Ligand compounds, organochromium compounds and catalyst compositions containing them

Abstract

The present invention relates to a ligand compound having a novel structure, which exhibits high catalytic activity while also exhibiting high selectivity to 1-hexene and 1-octene, and is capable of carrying out ethylene oligomerization with excellent efficiency; an organochromium compound; a catalyst composition containing the organochromium compound; and a method for ethylene oligomerization using the same.

Description

[Technical field]

[0001] The present invention claims the benefit of priority based on Korean Patent Application No. 10-2022-0031621, filed on March 14, 2022, and all contents disclosed in the documents of the Korean patent application are incorporated as part of this specification.

[0002] The present invention relates to a ligand compound, an organochromium compound, a catalyst composition containing the organochromium compound, and an ethylene oligomerization process using the same. [Background technology]

[0003] Linear alpha-olefins such as 1-hexene and 1-octene are used in detergents, lubricants, plasticizers, etc., and are mainly used as comonomers to adjust the density of polymers in the production of linear low-density polyethylene (LLDPE).

[0004] In the conventional manufacturing process of LLDPE (Linear Low-Density Polyethylene), ethylene is copolymerized with a comonomer such as α-olefin, e.g., 1-hexene, 1-octene, to form branches in the polymer backbone and adjust the density.

[0005] Therefore, in order to produce LLDPE with a high comonomer content, the price of the comonomer accounts for a large part of the production cost. Various attempts have been made to solve this problem.

[0006] Such linear α-olefins have been mainly produced by the Shell Higher Olefin Process, but this process requires a separate separation process to obtain a specific α-olefin because α-olefins of various lengths are simultaneously synthesized according to the Schultz-Flory distribution.

[0007] In order to solve these problems, a method for selectively synthesizing 1-hexene through the trimerization of ethylene or 1-octene through the tetramerization of ethylene has been proposed, and much research has been conducted on catalyst systems that enable such selective oligomerization of ethylene. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Pat. No. 5,064,802 Summary of the Invention [Problem to be solved by the invention]

[0009] The problem to be solved by the present invention is to provide a ligand compound having a novel structure, an organochromium compound, and a catalyst composition containing the same, which exhibit high catalytic activity while showing high selectivity to 1-hexene and 1-octene, and are capable of carrying out ethylene oligomerization with excellent efficiency. [Means for solving the problem]

[0010] To achieve the above object, the present invention provides a ligand compound, an organochromium compound, a catalyst composition and an ethylene oligomerization method.

[0011] (1) The present invention provides a ligand compound represented by the following chemical formula 1:

[0012] [Chemical formula 1] [ka] In the above formula 1, R 1 ~R 4 are each independently a trialkylsilyl group, where the alkyl group is an alkyl group having 1 to 4 carbon atoms, and R 5 is a substituent represented by any one of the following chemical formulas 2 to 4: [Chemical formula 2] [ka] [Chemical formula 3] [ka] [Chemical formula 4] [ka] In the above Chemical Formulae 2 to 4, X1 to X6 each independently represent -(CR 6 R 7 ) n -, -O- or -S-, but not all at the same time -O- or -S-; n is 0 or an integer selected from 1 to 3; R 6 and R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a trifluoroalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or -NR 8 R 9 and R 8 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * represents the site of binding to N in Chemical Formula 1.

[0013] (2) The present invention relates to the above-mentioned (1), 1 ~R 4 each independently represents a tripropylsilyl group or a tributylsilyl group.

[0014] (3) The present invention relates to the above (1) or (2), 5is a substituent represented by any one of the above chemical formulas 2 to 4, and X1, X2 and X5 each independently represent -(CR 6 R 7 ) n -, and X3 and X4 are each independently -(CR 6 R 7 ) n - or -O-, and X3 and X4 are not -O- at the same time, 6 is -S- and R 6 and R 7 each independently represents a hydrogen atom, a trifluoroalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or -NR 8 R 9 and R 8 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0015] (4) The present invention relates to any one of the above (1) to (3), 5 is a substituent represented by the above-mentioned chemical formula 2, X1 and X5 are -CH2-, and X2 to X4 are each independently -(CR 6 R 7 ) n -, -O- or -S-, and not -O- or -S- at the same time, R 6 and R 7 each independently represents a hydrogen atom, a trifluoroalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or -NR 8 R 9 and R 8 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0016] (5) The present invention provides a ligand compound according to any one of the above (1) to (4), wherein the ligand compound represented by Chemical Formula 1 is one selected from the group consisting of ligand compounds represented by the following Chemical Formulas 2-1 to 2-14:

[0017] [Chemical formula 2-1]

change

[0018] [Chemical formula 2-2]

change

[0019] [Chemical formula 2-3]

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[0020] [Chemical formula 2-4]

change

[0021] [Chemical formula 2-5]

change

[0022] [Chemical formula 2-6]

change

[0023] [Chemical formula 2-7]

change

[0024] [Chemical formula 2-8]

change

[0025] [Chemical formula 2-9]

change

[0026] [Chemical formula 2-10] [ka]

[0027] [Chemical formula 2-11] [ka]

[0028] [Chemical formula 2-12] [ka]

[0029] [Chemical formula 2-13] [ka]

[0030] [Chemical formula 2-14] [ka]

[0031] (6) The present invention relates to any one of the above (1) to (3), 5 is a substituent represented by Chemical Formula 3, and X6 is -O- or -S-.

[0032] (7) In any one of the above (1) to (3) and (6), the present invention provides a ligand compound represented by Chemical Formula 1, which is a ligand compound represented by the following Chemical Formula 3-1 or 3-2:

[0033] [Chemical formula 3-1] [ka]

[0034] [Chemical formula 3-2] [ka]

[0035] (8) In any one of the above (1) to (3), the present invention provides a ligand compound represented by Chemical Formula 1, which is a ligand compound represented by the following Chemical Formula 4-1 or 4-2:

[0036] [Chemical formula 4-1] [ka]

[0037] [Chemical formula 4-2] [ka]

[0038] (9) The present invention provides a ligand compound according to any one of (1) to (8) above, and an organochromium compound containing chromium coordinated to the ligand compound.

[0039] (10) The present invention provides an organochromium compound according to (9), in which at least one unshared electron pair of N and two P in the ligand compound represented by Chemical Formula 1 is coordinated to chromium.

[0040] (11) The present invention relates to a catalyst composition comprising the ligand compound according to any one of (1) to (8) above, chromium, and a co-catalyst.

[0041] (12) The present invention provides a catalyst composition according to the above (11), wherein the chromium is derived from a chromium source, and the chromium source comprises one or more selected from the group consisting of chromium(III) acetylacetonate, chromium(III) chloride tetrahydrofuran, chromium(III) 2-ethylhexanoate, chromium(III) acetate, chromium(III) butyrate, chromium(III) pentanoate, chromium(III) laurate, chromium(III) tris(2,2,6,6-tetramethyl-3.5-heptanedionate), and chromium(III) stearate.

[0042] (13) The present invention provides a catalyst composition according to the above (11) or (12), wherein the co-catalyst is one or more selected from the group consisting of compounds represented by the following chemical formulas 5 to 8:

[0043] [Chemical formula 5] -[Al(R 10 )-O] a - In the above formula 5, R 10 each independently represents a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group substituted with a halogen group and having 1 to 20 carbon atoms, and a is an integer of 2 or greater, [Chemical formula 6] E(R 11 )3 In the above formula 6, E is aluminum or boron, and R 11 each independently represents a hydrogen atom, 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, [Chemical formula 7] [LH] + [G(Y)4] - [Chemical formula 8] [L] + [G(Y)4] - In the above formulas 7 and 8, L is a neutral or cationic Lewis acid, [LH] +is a Bronsted acid, G is a Group 13 element, and each Y is 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, where, when the alkyl group or the 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.

[0044] (14) The present invention provides a method for producing linear α-olefins, comprising a step (S10) of oligomerizing ethylene in the presence of the catalyst composition according to any one of (11) to (13) above.

[0045] (15) The present invention provides a method for producing a linear α-olefin according to the above (14), wherein the linear α-olefin is 1-hexene, 1-octene or a mixture thereof. Effect of the Invention

[0046] When ethylene oligomerization is carried out using the organochromium compound and catalyst composition containing the ligand compound of the present invention, linear α-olefins can be produced with high selectivity to 1-hexene and 1-octene while having excellent productivity due to high catalytic activity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0047] The present invention will now be described in further detail to aid in understanding the invention.

[0048] The terms and words used in the description of the present invention and the claims should not be interpreted in a limited manner to their general or dictionary meanings, but should be interpreted as meanings and concepts that are consistent with the technical idea of ​​the present invention, based on the principle that an inventor can appropriately define the concept of a term in order to best describe his / her invention.

[0049] Ligand Compound The present invention provides a ligand compound applicable to a catalyst used in an ethylene oligomerization reaction. When the ligand compound is applied to an ethylene oligomerization reaction, specifically, a catalyst composition for forming linear α-olefins, the ligand compound exhibits excellent catalytic activity and high selectivity to linear α-olefins, and in particular, produces less solid polyethylene under the same reaction conditions compared to conventional PNP-based catalysts, thereby enabling linear α-olefins to be produced more efficiently.

[0050] According to one embodiment of the present invention, the organochromium compound coordinated with the ligand compound can be used to produce linear α-olefins using ethylene, and an oligomerization reaction can proceed under ethylene conditions to produce liquid α-olefins, specifically, liquid 1-hexene or 1-octene, with high selectivity. This is because the selectivity for α-olefins of a specific length is increased through a transition state in which a metal-containing ring compound (metallacycle) is formed in the oligomerization reaction of ethylene.

[0051] According to one embodiment of the present invention, the ligand compound includes a diphosphinoaminyl moiety, and an aryl having a specific substituent is connected to the end of the diphosphinoaminyl moiety, so that it can have a form that can act as a strong electron donor group by itself. Due to such structural characteristics, the ligand compound can be applied to an ethylene oligomerization catalyst system and exhibit high activity, and in particular, can exhibit high selectivity for 1-hexene, 1-octene, etc. This can be considered to be due to the interaction between the adjacent chromium active sites, and in particular, when an aryl substituted with a specific substituent is connected to the phosphorus (P) atom of the diphosphinoaminyl, the electron density increases at the phosphorus (P) atom and nitrogen (N) atom contained in the diphosphinoaminyl, and the electronic and steric properties of the entire ligand compound change. This causes a change in the bond between the ligand and the chromium atom, making the catalyst structure more stable and changing the transition state energy (activation energy) compared to the conventional metallacycloheptane or metallacyclononane forms, making it possible to form α-olefins with higher activity and selectivity, and further reducing the amount of by-products such as solid α-olefins with high molecular weights, such as polyethylene wax (PE wax).

[0052] According to one embodiment of the present invention, the ligand compound is characterized in that the phenyl at the end of the diphosphinoaminyl residue has a silyl group substituted with an alkyl group having a specific carbon number at the para position as a substituent. The substituent at the para position of the phenyl prevents two molecules of the ligand compound from binding to the chromium atom to generate inactive species, and reduces the rotational possibility of the nitrogen-phosphorus bond to prevent the ligand compound from dissociating from the catalyst, thereby producing a chromium catalyst with high stability, activity, and selectivity.

[0053] According to one embodiment of the present invention, the ligand compound has a bulky substituent such as a cycloalkyl group or a phenyl group bound to a nitrogen atom to which two phosphorus atoms are bound, and the bulky substituent bound to the nitrogen can prevent the nitrogen-phosphorus bond from rotating, thereby further improving the stability and activity of the catalyst.

[0054] According to one embodiment of the present invention, the ligand compound has a silyl group substituted with an alkyl group having a specific carbon number at the para position of the phenyl at the end of the diphosphinoaminyl residue, and the steric and electrical properties of the substituent substituted on the nitrogen atom can particularly improve the catalytic activity, selectivity and stability. Specifically, in order to produce 1-hexene and 1-octene, the reaction must proceed through a metallacycle, and metallacycloheptane and metallacyclononane intermediates must be effectively formed. If a metallacycle is not formed and general ethylene polymerization proceeds, the selectivity is significantly reduced and a problem occurs in which the process cannot be carried out due to a process problem caused by polyethylene polymer. In addition, even when the reaction proceeds while forming a metallacycle, the reaction may proceed in the direction of forming a by-product having 6 carbon atoms, such as methylcyclopentane or methylenecyclopentene. In addition, 1-hexene and 1-octene are again involved in the trimerization and tetramerization of ethylene to produce complex compounds having 10 to 14 carbon atoms, which corresponds to a major by-product production reaction. In order to effectively reduce this, it is very important that the nitrogen atom of the ligand compound has an appropriate substituent. In this regard, according to the ligand compound of the present invention, the nitrogen atom of the ligand compound has R of formula 1. 5As a specific example, when a substituent represented by the formula (I) is introduced into a cycloalkyl group such as a cyclohexyl group, or a ring compound containing a heteroatom such as oxygen or sulfur is introduced as a substituent, it forms an appropriate steric hindrance to prevent the polymerization reaction to polyethylene or the reaction proceeding through the mechanism of by-product generation, and effectively induces a reaction through the metallacycle mechanism to ensure high selectivity for 1-hexene and 1-octene. In addition, when the ligand compound contains the substituent on the nitrogen atom, the activation energy of the reaction through the metallacycle mechanism can be reduced due to steric and electrical effects, and thus the reaction can occur more easily even under the same temperature and pressure conditions, improving the activity of the oligomerization reaction. Thus, the introduction of a new substituent into the ligand compound according to the present invention makes it possible to develop an oligomerization catalyst with significantly improved performance, greatly improving the level of commercialization, and ensuring better economic efficiency.

[0055] According to one embodiment of the present invention, the ligand compound may be represented by the following Chemical Formula 1:

[0056] [Chemical formula 1] [ka]

[0057] In the above formula 1, R 1 ~R 4 may each independently be a trialkylsilyl group, where the alkyl group may be an alkyl group having 1 to 4 carbon atoms; R 5 may be a substituent represented by any one of the following chemical formulas 2 to 4.

[0058] [Chemical formula 2] [ka]

[0059] [Chemical formula 3] [ka]

[0060] [Chemical formula 4] [ka]

[0061] In the above Chemical Formulas 2 to 4, X 1 ~X 6 are each independently -(CR 6 R 7 ) n n is 0 or an integer selected from 1 to 3; R 6 and R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a trifluoroalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or -NR 8 R 9 R may be 8 and R 9 may each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms, and * represents the site of binding to N in Chemical Formula 1.

[0062] In the present invention, the term "alkyl group" may mean a linear, cyclic or branched hydrocarbon residue, and specific examples thereof may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a hexyl group, etc., depending on the defined carbon number.

[0063] In the present invention, the term "trialkylsilyl group" refers to a substituent represented by -SiR3, in which each R is independently an alkyl group, and when referring to the number of carbon atoms in a trialkylsilyl group, it can refer to the total number of carbon atoms in R.

[0064] In the present invention, unless otherwise specified, "aryl" refers to an optionally substituted benzene ring or a ring system that may be formed by fusing one or more optional substituents. Exemplary optional substituents include substituted C1-2 alkyl groups, substituted C2-3 alkenyl groups, substituted C2-3 alkynyl groups, heteroaryl groups, heterocyclic groups, aryl groups, alkoxy, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonylamino, carboxamido, aminocarbonyl, carboxy, oxo, hydroxy, mercapto, amino, nitro, cyano, halogen, or ureido. Such rings or ring systems may be optionally fused to an aryl ring (e.g., a benzene ring), a carbocyclic ring, or a heterocyclic ring, which may optionally have one or more substituents. It can include, but is not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl, or phenanthryl, and substituted derivatives thereof.

[0065] According to one embodiment of the present invention, R 1 ~R 4 may each independently be a tripropylsilyl group or a tributylsilyl group. That is, the ligand compound may have, as a substituent, a silyl group in which the phenyl located at the terminal of the diphosphinoaminyl residue is substituted with an alkyl group having 3 or 4 carbon atoms at the para position.

[0066] According to one embodiment of the present invention, R 5 may be a substituent represented by any one of the above chemical formulas 2 to 4, and X1, X2 and X5 each independently represent -(CR 6 R 7 ) n -, X3 and X4 may each independently be -(CR 6 R 7 ) n - or -O-, and X3 and X4 may not be -O- at the same time, X6 may be -S-, R6 and R 7 each independently represents a hydrogen atom, a trifluoroalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or -NR 8 R 9 R may be 8 and R 9 may each independently be a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In addition, n may be 1 or 2, but may not all be 2 at the same time.

[0067] According to one embodiment of the present invention, the ligand compound is R 5 may be a substituent represented by the above-mentioned chemical formula 2, X1 and X5 may be -CH2-, and X2 to X4 each independently represent -(CR 6 R 7 ) n -, -O-, or -S-, and may not all be -O- or -S- at the same time; R 6 and R 7 each independently represents a hydrogen atom, a trifluoroalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or -NR 8 R 9 R may be 8 and R 9 may each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms. As a specific example, the ligand compound represented by Chemical Formula 1 may be one selected from the group consisting of ligand compounds represented by Chemical Formulas 2-1 to 2-14 below.

[0068] [Chemical formula 2-1] [ka]

[0069] [Chemical formula 2-2] [ka]

[0070] [Chemical formula 2-3] [ka]

[0071] [Chemical formula 2-4]

change

[0072] [Chemical formula 2-5]

change

[0073] [Chemical formula 2-6]

change

[0074] [Chemical formula 2-7]

change

[0075] [Chemical formula 2-8]

change

[0076] [Chemical formula 2-9]

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[0077] [Chemical formula 2-10]

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[0078] [Chemical formula 2-11]

change

[0079] [Chemical formula 2-12] [ka]

[0080] [Chemical formula 2-13] [ka]

[0081] [Chemical formula 2-14] [ka]

[0082] According to one embodiment of the present invention, the ligand compound is R 5 is a substituent represented by the above formula 3, and X 6 may be -O- or -S-. As a specific example, the ligand compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 3-1 or 3-2.

[0083] [Chemical formula 3-1] [ka]

[0084] [Chemical formula 3-2] [ka]

[0085] According to one embodiment of the present invention, the ligand compound may be represented by the following formula 4-1 or 4-2.

[0086] [Chemical formula 4-1] [ka]

[0087] [Chemical formula 4-2] [ka]

[0088] According to one embodiment of the present invention, the ligand compound may be realized in various combinations other than the above specific examples as long as the above conditions are satisfied, and any compound represented by Chemical Formula 1 can be applied as the ligand compound of the present invention.

[0089] Organochromium compounds and catalyst compositions The present invention provides a ligand compound represented by Chemical Formula 1 and an organochromium compound including chromium (Cr) coordinated to the ligand compound.

[0090] According to one embodiment of the present invention, the organochromium compound is a chromium complex compound of the ligand compound, and the chromium source chromium may have a form in which at least one of N and two P's unshared electron pairs form a coordinate bond in the ligand compound represented by Chemical Formula 1. That is, the phosphorus atom or nitrogen atom of the diphosphinoaminyl residue provides an unshared electron pair to the chromium atom, and it is preferable that two pairs of unshared electron pairs are coordinated to form a bidentate state. Such an organochromium compound may be applied to a catalyst system for ethylene oligomerization reaction, and may exhibit excellent catalytic activity and high selectivity for 1-hexene or 1-octene.

[0091] In the present invention, the term "catalyst composition" refers to a state in which three components including a chromium source, a ligand compound, and a cocatalyst, or two components including a transition metal compound and a cocatalyst are added simultaneously or in any order to obtain an active catalyst composition. Here, the catalyst composition may also be called a catalyst system, and in the present invention, the catalyst composition and the catalyst system have the same meaning. The three or two components of the catalyst composition may be added in the presence or absence of a solvent and a monomer, and may be used in a supported or unsupported state.

[0092] The present invention provides a catalyst composition comprising the ligand compound, chromium, and a cocatalyst. The ligand compound represented by Chemical Formula 1 and chromium can be coordinated to form an organochromium compound as described above. That is, the catalyst system can be a three-component catalyst system comprising chromium, the ligand compound represented by Chemical Formula 1, and a cocatalyst, or a two-component catalyst system comprising the organochromium compound and a cocatalyst. As a specific example, the catalyst composition may comprise the ligand compound, an organochromium compound comprising chromium coordinated to the ligand compound, and a cocatalyst. The catalyst composition may also comprise a chromium compound in which a part of a cocatalyst component is bound to the organochromium compound.

[0093] According to one embodiment of the present invention, the chromium may be derived from a chromium source, which may be an organic or inorganic chromium compound with chromium oxidation state of 0-6. As a specific example, the chromium source may be chromium metal or a compound with any organic or inorganic radical bonded to chromium. Here, the organic radical may be an alkyl, alkoxy, ester, ketone, amide, carboxylate radical, etc. with 1-20 carbon atoms per radical, and the inorganic radical may be a halide, sulfate, oxide, etc.

[0094] According to one embodiment of the present invention, the chromium source is a compound that exhibits high activity in olefin oligomerization and is easy to use and obtain, and may be one or more compounds selected from the group consisting of chromium(III) acetylacetonate, chromium(III) chloride tetrahydrofuran, chromium(III) 2-ethylhexanoate, chromium(III) acetate, chromium(III) butyrate, chromium(III) pentanoate, chromium(III) laurate, chromium(III) tris(2,2,6,6-tetramethyl-3.5-heptanedionate), and chromium(III) stearate.

[0095] According to one embodiment of the present invention, the co-catalyst may be at least one selected from the group consisting of compounds represented by the following chemical formulas 5 to 8.

[0096] [Chemical formula 5] -[Al(R 10 )-O] a -

[0097] In the above formula 5, R 10 each independently represents 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 of 2 or greater.

[0098] [Chemical formula 6] E(R 11 )3

[0099] In the above formula 6, E is aluminum or boron, and R 11 are each independently a hydrogen atom, 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.

[0100] [Chemical formula 7] [LH] + [G(Y)4] -

[0101] [Chemical formula 8] [L] + [G(Y)4] -

[0102] In the above formulas 7 and 8, L is a neutral or cationic Lewis acid, [LH] + is a Bronsted acid, G is a Group 13 element, and each Y is 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, where, when the alkyl group or the 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.

[0103] According to one embodiment of the present invention, the catalyst composition may be prepared by a plurality of methods. As a specific example, first, the catalyst composition may be prepared by contacting the organic chromium compound with the compound represented by the formula 5 or 6. Second, the catalyst composition may be prepared by contacting the organic chromium compound with the compound represented by the formula 5 or 6 to obtain a mixture, and adding the compound represented by the formula 7 or 8 to the mixture. Third, the catalyst composition may be prepared by contacting the organic chromium compound with the compound represented by the formula 7 or 8. Fourth, the catalyst composition may be prepared by contacting the organic chromium compound with the compound represented by the formula 7 or 8 to obtain a mixture, and adding the compound represented by the formula 5 or 6 to the mixture. Fifth, the catalyst composition may be prepared by contacting the chromium source with the compound represented by the formula 7 or 8 to obtain a reactant, and contacting the ligand compound with the reactant.

[0104] According to an embodiment of the present invention, in the first or third method of the preparation of the catalyst composition, the molar ratio of the compound represented by Formula 5 or Formula 6 to the organochromium compound may be 1:2 to 5,000, specifically 1:100 to 3,000, and more specifically 1:300 to 1,500. Within this range, the alkylation of the organochromium compound can be fully carried out, the activity of the catalyst composition can be improved, and the activity of the alkylated organochromium compound can be prevented from being reduced due to a side reaction between the remaining alkylating agent, while the economy and the purity of the produced linear α-olefin can be improved.

[0105] According to one embodiment of the present invention, in the second method of preparing the catalyst composition, the molar ratio of the compound represented by Formula 7 or Formula 8 to the organochromium compound may be 1:1 to 500, specifically 1:1 to 50, and more specifically 1:1 to 1:25. Within this range, the amount of activator is sufficient, and activation of the metal compound is complete, improving the activity of the catalyst composition, and minimizing the amount of residual activator, thereby improving economy and the purity of the produced linear α-olefin.

[0106] According to an embodiment of the present invention, the compound represented by Chemical Formula 5 may be an alkylaluminoxane, specific examples of which include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., and a more specific example of which is methylaluminoxane.

[0107] According to an embodiment of the present invention, the compound represented by Chemical Formula 6 may be trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, dialkylaluminum hydride, alkylaluminum dihydride, trialkylboron, etc. Specific examples of the compound represented by Chemical Formula 6 include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, and tri-p-tolylaluminum; dialkylaluminum halides such as diethylaluminum chloride;Diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl-n-butyl dialkylaluminum hydrides such as benzyl-n-octyl aluminum hydride, p-tolyl isobutyl aluminum hydride, p-tolyl-n-octyl aluminum hydride, benzyl ethyl aluminum hydride, benzyl-n-propyl aluminum hydride, benzyl isopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzyl isobutyl aluminum hydride, or benzyl-n-octyl aluminum hydride; alkylaluminum dihydrides such as n-propyl aluminum dihydride, isopropyl aluminum dihydride, n-butyl aluminum dihydride, isobutyl aluminum dihydride, or n-octyl aluminum dihydride; trialkylborons such as trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, or tributyl boron;

[0108] According to an embodiment of the present invention, the compound represented by Chemical Formula 7 or Chemical Formula 8 is selected from the group consisting of trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, triethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, tributylammonium tetra(p-tolyl)borate, N,N-dimethylanilinium tetra(p-tolyl)borate, N,N-diethylanilinium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate, tripropylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(o,p-dimethylphenyl)borate, N,N-dimethylanilinium tetra(o,p-dimethylphenyl)borate, -dimethylphenyl)borate, N,N-diethylanilinium tetra(o,p-dimethylphenyl)borate, trimethylammonium tetrakis(p-trifluoromethylphenyl)borate, triethylammonium tetrakis(p-trifluoromethylphenyl)borate, tripropylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakis(p-trifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(p-trifluoromethylphenyl)borate, N,N-diethylanilinium tetrakis(p-trifluoromethylphenyl)borate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dioctadecylanilinium tetrakis(pentafluorophenyl)borate, trimethylphosphonium tetraphenylborate, triethylphosphonium tetraphenylborate, tripropylphosphonium tetraphenylborate, tributylphosphonium tetraphenylborate, trimethylcarbonium tetraphenylborate, triethylcarbonium tetraphenylborate, tripropylcarbonium tetraphenylborate, tributylcarbonium tetraphenylborate, trimethylammonium tetraphenylaluminate, triethylammonium tetraphenylaluminate, tripropylammonium tetraphenylaluminate, tributylammonium tetraphenylaluminate, trimethylammonium tetra(p-tolyl)aluminate, triethylammonium tetra(p-tolyl)aluminate, tripropylammonium tetra(p-tolyl)aluminate, tributylammonium tetra(p-tolyl)aluminate, etc. may also be used.

[0109] According to an embodiment of the present invention, the content ratio of the components forming the catalyst composition may be determined in consideration of catalytic activity and selectivity for linear α-olefins. As a specific example, when the catalyst composition is a three-component catalyst composition, the molar ratio of the diphosphinoaminyl residue of the ligand compound:chromium source:cocatalyst may be adjusted to about 1:1:1 to about 10:1:10,000, or about 1:1:100 to 5:1:3,000. In addition, when the catalyst composition is a two-component catalyst composition, the molar ratio of the diphosphinoaminyl residue of the organochromium compound:cocatalyst may be adjusted to 1:1 to 1:10,000, or 1:1 to 1:5,000, or 1:1 to 1:3,000.

[0110] According to one embodiment of the present invention, when preparing the catalyst composition, a reaction solvent may be used, which may be a hydrocarbon solvent such as pentane, hexane, heptane, etc.; or an aromatic solvent such as benzene, toluene, etc.

[0111] According to one embodiment of the present invention, the components forming the catalyst composition can be added simultaneously or in any order in the presence or absence of a suitable solvent and monomer to act as an active catalyst composition, where suitable solvents may be heptane, toluene, cyclohexane, methylcyclohexane, 1-hexene, 1-octene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, etc.

[0112] According to an embodiment of the present invention, the organochromium compound and the co-catalyst may be used in a form supported on a carrier, and in this case, the carrier may be silica or alumina.

[0113] According to an embodiment of the present invention, the catalyst composition may further include a carrier. As a specific example, the ligand compound represented by Chemical Formula 1 may be applied to the ethylene oligomerization reaction in a form supported on a carrier. The carrier may be a metal, metal salt, or metal oxide applied to a supported catalyst, and as a specific example, the carrier may be silica, silica-alumina, silica-magnesia, etc., and may include metal oxide, carbonate, sulfate, and nitrate components such as Na2O, K2CO3, BaSO4, Mg(NO3)2, etc.

[0114] According to one embodiment of the present invention, the catalyst composition can be used for the trimerization or tetramerization reaction of ethylene, and by doing as described above, 1-hexene or 1-octene can be produced with high selectivity.

[0115] Ethylene Oligomerization Process The present invention provides a method for producing linear α-olefins, which is an ethylene oligomerization method comprising the step (S10) of oligomerizing ethylene in the presence of the catalyst composition.

[0116] In the present invention, "oligomerization" means that olefins are polymerized into small units. Depending on the number of olefins polymerized, it is called trimerization or tetramerization, and these are collectively called multimerization. In particular, in this specification, it can mean the selective production of 1-hexene and 1-octene, which are the main comonomers of LLDPE, from ethylene.

[0117] According to one embodiment of the present invention, the ethylene oligomerization reaction may be an ethylene trimerization or tetramerization reaction, whereby 1-hexene or 1-octene is formed as a reaction product, and the linear α-olefin may be 1-hexene, 1-octene, or a mixture thereof.

[0118] According to one embodiment of the present invention, the ethylene oligomerization method may be carried out by using ethylene as a raw material and applying the above-mentioned catalyst composition and a general apparatus and contacting technique. As a specific example, the ethylene oligomerization reaction may be carried out in the presence or absence of an inert solvent as a homogeneous liquid phase reaction, or a slurry reaction in which the catalyst composition is partially or entirely undissolved, or a bulk phase reaction in which the product α-olefin acts as a main medium, or a gas phase reaction.

[0119] According to an embodiment of the present invention, the ethylene oligomerization reaction may be carried out in an inert solvent. Specific examples of the inert solvent include benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, and 2,2,4-trimethylpentane.

[0120] According to one embodiment of the present invention, the ethylene oligomerization reaction may be carried out at a temperature of 0° C. to 200° C., or 0° C. to 150° C., or 30° C. to 100° C., or 50° C. to 100° C. Also, the reaction may be carried out under a pressure of 15 psig to 3000 psig, or 15 psig to 1500 psig, or 15 psig to 1,000 psig.

[0121] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to exemplary embodiments thereof, so that those skilled in the art can easily practice the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments set forth herein.

[0122] Synthesis examples and comparative synthesis examples Synthesis Example 1: Synthesis of ligand compound represented by chemical formula 2-1

[0123] [Chemical formula 2-1] [ka]

[0124] 20 mmol (2 eq) of 4-(tripropylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of 4-(trifluoromethyl)cyclohexylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 2-1.

[0125] <Ligand compound represented by chemical formula 2-1> N-(bis(4-(tripropylsilyl)phenyl)phosphanyl)-N-(4-(trifluoromethyl)cyclohexyl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine

[0126] N-(bis(4-(tripropylsilyl)phenyl)phosphaneyl)-N-(4-(trifluoromethyl)cyclohexyl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine)

[0127] 1 H NMR(500MHz,C6D6):δ8.00-7.20(m,16H), 3.31(pent,1H), 2.52-2.38(m,2H ), 2.00-1.52(m,4H), 1.40-1.25(m,27H), 0.98(t,36H), 0.79-0.73(m,24H)

[0128] Synthesis Example 2: Synthesis of ligand compound represented by chemical formula 2-3 [Chemical formula 2-3] [ka]

[0129] 20 mmol (2 eq) of 4-(tripropylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, it was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) obtained was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of 3-(trifluoromethyl)cyclohexylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 2-3.

[0130] <Ligand compound represented by chemical formula 2-3> N-(bis(4-(tripropylsilyl)phenyl)phosphanyl)-N-(3-(trifluoromethyl)cyclohexyl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine)

[0131] N-(bis(4-(tripropylsilyl)phenyl)phosphaneyl)-N-(3-(trifluoromethyl)cyclohexyl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine)

[0132] 1 H NMR(500MHz,C6D6):δ8.00-7.20(m,16H), 3.95-3.82(m,0.18H), 3.33(pent,0.82H), 2.20- 2.00(m,2H), 1.70-1.55(m,2H), 1.53-1.25(m,27H), 1.05-0.92(m,36H), 0.80-0.70(m,24H)

[0133] Synthesis Example 3: Synthesis of ligand compound represented by chemical formula 2-5 [Chemical formula 2-5] [ka]

[0134] 20 mmol (2 eq) of 4-(tripropylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate (2.1 mmol (2.1 eq) obtained by dissolving the intermediate in 3.8 ml of dichloromethane was added with 3 mmol (3 eq) of triethylamine. Then, 1 mmol (1 eq) of 4-phenylcyclohexylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and the mixture was loaded on top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 2-5.

[0135] <Ligand compound represented by chemical formula 2-5> N-(bis(4-(tripropylsilyl)phenyl)phosphanyl)-N-(4-phenylcyclohexyl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine)

[0136] N-(bis(4-(tripropylsilyl)phenyl)phosphaneyl)-N-(4-phenylcyclohexyl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine)

[0137] 1 H NMR(500MHz,C6D6):δ8.00-6.90(m,21H), 3.65-3.45(m,0.88H), 3.40-3.28(m,0.12H), 2.80 -2.25(m,4H), 2.10-1.47(m,5H), 1.45-1.27(m,24H), 0.99-0.92(m,36H), 0.79-0.72(m,24H)

[0138] Synthesis Example 4: Synthesis of ligand compound represented by chemical formula 2-8 [Chemical formula 2-8] [ka]

[0139] 20 mmol (2 eq) of 4-(tripropylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of 4-(dimethylamino)cyclohexylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 2-8.

[0140] <Ligand compound represented by chemical formula 2-8> N 1 ,N 1 -Bis(bis(4-(tripropylsilyl)phenyl)phosphanyl)-N 4 ,N 4 -Dimethylcyclohexane-1,4-diamine

[0141] N 1 ,N 1 -bis(bis(4-(tripropylsilyl)phenyl)phosphaneyl)-N 4 ,N 4 -dimethylcyclohexane-1,4-diamine

[0142] 1 H NMR(500MHz,C6D6):δ8.00-7.18(m,16H), 3.25(pent,1H), 2.55-2.42(m,2H), 2.34-2.23(m ,1H), 2.12(s,6H), 1.85-1.65(m,4H), 1.40-1.25(m,24H), 0.98(t,36H), 0.87-0.75(m,24H)

[0143] Synthesis Example 5: Synthesis of ligand compound represented by chemical formula 2-10 [Chemical formula 2-10] [ka]

[0144] 20 mmol (2 eq) of 4-(tripropylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of 4-(diethylamino)cyclohexylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 2-10.

[0145] <Ligand compound represented by chemical formula 2-10> N 1 ,N 1 -Bis(bis(4-(tripropylsilyl)phenyl)phosphanyl)-N 4 ,N 4 -Diethylcyclohexane-1,4-diamine

[0146] N 1 ,N 1 -bis(bis(4-(tripropylsilyl)phenyl)phosphaneyl)-N 4 ,N 4 -diethylcyclohexane-1,4-diamine

[0147] 1 H NMR(500MHz,C6D6):δ8.00-7.18(m,16H), 3.21(pent,1H), 2.54-2.40(m,2H), 2.30-2.20(m,1H), 2.18(q,4H), 1.83-1.60(m,4H), 1.40-1.23(m,30H), 0.95(t,36H), 0.85-0.74(m,24H)

[0148] Synthesis Example 6: Synthesis of ligand compound represented by chemical formula 2-12 [Chemical formula 2-12] [ka]

[0149] 20 mmol (2 eq) of 4-(tripropylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of tetrahydro-2H-pyran-4-ylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 2-12.

[0150] <Ligand compound represented by chemical formula 2-12> N-(bis(4-(tripropylsilyl)phenyl)phosphanyl)-N-(tetrahydro-2H-pyran-4-yl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine)

[0151] N-(bis(4-(tripropylsilyl)phenyl)phosphanyl)-N-(tetrahydro-2H-pyran-4-yl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine)

[0152] 1 H NMR (500MHz,C6D6): δ8.00-7.25(m,16H), 3.84-3.76(m,2H), 3.60(q,1H), 2. 58-2.48(m,2H), 1.40-1.30(m,28H), 1.01-0.92(m,36H), 0.78-0.71(m,24H)

[0153] Synthesis Example 7: Synthesis of ligand compound represented by chemical formula 3-1 [Chemical formula 3-1] [ka]

[0154] 20 mmol (2 eq) of 4-(tripropylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, it was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) obtained was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of 2-oxotetrahydrothiophen-3-ylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 3-1.

[0155] <Ligand compound represented by chemical formula 3-1> 3-(Bis(bis(4-(tripropylsilyl)phenyl)phosphanyl)amino)dihydrothiophen-2(3H)-one

[0156] 3-(bis(bis(4-(tripropylsilyl)phenyl)phosphanyl)amino)dihydrothiophen-2(3H)-one

[0157] 1 H NMR (500MHz, C6D6): δ8.00-7.20 (m,16H), 4.70(t,1H), 3.05-2.95(m,2H), 2.43-2.31(m,2H), 1.40-1.28(m,24H), 1.10-0.87(m,36H), 0.88-0.75(m,24H)

[0158] Synthesis Example 8: Synthesis of the されるリガンド compound shown in Chemical Formula 4-1 [Chemical formula 4-1]

change

[0159] 20 mmol (2 eq) of 4-(tripropylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of (1R,2R,4S)-bicyclo[2.2.1]heptan-2-ylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 4-1.

[0160] <Ligand compound represented by chemical formula 4-1> N-((1R,2R,4S)-bicyclo[2.2.1]heptan-2-yl)-N-(bis(4-tripropylsilyl)phenyl)phosphanyl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine

[0161] N-((1R,2R,4S)-bicyclo[2.2.1]heptan-2-yl)-N-(bis(4-tripropylsilyl)phenyl)phosphanyl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine)

[0162] 1 H NMR (500MHz, C6D6): δ7.96-7.66(m,4H), 7.64-7.25(m,12H), 3.65-3.53(m,1H), 2.92(d,1H), 2.53-2.45( m,1H), 2.27(s,1H), 1.78(t,1H), 1.64(s,1H), 1.45-1.20(m,24H), 1.05-0.85(m,41H), 0.82-0.60(m,24H)

[0163] Synthesis Example 9: Synthesis of the されるリガンド compound shown in Chemical Formula 2-6 [Chemical formula 2-6]

change

[0164] 20 mmol (2 eq) of 4-(tributylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and 2 eq of HCl (in ether) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of 4-phenylcyclohexylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 2-6.

[0165] <Ligand compound represented by chemical formula 2-6> N-(bis(4-(tributylsilyl)phenyl)phosphanyl)-N-(4-phenylcyclohexyl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine)

[0166] N-(bis(4-(tributylsilyl)phenyl)phosphanyl)-N-(4-phenylcyclohexyl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine)

[0167] 1 H NMR (500MHz, C6D6): δ7.85-6.90(m,21H), 3.63-3.45(m,0.88H), 3.38-3.27(m,0.12H), 2.79 -2.24(m,4H), 2.08-1.45(m,5H), 1.45-1.27(m,48H), 1.01-0.92(m,36H), 0.78-0.70(m,24H)

[0168] Synthesis Example 10: Synthesis of the されるリガンド compound shown in Chemical Formula 2-4 [Chemical formula 2-4]

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[0169] 20 mmol (2 eq) of 4-(tributylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and 2 eq of HCl (in ether) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of 3-(trifluoromethyl)cyclohexylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 2-4.

[0170] <Ligand compound represented by chemical formula 2-4> N-(bis(4-(tributylsilyl)phenyl)phosphanyl)-1,1-bis(4-(tributylsilyl)phenyl)-N-(3-(trifluoromethyl)cyclohexyl)phosphanamine)

[0171] N-(bis(4-(tributylsilyl)phenyl)phosphanyl)-1,1-bis(4-(tributylsilyl)phenyl)-N-(3-(trifluoromethyl)cyclohexyl)phosphanamine)

[0172] 1 H NMR(500MHz,C6D6):δ8.00-7.15(m,16H), 3.94-3.80(m,0.18H), 3.30(pent,0.82H), 2.18- 1.97(m,2H), 1.68-1.53(m,2H), 1.50-1.21(m,51H), 1.05-0.90(m,36H), 0.79-0.70(m,24H)

[0173] Synthesis Example 11: Synthesis of ligand compound represented by chemical formula 2-7 [Chemical formula 2-7] [ka]

[0174] In a dried flask, 11 mmol (2.2 eq) of 4-phenylcyclohexylamine and 10 ml of dichloromethane were added under a nitrogen atmosphere, and stirring was started. 5 mmol (1 eq) of chlorobis(4-(tripropylsilyl)phenyl)phosphane was gradually added to the flask in a diluted state in 10 ml of dichloromethane. The reaction was stirred for 4 hours, and then the mixture was cooled to room temperature. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed through a filter, the solvent was removed under reduced pressure, and 5 mmol of the intermediate compound N-(4-phenylcyclohexyl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine was obtained by column chromatography.

[0175] Next, 5 mmol (1 eq) of N-(4-phenylcyclohexyl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine, which is the intermediate compound obtained above, and 13 ml of methyl tert-butyl ether were added to the dried flask under a nitrogen atmosphere, cooled to -78°C, and stirring was started. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was gradually added to the flask and stirred for 1 hour, after which 5 mmol (1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted in 10 ml of methyl tert-butyl ether was gradually added. The reaction was allowed to stir for 4 hours. 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed through a filter, the solvent was removed under reduced pressure, and 4 mmol (yield 80%) of the ligand compound represented by formula 4-1 was obtained by column chromatography.

[0176] <Ligand compound represented by chemical formula 2-7> N-(bis(4-(tributylsilyl)phenyl)phosphanyl)-N-(4-phenylcyclohexyl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine

[0177] N-(bis(4-(tributylsilyl)phenyl)phosphanyl)-N-(4-phenylcyclohexyl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine

[0178] 1 H NMR(500MHz,C6D6):δ7.98-6.90(m,21H), 3.64-3.46(m,0.88H), 3.39-3.28(m,0.12H), 2.80 -2.25(m,4H), 2.09-1.46(m,5H), 1.45-1.27(m,36H), 1.00-0.92(m,36H), 0.79-0.71(m,24H)

[0179] Synthesis Example 12: Synthesis of ligand compound represented by formula 2-14 [Chemical formula 2-14] [ka]

[0180] In a dried flask, 11 mmol (2.2 eq) of cycloheptylamine and 10 ml of dichloromethane were added under a nitrogen atmosphere, and stirring was started. 5 mmol (1 eq) of chlorobis(3-(tripropylsilyl)phenyl)phosphane was gradually added to the flask in a state diluted with 10 ml of dichloromethane. The reaction mixture was stirred for 4 hours, and then the mixture was cooled to room temperature. 1The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed through a filter, the solvent was removed under reduced pressure, and 5 mmol of the intermediate compound N-cycloheptyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine was obtained by column chromatography.

[0181] Next, the intermediate compound N-cycloheptyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine (5 mmol (1 eq)) and 13 ml of methyl tert-butyl ether were added to the dried flask under a nitrogen atmosphere, cooled to -78°C, and stirring was started. 2.1 ml (5.25 mmol, 1.05 eq) of a 2.5 M solution of n-butyl lithium in hexane was gradually added to the flask and stirred for 1 hour, and then 5 mmol (1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane diluted in 10 ml of methyl tert-butyl ether was gradually added. The reaction mixture was stirred for 4 hours, 1 The conversion was confirmed by H NMR. After the reaction was completed, the precipitated solid was removed through a filter, the solvent was removed under reduced pressure, and 4 mmol (yield 80%) of the ligand compound represented by formula 4-1 was obtained by column chromatography.

[0182] <Ligand compound represented by chemical formula 2-14> N-(bis(4-(tributylsilyl)phenyl)phosphanyl)-N-cycloheptyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine

[0183] N-(bis(4-(tributylsilyl)phenyl)phosphanyl)-N-cycloheptyl-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine

[0184] 1 H NMR (500MHz, C6D6): δ8.00-7.15(m,16H), 3.63(pent,1H), 2.33-2.20(m,2H), 1.94-1.85(m,2H), 1 .60-1.45(m,4H), 1.44-1.15(m,36H), 1.00-0.86(m,36H), 0.85-0.80(m,16H), 0.78-0.67(m,12H)

[0185] Comparative synthesis example 1: Synthesis of the chemical formula 9 of the されるリガンド compound [Chemical formula 9]

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[0186] 20 mmol (2 eq) of 4-(tripropylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of cyclohexylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 9.

[0187] Comparative Synthesis Example 2: Synthesis of the ligand compound represented by formula 10 [Chemical formula 10] [ka]

[0188] 20 mmol (2 eq) of 4-(tripropylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of isopropylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 10.

[0189] Comparative Synthesis Example 3: Synthesis of Ligand Compound Represented by Chemical Formula 11 [Chemical formula 11] [ka]

[0190] 20 mmol (2 eq) of 4-(tributylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and 2 eq of HCl (in ether) was added. After stirring for 15 minutes, it was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) obtained was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of cyclohexylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 11.

[0191] Comparative Synthesis Example 4: Synthesis of Ligand Compound Represented by Chemical Formula 12 [Chemical formula 12] [ka]

[0192] 20 mmol (2 eq) of 4-(trihexylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of isopropylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After performing silica filtration using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 12.

[0193] Comparative Synthesis Example 5: Synthesis of Ligand Compound Represented by Chemical Formula 13 [Chemical formula 13] [ka]

[0194] 20 mmol (2 eq) of 4-(trihexylsilyl)phenyl bromide was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. While maintaining the temperature, 20 mmol (2 eq) of n-butyl lithium was added dropwise and stirred for 3 hours. Then, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the intermediate obtained without further purification was dissolved in 30 ml of hexane and HCl (in ether, 2 eq) was added. After stirring for 15 minutes, the mixture was filtered, and the filtrate was dried under vacuum. The intermediate 2.1 mmol (2.1 eq) was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of 3-(trifluoromethyl)cyclohexylamine dissolved in 3.8 ml of dichloromethane was gradually added to the reaction system, and the mixture was stirred overnight at room temperature. Then, the solvent was removed using a vacuum, and the mixture was dissolved in 7.6 ml of hexane, and then loaded onto the top of silica gel. After silica filtration was performed using hexane to which 1% by volume of triethylamine was added, the resulting solution was concentrated to obtain the ligand compound represented by formula 13.

[0195] Examples and Comparative Examples Example 1 In an argon gas atmosphere, 0.5 mmol of chromium (III) chloride tetrahydrofuran (Cr(THF)3Cl3), 0.5 mmol of the ligand compound represented by formula 2-1 according to Synthesis Example 1, and 0.5 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) as a cocatalyst were placed in a flask, and then 30 ml of dichloromethane was added and stirred for 1 hour, after which the solvent was removed in a vacuum. The mixture was then dissolved in methylcyclohexane and filtered, after which the solvent was removed again in a vacuum, and the mixture was dissolved in methylcyclohexane to prepare a 0.15 mM (Cr basis) catalyst solution.

[0196] A Parr reactor with a capacity of 600 ml was prepared, and after maintaining the vacuum at 120°C for 2 hours, the inside was replaced with argon and the temperature was lowered to 70°C. Then, 180 ml of methylcyclohexane and 2 ml of activator, 725 μmol of diisobutylaluminum hydride, and 5 ml of the catalyst solution (0.75 μmol Cr) were injected. After stirring at 1,000 rpm for 2 minutes, the valve of the ethylene line adjusted to 40 bar was opened, the reactor was filled with ethylene, and then stirred at 1,000 rpm for 60 minutes. The ethylene line valve was closed, the reactor was cooled to 0°C using a dry ice / acetone bath, and the unreacted ethylene was gradually vented, and 0.5 ml of nonane (GC internal standard) was injected. After stirring for 10 seconds, 2 ml of the liquid portion of the reactor was taken and quenched with water, and the obtained organic portion was filtered with a PTFE syringe filter to prepare a GC-FID sample. The distribution of the liquid product was analyzed by GC (Agilent 6890N, Alltech AT-5 (30m x 0.32mm ID x 0.25μm; series No. 12446)). In addition, 400ml of ethanol / HCl (10vol% of aqueous 12M HCl solution) was added to the remaining reaction solution, stirred, filtered, and the amount of solid product was analyzed. The obtained polymer was dried overnight in a vacuum oven at 80℃.

[0197] Examples 2 to 12 and Comparative Examples 1 to 5 The same procedure as in Example 1 was carried out, except that the type of catalyst was changed as shown in Table 1 below.

[0198] [Table 1]

[0199] Experimental Example The results of the ethylene oligomerization reaction according to the above examples and comparative examples are shown in Table 2 below.

[0200] *Catalytic activity (ton / mol·Cr / hr): Catalytic activity was calculated from the total weight (ton) of the products obtained, which is the sum of the weight (ton) of the liquid product and the solid product.

[0201] *Selectivity of 1-C6 and 1-C8 (wt%): The contents of 1-hexene (1-C6) and 1-octene (1-C8) were calculated from the distribution of the liquid products analyzed by GC, and the wt% of 1-hexene or 1-octene was calculated based on the total weight of the products.

[0202] *Production amount (wt%) of Iso-C6, Iso-C8 and C10-C40: The contents of Iso-hexene (Iso-C6), Iso-octene (Iso-C8) and C10-C40 were calculated from the distribution of the liquid product by GC, and the wt% of Iso-hexene (Iso-C6), Iso-octene (Iso-C8) and C10-C40 were calculated based on the total weight of the product.

[0203] *Solid (wt%): The weight percent of the solid product was calculated based on the total weight of the product. This indicates the degree to which polyethylene with a carbon number of about 40 or more was produced, which is an insoluble solid that is not dissolved in the solvent.

[0204] [Table 2]

[0205] As shown in Table 2, when an ethylene oligomerization reaction is carried out using a catalyst composition containing a ligand compound according to the present invention, it was confirmed that the catalytic activity, selectivity and stability are all improved due to the steric and electrical properties of the substituent substituted on the nitrogen atom, in addition to the phenyl located at the end of the diphosphinoaminyl residue having a silyl group substituted with an alkyl group having a specific carbon number at the para position as a substituent.

[0206] From these results, it was confirmed that when ethylene oligomerization is carried out using the organochromium compound and catalyst composition containing the ligand compound of the present invention, linear α-olefins can be produced with high selectivity to 1-hexene and 1-octene while having excellent productivity due to high catalytic activity.

Claims

1. A ligand compound represented by the following chemical formula 1: [Chemical formula 1] 【Chemistry 1】 In the above Chemical Formula 1, R １ ~R ４ are each independently a trialkylsilyl group, wherein the alkyl group is an alkyl group having 1 to 4 carbon atoms; R ５ is a substituent represented by the following chemical formula 3, [Chemical formula 3] 【Chemistry 2】 In the above Chemical Formula 3, X ６ Ha- (CR ６ R ７ ) ｎ -, -O- or -S-, but not all at the same time -O- or -S-; n is 0 or an integer selected from 1 to 3; R ６ and R ７ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a trifluoroalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or -NR ８ R ９ and R ８ and R ９ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, * indicates the site of binding to N in Chemical Formula 1.

2. R １ ~R ４ The ligand compound according to claim 1 , wherein each of the groups is independently a tripropylsilyl group or a tributylsilyl group.

3. X ６ is -S-, R ６ and R ７ each independently represents a hydrogen atom, a trifluoroalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or -NR ８ R ９ and R ８ and R ９ The ligand compound according to claim 1, wherein each of the groups is independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

4. A ligand compound, which is one selected from the group consisting of ligand compounds represented by the following chemical formulas 2-1 to 2-14: [Chemical formula 2-1] 【Chemistry 3】 [Chemical formula 2-2] 【Chemistry 4】 [Chemical formula 2-3] 【Chemistry 5】 [Chemical formula 2-4] 【Chemistry 6】 [Chemical formula 2-5] 【Chemistry 7】 [Chemical formula 2-6] 【Chemistry 8】 [Chemical formula 2-7] 【Chemistry 9】 [Chemical formula 2-8] 【Chemistry 10】 [Chemical formula 2-9] 【Chemistry 11】 [Chemical formula 2-10] 【Chemistry 12】 [Chemical formula 2-11] 【Chemistry 13】 [Chemical formula 2-12] 【Chemistry 14】 [Chemical formula 2-13] 【Chemistry 15】 [Chemical formula 2-14] 【Chemistry 16】

5. X ６ The ligand compound according to claim 1, wherein is -O- or -S-.

6. The ligand compound represented by the formula 1 is represented by the following formula 3-1 or 3-2: [Chemical formula 3-1] 【Chemistry 17】 [Chemical formula 3-2] 【Chemistry 18】

7. A ligand compound represented by the following chemical formula 4-1 or 4-2: [Chemical formula 4-1] 【Chemistry 19】 [Chemical formula 4-2] 【Chemistry 20】

8. An organochromium compound comprising one or more ligand compounds selected from the ligand compound of claim 1, the ligand compound of claim 4, and the ligand compound of claim 7; and chromium coordinated to the ligand compound.

9. 9. The organochromium compound according to claim 8, wherein in the ligand compound represented by Chemical Formula 1, at least one unshared electron pair of N and two P is coordinated to chromium.

10. A catalyst composition for ethylene oligomerization, comprising: one or more ligand compounds selected from the ligand compound of claim 1, the ligand compound of claim 4, and the ligand compound of claim 7; chromium; and a cocatalyst.

11. the chromium is derived from a chromium source; 11. The catalyst composition for ethylene oligomerization according to claim 10, wherein the chromium source comprises one or more selected from the group consisting of chromium(III) acetylacetonate, chromium(III) chloride tetrahydrofuran, chromium(III) 2-ethylhexanoate, chromium(III) acetate, chromium(III) butyrate, chromium(III) pentanoate, chromium(III) laurate, chromium(III) tris(2,2,6,6-tetramethyl-3.5-heptanedionate), and chromium(III) stearate.

12. The catalyst composition for ethylene oligomerization according to claim 10, wherein the co-catalyst is at least one selected from the group consisting of compounds represented by the following chemical formulas 5 to 8: [Chemical formula 5] <h2 style=";text-align:left;direction:ltr">-[Al(R<h2 style=";text-align:left;direction:ltr"> １０ <h2 style=";text-align:left;direction:ltr"> ()-O]<h2 style=";text-align:left;direction:ltr"> ａ <h2 style=";text-align:left;direction:ltr"> - In the above Chemical Formula 5, R １０ each independently represents a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group substituted with a halogen group and having 1 to 20 carbon atoms, a is an integer of 2 or more, [Chemical formula 6] E(R １１ ) ３ In the above Chemical Formula 6, E is aluminum or boron; R １１ each independently represents a hydrogen atom, 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, [Chemical formula 7] [L-H] ＋ [G(Y) ４ ] － [Chemical formula 8] [L] ＋ [G(Y) ４ ] － In the above Chemical Formulas 7 and 8, L is a neutral or cationic Lewis acid; [L-H] ＋ is a Brønsted acid, G is a group 13 element; Each Y is 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, where when the alkyl group or the 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.

13. A method for producing a linear α-olefin, comprising: a step (S10) of oligomerizing ethylene in the presence of the catalyst composition for ethylene oligomerization according to claim 10.

14. The method for producing linear α-olefins according to claim 13, wherein the linear α-olefin is 1-hexene, 1-octene or a mixture thereof.

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