embodiment of the present invention, M is Ti, Zr or Hf, A is carbon or silicon, R1 to R4 are each independently hydrogen or C1-C4 alkyl, R5 to R12 are each independently hydrogen, C1-C4 alkyl or C1-C4 alkoxy, R13 and R14 are each independently C6-C10 aryl, and X is a conjugated or non-conjugated C4-C7 diene, the diene being: It may be further substituted with one or more substituents selected from the group consisting of C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 arylC1-C10 alkyl, C1-C10 alkylC6-C10 aryl, C1-C10 alkoxy, C6-C10 aryloxy, triC1-C10 alkylsilyl, and triC6-C10 arylsilyl, and the diene forms a π-complex with the central metal M.

[0054] In one embodiment of the present invention, the transition metal compound may be represented by the following Formula 2:

[0055] [ka]

[0056] [In the above Chemical Formula 2, M is Ti, Zr or Hf; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C4 alkyl; R13 and R14 are each independently a C6-C10 aryl; X is [ka] and R21 to R27 are each independently hydrogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 arylC1-C10 alkyl, C1-C10 alkylC6-C10 aryl, C1-C10 alkoxy, C6-C10 aryloxy, triC1-C10 alkylsilyl, or triC6-C10 arylsilyl; m is an integer from 1 to 3; The X forms a π-complex with the central metal M.]

[0057] Specifically, in one embodiment of the present invention, the transition metal compound may be selected from the following compounds:

[0058] [ka]

[0059] The transition metal compound according to one embodiment of the present invention may have a solubility in methylcyclohexane at 25° C. of 5% by weight or more, preferably 5.5 to 50% by weight.

[0060] The present invention also provides a transition metal catalyst composition for producing an ethylene homopolymer or an ethylene and an α-olefin copolymer, comprising the transition metal compound of the present invention. The transition metal catalyst composition of the present invention comprises a transition metal compound represented by the following Chemical Formula 1 and a cocatalyst:

[0061] [ka]

[0062] [In the above Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C20 alkyl; R5 to R12 are each independently hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkylC6-C20 aryl, triC1-C20 alkylsilyl, or triC6-C20 arylsilyl; or R5 to R12 may be linked to adjacent substituents by C3-C12 alkylene or C3-C12 alkenylene with or without a condensed ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring; R13 and R14 are each independently a C6-C20 aryl; X is a conjugated or non-conjugated C4-C20 diene; The diene may be further substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkylC6-C20 aryl, C1-C20 alkoxy, C6-C20 aryloxy, triC1-C20 alkylsilyl, and triC6-C20 arylsilyl; The diene forms a π-complex with a central metal M.]

[0063] The cocatalyst included in the transition metal catalyst composition may be an aluminum compound cocatalyst, a boron compound cocatalyst, or a mixture thereof.

[0064] The present invention also provides a process for producing an olefin polymer using the transition metal compound of the present invention.

[0065] The method for producing the olefin polymer includes a step of solution polymerizing one or more monomers selected from ethylene and an α-olefin in the presence of a transition metal compound represented by Chemical Formula 1, a cocatalyst, and a non-aromatic hydrocarbon solvent to obtain an olefin polymer.

[0066] The non-aromatic hydrocarbon solvent may be one or more selected from methylcyclohexane, cyclohexane, n-heptane, n-hexane, n-butane, isobutane, n-pentane, n-octane, isooctane, nonane, decane, and dodecane, and the solubility of the transition metal compound according to one embodiment of the present invention in the non-aromatic hydrocarbon solvent at 25° C. may be 5% by weight or more, preferably 5.5 to 50% by weight.

[0067] Preferably, in the method for producing an olefin polymer according to one embodiment of the present invention, the cocatalyst may be an aluminum compound cocatalyst, a boron compound cocatalyst, or a mixture thereof, and the molar ratio of the transition metal compound:cocatalyst may be 1:0.5-10,000.

[0068] Specifically, the boron compound promoter may be one or a mixture of two or more compounds selected from the compounds represented by the following chemical formulas 11 to 14. [ka] [ka] [ka] [ka] [In the above chemical formulas 11 to 14, B is a boron atom; R31 is phenyl, and the phenyl may be further substituted by 3 to 5 substituents selected from a fluorine atom, a C1-C20 alkyl, a C1-C20 alkyl substituted with a fluorine atom, a C1-C20 alkoxy, and a C1-C20 alkoxy substituted with a fluorine atom; R32 is a C5-C7 aromatic radical, a C1-C20 alkyl C6-C20 aryl radical or a C6-C20 aryl C1-C20 alkyl radical, such as a triphenylmethylium radical; Z is a nitrogen or phosphorus atom; R33 is a C1-C20 alkyl radical or an anilinium radical substituted with two C1-C10 alkyls along with the nitrogen atom; R34 is a C5-C20 alkyl; R35 is C5-C20 aryl or C1-C20 alkyl C6-C20 aryl; p is an integer of 2 or 3.

[0069] The boron compound promoter may be, for example, one or more selected from tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, bis(pentafluorophenyl)(phenyl)borane, and the like.

[0070] The boron compound cocatalyst may be one or more boron compounds having a borate anion selected from tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(2,2,4-trifluorophenyl)borate, tris(pentafluorophenyl)(phenyl)borate, and tetrakis(3,5-bistrifluoromethylphenyl)borate.

[0071] The boron compound cocatalyst may be one or more boron compounds having a cation selected from triphenylmethylium, triethylammonium, tripropylammonium, tri(n-butyl)ammonium, N,N-dimethylanilinium, N,N-diethylanilinium, N,N-2,4,6-pentamethylanilinium, diisopropylammonium, dicyclohexylammonium, triphenylphosphonium, tri(methylphenyl)phosphonium, and tri(dimethylphenyl)phosphonium.

[0072] Specifically, the boron compound promoter may be one or more boron compounds having a cation selected from triphenylmethylium, triethylammonium, tripropylammonium, tri(n-butyl)ammonium, N,N-dimethylanilinium, N,N-diethylanilinium, N,N-2,4,6-pentamethylanilinium, diisopropylammonium, dicyclohexylammonium, triphenylphosphonium, tri(methylphenyl)phosphonium, and tri(dimethylphenyl)phosphonium, and having a cation selected from tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(2,2,4-trifluorophenyl)borate, tris(pentafluorophenyl)(phenyl)borate, and tetrakis(3,5-bistrifluoromethylphenyl)borate.

[0073] More specifically, the boron compound promoter is selected from the group consisting of triphenylmethylinium tetrakis(pentafluorophenyl)borate, triphenylmethylinium tetrakis(3,5-bistrifluoromethylphenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate. The fluorine atom may be one or more selected from the group consisting of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0074] Specifically, the aluminum compound cocatalyst may be one or a mixture of two or more selected from the following aluminoxane compounds represented by Chemical Formula 15 or 16, organoaluminum compounds represented by Chemical Formula 17, or organoaluminum alkyloxides or organoaluminum aryloxide compounds represented by Chemical Formula 18 or 19. [ka] [ka] [ka] [ka] [ka] [In the above chemical formulas 15 to 19, R41 and R42 are each independently a C1-C20 alkyl group; r and s are each independently an integer from 5 to 20; R43 and R44 are each independently C1-C20 alkyl; E is hydrogen or halogen; t is an integer from 1 to 3; R45 is C1-C20 alkyl or C6-C30 aryl.

[0075] Examples of the aluminoxane compounds include methylaluminoxane, modified methylaluminoxane, and tetraisobutylaluminoxane. Examples of the organoaluminum compounds include trialkylaluminums, including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum; dialkylaluminum chlorides, including dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, and dihexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum chloride, and dialkylaluminum chlorides, including dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, and dihexylaluminum chloride; Examples of the aluminum dichlorides include alkyl aluminum dichlorides, such as butyl aluminum dichloride and hexyl aluminum dichloride; dialkyl aluminum hydrides, such as dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride and dihexyl aluminum hydride; and alkyl alkoxy aluminum, such as methyl dimethoxy aluminum, dimethyl methoxy aluminum, ethyl diethoxy aluminum, diethyl ethoxy aluminum, isobutyl dibutoxy aluminum, diisobutyl butoxy aluminum, hexyl dimethoxy aluminum, dihexyl methoxy aluminum and dioctyl methoxy aluminum.

[0076] Preferably, it may be methylaluminoxane, modified methylaluminoxane, tetraisobutylaluminoxane, trialkylaluminum, triethylaluminum, triisobutylaluminum or a mixture thereof, more preferably, it may be methylaluminoxane, modified methylaluminoxane or trialkylaluminum, in particular, triethylaluminum and triisobutylaluminum.

[0077] In the catalyst composition according to one embodiment of the present invention, when the aluminum compound is used as a co-catalyst, the ratio of the transition metal compound of the present invention to the co-catalyst may be preferably in the range of 1:10 to 1,000, specifically 1:25 to 500, in terms of the molar ratio of transition metal (M):aluminum atom (Al).

[0078] In the catalyst composition according to one embodiment of the present invention, when the aluminum compound and the boron compound are used simultaneously as co-catalysts, the preferred range of the ratio of the transition metal compound of the present invention to the co-catalyst may be, based on the molar ratio, 1:0.1 to 100:10 to 1,000, specifically 1:0.5 to 5:25 to 500. When the ratio of the transition metal compound of the present invention to the co-catalyst is within the above range, excellent catalytic activity for producing an olefin polymer is exhibited, and the range of the ratio changes depending on the purity of the reaction.

[0079] In yet another aspect according to an embodiment of the present invention, the method for preparing an olefin polymer using the transition metal compound may be carried out by contacting the transition metal compound, a cocatalyst, and ethylene or, if necessary, a vinyl comonomer in the presence of a non-aromatic hydrocarbon solvent. Here, the transition metal compound and the cocatalyst components may be separately charged into a reactor, or each component may be premixed and charged into the reactor, and the mixing conditions such as the charging order, temperature, or concentration are not particularly limited.

[0080] A preferred organic solvent that can be used in the production method may be a non-aromatic hydrocarbon solvent, and specifically, a non-aromatic hydrocarbon having 3 to 20 carbon atoms, such as butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, and methylcyclohexane.

[0081] Specifically, when a copolymer of ethylene and an α-olefin is produced, an α-olefin having 3 to 18 carbon atoms can be used as a comonomer together with ethylene, and preferably, one or more selected from propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 1-octadecene. More specifically, 1-butene, 1-hexene, 1-octene, or 1-decene may be copolymerized with ethylene, and the preferred ethylene pressure may be 1 to 1,000 atm, and more preferably 10 to 150 atm.

[0082] In the production of an olefin polymer according to one embodiment of the present invention, the solution polymerization may be carried out at 100 to 220°C, preferably 100 to 200°C, and more preferably 100 to 150°C.

[0083] The copolymer produced according to the method of the present invention may contain 50 to 99% by weight of ethylene, and specifically, may contain 60 to 99% by weight of ethylene.

[0084] In the method for producing an olefin polymer according to one embodiment of the present invention, linear low density polyethylene (LLDPE) produced using an α-olefin having 4 to 10 carbon atoms as a comonomer has a density range of 0.940 g / cc or less, and can be extended to very low density polyethylene (VLDPE, ULDPE, or olefin elastomer) having a density range of 0.900 g / cc or less. In addition, hydrogen may be used as a molecular weight regulator to control the molecular weight during the production of the ethylene copolymer according to the present invention, and the produced copolymer has a weight average molecular weight (Mw) of 80,000 to 500,000 g / mol.

[0085] As a specific example of the olefin-diene copolymer produced by the catalyst composition according to one embodiment of the present invention, an ethylene-propylene-diene copolymer having an ethylene content of 30 to 80% by weight, a propylene content of 20 to 70% by weight, and a diene content of 0 to 15% by weight may be produced. The diene monomers usable in the present invention are those having two or more double bonds, and include 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,7-nonadiene, 1,8-nonadiene, 1,8-decadiene, 1,9-decadiene, 1,12-tetradecadiene, 1,13-tetradecadiene, 3-methyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3-ethyl- 1,4-hexadiene, 3-ethyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene, 5-vinyl-2-norbornene, 2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5-norbornadiene, 7-propyl-2,5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-phenyl-2,5-norbornadiene, 7-hexyl-2,5-norbornadiene , 7,7-dimethyl-2,5-norbornadiene, 7-methyl-7-ethyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene, 7-bromo-2,5-norbornadiene, 7-fluoro-2,5-norbornadiene, 7,7-dichloro-2,5-norbornadiene, 1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene, 1-propyl-2,5-norbornadiene, 1-butyl-2,5-norbornadiene, 1-chloro -2,5-norbornadiene, 1-bromo-2,5-norbornadiene, 5-isopropyl-2-norbornene, 1,4-cyclohexadiene, bicyclo[2,2,1]hepta-2,5-diene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, bicyclo[2,2,2]octa-2,5-diene, 4-vinyl-1-cyclohexene, bicyclo[2,2,2]octa-2,6-diene, 1,7,7-trimethylbicyclo[2,2,1]hepta-2,The diene monomer may be one or more selected from 5-diene, dicyclopentadiene, phenyltetrahydroindene, 5-phenylbicyclo[2,2,1]hept-2-ene, 1,5-cyclooctadiene, 1,4-diphenylbenzene, butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-butadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene and 3-ethyl-1,3-pentadiene, and preferably 5-ethylidene-2-norbornene, dicyclopentadiene or a mixture thereof. The diene monomer may be selected according to the processing characteristics of the ethylene-propylene-diene copolymer.

[0086] The ethylene-olefin-diene copolymer produced according to one embodiment of the present invention may have an ethylene content of 30 to 80 wt %, an olefin content of 20 to 70 wt %, and a diene content of 0 to 15 wt %, based on the total weight.

[0087] Generally, when producing an ethylene-propylene-diene copolymer, the molecular weight of the copolymer decreases as the propylene content increases. However, in the case of producing an ethylene-propylene-diene copolymer according to one embodiment of the present invention, even if the propylene content is increased to 50% by weight, the molecular weight does not decrease and a product with a relatively high molecular weight can be produced.

[0088] The catalyst composition proposed in the present invention is present in a homogeneous form in the polymerization reactor, and is therefore preferably applied to a solution polymerization process carried out at a temperature equal to or higher than the melting point of the polymer, but may also be used in a slurry polymerization or gas phase polymerization process in the form of a heterogeneous catalyst composition obtained by supporting the transition metal compound and the cocatalyst on a porous metal oxide support, as disclosed in U.S. Patent No. 4,752,597.

[0089] Hereinafter, the novel transition metal compound, the catalyst composition containing the same, and the process for producing an olefin polymer using the same according to the present invention will be described in more detail with reference to specific examples.

[0090] Unless otherwise stated, all synthetic experiments of transition metal compounds were carried out under nitrogen atmosphere using standard Schlenk or glove box techniques, and organic solvents used in reactions were refluxed under sodium metal and benzophenone to remove moisture and distilled immediately before use. 1H-NMR analysis of synthesized transition metal compounds was carried out at room temperature using a Bruker 400 or 500 MHz spectrometer.

[0091] The polymerization solvent, normal heptane, was passed through a tube filled with molecular sieves 5Å and activated alumina, and bubbled with high-purity nitrogen to thoroughly remove moisture, oxygen and other catalyst poisons before use. The polymerized polymer was analyzed by the methods described below.

[0092] 1. Melt flow index MI Measured according to ASTM D1238 analysis method at 190°C and a load of 2.16 kg.

[0093] 2. Density The measurement was performed according to the ASTM D792 analysis method.

[0094] 3. Molecular weight and molecular weight distribution The measurements were performed using a gel chromatography system consisting of a three-stage mixed column, with the solvent being 1,2,4-trichlorobenzene, and the measurement temperature being 120°C.

[0095] [Example 1] Synthesis of Compound 1 [ka]

[0096] In a nitrogen atmosphere, 9-fluorenyl-1-diphenylmethylcyclopentadienyl zirconium dichloride (S-PCI, 10.0 g, 18.0 mmol) was dissolved in 100 mL of toluene in a 250 mL round-bottom flask. After lowering the temperature to -15°C, 1,3-pentadiene (cis-, trans-mixture, 3.7 g, 54.0 mmol) and 1.6 M butyllithium (22.5 mL, 35.9 mmol) were gradually added, and the temperature was raised to room temperature and stirred for 5 hours. The solvent was removed under vacuum, and the concentrated solution was dissolved in 200 mL of methylcyclohexane, and then filtered through a filter filled with dried celite to remove solids. The solvent in the filtrate was completely removed to obtain red compound 1 (9.98 g, 95.0% yield). 1H NMR (500 MHz, Chloroform-d): δ = 8.23 ​​(d, 2H), 7.88 (dd, 4H), 7.45 (m, 4H), 7.31 (m, 4H), 7.01 (m, 2H), 6.42 (m, 4H), 5.64 (m, 2H), 4.01 (dd, J = 9.3, 7.3 Hz, 1H), 3.86 (ddd, J = 13.2, 9.3, 8.9 Hz, 1H), 2.98 (dd, J = 8.9, 8 Hz, 1H), 2.13 (m, 1H), 1.90 (d, J = 5.5 Hz, 3H), 1.76 (dd, J = 13.2, 7.3 Hz, 1H)

[0097] [Comparative Example 1] [ka]

[0098] This was purchased from S-PCI.

[0099] [Comparative Example 2] [ka]

[0100] In a nitrogen atmosphere, 9-fluorenyl-1-diphenylmethylcyclopentadienyl zirconium dichloride (S-PCI, 10.0 g, 18.0 mmol) was dissolved in 100 mL of toluene in a 250 mL round-bottom flask. After lowering the temperature to -15°C, 1.5 M methyllithium (24.0 mL, 35.9 mmol) was gradually added, and the temperature was raised to room temperature and stirred for 3 hours, after which the solid matter was removed by filtration through a filter filled with dried celite. After filtration, the solvent in the filtrate was completely removed to obtain a yellow compound of Comparative Example 2 (8.5 g, yield 91.4%). 1H NMR (500 MHz, Chloroform-d): δ = 8.20 (d, 2H), 7.85 (dd, 4H), 7.41 (m, 4H), 7.28 (m, 4H), 6.89 (m, 2H), 6.28 (m, 4H), 5.54 (m, 2H), -1.69 (s, 6H).

[0101] [Experimental Example 1] Measurement of solubility of prepared transition metal compounds At 25°C in a nitrogen atmosphere, 1 g of a transition metal compound was dissolved in 4 g of each of the solvents listed in Table 1 below to prepare a saturated solution, and the solid matter was removed using a 0.45 μm filter. After removing all the solvent, the weight of the remaining catalyst was measured, and the solubility of the catalyst was calculated and shown in Table 1 below.

[0102] [Table 1]

[0103] As shown in Table 1, the transition metal compound prepared in Example 1 of the present invention has a much higher solubility in hydrocarbon solvents than those prepared in Comparative Examples 1 and 2, and in particular, it shows surprisingly improved solubility in non-aromatic hydrocarbon solvents.

[0104] [Example 2] Copolymerization of ethylene and 1-octene by a continuous solution polymerization process Copolymerization of ethylene and 1-octene was carried out in a continuous polymerization reactor equipped with a mechanical stirrer and capable of controlling the temperature.

[0105] The transition metal compound of Example 1 was used as the catalyst in the amount shown in Table 2 below, normal heptane was used as the solvent, and modified methylaluminoxane (20 wt%, Nouryon) was used as the cocatalyst. The catalyst was dissolved in toluene at a concentration of 0.2 g / L and injected, and polymerization was carried out using 1-octene as the comonomer. The conversion rate of the reactor could be estimated from the reaction conditions and the temperature gradient in the reactor when polymerizing one polymer under each reaction condition. In the case of a single active site catalyst, the molecular weight was controlled as a function of the reactor temperature and the 1-octene content, and the polymerization conditions and results are shown in Table 2 below.

[0106] [Comparative Example 3] The procedure of Example 2 was repeated, except that the transition metal compound of Comparative Example 2 was used as the catalyst instead of the transition metal compound of Example 1.

[0107] [Table 2] -Zr: means Zr in the catalyst. -Al: refers to Al in the promoter modified methylaluminoxane (20 wt%, Nouryon).

[0108] As shown in Table 2, Example 2, in which the transition metal compound of the present invention was used as a catalyst, maintained excellent activity despite the reduced catalyst usage amount compared to Comparative Example 3, in which the transition metal compound of Comparative Example 2 was used. This shows that the catalytic activity is significantly improved compared to existing catalysts.

[0109] The transition metal compound according to one embodiment of the present invention significantly increases the solubility in non-aromatic hydrocarbon solvents by introducing a diene functional group at a specific position, and maintains and improves the activity of a catalyst that can produce a polymer with excellent physical properties despite a reduced amount of catalyst used. Also, olefin polymers can be easily produced in a solution process, and the use of this compound can bring about economic savings in industrial processes.

Claims

1. A transition metal compound represented by the following chemical formula 1. 【Chemistry 1】 [In the above Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C20 alkyl; R5 to R12 are each independently hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 aryl C1-C20 alkyl, C1-C20 alkyl C6-C20 aryl, tri-C1-C20 alkylsilyl, or tri-C6-C20 arylsilyl; R5 to R12 may be linked to adjacent substituents by C3-C12 alkylene or C3-C12 alkenylene with or without a condensed ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring; R13 and R14 are each independently a C6-C20 aryl; X is a conjugated or non-conjugated C4-C20 diene; The diene may be further substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 aryl C1-C20 alkyl, C1-C20 alkyl C6-C20 aryl, C1-C20 alkoxy, C6-C20 aryloxy, triC1-C20 alkylsilyl, and triC6-C20 arylsilyl; The diene forms a π-complex with the central metal M.]

2. M in the formula 1 is a transition metal of Group 4 of the periodic table; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C10 alkyl; R5 to R12 are each independently hydrogen, C1-C10 alkyl, C1-C10 alkoxy, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 aryl C1-C10 alkyl, C1-C10 alkyl C6-C10 aryl, tri-C1-C10 alkylsilyl, or tri-C6-C10 arylsilyl; R5 to R12 may be linked to adjacent substituents via C3-C12 alkylene or C3-C12 alkenylene with or without a condensed ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring; R13 and R14 are each independently a C6-C10 aryl; X is a conjugated or non-conjugated C4-C10 diene; The diene may be further substituted with one or more substituents selected from the group consisting of C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 aryl C1-C10 alkyl, C1-C10 alkyl C6-C10 aryl, C1-C10 alkoxy, C6-C10 aryloxy, triC1-C10 alkylsilyl, and triC6-C10 arylsilyl; 2. The transition metal compound according to claim 1, wherein the diene forms a π-complex with a central metal M.

3. M in Formula 1 is Ti, Zr or Hf; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C4 alkyl; R5 to R12 are each independently hydrogen, C1-C4 alkyl or C1-C4 alkoxy; R13 and R14 are each independently a C6-C10 aryl; X is a conjugated or non-conjugated C4-C7 diene; The diene may be further substituted with one or more substituents selected from the group consisting of C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 aryl C1-C10 alkyl, C1-C10 alkyl C6-C10 aryl, C1-C10 alkoxy, C6-C10 aryloxy, triC1-C10 alkylsilyl, and triC6-C10 arylsilyl; 2. The transition metal compound according to claim 1, wherein the diene forms a π-complex with a central metal M.

4. The transition metal compound according to claim 1 , wherein the transition metal compound is represented by the following chemical formula 2: 【Chemistry 2】 [In the above Chemical Formula 2, M is Ti, Zr or Hf; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C4 alkyl; R13 and R14 are each independently a C6-C10 aryl; X is 【Chemistry 3】 and R21 to R27 are each independently hydrogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C6-C10 aryl C1-C10 alkyl, C1-C10 alkyl C6-C10 aryl, C1-C10 alkoxy, C6-C10 aryloxy, triC1-C10 alkylsilyl, or triC6-C10 arylsilyl; m is an integer from 1 to 3; The X forms a π-complex with the central metal M.]

5. 2. The transition metal compound of claim 1, selected from the following compounds: 【Chemistry 4】

6. 2. The transition metal compound according to claim 1, which has a solubility in methylcyclohexane of 5% by weight or more at 25°C.

7. A transition metal compound represented by the following chemical formula 1, A transition metal catalyst composition for the production of ethylene homopolymers or copolymers of ethylene and an α-olefin, comprising a cocatalyst. 【Chemistry 5】 [In the above Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C20 alkyl; R5 to R12 are each independently hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 aryl C1-C20 alkyl, C1-C20 alkyl C6-C20 aryl, tri-C1-C20 alkylsilyl, or tri-C6-C20 arylsilyl; R5 to R12 may be linked to adjacent substituents by C3-C12 alkylene or C3-C12 alkenylene with or without a condensed ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring; R13 and R14 are each independently a C6-C20 aryl; X is a conjugated or non-conjugated C4-C20 diene; The diene may be further substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 aryl C1-C20 alkyl, C1-C20 alkyl C6-C20 aryl, C1-C20 alkoxy, C6-C20 aryloxy, triC1-C20 alkylsilyl, and triC6-C20 arylsilyl; The diene forms a π-complex with the central metal M.]

8. 8. The transition metal compound of claim 7, wherein the cocatalyst is an aluminum compound cocatalyst, a boron compound cocatalyst, or a mixture thereof.

9. A method for producing an olefin polymer, comprising the step of solution polymerizing one or more monomers selected from ethylene and an α-olefin in the presence of a transition metal compound represented by the following chemical formula 1, a cocatalyst, and a non-aromatic hydrocarbon solvent to obtain an olefin polymer: 【Chemistry 6】 [In the above Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; A is carbon or silicon; R1 to R4 are each independently hydrogen or C1-C20 alkyl; R5 to R12 are each independently hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 aryl C1-C20 alkyl, C1-C20 alkyl C6-C20 aryl, tri-C1-C20 alkylsilyl, or tri-C6-C20 arylsilyl; R5 to R12 may be linked to adjacent substituents by C3-C12 alkylene or C3-C12 alkenylene with or without a condensed ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring; R13 and R14 are each independently a C6-C20 aryl; X is a conjugated or non-conjugated C4-C20 diene; The diene may be further substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 aryl C1-C20 alkyl, C1-C20 alkyl C6-C20 aryl, C1-C20 alkoxy, C6-C20 aryloxy, triC1-C20 alkylsilyl, and triC6-C20 arylsilyl; The diene forms a π-complex with the central metal M.]

10. The method for producing an olefin polymer according to claim 9, wherein the non-aromatic hydrocarbon solvent is one or more selected from the group consisting of methylcyclohexane, cyclohexane, n-heptane, n-hexane, n-butane, isobutane, n-pentane, n-octane, isooctane, nonane, decane, and dodecane.

11. The process for producing an olefin polymer according to claim 9, wherein the solubility of the transition metal compound in the non-aromatic hydrocarbon solvent is 5% by weight or more at 25°C.

12. The method for producing an olefin polymer according to claim 9, wherein the cocatalyst is an aluminum compound cocatalyst, a boron compound cocatalyst, or a mixture thereof.

13. The method for producing an olefin polymer according to claim 12, wherein the boron compound cocatalyst is a compound represented by the following chemical formulas 11 to 14: 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 【Chemistry 10】 [In the above chemical formulas 11 to 14, B is a boron atom; R31 is phenyl, and the phenyl may be further substituted by 3 to 5 substituents selected from a fluorine atom, a C1-C20 alkyl, a C1-C20 alkyl substituted with a fluorine atom, a C1-C20 alkoxy, and a C1-C20 alkoxy substituted with a fluorine atom; R32 is a C5-C7 aromatic radical, a C1-C20 alkyl C6-C20 aryl radical or a C6-C20 aryl C1-C20 alkyl radical; Z is a nitrogen or phosphorus atom; R33 is a C1-C20 alkyl radical or an anilinium radical substituted with two C1-C10 alkyls along with the nitrogen atom; R34 is a C5-C20 alkyl; R35 is C5-C20 aryl or C1-C20 alkyl C6-C20 aryl; p is an integer of 2 or 3.

14. The method for producing an olefin polymer according to claim 12, wherein the aluminum compound cocatalyst is a compound represented by the following chemical formulas 15 to 19: 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 [In the above chemical formulas 15 to 19, R41 and R42 are each independently a C1-C20 alkyl group; r and s are each independently an integer from 5 to 20; R43 and R44 are each independently a C1-C20 alkyl group; E is hydrogen or halogen; t is an integer from 1 to 3, R45 is C1-C20 alkyl or C6-C30 aryl.

15. The method for producing an olefin polymer according to claim 9, wherein the solution polymerization is carried out at 100 to 220°C.

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