Ligand compound, organic chromium compound, and catalyst composition containing same

Abstract

The present invention relates to a ligand compound having a novel structure, an organic chromium compound, a catalyst composition containing the organic chromium compound, and a method for oligomerizing ethylene using the catalyst composition, the ligand compound exhibiting high selectivity of 1-hexene and 1-octene while exhibiting high catalytic activity, and having excellent selectivity of 1-hexene and 1-octene. And ethylene oligomerization can be carried out with excellent efficiency.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0051230 filed on April 19, 2023, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0004] The present invention relates to a ligand compound, an organic chromium compound, a catalyst composition containing the organic chromium compound and an ethylene oligomerization method using the same. Background Art

[0005] Linear alpha-olefins like hexene or 1-octene are used as detergents, lubricants or plasticizers, and it is used as a comonomer to control polymer density, especially in the production of linear low-density polyethylene (LLDPE).

[0006] In conventional linear low density polyethylene (LLDPE) manufacturing processes, copolymerization with α-olefins (eg, comonomers such as 1-hexene or 1-octene) is allowed to occur to control density by forming branches in the polymer backbone with ethylene.

[0007] Therefore, in order to produce LLDPE with a high comonomer content, there is a problem that the price of the comonomer accounts for a large part of the production cost. In order to solve this problem, various attempts have been made.

[0008] Such linear α-olefins are mainly produced by the Shell Advanced Olefins Process. However, in this process, α-olefins with different lengths are simultaneously synthesized according to the Schultz-Flory distribution, so an additional separation process is required to obtain specific α-olefins, which is inconvenient.

[0009] In order to solve this problem, a method for selectively synthesizing 1-hexene by trimerization of ethylene or a method for selectively synthesizing 1-octene by tetramerization of ethylene has been proposed. In addition, a large number of studies have been conducted on catalyst systems that can achieve the selective oligomerization of ethylene.

[0010] Related technical literature

[0011] Patent Literature

[0012] Patent document 1: US 5064802 B2 Summary of the invention

[0013] Technical issues

[0014] The purpose of the present invention is to provide a ligand compound with a novel structure, an organic chromium compound and a catalyst composition containing the same, wherein the ligand compound exhibits high catalytic activity and high selectivity for 1-hexene and 1-octene, and can carry out ethylene oligomerization with excellent efficiency.

[0015] Technical Solution

[0016] In order to achieve the above object, the present invention provides a ligand compound, an organic chromium compound, a catalyst composition and an ethylene oligomerization method.

[0017] (1) The present invention provides a ligand compound represented by Chemical Formula 1.

[0018] [Chemical formula 1]

[0019]

[0020] In Chemical Formula 1, R 1 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 1 With R 6 Combine to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring; when R 6 Not with R 1 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 6 is hydrogen; R 2 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 2 With R 7 Combine to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring; when R 7 Not with R 2 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 7 is hydrogen; R 3 and R 4are each independently hydrogen, an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an arylalkoxyalkyl group having 7 to 30 carbon atoms, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), wherein R 3 and R 4 are not hydrogen at the same time; and R 5 It is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused with an aryl group having 6 to 10 carbon atoms.

[0021] (2) The present invention provides the ligand compound according to (1), wherein R 1 is fluorine, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or R 1 With R 6 Combined to form a monocyclic or polycyclic heterocycle, and

[0022] R 2 is fluorine, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or R 2 With R 7 Combine to form a monocyclic or polycyclic heterocycle.

[0023] (3) The present invention provides a ligand compound according to (1) or (2), wherein R 1 is fluoro, trifluoromethyl, methoxy, methyl, trifluoromethoxy, trifluoromethylthio, methylthio, methylsulfonate or trimethylsilyl, or R 1 With R 6 Combine to form furan or dibenzofuran, and R 2 is fluoro, trifluoromethyl, methoxy, methyl, trifluoromethoxy, trifluoromethylthio, methylthio, methylsulfonate or trimethylsilyl, or R 2 With R 7 Combine to form furans or dibenzofurans.

[0024] (4) The present invention provides a ligand compound according to any one of (1) to (3), wherein R 3 and R 4 Each is independently an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group or a tributylsilyl group.

[0025] (5) The present invention provides a ligand compound according to any one of (1) to (4), wherein R 3 and R 4 Each is independently n-decyl, tripropylsilyl or tributylsilyl.

[0026] (6) The present invention provides a ligand compound according to any one of (1) to (5), wherein R 5 It is an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms condensed with an aryl group having 6 to 10 carbon atoms.

[0027] (7) The present invention provides the ligand compound according to any one of (1) to (6), wherein the ligand compound represented by Chemical Formula 1 is represented by any one of Chemical Formulas 2 to 5.

[0028] [Chemical formula 2]

[0029]

[0030] [Chemical formula 3]

[0031]

[0032] [Chemical formula 4]

[0033]

[0034] [Chemical formula 5]

[0035]

[0036] In Chemical Formulae 2 to 5, R 1 To R 7 The same as defined in (1) to (6), respectively.

[0037] (8) The present invention provides a ligand compound according to any one of (1) to (7), wherein the ligand compound represented by Chemical Formula 1 is represented by any one of Chemical Formulas 2-1 to 2-66 or Chemical Formulas 3-1 to 3-20.

[0038] [Chemical formula 2-1]

[0039]

[0040] [Chemical formula 2-2]

[0041]

[0042] [Chemical formula 2-3]

[0043]

[0044] [Chemical formula 2-4]

[0045]

[0046] [Chemical formula 2-5]

[0047]

[0048] [Chemical formula 2-6]

[0049]

[0050] [Chemical formula 2-7]

[0051]

[0052] [Chemical formula 2-8]

[0053]

[0054] [Chemical formula 2-9]

[0055]

[0056] [Chemical formula 2-10]

[0057]

[0058] [Chemical formula 2-11]

[0059]

[0060] [Chemical formula 2-12]

[0061]

[0062] [Chemical formula 2-13]

[0063]

[0064] [Chemical formula 2-14]

[0065]

[0066] [Chemical formula 2-15]

[0067]

[0068] [Chemical formula 2-16]

[0069]

[0070] [Chemical formula 2-17]

[0071]

[0072] [Chemical formula 2-18]

[0073]

[0074] [Chemical formula 2-19]

[0075]

[0076] [Chemical formula 2-20]

[0077]

[0078] [Chemical formula 2-21]

[0079]

[0080] [Chemical formula 2-22]

[0081]

[0082] [Chemical formula 2-23]

[0083]

[0084] [Chemical formula 2-24]

[0085]

[0086] [Chemical formula 2-25]

[0087]

[0088] [Chemical formula 2-26]

[0089]

[0090] [Chemical formula 2-27]

[0091]

[0092] [Chemical formula 2-28]

[0093]

[0094] [Chemical formula 2-29]

[0095]

[0096] [Chemical formula 2-30]

[0097]

[0098] [Chemical formula 2-31]

[0099]

[0100] [Chemical formula 2-32]

[0101]

[0102] [Chemical formula 2-33]

[0103]

[0104] [Chemical formula 2-34]

[0105]

[0106] [Chemical formula 2-35]

[0107]

[0108] [Chemical formula 2-36]

[0109]

[0110] [Chemical formula 2-37]

[0111]

[0112] [Chemical formula 2-38]

[0113]

[0114] [Chemical formula 2-39]

[0115]

[0116] [Chemical formula 2-40]

[0117]

[0118] [Chemical formula 2-41]

[0119]

[0120] [Chemical formula 2-42]

[0121]

[0122] [Chemical formula 2-43]

[0123]

[0124] [Chemical formula 2-44]

[0125]

[0126] [Chemical formula 2-45]

[0127]

[0128] [Chemical formula 2-46]

[0129]

[0130] [Chemical formula 2-47]

[0131]

[0132] [Chemical formula 2-48]

[0133]

[0134] [Chemical formula 2-49]

[0135]

[0136] [Chemical formula 2-50]

[0137]

[0138] [Chemical formula 2-51]

[0139]

[0140] [Chemical formula 2-52]

[0141]

[0142] [Chemical formula 2-53]

[0143]

[0144] [Chemical formula 2-54]

[0145]

[0146] [Chemical formula 2-55]

[0147]

[0148] [Chemical formula 2-56]

[0149]

[0150] [Chemical formula 2-57]

[0151]

[0152] [Chemical formula 2-58]

[0153]

[0154] [Chemical formula 2-59]

[0155]

[0156] [Chemical formula 2-60]

[0157]

[0158] [Chemical formula 2-61]

[0159]

[0160] [Chemical formula 2-62]

[0161]

[0162] [Chemical formula 2-63]

[0163]

[0164] [Chemical formula 2-64]

[0165]

[0166] [Chemical formula 2-65]

[0167]

[0168] [Chemical formula 2-66]

[0169]

[0170] [Chemical formula 3-1]

[0171]

[0172] [Chemical formula 3-2]

[0173]

[0174] [Chemical formula 3-3]

[0175]

[0176] [Chemical formula 3-4]

[0177]

[0178] [Chemical formula 3-5]

[0179]

[0180] [Chemical formula 3-6]

[0181]

[0182] [Chemical formula 3-7]

[0183]

[0184] [Chemical formula 3-8]

[0185]

[0186] [Chemical formula 3-9]

[0187]

[0188] [Chemical formula 3-10]

[0189]

[0190] [Chemical formula 3-11]

[0191]

[0192] [Chemical formula 3-12]

[0193]

[0194] [Chemical formula 3-13]

[0195]

[0196] [Chemical formula 3-14]

[0197]

[0198] [Chemical formula 3-15]

[0199]

[0200] [Chemical formula 3-16]

[0201]

[0202] [Chemical formula 3-17]

[0203]

[0204] [Chemical formula 3-18]

[0205]

[0206] [Chemical formula 3-19]

[0207]

[0208] [Chemical formula 3-20]

[0209]

[0210] (9) The present invention provides an organic chromium compound comprising the ligand compound according to any one of (1) to (8), and

[0211] Chromium coordinated to the ligand compound.

[0212] (10) The present invention provides an organic chromium compound according to (9), wherein the organic chromium compound has a form in which any one or more unshared electron pairs of N and two P in the ligand compound represented by Chemical Formula 1 are coordinated to chromium.

[0213] (11) The present invention provides a catalyst composition comprising the ligand compound according to any one of (1) to (8), chromium and a co-catalyst.

[0214] (12) The present invention provides a catalyst composition according to (11), wherein the chromium is derived from a chromium source, and the chromium source comprises one or more selected from chromium (III) acetylacetonate, tetrahydrofuran chromium (III) chloride, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) valerate, chromium (III) laurate, tris(2,2,6,6-tetramethyl-3.5-heptanedione)chromium (III), and chromium (III) stearate.

[0215] (13) The present invention provides the catalyst composition according to (11) or (12), wherein the co-catalyst is at least one or more selected from the compounds represented by Chemical Formula 6 to Chemical Formula 9.

[0216] [Chemical formula 6]

[0217] -[Al(R 13 )-O] a -

[0218] In Chemical Formula 6, R 13 Each is independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group, and a is an integer of 2 or more.

[0219] [Chemical formula 7]

[0220] E(R 14 )3

[0221] In Chemical Formula 7, E is aluminum or boron, and

[0222] R 14 Each is independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group.

[0223] [Chemical formula 8]

[0224] [LH] + [G(Y)4] -

[0225] [Chemical formula 9]

[0226] [L] + [G(Y)4] -

[0227] In Formulas 8 and 9, L is a neutral or cationic Lewis acid, [LH] + is a Bronsted acid, G is a Group 13 element, and Y is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein, when the alkyl group or the aryl group is substituted, the substituent is a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0228] (14) The present invention provides a method for producing a linear α-olefin, comprising the step (S10) of oligomerizing ethylene in the presence of the catalyst composition according to any one of (11) to (13).

[0229] (15) The present invention provides the method for producing a linear α-olefin according to (14), wherein the linear α-olefin is 1-hexene, 1-octene, or a mixture thereof.

[0230] Beneficial Effects

[0231] 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 for 1-hexene and 1-octene while maintaining excellent productivity due to high catalytic activity. DETAILED DESCRIPTION

[0232] Below, the present invention is described in more detail to facilitate understanding of the present invention.

[0233] The terms and words used in the description of this specification and claims should not be restrictively interpreted as their ordinary meanings or dictionary meanings, but should be interpreted according to the meanings and concepts consistent with the technical ideas of the present invention based on the principle that the inventor can appropriately define the concepts of the terms to describe his invention in the best manner.

[0234] Ligand compounds

[0235] The present invention provides a ligand compound suitable for an ethylene oligomerization catalyst. When the ligand compound is applied to an ethylene oligomerization reaction, specifically, to a catalyst composition for forming linear α-olefins, while exhibiting excellent catalytic activity, a high selectivity for linear α-olefins can be obtained. In particular, compared with existing PNP catalysts and catalysts including symmetrical ligand compounds, even under the same reaction conditions, the amount of solid polyethylene produced is less, so that linear α-olefins can be produced more efficiently.

[0236] According to one embodiment of the present invention, when using ethylene to produce linear α-olefins, an organic chromium compound coordinated with a ligand compound can be used, and since the oligomerization reaction is a reaction carried out under ethylene conditions, liquid α-olefins, specifically liquid 1-hexene or 1-octene, can be formed with high selectivity. This is because, in the oligomerization reaction of ethylene, the selectivity of α-olefins with a specific length is increased by forming a transition state of a metal-containing cyclic compound (metal ring).

[0237] According to one embodiment of the present invention, the ligand compound includes diphosphino moiety, and the aryl with specific substituent is connected to the end of diphosphino moiety, so itself can have the form as strong electron donating group.Due to such structural characteristics, the ligand compound can be applied to ethylene oligomerization catalytic system to show high activity, particularly to 1-hexene, 1-octene etc. and show high selectivity.This may be due to the interaction between each adjacent chromium active site, particularly when the aryl replaced with specific substituent is connected to the phosphorus (P) atom of diphosphino, the electron density at phosphorus (P) atom and nitrogen (N) atom contained in diphosphino increases, so that the electrical properties and three-dimensional properties of the whole ligand compound change.As a result, the key between the ligand and the chromium atom changes, making the structure of the catalyst more stable.In addition, compared with existing metal cycloheptane or metal cyclononane form, the energy (activation energy) of transition state changes, which makes it possible to form alpha-olefins with higher activity and selectivity, and the amount of by-product can be further reduced, such as solid alpha-olefins with high molecular weight, such as polyethylene wax (PE wax).

[0238] According to one embodiment of the present invention, the ligand compound is characterized in that the phenyl at the end of the diphosphino part has the following groups as substituents in the ortho position: halogen groups, alkyl groups with 1 to 10 carbon atoms substituted or unsubstituted by halogen groups, alkoxy groups with 1 to 10 carbon atoms substituted or unsubstituted by halogen groups, alkylthio groups with 1 to 10 carbon atoms substituted or unsubstituted by halogen groups, alkylsulfonates with 1 to 10 carbon atoms substituted or unsubstituted by halogen groups, or trialkylsilyl groups (the alkyl groups of trialkylsilyl groups are each independently alkyl groups with 1 to 10 carbon atoms), or fused with phenyl to form monocyclic or polycyclic aromatic hydrocarbon rings or monocyclic or polycyclic heterocyclic rings, and each having the following groups as substituents in the meta position and the para position: alkyl groups with specific carbon atoms or silyl groups substituted by alkyl groups with specific carbon atoms. The substituents substituted in the ortho position of the phenyl group increase the steric strain around the metal atom, thereby improving the selectivity of 1-hexene. In addition, it protects the metal atom or directly forms a coordination bond, thereby improving the stability of the metal complex. At the same time, the substituents substituted at the meta-position and para-position of the phenyl group increase the solubility of the ligand compound and the metal complex in various polymerization solvents, thereby improving the activity and selectivity. Therefore, in the case of using the ligand compound, a chromium catalyst with high stability, excellent activity and excellent selectivity can be prepared.

[0239] According to one embodiment of the present invention, since a bulky substituent such as a cycloalkyl or phenyl group is combined on a nitrogen atom that is combined with two phosphorus atoms, and the bulky substituent group combined on nitrogen prevents the rotation of the bond between nitrogen and phosphorus, the ligand compound can further improve the stability and activity of the catalyst. In this case, the activity, stability and selectivity of the catalyst vary according to the three-dimensional properties of the substituent group combined on the nitrogen atom. In the case where the steric strain of the substituent group combined with the nitrogen atom is too high, the problem is that the synthesis of the ligand and the formation of the metal complex are difficult, and the generated complex is unstable. In addition, in the case where the steric strain of the substituent group combined with the nitrogen atom is too high, the problem is that it is difficult to approach raw materials such as ethylene, so the activity of the catalyst is reduced. In addition, in the case where the steric strain of the substituent group combined with the nitrogen atom is too low, the rotation of the bond between the nitrogen atom and the phosphorus atom cannot be prevented, and the metal central atom cannot be protected, resulting in a decrease in the activity and stability of the catalyst. That is, in the case where the steric strain of the substituent group combined with the nitrogen atom is too high or too low, the activity of the catalyst is reduced, and its stability is reduced, which can cause the problem of an increase in the amount of the by-product (such as polyethylene wax) produced. Therefore, it is very important to select a substituent bound to the nitrogen atom with an appropriate level of steric strain relative to the substituent bound to the phosphorus atom. In the ligand compound according to the present invention, as a substituent is introduced at the ortho position of the phenyl group bound to the phosphorus atom, the steric strain around the PNP functional group increases. Therefore, when R is introduced into the chemical formula 1, 5 In the case of a substituent represented by , the steric strain of the substituent bonded to the nitrogen atom does not increase too much, and the yield and selectivity can be improved in the ethylene oligomerization reaction by using a catalyst composition containing the ligand compound according to the present invention. In particular, when a substituent in the form of a secondary alkyl group is introduced as R in Chemical Formula 1, 5 In the case of substituents represented by, the efficiency is further improved, and for substituents in the form of primary alkyl groups, appropriate steric strain can be formed by introducing an aromatic group (e.g., phenyl) at the 1st or 2nd carbon position to compensate for the low steric strain, thereby improving the yield and selectivity.

[0240] According to one embodiment of the present invention, the ligand compound may be represented by Chemical Formula 1.

[0241] [Chemical formula 1]

[0242]

[0243] In Chemical Formula 1, R 1is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 1 With R 6 Combine to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring; when R 6 Not with R 1 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 6 is hydrogen; R 2 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 2 With R 7 Combine to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring; when R 7 Not with R 2 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 7 is hydrogen; R 3 and R 4 are each independently hydrogen, an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an arylalkoxyalkyl group having 7 to 30 carbon atoms, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), wherein R 3 and R 4 are not hydrogen at the same time; and R 5 It is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused with an aryl group having 6 to 10 carbon atoms.

[0244] In the present invention, the "halogen group" refers to fluorine (-F), chlorine (-Cl), bromine (-Br), and iodine (-I).

[0245] In the present invention, the term "substituted by a halogen group" may mean that at least one hydrogen atom bonded to a carbon atom of each substituent is replaced by a halogen group atom, and when the number of carbon atoms of each substituent is mentioned, it may mean the number of carbon atoms of each substituent.

[0246] In the present invention, "alkyl" may refer to a linear or branched hydrocarbon residue, and specific examples thereof may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and hexyl, depending on the number of carbon atoms defined.

[0247] In the present invention, "alkylthio group" may refer to an alkylthio group in which any one substituent around the sulfur bond center is an alkyl group, and in case of referring to the number of carbon atoms, it may refer to the number of carbon atoms of the alkyl group.

[0248] In the present invention, the "alkylsulfonate group" may refer to an alkylsulfonate group in which a sulfur atom of a sulfonate is substituted with an alkyl group, and in the case where the number of carbon atoms is mentioned, it may refer to the number of carbon atoms of the alkyl group.

[0249] In the present invention, "trialkylsilyl group" is represented by -SiR3, wherein each R independently represents an alkyl group as a substituent, and when the number of carbon atoms of the trialkylsilyl group is mentioned, it may refer to the total number of carbon atoms of each R.

[0250] In the present invention, a "monocyclic aromatic hydrocarbon ring" may refer to an aromatic hydrocarbon consisting of one ring, such as a benzene ring, and a "polycyclic aromatic hydrocarbon ring" may refer to an aromatic hydrocarbon consisting of two or more rings, such as a naphthalene ring.

[0251] In the present invention, "monocyclic heterocycle" may refer to a heterocycle consisting of one ring containing heteroatoms, such as furan, thiophene, pyrrole or pyridine; "polycyclic heterocycle" may refer to a heterocycle consisting of two or more rings containing heteroatoms, such as benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, benzopyrrole or dibenzopyrrole. The heterocycle may form an aliphatic ring or an aromatic ring.

[0252] In the present invention, "cycloalkyl" may mean a hydrocarbon residue having a ring form, and specific examples may include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, depending on the number of carbon atoms defined.

[0253] In the present invention, the "alkoxyalkyl group" may refer to an alkyl group substituted with an alkoxy group, and when the number of carbon atoms of the alkoxyalkyl group is mentioned, the sum of the carbon atoms of the alkoxy group and the alkyl group may be referred to.

[0254] In the present invention, the "arylalkoxyalkyl group" may refer to an alkyl group substituted with an alkoxy group containing an aryl group as a substituent, and when the number of carbon atoms of the arylalkoxyalkyl group is mentioned, the sum of the carbon atoms of the alkoxy group and the alkyl group may be referred to.

[0255] In the present invention, unless otherwise specified, "aryl" refers to an optionally substituted benzene ring or a ring system formed by fusing one or more optional substituents. Examples of optional substituents include substituted alkyl having 1 to 2 carbon atoms, substituted alkenyl having 2 to 3 carbon atoms, substituted alkynyl having 2 to 3 carbon atoms, heteroaryl, heterocyclyl, aryl, alkoxy optionally having 1 to 3 fluorine substituents, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonamido, carboxamide, aminocarbonyl, carboxyl, oxo, hydroxy, mercapto, amino, nitro, cyano, halogen or ureido. The ring or ring system may be optionally fused to an aromatic ring (e.g., a benzene ring), a carbocyclic ring, or a heterocyclic ring, which may optionally have one or more substituents, which may include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracenyl, and phenanthrenyl, and substituted derivatives thereof.

[0256] According to one embodiment of the present invention, R 1 R may be a fluorine group, a chlorine group, a bromine group, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or 1 With R 6 Combine to form a monocyclic or polycyclic heterocyclic ring. As a specific example, R 1 It may be a fluoro group, a trifluoromethyl group, a methoxy group, a methyl group, a trifluoromethoxy group, a trifluoromethylthio group, a methylthio group, a methylsulfonate group, or a trimethylsilyl group, or may be combined with R 6 Groups that combine to form furan or dibenzofuran.

[0257] According to one embodiment of the present invention, R 2 R may be a fluorine group, a chlorine group, a bromine group, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or 2 Can be used with R 7 Combine to form a monocyclic or polycyclic heterocyclic ring. As a specific example, R 2It may be a fluoro group, a trifluoromethyl group, a methoxy group, a methyl group, a trifluoromethoxy group, a trifluoromethylthio group, a methylthio group, a methylsulfonate group, or a trimethylsilyl group, or it may be a group with R 7 Groups that combine to form furan or dibenzofuran.

[0258] According to one embodiment of the present invention, R 1 and R 2 Can be identical to each other.

[0259] According to one embodiment of the present invention, R 3 and R 4 Each of them may be independently an alkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkoxyalkyl group having 6 to 12 carbon atoms, an arylalkoxyalkyl group having 10 to 20 carbon atoms, or a trialkylsilyl group, wherein the alkyl group of the trialkylsilyl group may be independently an alkyl group having 1 to 5 carbon atoms. As a specific example, R 3 and R 4 Each of the following may be independently an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group or a tributylsilyl group. As a more specific example, R 3 and R 4 can be independently tripropylsilyl, tributylsilyl or n-decyl. That is, the ligand compound can be: the phenyl group at the end of the diphosphino part has R 1 and R 2 The substituent has, at the meta-position or the para-position, an alkyl group having 10 carbon atoms or a silyl group substituted with an alkyl group having 3 or 4 carbon atoms as a substituent.

[0260] According to one embodiment of the present invention, R 5 It may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused to an aryl group having 6 to 10 carbon atoms. As a specific example, R 5 It may be an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms condensed with an aryl group having 6 to 10 carbon atoms.

[0261] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 1 may be a compound represented by any one of Chemical Formulas 2 to 5.

[0262] [Chemical formula 2]

[0263]

[0264] [Chemical formula 3]

[0265]

[0266] [Chemical formula 4]

[0267]

[0268] [Chemical formula 5]

[0269]

[0270] In Chemical Formulae 2 to 5, R 1 To R 7 are the same as defined in Chemical Formula 1, respectively.

[0271] According to one embodiment of the present invention, the ligand compound represented by Chemical Formula 1 may be represented by any one of Chemical Formulas 2-1 to 2-66 or Chemical Formulas 3-1 to 3-20.

[0272] [Chemical formula 2-1]

[0273]

[0274] [Chemical formula 2-2]

[0275]

[0276] [Chemical formula 2-3]

[0277]

[0278] [Chemical formula 2-4]

[0279]

[0280] [Chemical formula 2-5]

[0281]

[0282] [Chemical formula 2-6]

[0283]

[0284] [Chemical formula 2-7]

[0285]

[0286] [Chemical formula 2-8]

[0287]

[0288] [Chemical formula 2-9]

[0289]

[0290] [Chemical formula 2-10]

[0291]

[0292] [Chemical formula 2-11]

[0293]

[0294] [Chemical formula 2-12]

[0295]

[0296] [Chemical formula 2-13]

[0297]

[0298] [Chemical formula 2-14]

[0299]

[0300] [Chemical formula 2-15]

[0301]

[0302] [Chemical formula 2-16]

[0303]

[0304] [Chemical formula 2-17]

[0305]

[0306] [Chemical formula 2-18]

[0307]

[0308] [Chemical formula 2-19]

[0309]

[0310] [Chemical formula 2-20]

[0311]

[0312] [Chemical formula 2-21]

[0313]

[0314] [Chemical formula 2-22]

[0315]

[0316] [Chemical formula 2-23]

[0317]

[0318] [Chemical formula 2-24]

[0319]

[0320] [Chemical formula 2-25]

[0321]

[0322] [Chemical formula 2-26]

[0323]

[0324] [Chemical formula 2-27]

[0325]

[0326] [Chemical formula 2-28]

[0327]

[0328] [Chemical formula 2-29]

[0329]

[0330] [Chemical formula 2-30]

[0331]

[0332] [Chemical formula 2-31]

[0333]

[0334] [Chemical formula 2-32]

[0335]

[0336] [Chemical formula 2-33]

[0337]

[0338] [Chemical formula 2-34]

[0339]

[0340] [Chemical formula 2-35]

[0341]

[0342] [Chemical formula 2-36]

[0343]

[0344] [Chemical formula 2-37]

[0345]

[0346] [Chemical formula 2-38]

[0347]

[0348] [Chemical formula 2-39]

[0349]

[0350] [Chemical formula 2-40]

[0351]

[0352] [Chemical formula 2-41]

[0353]

[0354] [Chemical formula 2-42]

[0355]

[0356] [Chemical formula 2-43]

[0357]

[0358] [Chemical formula 2-44]

[0359]

[0360] [Chemical formula 2-45]

[0361]

[0362] [Chemical formula 2-46]

[0363]

[0364] [Chemical formula 2-47]

[0365]

[0366] [Chemical formula 2-48]

[0367]

[0368] [Chemical formula 2-49]

[0369]

[0370] [Chemical formula 2-50]

[0371]

[0372] [Chemical formula 2-51]

[0373]

[0374] [Chemical formula 2-52]

[0375]

[0376] [Chemical formula 2-53]

[0377]

[0378] [Chemical formula 2-54]

[0379]

[0380] [Chemical formula 2-55]

[0381]

[0382] [Chemical formula 2-56]

[0383]

[0384] [Chemical formula 2-57]

[0385]

[0386] [Chemical formula 2-58]

[0387]

[0388] [Chemical formula 2-59]

[0389]

[0390] [Chemical formula 2-60]

[0391]

[0392] [Chemical formula 2-61]

[0393]

[0394] [Chemical formula 2-62]

[0395]

[0396] [Chemical formula 2-63]

[0397]

[0398] [Chemical formula 2-64]

[0399]

[0400] [Chemical formula 2-65]

[0401]

[0402] [Chemical formula 2-66]

[0403]

[0404] [Chemical formula 3-1]

[0405]

[0406] [Chemical formula 3-2]

[0407]

[0408] [Chemical formula 3-3]

[0409]

[0410] [Chemical formula 3-4]

[0411]

[0412] [Chemical formula 3-5]

[0413]

[0414] [Chemical formula 3-6]

[0415]

[0416] [Chemical formula 3-7]

[0417]

[0418] [Chemical formula 3-8]

[0419]

[0420] [Chemical formula 3-9]

[0421]

[0422] [Chemical formula 3-10]

[0423]

[0424] [Chemical formula 3-11]

[0425]

[0426] [Chemical formula 3-12]

[0427]

[0428] [Chemical formula 3-13]

[0429]

[0430] [Chemical formula 3-14]

[0431]

[0432] [Chemical formula 3-15]

[0433]

[0434] [Chemical formula 3-16]

[0435]

[0436] [Chemical formula 3-17]

[0437]

[0438] [Chemical formula 3-18]

[0439]

[0440] [Chemical formula 3-19]

[0441]

[0442] [Chemical formula 3-20]

[0443]

[0444] According to one embodiment of the present invention, in addition to the above specific examples, the ligand compound may be implemented in various combinations within the range satisfying the above conditions, and any compound represented by Chemical Formula 1 may be used as the ligand compound according to the present invention.

[0445] Organic chromium compounds and catalyst compositions

[0446] The present invention provides an organic chromium compound including a ligand compound represented by Chemical Formula 1 and chromium (Cr) coordinated to the ligand compound.

[0447] According to one embodiment of the present invention, the organic chromium compound is a chromium complex of a ligand compound, which has a form in which the chromium of the chromium source forms a coordination bond with any one or more of the unshared electron pairs of N and two P in the ligand compound represented by Chemical Formula 1. That is, the phosphorus atom or nitrogen atom of the diphosphino part provides a structure in which the chromium atom provides an unshared electron pair, and in particular, a bidentate state in which two pairs of unshared electron pairs are coordinated is ideal. The organic chromium compound can be applied to a catalytic system for ethylene oligomerization to exhibit excellent catalytic activity and high selectivity for 1-hexene or 1-octene.

[0448] In the present invention, "catalyst composition" refers to a catalyst composition in a state as an active catalyst composition that can be obtained by adding three components including a chromium source, a ligand compound and a co-catalyst, or two components including a transition metal compound and a co-catalyst simultaneously or in any order. Here, the catalyst composition may also be referred to as a catalyst system, and in the present invention, the catalyst composition and the catalyst system have the same meaning. The catalyst composition may be added in the presence or absence of a solvent and a monomer, and a three-component or two-component catalyst composition may be used in a supported or unsupported state.

[0449] The present invention provides a catalyst composition comprising a ligand compound, chromium and a co-catalyst. As described above, the ligand compound represented by Chemical Formula 1 and chromium can coordinate to form an organic chromium compound. That is, the catalyst system can be a three-component catalyst system comprising chromium, a ligand compound represented by Chemical Formula 1 and a co-catalyst, or can be a two-component catalyst system comprising an organic chromium compound and a co-catalyst. As a specific example, the catalyst composition can be a composition comprising a ligand compound, an organic chromium compound containing chromium coordinated with the ligand compound, and a co-catalyst. In addition, the catalyst composition can be a composition comprising a chromium compound, wherein some components of the co-catalyst are combined with the organic chromium compound.

[0450] 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 having an oxidation state of 0 to 6. As a specific example, the chromium source may be chromium metal or a compound in which any organic or inorganic group is bonded to chromium. Here, the organic group may be, for example, an alkyl, alkoxy, ester, ketone, amide or carboxylate group, each having 1 to 20 carbon atoms, and the inorganic group may be a halide, sulfate, oxide, etc.

[0451] According to one embodiment of the present invention, the chromium source is a compound that exhibits high activity in olefin oligomerization reactions, is easy to use, and is easy to obtain, and it can be one or more compounds selected from chromium (III) acetylacetonate, tetrahydrofuran chromium (III) chloride, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) valerate, chromium (III) laurate, tris (2,2,6,6-tetramethyl-3.5-heptanedione) chromium (III), and chromium (III) stearate.

[0452] According to one embodiment of the present invention, the co-catalyst may be at least one or more selected from the group consisting of compounds represented by Chemical Formula 6 to Chemical Formula 9.

[0453] [Chemical formula 6]

[0454] -[Al(R 13 )-O] a -

[0455] In Chemical Formula 6, R 13 Each is independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group, and a is an integer of 2 or more.

[0456] [Chemical formula 7]

[0457] E(R 14 )3

[0458] In Chemical Formula 7, E is aluminum or boron, and R 14 Each is independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group.

[0459] [Chemical formula 8]

[0460] [LH] + [G(Y)4] -

[0461] [Chemical formula 9]

[0462] [L] + [G(Y)4] -

[0463] In Formulas 8 and 9, L is a neutral or cationic Lewis acid, [LH] +is a Bronsted acid, G is a Group 13 element, and Y is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein, when the alkyl group or the aryl group is substituted, the substituent is a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0464] According to one embodiment of the present invention, the catalyst composition can be prepared by any of a variety of methods. As a specific example, first, the catalyst composition can be prepared by a step including contacting an organic chromium compound with a compound represented by Chemical Formula 6 or Chemical Formula 7. Second, the catalyst composition can be prepared by a step including contacting an organic chromium compound with a compound represented by Chemical Formula 6 or Chemical Formula 7 to obtain a mixture; and a step of adding a compound represented by Chemical Formula 8 or Chemical Formula 9 to the mixture. Third, the catalyst composition can be prepared by a step including contacting an organic chromium compound with a compound represented by Chemical Formula 8 or Chemical Formula 9. Fourth, the catalyst composition can be prepared by a step including contacting an organic chromium compound with a compound represented by Chemical Formula 8 or Chemical Formula 9 to obtain a mixture; and a step of adding a compound represented by Chemical Formula 6 or Chemical Formula 7 to the mixture. Fifth, the catalyst composition can be prepared by a step including contacting a chromium source with a compound represented by Chemical Formula 8 or Chemical Formula 9 to obtain a mixture; and a step of contacting a ligand compound with a reactant.

[0465] According to one embodiment of the present invention, in the case of the first method or the third method in the catalyst composition preparation method, the molar ratio of the compound represented by Chemical Formula 6 or Chemical Formula 7 to the organic chromium compound may be 1:2 to 1:5,000, as a specific example, 1:100 to 1:3,000, and as a more specific example, 1:300 to 1:1,500. Within this range, the alkylation of the organic chromium compound can be completely performed, thereby improving the activity of the catalyst composition, and the activity of the alkylated organic chromium compound can be prevented from being reduced due to a side reaction between the remaining alkylating agents, while improving the economic efficiency and the purity of the prepared linear α-olefin.

[0466] According to one embodiment of the present invention, in the case of the second method in the catalyst composition preparation method, the molar ratio of the compound represented by Chemical Formula 8 or Chemical Formula 9 to the organic chromium compound may be 1:1 to 1:500, as a specific example, 1:1 to 1:50, and as a more specific example, 1:1 to 1:25. Within this range, the amount of the activator is sufficient, so the metal compound is fully activated, thereby improving the activity of the catalyst composition. In addition, the amount of the remaining activator is minimized, which makes it possible to improve the economic efficiency and the purity of the prepared linear α-olefin.

[0467] According to one embodiment of the present invention, the compound represented by Chemical Formula 6 may be an alkylaluminoxane, and as a specific example may be methylaluminoxane, ethylaluminoxane, isobutylaluminoxane or butylaluminoxane, and as a more specific example may be methylaluminoxane.

[0468] According to one embodiment of the present invention, the compound represented by Chemical Formula 7 may be trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, dialkylaluminum hydride, alkylaluminum dihydride, trialkylboron, or the like. As a specific example, the compound represented by Chemical Formula 6 may be a trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum or tri-p-tolylaluminum; a dialkylaluminum halide such as diethylaluminum chloride; a dialkylaluminum hydride such as 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, phenethylaluminum hydride, phenyl-n-propylaluminum hydride or n-octylaluminum hydride; or a trialkylboron such as trimethylboron, triethylboron, triisobutylboron, tripropylboron, or tributylboron.

[0469] According to one embodiment of the present invention, the compound represented by Chemical Formula 8 or Chemical Formula 9 may be trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dioctadecylanilinium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, triethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, tributylammonium tetra(p-tolyl)borate, methyldioctadecylammonium tetra(p-tolyl)borate, N,N-dimethylanilinium tetra(p-tolyl)borate 、N,N-diethylanilinium tetra(p-tolyl)borate、N,N-dioctadecylanilinium 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、methyldioctadecylammonium tetra(o-p-dimethylphenyl)borate、N,N-dimethylanilinium tetra(o-p-dimethylphenyl)borate、N,N-diethylanilinium tetra(o-p-dimethylphenyl)borate、N,N-dioctadecylanilinium tetra(o-p-dimethylphenyl)borate、trimethylammonium tetra(p-trifluoromethylphenyl)borate、triethylammonium tetra(o-p-dimethylphenyl)borate (p-trifluoromethylphenyl)borate, tripropylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakis(p-trifluoromethylphenyl)borate, methyldioctadecylammonium tetrakis(p-trifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(p-trifluoromethylphenyl)borate, N,N-diethylanilinium tetrakis(p-trifluoromethylphenyl)borate, N,N-dioctadecylammonium tetrakis(p-trifluoromethylphenyl)borate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate Salt, 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, tripropyltetraphenylaluminate, tributylammonium tetraphenylaluminate, trimethylammonium tetra(p-tolyl)aluminate, triethylammonium tetra(p-tolyl)aluminate, tripropylammonium tetra(p-tolyl)aluminate, tributylammonium tetra(p-tolyl)aluminate, and the like.

[0470] According to one embodiment of the present invention, the content ratio between the components forming the catalyst composition can be determined in consideration of factors such as catalytic activity, selectivity of linear α-olefins, etc. As a specific example, in the case where the catalyst composition is a three-component based catalyst composition, the molar ratio (diphosphino moiety: chromium source: co-catalyst) in the ligand compound can 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, in the case where the catalyst composition is a two-component based catalyst composition, the molar ratio (diphosphino moiety: co-catalyst) in the organic chromium compound can be adjusted to about 1:1 to 1:10,000, 1:1 to 1:5,000, or 1:1 to 1:3,000.

[0471] According to one embodiment of the present invention, in the production of the catalyst composition, the reaction solvent used may be a hydrocarbon-based solvent such as pentane, hexane or heptane; and an aromatic solvent such as benzene or toluene.

[0472] According to one embodiment of the present invention, the components forming the catalyst composition are added simultaneously or in any order in the presence or absence of a suitable solvent and monomer, so that the catalyst composition can be used as an active catalyst composition. In this case, the suitable solvent can be heptane, toluene, cyclohexane, methylcyclohexane, 1-hexene, 1-octene, ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, etc.

[0473] According to one embodiment of the present invention, the organic chromium compound and the co-catalyst may be used in a form in which the organic chromium compound and the co-catalyst are supported on a carrier, and in this case, the carrier may be silicon oxide or aluminum oxide.

[0474] According to one 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 ethylene oligomerization in the form of a ligand compound represented by chemical formula 1 supported on a carrier. The carrier may be a metal, a metal salt or a metal oxide, applied to a supported catalyst. As a specific example, the carrier may be silicon oxide, silicon oxide-aluminum oxide or silicon oxide-magnesium oxide, and may include metal oxide, carbonate, sulfate or nitrate components, such as Na2O, K2CO3, BaSO4 or Mg(NO3)2.

[0475] According to one embodiment of the present invention, the catalyst composition can be used for the trimerization or tetramerization reaction of ethylene, and can produce 1-hexene or 1-octene with high selectivity as described above.

[0476] Ethylene oligomerization process

[0477] The present invention provides a method for producing linear α-olefins as an ethylene oligomerization method, comprising a step (S10) of oligomerizing ethylene in the presence of a catalyst composition.

[0478] In the present invention, "oligomerization" means that olefins are oligomerized. Depending on the number of olefins to be polymerized, it is called trimerization or tetramerization, and is generally called polymerization. In particular, in this specification, it may refer to the selective generation of 1-hexene and 1-octene as the main comonomers of LLDPE from ethylene.

[0479] According to one embodiment of the present invention, the oligomerization reaction of ethylene may be a trimerization or tetramerization reaction of ethylene to produce 1-hexene or 1-octene as a reaction result, and thus the linear α-olefin may be 1-hexene, 1-octene, or a mixture thereof.

[0480] According to one embodiment of the present invention, the ethylene oligomerization method can be carried out by using ethylene as a raw material and adopting the above-mentioned catalyst composition and conventional equipment and contact technology. As a specific example, the oligomerization reaction of ethylene can be carried out as a homogeneous liquid phase reaction in the presence or absence of an inert solvent, or as a slurry reaction in a partially or completely insoluble form of the catalyst composition, or as a bulk phase reaction or gas phase reaction with the product alpha-olefin as the main medium.

[0481] According to one embodiment of the present invention, the oligomerization reaction of ethylene can be carried out in an inert solvent. As a specific example, the inert solvent can be benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, or 2,2,4-trimethylpentane.

[0482] According to one embodiment of the present invention, the oligomerization reaction of ethylene may be carried out at a temperature of 0° C. to 200° C., 0° C. to 150° C., 30° C. to 100° C., or 50° C. to 100° C. In addition, the above reaction may be carried out at a pressure of 15 psig to 3,000 psig, 15 psig to 1,500 psig, or 15 psig to 1,000 psig.

[0483] The embodiments of the present invention will be described in detail below so that those skilled in the art can easily implement the embodiments of the present invention. However, the present invention can be implemented in various different forms and is therefore not limited to the embodiments described herein.

[0484] Synthesis Examples and Comparative Synthesis Examples

[0485] Synthesis Example 1 to Synthesis Example 66: Synthesis of Ligand Compounds Represented by Chemical Formula 2-1 to Chemical Formula 2-66

[0486] 20mmol (2 equivalents) of p-bromo-(tri-n-butylsilyl)-C6H4 was dissolved in 20ml of tetrahydrofuran and then cooled to -78°C. While maintaining the temperature, 20mmol (2 equivalents) of n-butyllithium was added dropwise thereto and then stirred for 3 hours. Next, 10mmol (1 equivalent) of dichloro(diethylamino)phosphine dissolved in 10ml of tetrahydrofuran was added dropwise thereto, then the temperature was raised to room temperature and then stirred overnight. Afterwards, the solvent was removed by vacuum, the intermediate obtained was dissolved in 30ml of hexane, HCl (2 equivalents in ether) was then added thereto, then stirred for 15 minutes and filtered. The filtrate was vacuum dried to obtain (p-(tri-n-butylsilyl)-C6H4)2PCl. 11mmol (2.2 equivalents) of R 5 -NH2 and 10 ml of dichloromethane were added to the dried flask and stirring was started. 5 mmol (1 equivalent) of (p-(tri-n-butylsilyl)-C6H4)2PCl was diluted in 10 ml of dichloromethane and then slowly added to the flask. After the reaction was completed by stirring for 4 hours, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and (p-(tri-n-butylsilyl)-C6H4)2P-NHR was obtained by column chromatography. 5 .

[0487] 5mmol (1 equivalent) of PCl3 was dissolved in 10ml of ether and then cooled to 0°C. After that, 10mmol (2 equivalents) of HNEt2 dissolved in 10ml of ether was slowly added and stirred overnight. The solid was removed by a filter, and 2 equivalents of ArMgBr prepared from Ar and Mg turnings were slowly added thereto, and then stirred at room temperature overnight. Thereafter, HCl (2 equivalents in ether) was added and stirred at room temperature for 30 minutes. The solid was removed by a filter and Ar2PCl was obtained by decompression. 5mmol (1 equivalent) of Ar2PCl was dissolved in 10ml of dichloromethane, and then 15mmol (3 equivalents) of triethylamine was added thereto. Subsequently, 5mmol (1 equivalent) of (p-(tri-n-butylsilyl)-C6H4)2P-NHR 5 The mixture was dissolved in dichloromethane, slowly added thereto, and stirred at room temperature overnight. The solvent was removed by vacuum extraction, and then dissolved in hexane, and column chromatography was performed to obtain ligand compounds represented by Chemical Formulas 2-1 to 2-66.

[0488] Substituent R of the reactants used in Synthesis Examples 1 to 66 5 and Ar are shown in Table 1 below, and the structures and 1 The H NMR data are shown below.

[0489] [Table 1]

[0490]

[0491]

[0492]

[0493]

[0494]

[0495]

[0496]

[0497]

[0498] Synthesis Example 1 (Chemical Formula 2-1)

[0499]

[0500] N-(Bis(2-fluorophenyl)phosphino)-N-methyl-1,1-bis(4-(tributylsilyl)phenyl)phosphine

[0501] 1 H NMR (500MHz, CDCl3): δ7.44(m,4H),7.40(m,2H),7.27(m,2H),7.19(m,6H),7.0 6(m,2H),2.53(m,3H),1.47(m,12H),1.39(m,12H),1.32(m,12H),0.95(m,18H)

[0502] Synthesis Example 2 (Chemical Formula 2-2)

[0503]

[0504] N-(Bis(2-(trifluoromethyl)phenyl)phosphino)-N-methyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0505] 1 H NMR (500MHz, CDCl3): δ7.49(m,2H),7.46(m,2H),7.42(m,4H),7.22(m,2H),7.10(m,4 H),7.07(m,2H),2.49(m,3H),1.43(m,12H),1.38(m,12H),1.30(m,12H),0.99(m,18H)

[0506] Synthesis Example 3 (Chemical Formula 2-3)

[0507]

[0508] N-(Bis(2-methoxyphenyl)phosphino)-N-methyl-1,1-bis(4-(tributylsilyl)phenyl)phosphineamine

[0509] 1 H NMR (500MHz, CDCl3): δ7.43(m,2H),7.41(m,4H),7.14(m,2H),7.13(m,2H),7.09(m,4H),7.0 4(m,2H),3.99(m,6H),2.52(m,3H),1.49(m,12H),1.41(m,12H),1.24(m,12H),0.95(m,18H)

[0510] Synthesis Example 4 (Chemical Formula 2-4)

[0511]

[0512] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1,1-di-o-tolylphosphinamide

[0513] 1 H NMR (500MHz, CDCl3): δ7.46(m,4H),7.33(m,2H),7.25(m,2H),7.15(m,4H),7.13(m,2H),7.0 9(m,2H),2.53(m,3H),2.36(m,6H),1.46(m,12H),1.42(m,12H),1.30(m,12H),0.98(m,18H)

[0514] Synthesis Example 5 (Chemical Formula 2-5)

[0515]

[0516] N-(Bis(2-(trifluoromethoxy)phenyl)phosphino)-N-methyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0517] 1 H NMR (500MHz, CDCl3): δ7.48(m,4H),7.41(m,2H),7.18(m,2H),7.14(m,4H),7.12(m,2 H),7.04(m,2H),2.51(m,3H),1.52(m,12H),1.38(m,12H),1.26(m,12H),1.00(m,18H)

[0518] Synthesis Example 6 (Chemical Formula 2-6)

[0519]

[0520] N-(Bis(2-((trifluoromethyl)thio)phenyl)phosphino)-N-methyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0521] 1 H NMR (500MHz, CDCl3): δ7.42(m,4H),7.21(m,2H),7.19(m,4H),7.18(m,4H),7.0 5(m,2H),2.52(m,3H),1.52(m,12H),1.40(m,12H),1.33(m,12H),0.94(m,18H)

[0522] Synthesis Example 7 (Chemical Formula 2-7)

[0523]

[0524] N-(Bis(2-(methylthio)phenyl)phosphino)-N-methyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamide

[0525] 1 H NMR (500MHz, CDCl3): δ7.43(m,4H),7.25(m,4H),7.17(m,6H),7.07(m,2H),2.5 3(m,3H),2.52(m,6H),1.49(m,12H),1.38(m,12H),1.29(m,12H),0.97(m,18H)

[0526] Synthesis Example 8 (Chemical Formula 2-8)

[0527]

[0528] (((Bis(4-(tributylsilyl)phenyl)phosphino)(methyl)amino)phosphinediyl)bis(2,1-phenylene) dimethanesulfonate

[0529] 1 H NMR (500MHz, CDCl3): δ7.53(m,2H),7.43(m,6H),7.39(m,2H),7.23(m,2H),7.17(m,4 H),3.55(m,6H),2.54(m,3H),1.45(m,12H),1.37(m,12H),1.28(m,12H),0.99(m,18H)

[0530] Synthesis Example 9 (Chemical Formula 2-9)

[0531]

[0532] N-(Bis(2-(trimethylsilyl)phenyl)phosphino)-N-methyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0533] 1 H NMR (500MHz, CDCl3): δ7.46(m,8H),7.27(m,2H),7.09(m,6H),2.48(m,3H),1.46(m,12H),1.41(m,12H),1.25(m,12H),0.92(m,18H),0.27(m,18H)

[0534] Synthesis Example 10 (Chemical Formula 2-10)

[0535]

[0536] 1,1-Bis(benzofuran-7-yl)-N-(bis(4-(tributylsilyl)phenyl)phosphino)-N-methylphosphinamine

[0537] 1 H NMR (500MHz, CDCl3): δ7.46(m,4H),7.25(m,2H),7.14(m,4H),7.09(m,4H),4.37(m,4 H),2.99(m,4H),2.48(m,3H),1.50(m,12H),1.36(m,12H),1.30(m,12H),0.95(m,18H)

[0538] Synthesis Example 11 (Chemical Formula 2-11)

[0539]

[0540] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1,1-bis(dibenzo[b,d]furan-4-yl)-N-methylphosphinamine

[0541] 1 H NMR (500MHz, CDCl3): δ8.00(m,4H),7.56(m,2H),7.49(m,4H),7.39(m,2H),7.36(m,2H),7.2 8(m,4H),7.13(m,4H),2.53(m,3H),1.52(m,12H),1.36(m,12H),1.28(m,12H),0.95(m,18H)

[0542] Synthesis Example 12 (Chemical Formula 2-12)

[0543]

[0544] N-(Bis(2-fluorophenyl)phosphino)-N-butyl-1,1-bis(4-(tributylsilyl)phenyl)phosphine

[0545] 1 H NMR (500MHz, CDCl3): δ7.43(m,4H),7.40(m,2H),7.25(m,2H),7.15(m,6H),7.13(m,2H),2.7 1(m,2H),1.48(m,2H),1.43(m,12H),1.40(m,14H),1.30(m,12H),0.95(m,18H),0.92(m,3H)

[0546] Synthesis Example 13 (Chemical Formula 2-13)

[0547]

[0548] N-(Bis(2-(trifluoromethyl)phenyl)phosphino)-N-butyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0549] 1 H NMR (500MHz, CDCl3): δ7.47(m,2H),7.46(m,4H),7.42(m,2H),7.26(m,2H),7.14(m,4H),7.09(m,2H),2.6 6(m,2H),1.49(m,12H),1.45(m,2H),1.43(m,12H),1.38(m,2H),1.31(m,12H),0.94(m,18H),0.91(m,3H)

[0550] Synthesis Example 14 (Chemical Formula 2-14)

[0551]

[0552] N-(Bis(2-methoxyphenyl)phosphino)-N-butyl-1,1-bis(4-(tributylsilyl)phenyl)phosphine

[0553] 1H NMR (500MHz, CDCl3): δ7.48(m,4H),7.40(m,2H),7.16(m,4H),7.12(m,4H),7.02(m,2H),3.91(m,6H),2.7 0(m,2H),1.48(m,12H),1.45(m,2H),1.42(m,12H),1.37(m,2H),1.27(m,12H),1.02(m,18H),0.92(m,3H)

[0554] Synthesis Example 15 (Chemical Formula 2-15)

[0555]

[0556] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1,1-di-o-tolylphosphinamide

[0557] 1 H NMR (500MHz, CDCl3): δ7.46(m,4H),7.35(m,2H),7.28(m,2H),7.17(m,4H),7.15(m,2H),7.07(m,2H),2.64(m,2 H),2.39(m,6H),1.51(m,12H),1.49(m,2H),1.38(m,12H),1.33(m,2H),1.27(m,12H),0.98(m,3H),0.93(m,18H)

[0558] Synthesis Example 16 (Chemical Formula 2-16)

[0559]

[0560] N-(Bis(2-(trifluoromethoxy)phenyl)phosphino)-N-butyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0561] 1 H NMR (500MHz, CDCl3): δ7.47(m,4H),7.45(m,2H),7.20(m,2H),7.16(m,2H),7.15(m,4H),7.04(m,2H),2.6 4(m,2H),1.49(m,2H),1.47(m,12H),1.41(m,12H),1.34(m,2H),1.23(m,12H),0.95(m,3H),0.93(m,18H)

[0562] Synthesis Example 17 (Chemical Formula 2-17)

[0563]

[0564] N-(Bis(2-((trifluoromethyl)thio)phenyl)phosphino)-N-butyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0565] 1 H NMR (500MHz, CDCl3): δ7.50(m,4H),7.25(m,2H),7.20(m,4H),7.15(m,4H),7.10(m,2H),2.69(m,2 H),1.46(m,12H),1.45(m,2H),1.44(m,12H),1.38(m,2H),1.31(m,12H),0.97(m,18H),0.91(m,3H)

[0566] Synthesis Example 18 (Chemical Formula 2-18)

[0567]

[0568] N-(Bis(2-(methylthio)phenyl)phosphino)-N-butyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0569] 1 H NMR (500MHz, CDCl3): δ7.48(m,4H),7.25(m,4H),7.23(m,2H),7.10(m,4H),7.09(m,2H),2.66(m,2H),2.5 2(m,6H),1.50(m,2H),1.43(m,12H),1.37(m,12H),1.34(m,2H),1.27(m,12H),0.95(m,3H),0.93(m,18H)

[0570] Synthesis Example 19 (Chemical Formula 2-19)

[0571]

[0572] (((Bis(4-(tributylsilyl)phenyl)phosphino)(butyl)amino)phosphinediyl)bis(2,1-phenylene) dimethanesulfonate

[0573] 1H NMR (500MHz, CDCl3): δ7.54(m,2H),7.42(m,2H),7.40(m,4H),7.39(m,2H),7.20(m,2H),7.15(m,4H),3.53(m,6 H),2.65(m,2H),1.52(m,2H),1.45(m,12H),1.41(m,2H),1.40(m,12H),1.31(m,12H),1.02(m,18H),0.97(m,3H)

[0574] Synthesis Example 20 (Chemical Formula 2-20)

[0575]

[0576] N-(Bis(2-(trimethylsilyl)phenyl)phosphino)-N-butyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0577] 1 H NMR (500MHz, CDCl3): δ7.45(m,8H),7.34(m,2H),7.15(m,6H),2.65(m,2H),1.51(m,12H),1. 46(m,2H),1.42(m,12H),1.35(m,2H),1.25(m,12H),1.00(m,3H),0.96(m,18H),0.34(m,18H)

[0578] Synthesis Example 21 (Chemical Formula 2-21)

[0579]

[0580] 1,1-Bis(benzofuran-7-yl)-N-(bis(4-(tributylsilyl)phenyl)phosphino)-N-butylphosphinamide

[0581] 1 H NMR (500MHz, CDCl3): δ7.50(m,4H),7.27(m,2H),7.13(m,4H),7.03(m,4H),4.32(m,4H),3.02(m,4 H),2.72(m,2H),1.54(m,2H),1.53(m,12H),1.44(m,12H),1.35(m,2H),1.25(m,12H),0.98(m,21H)

[0582] Synthesis Example 22 (Chemical Formula 2-22)

[0583]

[0584] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1,1-bis(dibenzo[b,d]furan-4-yl)phosphinamine

[0585] 1 H NMR (500MHz, CDCl3): δ8.08(m,4H),7.61(m,2H),7.49(m,4H),7.42(m,2H),7.31(m,4H),7.30(m,2H),7.18(m,4 H),2.69(m,2H),1.51(m,12H),1.46(m,2H),1.44(m,12H),1.37(m,2H),1.26(m,12H),1.01(m,3H),0.93(m,18H)

[0586] Synthesis Example 23 (Chemical Formula 2-23)

[0587]

[0588] N-(Bis(2-fluorophenyl)phosphino)-N-isopropyl-1,1-bis(4-(tributylsilyl)phenyl)phosphine

[0589] 1 H NMR (500MHz, CDCl3): δ7.48(m,4H),7.32(m,2H),7.20(m,2H),7.12(m,6H),7.07(m,2 H),2.88(m,1H),1.46(m,12H),1.45(m,12H),1.24(m,12H),1.14(m,6H),1.02(m,18H)

[0590] Synthesis Example 24 (Chemical Formula 2-24)

[0591]

[0592] N-(Bis(2-(trifluoromethyl)phenyl)phosphino)-N-isopropyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0593] 1 H NMR (500MHz, CDCl3): δ7.47(m,2H),7.44(m,2H),7.42(m,4H),7.18(m,2H),7.15(m,4H),7.0 4(m,2H),2.93(m,1H),1.47(m,12H),1.46(m,12H),1.25(m,12H),1.08(m,6H),0.98(m,18H)

[0594] Synthesis Example 25 (Chemical Formula 2-25)

[0595]

[0596] N-(Bis(2-methoxyphenyl)phosphino)-N-isopropyl-1,1-bis(4-(tributylsilyl)phenyl)phosphineamine

[0597] 1 H NMR (500MHz, CDCl3): δ7.46(m,4H),7.40(m,2H),7.20(m,2H),7.18(m,4H),7.15(m,2H),7.02(m,2 H),3.93(m,6H),2.86(m,1H),1.47(m,12H),1.45(m,12H),1.25(m,12H),1.15(m,6H),0.94(m,18H)

[0598] Synthesis Example 26 (Chemical Formula 2-26)

[0599]

[0600] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1,1-di-o-tolylphosphine

[0601] 1 H NMR (500MHz, CDCl3): δ7.46(m,4H),7.33(m,2H),7.27(m,2H),7.18(m,4H),7.15(m,2H),7.13(m,2 H),2.84(m,1H),2.40(m,6H),1.50(m,12H),1.37(m,12H),1.25(m,12H),1.15(m,6H),1.00(m,18H)

[0602] Synthesis Example 27 (Chemical Formula 2-27)

[0603]

[0604] N-(Bis(2-(trifluoromethoxy)phenyl)phosphino)-N-isopropyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0605] 1H NMR (500MHz, CDCl3): δ7.42(m,2H),7.41(m,4H),7.20(m,2H),7.15(m,2H),7.10(m,4H),7.0 2(m,2H),2.87(m,1H),1.45(m,12H),1.43(m,12H),1.24(m,12H),1.15(m,6H),0.99(m,18H)

[0606] Synthesis Example 28 (Chemical Formula 2-28)

[0607]

[0608] N-(Bis(2-((trifluoromethyl)thio)phenyl)phosphino)-N-isopropyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0609] 1 H NMR (500MHz, CDCl3): δ7.47(m,4H),7.24(m,6H),7.17(m,4H),7.08(m,2H),2.8 9(m,1H),1.48(m,12H),1.41(m,12H),1.27(m,12H),1.13(m,6H),0.97(m,18H)

[0610] Synthesis Example 29 (Chemical Formula 2-29)

[0611]

[0612] N-(Bis(2-(methylthio)phenyl)phosphino)-N-isopropyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0613] 1 H NMR (500MHz, CDCl3): δ7.47(m,4H),7.20(m,4H),7.18(m,2H),7.14(m,4H),7.10(m,2H),2.8 7(m,1H),2.51(m,6H),1.47(m,12H),1.39(m,12H),1.23(m,12H),1.08(m,6H),0.94(m,18H)

[0614] Synthesis Example 30 (Chemical Formula 2-30)

[0615]

[0616] (((Bis(4-(tributylsilyl)phenyl)phosphino)(isopropyl)amino)phosphinediyl)bis(2,1-phenylene) dimethanesulfonate

[0617] 1 H NMR (500MHz, CDCl3): δ7.54(m,2H),7.48(m,2H),7.46(m,4H),7.34(m,2H),7.25(m,2H),7.18(m,4 H),3.58(m,6H),2.92(m,1H),1.46(m,12H),1.43(m,12H),1.27(m,12H),1.08(m,6H),0.92(m,18H)

[0618] Synthesis Example 31 (Chemical Formula 2-31)

[0619]

[0620] N-(Bis(2-(trimethylsilyl)phenyl)phosphino)-N-isopropyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0621] 1 H NMR (500MHz, CDCl3): δ7.48(m,8H),7.32(m,2H),7.16(m,6H),2.86(m,1H),1.4 4(m,12H),1.37(m,12H),1.32(m,12H),1.11(m,6H),0.92(m,18H),0.27(m,18H)

[0622] Synthesis Example 32 (Chemical Formula 2-32)

[0623]

[0624] 1,1-Bis(benzofuran-7-yl)-N-(bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropylphosphinamide

[0625] 1 H NMR (500MHz, CDCl3): δ7.68(m,1H),7.64(m,1H),7.46(m,4H),7.32(m,1H),7.28(m,1H),7.26(m,1H),7.12(m,4H),7.10(m,2 H),6.79(m,1H),4.30(m,2H),3.03(m,2H),2.86(m,1H),1.49(m,12H),1.43(m,12H),1.31(m,12H),1.15(m,6H),0.94(m,18H)

[0626] Synthesis Example 33 (Chemical Formula 2-33)

[0627]

[0628] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1,1-bis(dibenzo[b,d]furan-4-yl)-N-isopropylphosphinamine

[0629] 1 H NMR (500MHz, CDCl3): δ8.01(m,4H),7.60(m,2H),7.48(m,4H),7.41(m,2H),7.31(m,2H),7.30(m,2H),7.2 3(m,2H),7.15(m,4H),2.88(m,1H),1.48(m,12H),1.39(m,12H),1.24(m,12H),1.10(m,6H),0.95(m,18H)

[0630] Synthesis Example 34 (Chemical Formula 2-34)

[0631]

[0632] N-(Bis(2-fluorophenyl)phosphino)-N-cyclohexyl-1,1-bis(4-(tributylsilyl)phenyl)phosphine

[0633] 1 H NMR (500MHz, CDCl3): δ7.46(m,4H),7.30(m,2H),7.28(m,2H),7.16(m,6H),7.12(m,2H),2.61(m,1H),1.74(m,2H),1.5 0(m,2H),1.49(m,12H),1.48(m,1H),1.46(m,1H),1.42(m,12H),1.26(m,12H),1.23(m,2H),1.21(m,2H),0.98(m,18H)

[0634] Synthesis Example 35 (Chemical Formula 2-35)

[0635]

[0636] N-(Bis(2-(trifluoromethyl)phenyl)phosphino)-N-cyclohexyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0637] 1H NMR (500MHz, CDCl3): δ7.50(m,2H),7.48(m,4H),7.42(m,2H),7.18(m,6H),7.06(m,2H),2.61(m,1H),1.84(m,2H),1.5 6(m,2H),1.51(m,1H),1.49(m,1H),1.48(m,12H),1.39(m,12H),1.25(m,2H),1.23(m,12H),1.19(m,2H),0.98(m,18H)

[0638] Synthesis Example 36 (Chemical Formula 2-36)

[0639]

[0640] N-(Bis(2-methoxyphenyl)phosphino)-N-cyclohexyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0641] 1 H NMR (500MHz, CDCl3): δ7.43(m,6H),7.17(m,2H),7.16(m,4H),7.15(m,2H),7.06(m,2H),3.98(m,6H),2.61(m,1H),1.77(m,2 H),1.50(m,1H),1.49(m,2H),1.48(m,1H),1.46(m,12H),1.38(m,12H),1.31(m,12H),1.25(m,2H),1.19(m,2H),0.94(m,18H)

[0642] Synthesis Example 37 (Chemical Formula 2-37)

[0643]

[0644] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1,1-di-o-tolylphosphinamide

[0645] 1H NMR (500MHz, CDCl3): δ7.40(m,4H),7.33(m,2H),7.24(m,2H),7.20(m,2H),7.10(m,4H),7.07(m,2H),2.65(m,1H),2.34(m,6H),1.8 0(m,2H),1.56(m,2H),1.53(m,1H),1.50(m,1H),1.49(m,12H),1.40(m,12H),1.27(m,2H),1.24(m,12H),1.11(m,2H),0.98(m,18H)

[0646] Synthesis Example 38 (Chemical Formula 2-38)

[0647]

[0648] N-(Bis(2-(trifluoromethoxy)phenyl)phosphino)-N-cyclohexyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0649] 1 H NMR (500MHz, CDCl3): δ7.49(m,4H),7.37(m,2H),7.18(m,2H),7.15(m,2H),7.13(m,4H),7.01(m,2H),2.63(m,1H),1.83(m,2 H),1.53(m,1H),1.52(m,1H),1.49(m,2H),1.46(m,12H),1.37(m,12H),1.26(m,12H),1.21(m,2H),1.13(m,2H),0.95(m,18H)

[0650] Synthesis Example 39 (Chemical Formula 2-39)

[0651]

[0652] N-(Bis(2-((trifluoromethyl)thio)phenyl)phosphino)-N-cyclohexyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0653] 1H NMR (500MHz, CDCl3): δ7.42(m,4H),7.24(m,2H),7.22(m,4H),7.11(m,2H),7.09(m,4H),2.67(m,1H),1.83(m,2H),1.5 7(m,2H),1.55(m,1H),1.50(m,1H),1.44(m,12H),1.40(m,12H),1.25(m,12H),1.21(m,2H),1.11(m,2H),0.92(m,18H)

[0654] Synthesis Example 40 (Chemical Formula 2-40)

[0655]

[0656] N-(Bis(2-(methylthio)phenyl)phosphino)-N-cyclohexyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0657] 1 H NMR (500MHz, CDCl3): δ7.45(m,4H),7.23(m,4H),7.20(m,2H),7.11(m,4H),7.05(m,2H),2.57(m,1H),2.55(m,6H),1.80(m,2 H),1.53(m,1H),1.50(m,2H),1.49(m,1H),1.47(m,12H),1.39(m,12H),1.30(m,12H),1.27(m,2H),1.20(m,2H),0.96(m,18H)

[0658] Synthesis Example 41 (Chemical Formula 2-41)

[0659]

[0660] (((Bis(4-(tributylsilyl)phenyl)phosphino)(cyclohexyl)amino)phosphinediyl)bis(2,1-phenylene) dimethanesulfonate

[0661] 1H NMR (500MHz, CDCl3): δ7.53(m,2H),7.47(m,2H),7.42(m,4H),7.32(m,2H),7.22(m,2H),7.15(m,4H),3.56(m,6H),2.64(m,1H),1.7 6(m,2H),1.58(m,2H),1.53(m,1H),1.51(m,1H),1.50(m,12H),1.42(m,12H),1.29(m,12H),1.26(m,2H),1.16(m,2H),1.02(m,18H)

[0662] Synthesis Example 42 (Chemical Formula 2-42)

[0663]

[0664] N-(Bis(2-(trimethylsilyl)phenyl)phosphino)-N-cyclohexyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0665] 1 H NMR (500MHz, CDCl3): δ7.49(m,8H),7.29(m,2H),7.17(m,6H),2.61(m,1H),1.76(m,2H),1.56(m,2H),1.5 5(m,1H),1.44(m,13H),1.39(m,12H),1.25(m,12H),1.23(m,2H),1.13(m,2H),1.00(m,18H),0.27(m,18H)

[0666] Synthesis Example 43 (Chemical Formula 2-43)

[0667]

[0668] 1,1-Bis(benzofuran-7-yl)-N-(bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexylphosphinamine

[0669] 1 H NMR (500MHz, CDCl3): δ7.65(m,2H),7.62(m,2H),7.44(m,4H),7.36(m,2H),7.32(m,2H),7.11(m,4H),6.79(m,2H),2.5 7(m,1H),1.78(m,2H),1.51(m,3H),1.50(m,13H),1.46(m,12H),1.29(m,2H),1.27(m,12H),1.16(m,2H),0.94(m,18H)

[0670] Synthesis Example 44 (Chemical Formula 2-44)

[0671]

[0672] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1,1-bis(dibenzo[b,d]furan-4-yl)phosphinamine

[0673] 1 H NMR (500MHz, CDCl3): δ8.05(m,4H),7.56(m,2H),7.49(m,2H),7.48(m,4H),7.39(m,2H),7.34(m,2H),7.23(m,2H),7.12(m,4H),2.60(m,1 H),1.80(m,2H),1.52(m,1H),1.51(m,2H),1.48(m,1H),1.46(m,12H),1.43(m,12H),1.31(m,12H),1.28(m,2H),1.11(m,2H),0.99(m,18H)

[0674] Synthesis Example 45 (Chemical Formula 2-45)

[0675]

[0676] N-Benzyl-N-(bis(2-fluorophenyl)phosphino)-1,1-bis(4-(tributylsilyl)phenyl)phosphine

[0677] 1 H NMR (500MHz, CDCl3): δ7.44(m,4H),7.40(m,4H),7.39(m,1H),7.36(m,2H),7.26(m,2H),7.1 3(m,6H),7.07(m,2H),3.95(m,2H),1.46(m,12H),1.38(m,12H),1.26(m,12H),1.01(m,18H)

[0678] Synthesis Example 46 (Chemical Formula 2-46)

[0679]

[0680] N-Benzyl-N-(bis(2-(trifluoromethyl)phenyl)phosphino)-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0681] 1H NMR (500MHz, CDCl3): δ7.52(m,2H),7.49(m,2H),7.42(m,4H),7.39(m,1H),7.37(m,4H),7.2 3(m,2H),7.13(m,6H),4.00(m,2H),1.45(m,12H),1.41(m,12H),1.25(m,12H),0.96(m,18H)

[0682] Synthesis Example 47 (Chemical Formula 2-47)

[0683]

[0684] N-Benzyl-N-(bis(2-methoxyphenyl)phosphino)-1,1-bis(4-(tributylsilyl)phenyl)phosphine

[0685] 1 H NMR (500MHz, CDCl3): δ7.48(m,4H),7.43(m,2H),7.34(m,4H),7.30(m,1H),7.18(m,6H),7.1 3(m,2H),7.06(m,2H),3.93(m,8H),1.47(m,12H),1.40(m,12H),1.25(m,12H),1.00(m,18H)

[0686] Synthesis Example 48 (Chemical Formula 2-48)

[0687]

[0688] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1,1-di-o-tolylphosphine

[0689] 1 H NMR (500MHz, CDCl3): δ7.48(m,4H),7.41(m,2H),7.38(m,4H),7.32(m,1H),7.21(m,2H),7.13(m,2H),7.1 0(m,2H),7.09(m,4H),3.94(m,2H),2.32(m,6H),1.44(m,12H),1.38(m,12H),1.25(m,12H),1.01(m,18H)

[0690] Synthesis Example 49 (Chemical Formula 2-49)

[0691]

[0692] N-Benzyl-N-(bis(2-(trifluoromethoxy)phenyl)phosphino)-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0693] 1 H NMR (500MHz, CDCl3): δ7.43(m,6H),7.38(m,4H),7.29(m,1H),7.17(m,2H),7.12(m,4 H),7.11(m,2H),7.04(m,2H),3.96(m,2H),1.45(m,24H),1.27(m,12H),0.92(m,18H)

[0694] Synthesis Example 50 (Chemical Formula 2-50)

[0695]

[0696] N-Benzyl-N-(bis(2-((trifluoromethyl)thio)phenyl)phosphino)-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0697] 1 H NMR (500MHz, CDCl3): δ7.43(m,4H),7.33(m,1H),7.32(m,4H),7.23(m,2H),7.19(m,4H),7.1 8(m,4H),7.10(m,2H),3.95(m,2H),1.53(m,12H),1.37(m,12H),1.32(m,12H),0.98(m,18H)

[0698] Synthesis Example 51 (Chemical Formula 2-51)

[0699]

[0700] N-Benzyl-N-(bis(2-(methylthio)phenyl)phosphino)-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0701] 1 H NMR (500MHz, CDCl3): δ7.49(m,4H),7.35(m,4H),7.30(m,1H),7.26(m,4H),7.21(m,2H),7. 14(m,4H),7.10(m,2H),3.93(m,2H),2.55(m,6H),1.45(m,24H),1.24(m,12H),0.94(m,18H)

[0702] Synthesis Example 52 (Chemical Formula 2-52)

[0703]

[0704] ((Benzyl(bis(4-(tributylsilyl)phenyl)phosphino)amino)phosphinediyl)bis(2,1-phenylene) dimethanesulfonate

[0705] 1 H NMR (500MHz, CDCl3): δ7.47(m,2H),7.44(m,2H),7.41(m,4H),7.35(m,4H),7.29(m,3H),7. 24(m,2H),7.10(m,4H),3.97(m,2H),3.63(m,6H),1.44(m,24H),1.33(m,12H),0.97(m,18H)

[0706] Synthesis Example 53 (Chemical Formula 2-53)

[0707]

[0708] N-Benzyl-N-(bis(2-(trimethylsilyl)phenyl)phosphino)-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0709] 1 H NMR (500MHz, CDCl3): δ7.47(m,8H),7.40(m,4H),7.33(m,2H),7.32(m,1H),7.13(m,6H) ),3.95(m,2H),1.52(m,12H),1.44(m,12H),1.29(m,12H),0.95(m,18H),0.26(m,18H)

[0710] Synthesis Example 54 (Chemical Formula 2-54)

[0711]

[0712] 1,1-Bis(benzofuran-7-yl)-N-benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)phosphine

[0713] 1 H NMR (500MHz, CDCl3): δ7.70(m,2H),7.64(m,2H),7.45(m,4H),7.33(m,4H),7.31(m,2H),7.30(m,2H),7.2 9(m,1H),7.11(m,4H),6.81(m,2H),3.94(m,2H),1.44(m,12H),1.39(m,12H),1.31(m,12H),0.93(m,18H)

[0714] Synthesis Example 55 (Chemical Formula 2-55)

[0715]

[0716] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1,1-bis(dibenzo[b,d]furan-4-yl)phosphinamine

[0717] 1 H NMR (500MHz, CDCl3): δ8.07(m,4H),7.63(m,2H),7.47(m,4H),7.46(m,2H),7.40(m,6H),7.38(m,2H),7.3 4(m,1H),7.27(m,2H),7.19(m,4H),3.94(m,2H),1.49(m,12H),1.39(m,12H),1.31(m,12H),1.00(m,18H)

[0718] Synthesis Example 56 (Chemical Formula 2-56)

[0719]

[0720] N-(Bis(2-fluorophenyl)phosphino)-N-phenyl-1,1-bis(4-(tributylsilyl)phenyl)phosphine

[0721] 1 H NMR (500MHz, CDCl3): δ7.45(m,4H),7.30(m,2H),7.26(m,2H),7.17(m,6H),7.15(m,2H),7.1 4(m,2H),6.82(m,1H),6.69(m,2H),1.52(m,12H),1.43(m,12H),1.28(m,12H),0.98(m,18H)

[0722] Synthesis Example 57 (Chemical Formula 2-57)

[0723]

[0724] N-(Bis(2-(trifluoromethyl)phenyl)phosphino)-N-phenyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0725] 1H NMR (500MHz, CDCl3): δ7.51(m,2H),7.48(m,2H),7.46(m,4H),7.22(m,2H),7.18(m,4H),7.13(m,2 H),7.04(m,2H),6.77(m,1H),6.61(m,2H),1.48(m,12H),1.43(m,12H),1.27(m,12H),1.00(m,18H)

[0726] Synthesis Example 58 (Chemical Formula 2-58)

[0727]

[0728] N-(Bis(2-methoxyphenyl)phosphino)-N-phenyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0729] 1 H NMR (500MHz, CDCl3): δ7.50(m,4H),7.44(m,2H),7.19(m,4H),7.16(m,2H),7.13(m,2H),7.12(m,2H),6.9 8(m,2H),6.77(m,1H),6.61(m,2H),4.00(m,6H),1.47(m,12H),1.40(m,12H),1.26(m,12H),0.98(m,18H)

[0730] Synthesis Example 59 (Chemical Formula 2-59)

[0731]

[0732] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-phenyl-1,1-di-o-tolylphosphinamide

[0733] 1 H NMR (500MHz, CDCl3): δ7.49(m,4H),7.39(m,2H),7.20(m,2H),7.18(m,4H),7.16(m,2H),7.09(m,2H),7.0 8(m,2H),6.80(m,1H),6.66(m,2H),2.33(m,6H),1.48(m,12H),1.46(m,12H),1.25(m,12H),1.01(m,18H)

[0734] Synthesis Example 60 (Chemical Formula 2-60)

[0735]

[0736] N-(Bis(2-(trifluoromethoxy)phenyl)phosphino)-N-phenyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0737] 1 H NMR (500MHz, CDCl3): δ7.43(m,6H),7.20(m,2H),7.19(m,4H),7.17(m,2H),7.10(m,2H),7.0 5(m,2H),6.79(m,1H),6.66(m,2H),1.52(m,12H),1.39(m,12H),1.26(m,12H),1.01(m,18H)

[0738] Synthesis Example 61 (Chemical Formula 2-61)

[0739]

[0740] N-(Bis(2-((trifluoromethyl)thio)phenyl)phosphino)-N-phenyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0741] 1 H NMR (500MHz, CDCl3): δ7.43(m,4H),7.26(m,4H),7.24(m,2H),7.16(m,2H),7.14(m,4H),7.0 4(m,2H),6.85(m,1H),6.63(m,2H),1.45(m,12H),1.39(m,12H),1.29(m,12H),0.95(m,18H)

[0742] Synthesis Example 62 (Chemical Formula 2-62)

[0743]

[0744] N-(Bis(2-(methylthio)phenyl)phosphino)-N-phenyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0745] 1 H NMR (500MHz, CDCl3): δ7.43(m,4H),7.25(m,2H),7.18(m,8H),7.16(m,2H),7.10(m,2H),6.8 1(m,1H),6.68(m,2H),2.55(m,6H),1.49(m,12H),1.40(m,12H),1.26(m,12H),0.95(m,18H)

[0746] Synthesis Example 63 (Chemical Formula 2-63)

[0747]

[0748] (((Bis(4-(tributylsilyl)phenyl)phosphino)(phenyl)amino)phosphinediyl)bis(2,1-phenylene) dimethanesulfonate

[0749] 1 H NMR (500MHz, CDCl3): δ7.53(m,2H),7.51(m,2H),7.41(m,4H),7.33(m,2H),7.24(m,2H),7.16(m,2H),7.1 2(m,4H),6.82(m,1H),6.63(m,2H),3.60(m,6H),1.47(m,12H),1.45(m,12H),1.27(m,12H),0.97(m,18H)

[0750] Synthesis Example 64 (Chemical Formula 2-64)

[0751]

[0752] N-(Bis(2-(trimethylsilyl)phenyl)phosphino)-N-phenyl-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0753] 1 H NMR (500MHz, CDCl3): δ7.42(m,8H),7.30(m,2H),7.19(m,6H),7.18(m,2H),6.86(m,1H ),6.69(m,2H),1.49(m,12H),1.44(m,12H),1.32(m,12H),1.02(m,18H),0.25(m,18H)

[0754] Synthesis Example 65 (Chemical Formula 2-65)

[0755]

[0756] 1,1-Bis(benzofuran-7-yl)-N-(bis(4-(tributylsilyl)phenyl)phosphino)-N-phenylphosphinamine

[0757] 1H NMR (500MHz, CDCl3): δ7.69(m,2H),7.62(m,2H),7.48(m,4H),7.36(m,2H),7.31(m,2H),7.15(m,2H),7.1 4(m,4H),6.86(m,1H),6.76(m,2H),6.61(m,2H),1.45(m,12H),1.37(m,12H),1.31(m,12H),0.98(m,18H)

[0758] Synthesis Example 66 (Chemical Formula 2-66)

[0759]

[0760] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1,1-bis(dibenzo[b,d]furan-4-yl)-N-phenylphosphinamine

[0761] 1 H NMR (500MHz, CDCl3): δ8.08(m,4H),7.56(m,2H),7.50(m,4H),7.42(m,2H),7.36(m,2H),7.35(m,2H),7.25(m,2 H),7.14(m,2H),7.12(m,4H),6.84(m,1H),6.62(m,2H),1.48(m,12H),1.37(m,12H),1.26(m,12H),0.95(m,18H)

[0762] Synthesis Example 67 to Synthesis Example 86: Synthesis of Ligand Compounds Represented by Chemical Formula 3-1 to Chemical Formula 3-20

[0763] 20mmol (2 equivalents) of m-bromo-(tri-n-butylsilyl)-C6H4 was dissolved in 20ml of tetrahydrofuran and then cooled to -78°C. While maintaining the temperature, 20mmol (2 equivalents) of n-butyllithium were added dropwise thereto and then stirred for 3 hours. Next, 10mmol (1 equivalent) of dichloro(diethylamino)phosphine dissolved in 10ml of tetrahydrofuran was added dropwise thereto, then the temperature was raised to room temperature and then stirred overnight. Afterwards, the solvent was removed in vacuo, the resulting intermediate was dissolved in 30ml of hexane, HCl (2 equivalents in ether) was then added thereto, then stirred for 15 minutes and filtered. The filtrate was dried in vacuo to obtain (m-(tri-n-butylsilyl)-C6H4)2PCl. 11mmol (2.2 equivalents) of R 5-NH2 and 10 ml of dichloromethane were added to a dried flask and stirring was started. 5 mmol (1 equivalent) of (m-(tri-n-butylsilyl)-C6H4)2PCl was diluted in 10 ml of dichloromethane and then slowly added to the flask. After the reaction was completed by stirring for 4 hours, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and (m-(tri-n-butylsilyl)-C6H4)2P-NHR was obtained by column chromatography. 5 .

[0764] 5mmol (1 equivalent) of PCl3 was dissolved in 10ml of ether and then cooled to 0°C. Then, 10mmol (2 equivalents) of HNEt2 dissolved in 10ml of ether was slowly added and stirred overnight. The solid was removed by a filter, and 2 equivalents of ArMgBr prepared from Ar and Mg turnings were slowly added thereto, and then stirred at room temperature overnight. Thereafter, HCl (2 equivalents in ether) was added and stirred at room temperature for 30 minutes. The solid was removed by a filter and Ar2PCl was obtained by decompression. 5mmol (1 equivalent) of Ar2PCl was dissolved in 10ml of dichloromethane, and then 15mmol (3 equivalents) of triethylamine was added thereto. Subsequently, 5mmol (1 equivalent) of (m-(tri-n-butylsilyl)-C6H4)2P-NHR 5 The mixture was dissolved in dichloromethane and slowly added thereto, and stirred at room temperature overnight. The solvent was removed by vacuum extraction, and then dissolved in hexane, and column chromatography was performed to obtain ligand compounds represented by Chemical Formulas 3-1 to 3-20.

[0765] The substituent R of the reactants used in Synthesis Examples 67 to 86 5 and Ar are shown in Table 2 below, and the structures and 1 H NMR data are listed below.

[0766] [Table 2]

[0767]

[0768]

[0769]

[0770] Synthesis Example 67 (Chemical Formula 3-1)

[0771]

[0772] N-(Bis(2-fluorophenyl)phosphino)-N-methyl-1,1-bis(3-(tributylsilyl)phenyl)phosphine

[0773] 1 H NMR (500MHz, CDCl3): δ7.60(m,2H),7.43(m,2H),7.35(m,2H),7.31(m,2H),7.24(m,2H),7.1 2(m,4H),7.05(m,2H),2.48(m,3H),1.48(m,12H),1.38(m,12H),1.28(m,12H),0.95(m,18H)

[0774] Synthesis Example 68 (Chemical Formula 3-2)

[0775]

[0776] N-(Bis(2-(trifluoromethyl)phenyl)phosphino)-N-methyl-1,1-bis(3-(tributylsilyl)phenyl)phosphinamine

[0777] 1 H NMR (500MHz, CDCl3): δ7.60(m,2H),7.49(m,4H),7.41(m,2H),7.31(m,2H),7.21(m,2H),7.1 1(m,2H),7.07(m,2H),2.50(m,3H),1.50(m,12H),1.38(m,12H),1.31(m,12H),1.01(m,18H)

[0778] Synthesis Example 69 (Chemical Formula 3-3)

[0779]

[0780] N-(Bis(2-methoxyphenyl)phosphino)-N-methyl-1,1-bis(3-(tributylsilyl)phenyl)phosphine

[0781] 1 H NMR (500MHz, CDCl3): δ7.63(m,2H),7.46(m,2H),7.39(m,2H),7.33(m,2H),7.12(m,2H),7.11(m,4 H),7.05(m,2H),3.98(m,6H),2.51(m,3H),1.46(m,12H),1.43(m,12H),1.29(m,12H),0.95(m,18H)

[0782] Synthesis Example 70 (Chemical Formula 3-4)

[0783]

[0784] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-methyl-1,1-di-o-tolylphosphinamide

[0785] 1 H NMR (500MHz, CDCl3): δ7.57(m,2H),7.50(m,2H),7.36(m,2H),7.35(m,2H),7.25(m,2H),7.14(m,2H),7.1 3(m,2H),7.11(m,2H),2.51(m,3H),2.38(m,6H),1.51(m,12H),1.38(m,12H),1.31(m,12H),1.00(m,18H)

[0786] Synthesis Example 71 (Chemical Formula 3-5)

[0787]

[0788] N-(Bis(2-(trifluoromethoxy)phenyl)phosphino)-N-methyl-1,1-bis(3-(tributylsilyl)phenyl)phosphinamine

[0789] 1 H NMR (500MHz, CDCl3): δ7.56(m,2H),7.41(m,2H),7.40(m,2H),7.34(m,2H),7.14(m,2H),7.13(m,2 H),7.12(m,2H),7.03(m,2H),2.47(m,3H),1.46(m,12H),1.42(m,12H),1.27(m,12H),0.96(m,18H)

[0790] Synthesis Example 72 (Chemical Formula 3-6)

[0791]

[0792] N-(Bis(2-fluorophenyl)phosphino)-N-butyl-1,1-bis(3-(tributylsilyl)phenyl)phosphine

[0793] 1 H NMR (500MHz, CDCl3): δ7.59(m,2H),7.41(m,2H),7.38(m,2H),7.33(m,2H),7.26(m,2H),7.13(m,2H),7.1 1(m,4H),2.72(m,2H),1.54(m,2H),1.50(m,12H),1.38(m,12H),1.36(m,2H),1.29(m,12H),0.94(m,21H)

[0794] Synthesis Example 73 (Chemical Formula 3-7)

[0795]

[0796] N-(Bis(2-(trifluoromethyl)phenyl)phosphino)-N-butyl-1,1-bis(3-(tributylsilyl)phenyl)phosphinamine

[0797] 1 H NMR (500MHz, CDCl3): δ7.58(m,2H),7.49(m,4H),7.48(m,2H),7.35(m,2H),7.23(m,2H),7.18(m,2H),7.14(m,2 H),2.70(m,2H),1.50(m,12H),1.48(m,2H),1.43(m,12H),1.35(m,2H),1.32(m,12H),0.96(m,3H),0.94(m,18H)

[0798] Synthesis Example 74 (Chemical Formula 3-8)

[0799]

[0800] N-(Bis(2-methoxyphenyl)phosphino)-N-butyl-1,1-bis(3-(tributylsilyl)phenyl)phosphineamine

[0801] 1 H NMR (500MHz, CDCl3): δ7.58(m,2H),7.46(m,2H),7.45(m,2H),7.39(m,2H),7.20(m,2H),7.12(m,2H),7.11(m,2H),6.98(m,2 H),3.98(m,6H),2.72(m,2H),1.52(m,2H),1.46(m,12H),1.41(m,12H),1.33(m,2H),1.26(m,12H),1.00(m,18H),0.91(m,3H)

[0802] Synthesis Example 75 (Chemical Formula 3-9)

[0803]

[0804] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-butyl-1,1-di-o-tolylphosphinamide

[0805] 1H NMR (500MHz, CDCl3): δ7.57(m,2H),7.41(m,2H),7.39(m,4H),7.28(m,2H),7.19(m,2H),7.15(m,2H),7.12(m,2H),2.6 6(m,2H),2.33(m,6H),1.54(m,2H),1.49(m,12H),1.41(m,2H),1.36(m,12H),1.24(m,12H),1.00(m,18H),0.92(m,3H)

[0806] Synthesis Example 76 (Chemical Formula 3-10)

[0807]

[0808] N-(Bis(2-(trifluoromethoxy)phenyl)phosphino)-N-butyl-1,1-bis(3-(tributylsilyl)phenyl)phosphinamine

[0809] 1 H NMR (500MHz, CDCl3): δ7.63(m,2H),7.48(m,2H),7.42(m,2H),7.34(m,2H),7.16(m,2H),7.14(m,4H),7.0 2(m,2H),2.67(m,2H),1.52(m,2H),1.47(m,12H),1.39(m,14H),1.24(m,12H),0.96(m,18H),0.94(m,3H)

[0810] Synthesis Example 77 (Chemical Formula 3-11)

[0811]

[0812] N-(Bis(2-fluorophenyl)phosphino)-N-isopropyl-1,1-bis(3-(tributylsilyl)phenyl)phosphineamine

[0813] 1 H NMR (500MHz, CDCl3): δ7.63(m,2H),7.44(m,2H),7.37(m,2H),7.36(m,2H),7.21(m,2H),7.17(m,4 H),7.11(m,2H),2.87(m,1H),1.52(m,12H),1.42(m,12H),1.29(m,12H),1.09(m,6H),1.01(m,18H)

[0814] Synthesis Example 78 (Chemical Formula 3-12)

[0815]

[0816] N-(Bis(2-(trifluoromethyl)phenyl)phosphino)-N-isopropyl-1,1-bis(3-(tributylsilyl)phenyl)phosphinamine

[0817] 1 H NMR (500MHz, CDCl3): δ7.57(m,2H),7.53(m,2H),7.45(m,2H),7.42(m,2H),7.40(m,2H),7.21(m,2 H),7.15(m,2H),7.11(m,2H),2.85(m,1H),1.44(m,24H),1.23(m,12H),1.15(m,6H),0.94(m,18H)

[0818] Synthesis Example 79 (Chemical Formula 3-13)

[0819]

[0820] N-(Bis(2-methoxyphenyl)phosphino)-N-isopropyl-1,1-bis(3-(tributylsilyl)phenyl)phosphineamine

[0821] 1 H NMR (500MHz, CDCl3): δ7.56(m,2H),7.46(m,2H),7.41(m,2H),7.36(m,2H),7.13(m,4H),7.12(m,2H),7.0 3(m,2H),3.92(m,6H),2.86(m,1H),1.51(m,12H),1.43(m,12H),1.24(m,12H),1.16(m,6H),0.96(m,18H)

[0822] Synthesis Example 80 (Chemical Formula 3-14)

[0823]

[0824] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1,1-di-o-tolylphosphine

[0825] 1H NMR (500MHz, CDCl3): δ7.58(m,2H),7.46(m,2H),7.35(m,2H),7.34(m,2H),7.28(m,2H),7.18(m,2H),7.17(m,2 H),7.06(m,2H),2.91(m,1H),2.39(m,6H),1.52(m,12H),1.40(m,12H),1.24(m,12H),1.06(m,6H),0.99(m,18H)

[0826] Synthesis Example 81 (Chemical Formula 3-15)

[0827]

[0828] N-(Bis(2-(trifluoromethoxy)phenyl)phosphino)-N-isopropyl-1,1-bis(3-(tributylsilyl)phenyl)phosphinamine

[0829] 1 H NMR (500MHz, CDCl3): δ7.57(m,2H),7.41(m,4H),7.40(m,2H),7.18(m,2H),7.14(m,2H),7.13(m,2 H),7.01(m,2H),2.90(m,1H),1.49(m,12H),1.39(m,12H),1.23(m,12H),1.07(m,6H),0.93(m,18H)

[0830] Synthesis Example 82 (Chemical Formula 3-16)

[0831]

[0832] N-(Bis(2-fluorophenyl)phosphino)-N-cyclohexyl-1,1-bis(3-(tributylsilyl)phenyl)phosphine

[0833] 1 H NMR (500MHz, CDCl3): δ7.59(m,2H),7.42(m,2H),7.34(m,2H),7.32(m,2H),7.27(m,2H),7.12(m,4H),7.10(m,2H),2.61(m,1H),1.8 2(m,2H),1.53(m,1H),1.50(m,2H),1.48(m,1H),1.44(m,12H),1.40(m,12H),1.26(m,12H),1.21(m,2H),1.12(m,2H),0.96(m,18H)

[0834] Synthesis Example 83 (Chemical Formula 3-17)

[0835]

[0836] N-(Bis(2-(trifluoromethyl)phenyl)phosphino)-N-cyclohexyl-1,1-bis(3-(tributylsilyl)phenyl)phosphinamine

[0837] 1 H NMR (500MHz, CDCl3): δ7.59(m,2H),7.52(m,2H),7.45(m,2H),7.41(m,2H),7.34(m,2H),7.20(m,2H),7.19(m,2H),7.11(m,2H),2.57(m,1 H),1.82(m,2H),1.58(m,2H),1.49(m,12H),1.48(m,1H),1.46(m,1H),1.44(m,12H),1.26(m,12H),1.23(m,2H),1.17(m,2H),0.99(m,18H)

[0838] Synthesis Example 84 (Chemical Formula 3-18)

[0839]

[0840] N-(Bis(2-methoxyphenyl)phosphino)-N-cyclohexyl-1,1-bis(3-(tributylsilyl)phenyl)phosphineamine

[0841] 1 H NMR (500MHz, CDCl3): δ7.56(m,2H),7.46(m,2H),7.41(m,2H),7.37(m,2H),7.15(m,2H),7.13(m,2H),7.09(m,2H),7.00(m,2H),3.93(m,6 H),2.63(m,1H),1.80(m,2H),1.56(m,3H),1.50(m,12H),1.45(m,12H),1.44(m,1H),1.30(m,12H),1.23(m,2H),1.16(m,2H),0.99(m,18H)

[0842] Synthesis Example 85 (Chemical Formula 3-19)

[0843]

[0844] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1,1-di-o-tolylphosphinamide

[0845] 1H NMR (500MHz, CDCl3): δ7.62(m,2H),7.49(m,2H),7.42(m,2H),7.40(m,2H),7.28(m,2H),7.19(m,2H),7.15(m,2H),7.09(m,2H),2.58(m,1H),2.3 9(m,6H),1.75(m,2H),1.57(m,2H),1.56(m,1H),1.53(m,1H),1.44(m,1 2H),1.41(m,12H),1.27(m,2H),1.25(m,12H),1.19(m,2H),1.02(m,18H)

[0846] Synthesis Example 86 (Chemical Formula 3-20)

[0847]

[0848] N-(Bis(2-(trifluoromethoxy)phenyl)phosphino)-N-cyclohexyl-1,1-bis(3-(tributylsilyl)phenyl)phosphinamine

[0849] 1 H NMR (500MHz, CDCl3): δ7.63(m,2H),7.48(m,2H),7.38(m,2H),7.32(m,2H),7.13(m,2H),7.12(m,4H),7.03(m,2H),2.58(m,1 H),1.79(m,2H),1.51(m,12H),1.49(m,3H),1.47(m,1H),1.36(m,12H),1.29(m,2H),1.26(m,12H),1.16(m,2H),1.02(m,18H)

[0850] Comparative Synthesis Example 1: Synthesis of the Ligand Compound Represented by Chemical Formula 10

[0851] 5.5 mmol (0.5 equivalent) of 3-methyl-2-butylamine, 22 mmol (2 equivalents) of triethylamine and 10 ml of dichloromethane were added to a dry flask under a nitrogen atmosphere, and stirring was started. Then, after cooling to 0°C, 11 mmol (1 equivalent) of chlorobis(4-(tributylsilyl)phenyl)phosphine was slowly added thereto. After the reaction was completed, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and the compound represented by Chemical Formula 10 was obtained by column chromatography.

[0852] [Chemical formula 10]

[0853]

[0854] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-(3-methylbutan-2-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0855] 1 H NMR (500MHz, C6D6): δ7.96-7.34(m,16H),3.64-3.53(m,1H),1.81-1.72(m,1H),1. 38-1.29(m,48H),1.05(d,3H),0.91-0.84(m,39H),0.82-0.76(m,24H),0.55(d,3H)

[0856] Comparative Synthesis Example 2: Synthesis of the Ligand Compound Represented by Chemical Formula 11

[0857] 5.5 mmol (0.5 equivalent) of cyclohexylamine, 22 mmol (2 equivalents) of triethylamine and 10 ml of dichloromethane were added to a dry flask under a nitrogen atmosphere, and stirring was started. Then, after cooling to 0°C, 11 mmol (1 equivalent) of chlorobis (4-cyclohexylphenyl) phosphine was slowly added thereto. After the reaction was completed, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and the compound represented by Chemical Formula 11 was obtained by column chromatography.

[0858] [Chemical formula 11]

[0859]

[0860] N-(Bis(4-cyclohexylphenyl)phosphino)-N-cyclohexyl-1,1-bis(4-cyclohexylphenyl)phosphinamide

[0861] 1 H NMR (500MHz, C6D6): δ7.58(br.s,8H),7.08(d,8H),3.47(pent,1H),2.35(t, 4H),2.21-2.11(m,2H),1.80(d,8H),1.71-1.56(m,16H),1.44-1.11(m,24H)

[0862] Comparative Synthesis Example 3: Synthesis of the Ligand Compound Represented by Chemical Formula 12

[0863] 5.5 mmol (0.5 equivalent) of cyclohexylamine, 22 mmol (2 equivalents) of triethylamine and 10 ml of dichloromethane were added to a dry flask under a nitrogen atmosphere, and stirring was started. Then, after cooling to 0°C, 11 mmol (1 equivalent) of chlorobis(4-phenylphenyl)phosphine was slowly added thereto. After the reaction was completed, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and the compound represented by Chemical Formula 12 was obtained by column chromatography.

[0864] [Chemical formula 12]

[0865]

[0866] 1,1-Bis([1,1'-biphenyl]-4-yl)-N-cyclohexyl-N-(bis([1,1'-biphenyl]-4-yl)phosphino)phosphine

[0867] 1 H NMR (500MHz, C6D6): δ7.92-7.42(m,24H),7.17(t,8H),7.10(t,4H),3.58(pent,1H),2.28 -2.17(m,2H),1.84-1.77(m,2H),1.67-1.60(m,2H),1.48-1.42(m,1H),1.18-1.07(m,3H)

[0868] Comparative Synthesis Example 4: Synthesis of the Ligand Compound Represented by Chemical Formula 13

[0869] 5.5 mmol (0.5 equivalent) of cyclohexylamine, 22 mmol (2 equivalents) of triethylamine and 10 ml of dichloromethane were added to a dry flask under a nitrogen atmosphere and stirring was started. Then, after cooling to 0°C, 11 mmol (1 equivalent) of chlorobis(3,5-dimethylphenyl)phosphine was slowly added thereto. After the reaction was completed, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and the compound represented by Chemical Formula 13 was obtained by column chromatography.

[0870] [Chemical formula 13]

[0871]

[0872] N-(Bis(3,5-dimethylphenyl)phosphino)-N-cyclohexyl-1,1-bis(3,5-dimethylphenyl)phosphinamine

[0873] 1H NMR (500MHz, C6D6): δ7.38(br.s,8H),6.79(s,4H),3.63(pent,1H),2.24-2.13(m, 2H),2.10(s,24H),1.77(d,2H),1.60(d,2H),1.45-1.39(m,1H),1.19-1.00(m,3H)

[0874] Examples and Comparative Examples

[0875] Example 1

[0876] In an argon atmosphere, 0.5 mmol of tetrahydrofuran chromium chloride (III) (Cr (THF) 3 Cl 3), 0.5 mmol of the ligand compound represented by Chemical 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. Then, 30 ml of dichloromethane was added thereto, stirred for 1 hour, and then the solvent was removed by vacuuming. Then, after dissolving in methylcyclohexane and filtering, the solvent was vacuumed again, and dissolved in methylcyclohexane to prepare a 0.15 mM (Cr-based) catalyst solution.

[0877] Prepare a Parr reactor with a capacity of 600ml, and evacuate at 120 ℃ for 2 hours. Then, replace it with argon inside, and reduce the temperature to 70 ℃. After this, inject 180ml of methylcyclohexane and 2ml 725μmol of diisobutylaluminum hydride as activator, and inject 5ml (0.75μmol Cr) catalyst solution. After stirring at 1,000rpm for 2 minutes, open the ethylene pipeline valve set to 40bar, so as to fill the reactor with ethylene, then stir at 1,000rpm for 60 minutes. Close the ethylene pipeline valve, use dry ice / acetone bath to cool the reactor to 0 ℃. Then, slowly discharge unreacted ethylene, then add 0.5ml nonane (GC internal standard) thereto. After stirring for 10 seconds, take out the 2ml liquid part in the reactor and quench with water, the gained organic part is filtered by PTFE injection filter to make GC-FID sample. Then, the distribution of the liquid product was analyzed by GC (Agilent 6890N, manufactured by Agilent Technologies, Alltech AT-530mX0.32mm IDX0.25μm; serial number 12446). In addition, 400ml of ethanol / HCl (10vol% 12M HCl aqueous solution) was added to the remaining reaction solution, the resulting mixture was stirred and filtered, and then the amount of solid product was analyzed. The resulting polymer was dried in a vacuum oven at 80°C overnight.

[0878] Examples 2 to 86 and Comparative Examples 1 to 4

[0879] The same method as Example 1-1 was performed except that the type of catalyst was changed as shown in Table 3 below.

[0880] [Table 3]

[0881]

[0882]

[0883]

[0884]

[0885] Experimental example

[0886] Table 4 below shows the results of ethylene oligomerization according to the above examples and comparative examples.

[0887] Catalytic activity (tons / mol·Cr / hr): The catalytic activity is calculated from the total weight (tons) of the product, which is obtained by adding the weight (tons) of the obtained liquid product and the obtained solid product.

[0888] Selectivity of 1-C6 and 1-C8 (wt%): The contents of 1-hexene (1-C6) and 1-octene (1-C8) were calculated from the results of GC analysis of the distribution of the liquid product, and then the weight percentage of 1-hexene or 1-octene in the total weight of the product was calculated.

[0889] Solids (wt%): Calculate the weight percent of solid product relative to the total weight of the product. This indicates the extent to which polyethylene having a carbon number of about 40 or more is produced, where polyethylene is an insoluble solid that is insoluble in the solvent.

[0890] [Table 4]

[0891]

[0892]

[0893]

[0894]

[0895] As shown in Table 4 above, it was confirmed that in the case of conducting ethylene oligomerization using a catalyst composition containing the ligand compound according to the present invention, the phenyl group located at the terminal of the diphosphino amino moiety had a specific substituent at the ortho position, and had an alkyl group having a specific number of carbon atoms or a silyl group substituted with an alkyl group having a specific number of carbon atoms as a substituent at each of the meta and para positions, and further, due to the substituent substituted on the nitrogen atom, the steric strain around the PNP functional group was controlled, which improved the catalytic activity, selectivity and stability.

[0896] From these results, it can be confirmed that in the case of ethylene oligomerization using an organic chromium compound and a catalyst composition containing the ligand compound according to the present invention, linear α-olefins with high selectivity for 1-hexene and 1-octene can be produced while maintaining excellent productivity due to high catalytic activity.

Claims

1. A ligand compound represented by Chemical Formula 1: [Chemical formula 1] In Chemical Formula 1, R 1 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 1 With R 6 Combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, When R 6 Not with R 1 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 6 For hydrogen, R 2 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 2 With R 7 Combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, When R 7 Not with R 2 When combined to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 7 For hydrogen, R 3 and R 4 Each is independently hydrogen, an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an arylalkoxyalkyl group having 7 to 30 carbon atoms, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), wherein, R 3 and R 4 are not simultaneously hydrogen, and R 5 It is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused with an aryl group having 6 to 10 carbon atoms.

2. The ligand compound according to claim 1, in, R 1 is fluorine, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or R 1 With R 6 Combined to form a monocyclic or polycyclic heterocycle, and R 2 is fluorine, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or R 2 With R 7 Combine to form a monocyclic or polycyclic heterocycle.

3. The ligand compound according to claim 1, in, R 1 is fluoro, trifluoromethyl, methoxy, methyl, trifluoromethoxy, trifluoromethylthio, methylthio, methylsulfonate or trimethylsilyl, or R 1 With R 6 Combine to form furans or dibenzofurans, and R 2 is fluoro, trifluoromethyl, methoxy, methyl, trifluoromethoxy, trifluoromethylthio, methylthio, methylsulfonate or trimethylsilyl, or R 2 With R 7 Combine to form furans or dibenzofurans.

4. The ligand compound according to claim 1, in, R 3 and R 4 Each is independently an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group or a tributylsilyl group.

5. The ligand compound according to claim 1, in, R 3 and R 4 Each is independently n-decyl, tripropylsilyl or tributylsilyl.

6. The ligand compound according to claim 1, in, R 5 It is an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms condensed with an aryl group having 6 to 10 carbon atoms.

7. The ligand compound according to claim 1, in, The ligand compound represented by Chemical Formula 1 is represented by any one of Chemical Formulas 2 to 5: [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] [Chemical formula 5] In Chemical Formulae 2 to 5, R 1 To R 7 The same as defined in claim 1 respectively.

8. The ligand compound according to claim 1, in, The ligand compound represented by Chemical Formula 1 is represented by any one of Chemical Formulas 2-1 to 2-66 or Chemical Formulas 3-1 to 3-20: [Chemical formula 2-1] [Chemical formula 2-2] [Chemical formula 2-3] [Chemical formula 2-4] [Chemical formula 2-5] [Chemical formula 2-6] [Chemical formula 2-7] [Chemical formula 2-8] [Chemical formula 2-9] [Chemical formula 2-10] [Chemical formula 2-11] [Chemical formula 2-12] [Chemical formula 2-13] [Chemical formula 2-14] [Chemical formula 2-15] [Chemical formula 2-16] [Chemical formula 2-17] [Chemical formula 2-18] [Chemical formula 2-19] [Chemical formula 2-20] [Chemical formula 2-21] [Chemical formula 2-22] [Chemical formula 2-23] [Chemical formula 2-24] [Chemical formula 2-25] [Chemical formula 2-26] [Chemical formula 2-27] [Chemical formula 2-28] [Chemical formula 2-29] [Chemical formula 2-30] [Chemical formula 2-31] [Chemical formula 2-32] [Chemical formula 2-33] [Chemical formula 2-34] [Chemical formula 2-35] [Chemical formula 2-36] [Chemical formula 2-37] [Chemical formula 2-38] [Chemical formula 2-39] [Chemical formula 2-40] [Chemical formula 2-41] [Chemical formula 2-42] [Chemical formula 2-43] [Chemical formula 2-44] [Chemical formula 2-45] [Chemical formula 2-46] [Chemical formula 2-47] [Chemical formula 2-48] [Chemical formula 2-49] [Chemical formula 2-50] [Chemical formula 2-51] [Chemical formula 2-52] [Chemical formula 2-53] [Chemical formula 2-54] [Chemical formula 2-55] [Chemical formula 2-56] [Chemical formula 2-57] [Chemical formula 2-58] [Chemical formula 2-59] [Chemical formula 2-60] [Chemical formula 2-61] [Chemical formula 2-62] [Chemical formula 2-63] [Chemical formula 2-64] [Chemical formula 2-65] [Chemical formula 2-66] [Chemical formula 3-1] [Chemical formula 3-2] [Chemical formula 3-3] [Chemical formula 3-4] [Chemical formula 3-5] [Chemical formula 3-6] [Chemical formula 3-7] [Chemical formula 3-8] [Chemical formula 3-9] [Chemical formula 3-10] [Chemical formula 3-11] [Chemical formula 3-12] [Chemical formula 3-13] [Chemical formula 3-14] [Chemical formula 3-15] [Chemical formula 3-16] [Chemical formula 3-17] [Chemical formula 3-18] [Chemical formula 3-19] [Chemical formula 3-20] 9. An organic chromium compound comprising: The ligand compound according to claim 1; as well as Chromium coordinated to the ligand compound.

10. The organochromium compound according to claim 9, The organic chromium compound has a form in which any one or more unshared electron pairs of N and two Ps in the ligand compound represented by Chemical Formula 1 are coordinated with chromium.

11. A catalyst composition comprising: The ligand compound according to claim 1; chromium; as well as Promoter catalyst.

12. The catalyst composition according to claim 11, in, The chromium is derived from a chromium source, and The chromium source comprises one or more selected from chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) valerate, chromium (III) laurate, tris (2,2,6,6-tetramethyl-3.5-heptanedione) chromium (III), and chromium (III) stearate.

13. The catalyst composition according to claim 11, in, The co-catalyst is at least one or more selected from the compounds represented by Chemical Formula 6 to Chemical Formula 9: [Chemical formula 6] <h2 style=";text-align:left;direction:ltr">-[Al(R<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> )-O]<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> - In Chemical Formula 6, R 13 are each independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group, and a is an integer greater than or equal to 2, [Chemical formula 7] E(R 14 )3 In Chemical Formula 7, E is aluminum or boron, and R 14 are each independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group, [Chemical formula 8] [L-H] + [G(Y)4] - [Chemical formula 9] [L] + [G(Y)4] - In chemical formulas 8 and 9, L is a neutral or cationic Lewis acid, [LH] + is a Bronsted acid, G is a Group 13 element, and Y is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein, when the alkyl group or the aryl group is substituted, the substituent is a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

14. A method for producing linear α-olefins, comprising: A step (S10) of oligomerizing ethylene in the presence of the catalyst composition according to claim 11.

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

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