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

Abstract

The present invention relates to: a ligand compound that has a novel structure that exhibits high 1-hexene and 1-octene selectivity whilst also exhibiting high catalytic activity, and thus can perform ethylene oligomerization with excellent efficiency; an organic chromium compound; a catalyst composition comprising the organic chromium compound; and a method for oligomerizing ethylene using same.

Description

Ligand compound, organic chromium compound and catalyst composition comprising the same

[0001] [Cross-citation with related applications]

[0002] This invention claims the benefit of priority to Korean Patent Application No. 10-2024-0005035, filed January 11, 2024, the entire contents of which are incorporated herein by reference.

[0003] [Technical Field]

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

[0005] Linear alpha-olefins such as 1-hexene and 1-octene are used as detergents, lubricants, plasticizers, etc., and are mainly used as comonomers for controlling the density of polymers in the production of linear low-density polyethylene (LLDPE).

[0006] In the conventional LLDPE (Linear Low-Density Polyethylene) manufacturing process, copolymerization is performed with comonomers such as alpha-olefins, 1-hexene and 1-octene, to form branches in the polymer backbone together with ethylene and control the density.

[0007] Therefore, the production of LLDPE with a high comonomer content has been hampered by the fact that the cost of comonomers accounts for a significant portion of the manufacturing cost. Various attempts have been made to address this issue.

[0008] These linear alpha-olefins were primarily produced through the Shell Higher Olefin Process. However, this process was cumbersome because alpha-olefins of various lengths were simultaneously synthesized according to the Schultz-Flory distribution, requiring a separate separation process to obtain specific alpha-olefins.

[0009] To address these issues, methods have been proposed for selectively synthesizing 1-hexene through ethylene trimerization or 1-octene through ethylene tetramerization. Furthermore, extensive research is being conducted on catalyst systems that enable this selective ethylene oligomerization.

[0010] [Prior Art Literature]

[0011] [Patent Document]

[0012] (Patent Document 1) US 5064802 B2

[0013] The problem to be solved in the present invention is to provide a novel structural ligand compound, an organic chromium compound, and a catalyst composition comprising the same, which can perform ethylene oligomerization with excellent efficiency by exhibiting high catalytic activity and high 1-hexene and 1-octene selectivity while significantly reducing the production of 1-hexene and 1-octene isomers.

[0014] To solve the above problems, the present invention provides a ligand compound, an organic chromium compound, a catalyst composition, and an ethylene oligomerization method.

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

[0016] [Chemical Formula 1]

[0017]

[0018] In the above chemical formula 1, R 1 Inland R 4are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or -Si(R 7 )3, and m, n, o and p are each independently integers selected from 0 or 1 to 5, but when m, n, o and p are 2 or more, multiple R 1 Inland R 4 are identical or different, and R 5 is an alkyl group having 21 to 30 carbon atoms, and R 7 is an alkyl group having 1 to 20 carbon atoms, and multiple R 7 are identical or different from each other.

[0019] (2) The present invention, in the above (1), R 1 Inland R 4 are each independently an alkyl group having 1 to 20 carbon atoms or -Si(R 7 ) provides a ligand compound of 3.

[0020] (3) The present invention, in the above (1) or (2), R 1 Inland R 4 are each independently -Si(R 7 )3, and R 7 is an alkyl group having 1 to 10 carbon atoms, and multiple R 7 provides ligand compounds which are identical or different from each other.

[0021] (4) The present invention is one of (1) to (3), R 1 Inland R 4 Each independently provides a ligand compound which is a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a tri-n-butylsilyl group, a tri-n-octylsilyl group or a dimethyl(n-octyl)silyl group.

[0022] (5) The present invention provides a ligand compound in any one of the above (1) to (4), wherein m, n, o and p are 1.

[0023] (6) The present invention is one of (1) to (5), R 5 Provides a ligand compound which is a branched alkyl group having 21 to 30 carbon atoms.

[0024] (7) The present invention provides a ligand compound represented by the chemical formula 1 in any one of the above (1) to (6), wherein the ligand compound is represented by the following chemical formula 2 or chemical formula 3.

[0025] [Chemical Formula 2]

[0026]

[0027] [Chemical Formula 3]

[0028]

[0029] In the above chemical formulas 2 and 3, R 1 Inland R 5 are identical to those defined in (1) to (6), respectively.

[0030] (8) The present invention provides a ligand compound represented by the chemical formula 1 in any one of the above (1) to (6), wherein the ligand compound is represented by the following chemical formula 4.

[0031] [Chemical Formula 4]

[0032]

[0033] In the above chemical formula 4, R 1 Inland R 4 and m, n, o and p are the same as defined in (1) to (6), respectively, and R 6 and R 7 are each independently an alkyl group having 1 to 27 carbon atoms, and R 6 and R 7 The sum of the carbon atoms is 20 to 29.

[0034] (9) The present invention provides a ligand compound represented by the chemical formula 1 in any one of the above (1) to (8), wherein the ligand compound is represented by the following chemical formula 5 or chemical formula 6.

[0035] [Chemical Formula 5]

[0036]

[0037] [Chemical Formula 6]

[0038]

[0039] In the above chemical formulas 5 and 6, R 1 Inland R 4 are each identical to those defined in (1) to (8), and R 6 and R 7 are each independently an alkyl group having 1 to 27 carbon atoms, and R 6 and R 7 The sum of the carbon atoms is 20 to 29.

[0040] (10) The present invention provides a ligand compound represented by the chemical formula 1 in any one of the above (1) to (9), wherein the ligand compound is represented by any one of the following chemical formulas 1-1 to 1-12.

[0041] [Chemical Formula 1-1]

[0042]

[0043] [Chemical Formula 1-2]

[0044]

[0045] [Chemical Formula 1-3]

[0046]

[0047] [Chemical Formula 1-4]

[0048]

[0049] [Chemical Formula 1-5]

[0050]

[0051] [Chemical Formula 1-6]

[0052]

[0053] [Chemical Formula 1-7]

[0054]

[0055] [Chemical Formula 1-8]

[0056]

[0057] [Chemical Formula 1-9]

[0058]

[0059] [Chemical Formula 1-10]

[0060]

[0061] [Chemical Formula 1-11]

[0062]

[0063] [Chemical Formula 1-12]

[0064]

[0065] (11) The present invention provides an organic chromium compound comprising a ligand compound according to any one of (1) to (10) above and chromium coordinated to the ligand compound.

[0066] (12) The present invention provides an organic chromium compound in which at least one unshared electron pair among N and two P in the ligand compound represented by the chemical formula 1 is coordinated to chromium in the above (11).

[0067] (13) The present invention provides a catalyst composition comprising a ligand compound according to any one of (1) to (10), chromium, and a cocatalyst.

[0068] (14) The present invention provides a catalyst composition in the above (13), wherein the chromium is derived from a chromium source, and the chromium source includes at least one selected from the group consisting of chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III) laurate, chromium (III) tris(2,2,6,6-tetramethyl-3.5-heptaneindionate), and chromium (III) stearate.

[0069] (15) The present invention provides a catalyst composition in (13) or (14), wherein the cocatalyst is at least one selected from the group consisting of compounds represented by the following chemical formulas 10 to 13.

[0070] [Chemical Formula 10]

[0071] -[Al(R 13 )-O] a -

[0072] In the above chemical formula 10, R 13 are each independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and a is an integer of 2 or more,

[0073] [Chemical Formula 11]

[0074] E(R 14 )3

[0075] In the above chemical formula 11, E is aluminum or boron, and R 14 are each independently hydrogen, a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group,

[0076] [Chemical Formula 12]

[0077] [LH] + [G(Y)4] -

[0078] [Chemical Formula 13]

[0079] [L] + [G(Y)4] -

[0080] In the above chemical formulas 12 and 13, L is a neutral or cationic Lewis acid, and [LH] + is a Bronsted acid, G is a group 13 element, 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 aryl group is substituted, the substituent is a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0081] (16) The present invention provides a method for producing linear alpha-olefin, comprising a step (S10) of oligomerizing ethylene in the presence of a catalyst composition according to any one of (13) to (15) above.

[0082] (17) The present invention provides a method for producing linear alpha-olefin in the above (16), wherein the linear alpha-olefin is 1-hexene, 1-octene or a mixture thereof.

[0083] When ethylene oligomerization is performed using an organic chromium compound and a catalyst composition including the ligand compound of the present invention, the production of 1-hexene and 1-octene isomers is significantly reduced while having excellent productivity due to high catalytic activity, thereby producing linear alpha-olefins with significantly improved 1-hexene and 1-octene selectivity.

[0084] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0085] The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0086]

[0087] ligand compounds

[0088] The present invention provides a ligand compound applicable to a catalyst used in an ethylene oligomerization reaction. When the ligand compound is applied to an ethylene oligomerization reaction, specifically, a catalyst composition for forming linear alpha-olefins, it exhibits excellent catalytic activity while also having high selectivity for linear alpha-olefins, and in particular, compared to existing PNP-based catalysts, the amount of isomers of 1-hexene and 1-octene produced is reduced even under the same reaction conditions, thereby enabling more efficient production of linear alpha-olefins.

[0089] According to one embodiment of the present invention, the organic chromium compound coordinated with the ligand compound can be utilized in the production of linear alpha-olefin using ethylene, and an oligomerization reaction can proceed in the reaction under ethylene conditions, thereby forming alpha-olefin in liquid form, specifically, 1-hexene or 1-octene in liquid form, with high selectivity. This is because the selectivity for alpha-olefins of a specific length is increased through a transition state that forms a metallacycle in the oligomerization reaction of ethylene.

[0090] According to one embodiment of the present invention, the ligand compound includes a diphosphino aminyl moiety, and an aryl group having a specific substituent is connected to the terminal of the diphosphino aminyl moiety, so that it can have a form that can act as a strong electron donating group in itself. Due to this structural feature, the ligand compound can be applied to an ethylene oligomerization catalyst system to exhibit high activity, and in particular, it can exhibit high selectivity for 1-hexene, 1-octene, etc., with a small amount of isomers of 1-hexene and 1-octene produced. This can be seen as due to the interaction between each adjacent chromium active site, and in particular, when an aryl group having a specific substituent is connected to the phosphorus (P) atom of the diphosphino aminyl moiety, the electron density increases at the phosphorus (P) atom and nitrogen (N) atom included in the diphosphino aminyl moiety, and the electrical and steric properties of the entire ligand compound change. Accordingly, the bond between the ligand and the chromium atom is changed, so that the structure of the catalyst can become more stable, and compared to the existing metallacycloheptane or metallacyclononane form, the energy of the transition state (activation energy) is changed, so that alpha-olefin can be formed with higher activity and selectivity, and the amount of byproducts such as high molecular weight solid alpha-olefins such as polyethylene wax (PE wax) can be further reduced.

[0091] According to one embodiment of the present invention, the ligand compound is characterized in that the phenyl located at the terminal of the diphosphino aminyl moiety has a silyl group substituted with an alkyl group having a specific carbon number at the meta position and the para position, respectively, as a substituent. The substituents substituted at the meta position and the para position of the phenyl can increase the solubility of the ligand compound and the metal complex compound in a polymerization solvent, thereby improving the activity and selectivity. Accordingly, when the ligand compound is used, a chromium catalyst with high stability and excellent activity and selectivity can be produced.

[0092] According to one embodiment of the present invention, the ligand compound has a bulky substituent, such as an alkyl group having 21 to 30 carbon atoms, bonded to a nitrogen atom to which two phosphorus atoms are bonded, and the bulky substituent bonded to the nitrogen can prevent rotation of the bond between the nitrogen and phosphorus, thereby further improving the stability and activity of the catalyst. At this time, the activity, stability, selectivity, etc. of the catalyst change depending on the steric properties of the substituent bonded to the nitrogen atom. If the steric group of the substituent bonded to the nitrogen atom is too high, ligand synthesis and the formation of a metal complex become difficult, and the resulting complex becomes unstable. In addition, if the steric group of the substituent bonded to the nitrogen atom is too high, the access of raw materials such as ethylene becomes difficult, which causes a problem of reduced catalytic activity. In addition, if the steric group of the substituent bonded to the nitrogen atom is too low, rotation of the bond between the nitrogen atom and the phosphorus atom cannot be prevented, and the metal central atom cannot be protected, which causes reduced activity and stability of the catalyst. That is, if the stereoscopic group of the substituent bonded to the nitrogen atom is too high or too low, the activity of the catalyst is lowered, the stability is reduced, and the problem of increased production of by-products such as polyethylene wax occurs.

[0093] In particular, in the stereochemical group of the substituent bonded to the nitrogen atom, when the substituent is an alkyl group having 20 or fewer carbon atoms, the stereochemical group is not sufficiently large, making it difficult to achieve a sufficient effect in reducing the isomers of 1-hexene and 1-octene. In addition, when the substituent is an alkyl group having 31 or more carbon atoms, the ratio of the isomers of 1-hexene and 1-octene may decrease, but the stereochemical group becomes too large, making it difficult for the substrate to approach, thereby reducing the activity of the catalyst. Therefore, when the substituent bonded to the nitrogen atom is an alkyl group having 21 or more and 30 or less carbon atoms, the most appropriate stereochemical group can be formed, thereby reducing the production ratio of the isomers of 1-hexene and 1-octene without decreasing the activity of the catalyst. Furthermore, the reduced ratio of the isomers of 1-hexene and 1-octene can reduce the number of column stages in the process of purifying the product, and can also reduce the energy cost used during purification.

[0094] According to one embodiment of the present invention, the ligand compound may be represented by the following chemical formula 1.

[0095] [Chemical Formula 1]

[0096]

[0097] In the above chemical formula 1, R 1 Inland R 4 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or -Si(R 7 )3, and m, n, o and p are each independently integers selected from 0 or 1 to 5, but when m, n, o and p are 2 or more, multiple R 1 Inland R 4 are identical or different, and R 5 is an alkyl group having 21 to 30 carbon atoms, and R 7 is an alkyl group having 1 to 20 carbon atoms, and multiple R7 are identical or different from each other.

[0098] In the present invention, "alkyl group" may mean a straight-chain or branched hydrocarbon residue, and specific examples thereof may include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, and a hexyl group, depending on the defined carbon number.

[0099] In the present invention, "cycloalkyl group" may mean a cyclic hydrocarbon residue, and specific examples thereof may include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, depending on the defined carbon number.

[0100] In the present invention, "trialkylsilyl group" is represented by -SiR3 and means a substituent in which each R is independently an alkyl group, and when referring to the carbon number of the trialkylsilyl group, it may mean the sum of the carbon numbers of all R's.

[0101] As used herein, "aryl" refers to an optionally substituted benzene ring, or a ring system that can be formed by fusing one or more optional substituents, unless otherwise stated. Exemplary optional substituents include a substituted alkyl group having 1 to 2 carbon atoms, a substituted alkenyl group having 2 to 3 carbon atoms, a substituted alkynyl group having 2 to 3 carbon atoms, a heteroaryl group, a heterocyclic group, an aryl group, an alkoxy, an aryloxy, an aralkoxy, an acyl, an aroyl, a heteroaroyl, an acyloxy, an aroyloxy, a heteroaroyloxy, a sulfanyl, a sulfinyl, a sulfonyl, an aminosulfonyl, a sulfonylamino, a carboxyamide, an aminocarbonyl, a carboxy, an oxo, a hydroxy, a mercapto, an amino, a nitro, a cyano, a halogen, or a ureido. Such rings or ring systems may optionally be fused to an aryl ring (e.g., a benzene ring), a carbocyclic ring, or a heterocyclic ring, optionally having one or more substituents, including but not limited to phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl, or phenanthryl, and substituted derivatives thereof.

[0102] According to one embodiment of the present invention, R 1 Inland R 4 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or -Si(R 7 ) can be 3. As a specific example, R 1 Inland R 4 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -Si(R 7 )3 can be, and as a more specific example, R 1 Inland R 4 are each independently -Si(R 7 ) can be 3. At this time, R 7 is an alkyl group having 1 to 20 carbon atoms, and multiple R7 can be identical or different. As a specific example, R 7 can be an alkyl group having 1 to 10 carbon atoms, and more specifically, R 7 may be an alkyl group having 1 to 5 carbon atoms.

[0103] According to one embodiment of the present invention, the R 1 Inland R 4 Each of may independently be a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a tri-n-butylsilyl group, a tri-n-octylsilyl group, or a dimethyl(n-octyl)silyl group. That is, the ligand compound may have a silyl group substituted with an alkyl group having a specific carbon number at the meta position and the para position of the phenyl located at the end of the diphosphino aminyl moiety as a substituent.

[0104] According to one embodiment of the present invention, m, n, o and p can each independently be an integer selected from 0 or 1 to 5, and when m, n, o and p are 2 or more, a plurality of R 1 Inland R 4 may be the same or different from each other. As a specific example, m, n, o, and p may each independently be 0, 1, or 2, and as a more specific example, m, n, o, and p may be 1.

[0105] According to one embodiment of the present invention, R 5 may be an alkyl group having 21 to 30 carbon atoms, and as a specific example, R 5 may be a branched alkyl group having 21 to 30 carbon atoms. As a more specific example, R 5 It may be a branched alkyl group having 21 or more, 22 or more, or 23 or more carbon atoms, and may also be a branched alkyl group having 30 or less, 29 or less, 28 or less, or 27 or less carbon atoms.

[0106] According to one embodiment of the present invention, the ligand compound represented by the chemical formula 1 may be represented by the following chemical formula 2 or chemical formula 3.

[0107] [Chemical Formula 2]

[0108]

[0109] [Chemical Formula 3]

[0110]

[0111] In the above chemical formulas 2 and 3, R 1 Inland R 5 are each identical to those defined previously.

[0112] According to one embodiment of the present invention, the ligand compound represented by the chemical formula 1 may be represented by the following chemical formula 4.

[0113] [Chemical Formula 4]

[0114]

[0115] In the above chemical formula 4, R 1 Inland R 4 and m, n, o and p are each the same as defined above. Also, R 6 and R 7 are each independently an alkyl group having 1 to 27 carbon atoms, and R 6 and R 7 The sum of the carbon numbers of R can be 20 to 29. As a specific example, R 6 and R 7 are each independently an alkyl group having 7 to 17 carbon atoms, and R 6 and R 7 The sum of the carbon numbers of R can be 20 to 29. As a more specific example, R 6 and R 7 Each independently may be an alkyl group having 7 or more, 8 or more, 9 or more, 10 or more, or 11 or more carbon atoms, and may also be an alkyl group having 17 or less, 16 or less, 15 or less, 14 or less, or 13 or less, and in this case, R6 and R 7 The sum of the carbon atoms may be 20 to 29.

[0116] According to one embodiment of the present invention, the ligand compound represented by the chemical formula 1 may be represented by the following chemical formula 5 or chemical formula 6.

[0117] [Chemical Formula 5]

[0118]

[0119] [Chemical Formula 6]

[0120]

[0121] In the above chemical formulas 5 and 6, R 1 Inland R 4 , R 6 and R 7 are each identical to those defined previously.

[0122] According to one embodiment of the present invention, the ligand compound represented by the chemical formula 1 may be a ligand compound represented by any one of the following chemical formulas 1-1 to 1-12.

[0123] [Chemical Formula 1-1]

[0124]

[0125] [Chemical Formula 1-2]

[0126]

[0127] [Chemical Formula 1-3]

[0128]

[0129] [Chemical Formula 1-4]

[0130]

[0131] [Chemical Formula 1-5]

[0132]

[0133] [Chemical Formula 1-6]

[0134]

[0135] [Chemical Formula 1-7]

[0136]

[0137] [Chemical Formula 1-8]

[0138]

[0139] [Chemical Formula 1-9]

[0140]

[0141] [Chemical Formula 1-10]

[0142]

[0143] [Chemical Formula 1-11]

[0144]

[0145] [Chemical Formula 1-12]

[0146]

[0147] According to one embodiment of the present invention, the ligand compound may be implemented in various combinations within a range satisfying the conditions described above in addition to the specific examples described above, and any compound represented by Chemical Formula 1 may be applied as the ligand compound of the present invention.

[0148]

[0149] Organic chromium compounds and catalyst compositions

[0150] The present invention provides an organic chromium compound comprising a ligand compound represented by the above chemical formula 1 and chromium (Cr) coordinated to the ligand compound.

[0151] According to one embodiment of the present invention, the organic chromium compound is a chromium complex compound of the ligand compound, and may have a form in which the chromium of the chromium source forms a coordinate bond with N; and at least one unshared electron pair of two P's in the ligand compound represented by Chemical Formula 1. That is, a structure in which a phosphorus atom or a nitrogen atom of a diphosphino aminyl moiety provides an unshared electron pair to a chromium atom, and in particular, a bidentated state in which two pairs of unshared electron pairs are coordinated may be preferable. Such an organic chromium compound can be applied to a catalyst system for an oligomerization reaction of ethylene, and can exhibit excellent catalytic activity and high selectivity for 1-hexene or 1-octene.

[0152] In the present invention, the term "catalyst composition" means a state in which three components including a chromium source, a ligand compound, and a cocatalyst, or two components including a transition metal compound and a cocatalyst are added simultaneously or in any order to obtain an active catalyst composition. Here, the catalyst composition may also be referred to as a catalyst system, and in the present invention, the terms catalyst composition and catalyst system have the same meaning. The three or two components of the catalyst composition may be added in the presence or absence of a solvent and a monomer, and may be used in a supported or unsupported state.

[0153] The present invention provides a catalyst composition comprising the ligand compound, chromium, and a cocatalyst. The ligand compound represented by the above chemical formula 1 and chromium can be coordinated to form an organochromium compound as described above. That is, the catalyst system may be a three-component catalyst system comprising chromium, the ligand compound represented by the above chemical formula 1, and a cocatalyst, or a two-component catalyst system comprising the organochromium compound and a cocatalyst. As a specific example, the catalyst composition may comprise the ligand compound, an organochromium compound comprising chromium coordinated to the ligand compound, and a cocatalyst. In addition, the catalyst composition may comprise a chromium compound in which a part of a cocatalyst is bound to the organochromium compound.

[0154] According to one embodiment of the present invention, the chromium may be derived from a chromium source, and the chromium source may be an organic or inorganic chromium compound having an oxidation state of chromium of 0 to 6. As a specific example, the chromium source may be chromium metal, or a compound in which any organic or inorganic radical is bonded to chromium. Here, the organic radical may be an alkyl, alkoxy, ester, ketone, amido, carboxylate radical, etc. having 1 to 20 carbon atoms per radical, and the inorganic radical may be a halide, sulfate, oxide, etc.

[0155] According to one embodiment of the present invention, the chromium source may be a compound that exhibits high activity in oligomerization of olefins and is easy to use and obtain, and may be at least one compound selected from the group consisting of chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III) laurate, chromium (III) tris (2,2,6,6-tetramethyl-3.5-heptaneindionate), and chromium (III) stearate.

[0156] According to one embodiment of the present invention, the cocatalyst may be at least one selected from the group consisting of compounds represented by the following chemical formulas 10 to 13.

[0157] [Chemical Formula 10]

[0158] -[Al(R 13 )-O] a -

[0159] In the above chemical formula 10, R 13 are each independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and a is an integer of 2 or more.

[0160] [Chemical Formula 11]

[0161] E(R 14 )3

[0162] In the above chemical formula 11, E is aluminum or boron, and R 14 are each independently hydrogen, a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group.

[0163] [Chemical Formula 12]

[0164] [LH] + [G(Y)4] -

[0165] [Chemical Formula 13]

[0166] [L] + [G(Y)4] -

[0167] In the above chemical formulas 12 and 13, L is a neutral or cationic Lewis acid, and [LH] + is a Bronsted acid, G is a group 13 element, 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 aryl group is substituted, the substituent is a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0168] According to one embodiment of the present invention, the catalyst composition can be prepared by a plurality of methods. As a specific example, first, the catalyst composition can be prepared by including a step of contacting the organic chromium compound with a compound represented by Chemical Formula 10 or Chemical Formula 11. Second, the catalyst composition can be prepared by including a step of contacting the organic chromium compound with a compound represented by Chemical Formula 10 or Chemical Formula 11 to obtain a mixture; and a step of adding a compound represented by Chemical Formula 12 or Chemical Formula 13 to the mixture. Third, the catalyst composition can be prepared by including a step of contacting the organic chromium compound with a compound represented by Chemical Formula 12 or Chemical Formula 13. Fourth, the catalyst composition can be prepared by including a step of contacting the organic chromium compound with a compound represented by Chemical Formula 12 or Chemical Formula 13 to obtain a mixture; and a step of adding a compound represented by Chemical Formula 10 or Chemical Formula 11 to the mixture. Fifth, the catalyst composition can be prepared by including a step of contacting the chromium source with a compound represented by Chemical Formula 12 or Chemical Formula 13 to obtain a reactant; And it can be prepared by including a step of contacting the ligand compound with the above reactant.

[0169] According to one embodiment of the present invention, in the case of the first method or the third method among the methods for preparing the catalyst composition, the molar ratio of the compound represented by the chemical formula 10 or 11 to the organic chromium compound may be 1:2 to 5,000, specifically 1:100 to 3,000, and more specifically 1:300 to 1,500, and within this range, the alkylation of the organic chromium compound may be completely performed, thereby improving the activity of the catalyst composition, and preventing the activation of the alkylated organic chromium compound from being lowered due to a side reaction between the remaining alkylating agents, while improving the economy and the purity of the linear alpha-olefin produced.

[0170] According to one embodiment of the present invention, in the second method among the methods for preparing the catalyst composition, the molar ratio of the compound represented by Chemical Formula 12 or Chemical Formula 13 to the organic chromium compound may be 1:1 to 500, specifically 1:1 to 50, and more specifically 1:1 to 1:25, and within this range, the amount of the activator is sufficient so that the metal compound is completely activated, thereby improving the activity of the catalyst composition, and minimizing the residual activator, thereby improving the economy and the purity of the manufactured linear alpha-olefin.

[0171] According to one embodiment of the present invention, the compound represented by the chemical formula 10 may be an alkylaluminoxane, and specific examples thereof may include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., and a more specific example may be methylaluminoxane.

[0172] According to one embodiment of the present invention, the compound represented by the above chemical formula 11 may be trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, dialkyl aluminum hydride, alkyl aluminum dihydride, trialkylboron, etc. As a specific example, the compound represented by the above chemical formula 11 may be trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, etc.; dialkyl aluminum halides such as diethylaluminum chloride;Diethyl aluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride (DIBAH), di-n-octyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenylethyl aluminum hydride, phenyl-n-propyl aluminum hydride, phenylisopropyl aluminum hydride, phenyl-n-butyl aluminum hydride, phenylisobutyl aluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, p-tolylisopropyl aluminum hydride, p-tolyl-n-butyl aluminum hydride, p-tolylisobutyl aluminum hydride, p-tolyl-n-octyl aluminum hydride, benzylethyl aluminum Dialkyl aluminum hydrides such as hydride, benzyl-n-propyl aluminum hydride, benzylisopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzylisobutyl aluminum hydride, or benzyl-n-octyl aluminum hydride; alkyl aluminum dihydrides such as n-propyl aluminum dihydride, isopropyl aluminum dihydride, n-butyl aluminum dihydride, isobutyl aluminum dihydride, or n-octyl aluminum dihydride; trialkyl borone such as trimethyl boron, triethylboron, triisobutylboron, tripropylboron, or tributylboron;

[0173] According to one embodiment of the present invention, the compound represented by the chemical formula 12 or 13 is trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, methyl dioctadecylammonium 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, methyl dioctadecylammonium 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, methyl dioctadecylammonium 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 tetrakis(p-trifluoromethylphenyl)borate, triethylammonium Tetrakis(p-trifluoromethylphenyl)borate, tripropylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakis(p-trifluoromethylphenyl)borate, methyl dioctadecylammonium tetrakis(p-trifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(p-trifluoromethylphenyl)borate, N,N-diethylanilinium tetrakis(p-trifluoromethylphenyl)borate, N,N-dioctadecylanilinium tetrakis(p-trifluoromethylphenyl)borate, trimethylammonium tetrakis(pentafluorophenyl)borate,Triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, methyl dioctadecylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dioctadecylanilinium tetrakis(pentafluorophenyl)borate, trimethylphosphonium tetraphenylborate, triethylphosphonium tetraphenylborate, tripropylphosphonium tetraphenylborate, tributylphosphonium tetraphenylborate, trimethylcarbonium tetraphenylborate, triethylcarbonium tetraphenylborate, tripropylcarbonium tetraphenylborate, tributylcarbonium tetraphenylborate, It may be trimethylammonium tetraphenylaluminate, triethylammonium tetraphenylaluminate, tripropylammonium tetraphenylaluminate, tributylammonium tetraphenylaluminate, trimethylammonium tetra(p-tolyl)aluminate, triethylammonium tetra(p-tolyl)aluminate, tripropylammonium tetra(p-tolyl)aluminate, tributylammonium tetra(p-tolyl)aluminate, etc.

[0174] According to one embodiment of the present invention, the content ratio of the components forming the catalyst composition can be determined in consideration of the catalyst activity and the selectivity for linear alpha-olephene, etc. As a specific example, when the catalyst composition is a ternary catalyst composition, the molar ratio of the diphosphino aminyl moiety of the ligand compound: the chromium source: the cocatalyst 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, when the catalyst composition is a binary catalyst composition, the molar ratio of the diphosphino aminyl moiety of the organic chromium compound: the cocatalyst can be adjusted to 1:1 to 1:10,000, or 1:1 to 1:5,000, or 1:1 to 1:3,000.

[0175] According to one embodiment of the present invention, when preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, etc.; an aromatic solvent such as benzene, toluene, etc. may be used as the reaction solvent.

[0176] According to one embodiment of the present invention, the components forming the catalyst composition can be added simultaneously or in any order, in the presence or absence of a suitable solvent and monomer, to function as an active catalyst composition. Suitable solvents include heptane, toluene, cyclohexane, methylcyclohexane, 1-hexene, 1-octene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, and the like.

[0177] According to one embodiment of the present invention, the organic chromium compound and the cocatalyst can be used in a form supported on a carrier, and at this time, the carrier can be silica or alumina.

[0178] 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 the above chemical formula 1 may be applied to an ethylene oligomerization reaction in a form supported on a carrier. The carrier may be a metal, metal salt, metal oxide, etc. applied to a supported catalyst, and as a specific example, the carrier may be silica, silica-alumina, silica-magnesia, etc., and may include a metal oxide, carbonate, sulfate, or nitrate component such as Na2O, K2CO3, BaSO4, Mg(NO3)2, etc.

[0179] According to one embodiment of the present invention, the catalyst composition can be used for trimerization or tetramerization reaction of ethylene, and can produce 1-hexene or 1-octene with high selectivity as described above.

[0180]

[0181] Ethylene oligomerization method

[0182] The present invention provides a method for producing linear alpha-olefin as an ethylene oligomerization method including a step (S10) of oligomerizing ethylene in the presence of the above catalyst composition.

[0183] In the present invention, "oligomerization" refers to the oligomerization of olefins. Depending on the number of olefins polymerized, it is called trimerization or tetramerization, and this is collectively called multimerization. In particular, in the present specification, it may refer to the selective production of 1-hexene and 1-octene, the main comonomers of LLDPE, from ethylene.

[0184] According to one embodiment of the present invention, the oligomerization reaction of ethylene may be a trimerization or tetramerization reaction of ethylene, and 1-hexene or 1-octene may be formed as a result of the reaction, so that the linear alpha-olefin may be 1-hexene, 1-octene, or a mixture thereof.

[0185] According to one embodiment of the present invention, the ethylene oligomerization method can be performed by applying the catalyst composition described above to ethylene as a raw material and conventional equipment and contact techniques. As a specific example, the ethylene oligomerization reaction can be performed in the presence or absence of an inert solvent, as a homogeneous liquid-phase reaction, a slurry reaction in which part or all of the catalyst composition is not dissolved, a bulk-phase reaction in which the product alpha-olefin acts as the main medium, or a gas-phase reaction.

[0186] According to one embodiment of the present invention, the oligomerization reaction of ethylene may be performed in an inert solvent. As a specific example, the inert solvent may be benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, and 2,2,4-trimethylpentane.

[0187] According to one embodiment of the present invention, the ethylene oligomerization reaction may be performed at a temperature of 0° C. to 200° C., or 0° C. to 150° C., or 30° C. to 100° C., or 50° C. to 100° C. In addition, the reaction may be performed under a pressure of 15 psig to 3000 psig, or 15 psig to 1500 psig, or 15 psig to 1,000 psig.

[0188]

[0189] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0190]

[0191] Synthesis examples and comparative synthesis examples

[0192] Synthesis Example 1: Synthesis of a ligand compound represented by Chemical Formula 1-1

[0193] 20 mmol (2 eq) of 1-bromo-4-(tripropylsilyl)benzene was dissolved in 20 ml of tetrahydrofuran, and the mixture was cooled to -78 °C. While maintaining the temperature, 20 mmol (2 eq) of n-butyllithium was added dropwise, and the mixture was stirred for 3 hours. Subsequently, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the mixture was warmed to room temperature and stirred overnight. Thereafter, the solvent was removed using a vacuum. The obtained first intermediate was dissolved in 30 ml of n-hexane without further purification, and then HCl (in ether, 2 eq) was added, stirred for 15 minutes, and filtered. The filtrate was dried in vacuo. 2.1 mmol (2.1 eq) of the obtained second intermediate was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of tricosan-12-amine dissolved in dichloromethane was slowly added, and stirred at room temperature overnight. After removing the solvent in vacuo, it was dissolved in 7.6 ml of n-hexane, and loaded onto the top of the silica column chromatography. Silica filtration was performed using n-hexane containing 1 wt% of triethylamine, and the resulting solution was concentrated to obtain a ligand compound represented by chemical formula 1-1.

[0194] [Chemical Formula 1-1]

[0195]

[0196] N-(bis(4-(tripropylsilyl)phenyl)phosphaneyl)-N-(tricosan-12-yl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine

[0197] 1 H NMR (500 MHz, CDCl3): δ 7.44 (m, 8H), 7.09 (m, 8H), 2.50 (m, 1H), 1.50 (m, 4H), 1.48 (m, 24H), 1.38 (m, 4H), 1.35 (m, 24H), 1.34(m, 32H), 1.03(m, 36H), 0.92(m, 6H)

[0198]

[0199] Synthesis Example 2: Synthesis of a ligand compound represented by Chemical Formula 1-2

[0200] In the above Synthesis Example 1, except that 1 mmol (1 eq) of heptacosan-14-amine was used instead of 1 mmol (1 eq) of tricosan-12-amine, the same method as in Synthesis Example 1 was performed to obtain a ligand compound represented by Chemical Formula 1-2.

[0201] [Chemical Formula 1-2]

[0202]

[0203] N-(bis(4-(tripropylsilyl)phenyl)phosphaneyl)-N-(heptacosan-14-yl)-1,1-bis(4-(tripropylsilyl)phenyl)phosphanamine

[0204] 1 H NMR (500 MHz, CDCl3): δ 7.41(m, 8H), 7.10(m, 8H), 2.50(m, 1H), 1.49(m, 24H), 1.48(m, 4H), 1.38(m, 24H), 1.36(m, 4H), 1.30(m, 40H), 1.03(m, 36H), 0.91(m, 6H)

[0205]

[0206] Synthesis Example 3: Synthesis of a ligand compound represented by Chemical Formula 1-3

[0207] In the above Synthesis Example 1, except that 20 mmol (2 eq) of 1-bromo-3-(tripropylsilyl)benzene was used instead of 20 mmol (2 eq) of 1-bromo-4-(tripropylsilyl)benzene, the same method as in Synthesis Example 1 was performed to obtain a ligand compound represented by Chemical Formula 1-3.

[0208] [Chemical Formula 1-3]

[0209]

[0210] N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-(tricosan-12-yl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine

[0211] 1 H NMR (500 MHz, CDCl3): δ 7.57(m, 4H), 7.44(m, 4H), 7.33(m, 4H), 7.17(m, 4H), 2.53(m, 1H), 1.52(m, 4H), 1.45(m, 24H), 1.35(m, 28H), 1.30(m, 32H), 1.06(m, 36H), 0.95(m, 6H)

[0212]

[0213] Synthesis Example 4: Synthesis of a ligand compound represented by Chemical Formula 1-4

[0214] In the above Synthesis Example 1, 20 mmol (2 eq) of 1-bromo-3-(tripropylsilyl)benzene was used instead of 20 mmol (2 eq) of 1-bromo-4-(tripropylsilyl)benzene, and 1 mmol (1 eq) of heptacosan-14-amine was used instead of 1 mmol (1 eq) of tricosan-12-amine, and the same method as in Synthesis Example 1 was performed to obtain a ligand compound represented by Chemical Formula 1-4.

[0215] [Chemical Formula 1-4]

[0216]

[0217] N-(bis(3-(tripropylsilyl)phenyl)phosphaneyl)-N-(heptacosan-14-yl)-1,1-bis(3-(tripropylsilyl)phenyl)phosphanamine

[0218] 1 H NMR (500 MHz, CDCl3): δ 7.65(m, 4H), 7.43(m, 4H), 7.36(m, 4H), 7.10(m, 4H), 2.52(m, 1H), 1.53(m, 4H), 1.51(m, 24H), 1.40(m, 4H), 1.32(m, 24H), 1.29(m, 40H), 1.03(m, 36H), 0.93(m, 6H)

[0219]

[0220] Synthesis Example 5: Synthesis of a ligand compound represented by Chemical Formula 1-5

[0221] In the above Synthesis Example 1, except that 20 mmol (2 eq) of 1-bromo-4-decylbenzene was used instead of 20 mmol (2 eq) of 1-bromo-4-(tripropylsilyl)benzene, the same method as in Synthesis Example 1 was performed to obtain a ligand compound represented by Chemical Formula 1-5.

[0222] [Chemical Formula 1-5]

[0223]

[0224] N-(bis(4-decylphenyl)phosphaneyl)-1,1-bis(4-decylphenyl)-N-(tricosan-12-yl)phosphanamine

[0225] 1 H NMR (500 MHz, CDCl3): δ 7.26(m, 8H), 7.20(m, 8H), 2.67(m, 8H), 2.44(m, 1H), 1.64(m, 8H), 1.51(m, 4H), 1.38(m, 4H), 1.30(m, 88H), 0.91(m, 18H)

[0226]

[0227] Synthesis Example 6: Synthesis of a ligand compound represented by Chemical Formula 1-6

[0228] In the above Synthesis Example 1, 20 mmol (2 eq) of 1-bromo-4-decylbenzene was used instead of 20 mmol (2 eq) of 1-bromo-4-(tripropylsilyl)benzene, and 1 mmol (1 eq) of heptacosan-14-amine was used instead of 1 mmol (1 eq) of tricosan-12-amine, and the same method as in Synthesis Example 1 was performed to obtain a ligand compound represented by Chemical Formula 1-6.

[0229] [Chemical Formula 1-6]

[0230]

[0231] N-(bis(4-decylphenyl)phosphaneyl)-1,1-bis(4-decylphenyl)-N-(heptacosan-14-yl)phosphanamine

[0232] 1 H NMR (500 MHz, CDCl3): δ 7.21(m, 8H), 7.18(m, 8H), 2.67(m, 8H), 2.47(m, 1H), 1.68(m, 8H), 1.48(m, 4H), 1.42(m, 4H), 1.29(m, 96H), 0.97(m, 18H)

[0233]

[0234] Synthesis Example 7: Synthesis of a ligand compound represented by Chemical Formula 1-7

[0235] In the above Synthesis Example 1, except that 20 mmol (2 eq) of 1-bromo-3-decylbenzene was used instead of 20 mmol (2 eq) of 1-bromo-4-(tripropylsilyl)benzene, the same method as in Synthesis Example 1 was performed to obtain a ligand compound represented by Chemical Formula 1-7.

[0236] [Chemical Formula 1-7]

[0237]

[0238] N-(bis(3-decylphenyl)phosphaneyl)-1,1-bis(3-decylphenyl)-N-(tricosan-12-yl)phosphanamine

[0239] 1H NMR (500 MHz, CDCl3): δ 7.39(m, 4H), 7.30(m, 4H), 7.23(m, 4H), 7.05(m, 4H), 2.68(m, 8H), 2.44(m, 1H), 1.62(m, 8H), 1.49(m, 4H), 1.34(m, 4H), 1.28(m, 88H), 0.97(m, 18H)

[0240]

[0241] Synthesis Example 8: Synthesis of a ligand compound represented by Chemical Formula 1-8

[0242] In the above Synthesis Example 1, 20 mmol (2 eq) of 1-bromo-3-decylbenzene was used instead of 20 mmol (2 eq) of 1-bromo-4-(tripropylsilyl)benzene, and 1 mmol (1 eq) of heptacosan-14-amine was used instead of 1 mmol (1 eq) of tricosan-12-amine, and the same method as in Synthesis Example 1 was performed to obtain a ligand compound represented by Chemical Formula 1-8.

[0243] [Chemical Formula 1-8]

[0244]

[0245] N-(bis(3-decylphenyl)phosphaneyl)-1,1-bis(3-decylphenyl)-N-(heptacosan-14-yl)phosphanamine

[0246] 1 H NMR (500 MHz, CDCl3): δ 7.42(m, 4H), 7.35(m, 4H), 7.21(m, 4H), 7.07(m, 4H), 2.71(m, 8H), 2.50(m, 1H), 1.67(m, 8H), 1.47(m, 4H), 1.41(m, 4H), 1.35(m, 96H), 0.93(m, 18H)

[0247]

[0248] Comparative Synthesis Example 1: Synthesis of a Ligand Compound Represented by Chemical Formula 14

[0249] 20 mmol (2 eq) of 1-bromo-4-(tributylsilyl)benzene was dissolved in 20 ml of tetrahydrofuran, and the mixture was cooled to -78 °C. While maintaining the temperature, 20 mmol (2 eq) of n-butyllithium was added dropwise, and the mixture was stirred for 3 hours. Subsequently, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and the mixture was warmed to room temperature and stirred overnight. The solvent was then removed using a vacuum. The obtained first intermediate was dissolved in 30 ml of n-hexane without further purification, and then HCl (in ether, 2 eq) was added, stirred for 15 minutes, and filtered. The filtrate was dried in vacuo. 2.1 mmol (2.1 eq) of the obtained second intermediate was dissolved in 3.8 ml of dichloromethane, and then 3 mmol (3 eq) of triethylamine was added. Then, 1 mmol (1 eq) of isopropylamine dissolved in dichloromethane was slowly added, and the mixture was stirred at room temperature overnight. After removing the solvent in vacuo, it was dissolved in 7.6 ml of n-hexane, and loaded onto the top of the silica column chromatography. Silica filtration was performed using n-hexane containing 1 wt% of triethylamine, and the resulting solution was concentrated to obtain a ligand compound represented by chemical formula 14.

[0250] [Chemical Formula 14]

[0251]

[0252] N-(bis(4-(tributylsilyl)phenyl)phosphaneyl)-N-isopropyl-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine

[0253] 1 H NMR (500 MHz, C6D6): δ 8.12-7.22(br, 8H), 7.51(d, 8H), 3.87(m, 1H), 1.45-1.28(br, 48H), 1.25(d, 6H), 0.92(t, 36H), 0.92-0.79(br, 24H)

[0254]

[0255] Comparative Synthesis Example 2: Synthesis of a Ligand Compound Represented by Chemical Formula 15

[0256] In the above comparative synthesis example 1, except that 1 mmol (1 eq) of pentadecane-8-amine was used instead of 1 mmol (1 eq) of isopropylamine, the same method as in the above comparative synthesis example 1 was performed to obtain a ligand compound represented by chemical formula 15.

[0257] [Chemical Formula 15]

[0258]

[0259] N-(bis(4-(tributylsilyl)phenyl)phosphaneyl)-N-(pentadecane-8-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine

[0260] 1H NMR (500 MHz, C6D6): δ 8.15-7.79(br, 4H), 7.52(s, 8H), 7.71-7.33(br, 4H), 3.59(m, 1H), 2.13(m, 2H), 1.84(m, 2H), 1.61-1.09(m, 92H), 1.09-0.10(m, 42H)

[0261]

[0262] Comparative Synthesis Example 3: Synthesis of a Ligand Compound Represented by Chemical Formula 16

[0263] In the above Comparative Synthesis Example 1, except that 1 mmol (1 eq) of hentriacontane-16-amine was used instead of 1 mmol (1 eq) of isopropylamine, the same method as in Comparative Synthesis Example 1 was performed to obtain a ligand compound represented by Chemical Formula 16.

[0264] [Chemical Formula 16]

[0265]

[0266] N-(bis(4-(tributylsilyl)phenyl)phosphaneyl)-N-(hentriacontane-16-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine

[0267] 1 H NMR (500 MHz, C6D6): δ 8.14-7.78(br, 4H), 7.53(s, 8H), 7.70-7.34(br, 4H), 3.62(m, 1H), 2.11(m, 2H), 1.86(m, 2H), 1.62-1.10(br, 100H), 1.10-0.08(m, 66H)

[0268]

[0269] Comparative Synthesis Example 4: Synthesis of a Ligand Compound Represented by Chemical Formula 17

[0270] In the above Comparative Synthesis Example 1, except that 1 mmol (1 eq) of pentatriacontane-18-amine was used instead of 1 mmol (1 eq) of isopropylamine, the same method as in Comparative Synthesis Example 1 was performed to obtain a ligand compound represented by Chemical Formula 17.

[0271] [Chemical Formula 17]

[0272]

[0273] N-(bis(4-(tributylsilyl)phenyl)phosphaneyl)-N-(pentatriacontane-18-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine

[0274] 1 H NMR (500 MHz, C6D6): δ 8.15-7.80 (br, 4H), 7.53 (s, 8H), 7.70-7.35 (br, 4H), 3.63 (m, 1H), 2.12 (m, 2H), 1.85 (m, 2H), 1.60-1.08(br, 108H), 1.08-0.07(m, 66H)

[0275]

[0276] Examples and Comparative Examples

[0277] Example 1

[0278] Under an argon gas atmosphere, 0.5 mmol of chromium (III) chloride tetrahydrofuran (Cr(THF)3Cl3), 0.5 mmol of the ligand compound represented by the chemical formula 1-1 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, 30 ml of dichloromethane was added, and the mixture was stirred for 1 hour, and the solvent was removed in vacuo. Thereafter, the mixture was dissolved in methylcyclohexane, filtered, the solvent was removed in vacuo again, and dissolved in methylcyclohexane to prepare a 0.15 mM (based on Cr) catalyst solution.

[0279] A Parr reactor with a capacity of 600 ml was prepared, vacuumed at 120 °C for 2 hours, then the interior was purged with argon and the temperature was lowered to 70 °C. After that, 180 ml of methylcyclohexane and 2 ml of 725 μmol of diisobutyl aluminum hydride as an activator were injected, and 5 ml (0.75 μmol Cr) of the above catalyst solution was injected. After stirring at 1,000 rpm for 2 minutes, the valve of the ethylene line set to 40 bar was opened to fill the reactor with ethylene, and then the reactor was stirred at 1,000 rpm for 60 minutes. The ethylene line valve was closed, the reactor was cooled to 0 °C using a dry ice / acetone bath, unreacted ethylene was slowly vented, and 0.5 ml of nonane (GC internal standard) was added. After stirring for 10 seconds, 2 ml of the liquid portion of the reactor was quenched with water, and the obtained organic portion was filtered through a PTFE syringe filter to prepare a GC-FID sample. Then, the distribution of the liquid product was analyzed by GC (Agilent 6890N, Alltech AT-5 (30 mm Х 0.32 mm ID Х 0.25 μm; series no. 12446)). In addition, 400 ml of ethanol / HCl (10 vol% of aqueous 12 M HCl solution) was added to the remaining reaction solution, stirred, filtered, and the amount of the solid product was analyzed. The obtained polymer was dried overnight in a vacuum oven at 80 °C.

[0280]

[0281] Examples 2 to 8 and Comparative Examples 1 to 4

[0282] The same method as Example 1-1 was performed, except that the catalyst type was changed as shown in Table 1 below.

[0283]

[0284] Distinctive ligand compound promoter chromium source Example 1 Synthesis Example 1 (Chemical Formula 1-1) ABCr(THF)3Cl3 Example 2 Synthesis Example 2 (Chemical Formula 1-2) ABCr(THF)3Cl3 Example 3 Synthesis Example 3 (Chemical Formula 1-3) ABCr(THF)3Cl3 Example 4 Synthesis Example 4 (Chemical Formula 1-4) ABCr(THF)3Cl3 Example 5 Synthesis Example 5 (Chemical Formula 1-5) ABCr(THF)3Cl3 Example 6 Synthesis Example 6 (Chemical Formula 1-6) ABCr(THF)3Cl3 Example 7 Synthesis Example 7 (Chemical Formula 1-7) ABCr(THF)3Cl3 Example 8 Synthesis Example 8 (Chemical Formula 1-8) ABCr(THF)3Cl3 Comparative Example 1 Comparative Synthesis Example 1 (Chemical Formula 14) ABCr(THF)3Cl3Comparative Example 2Comparative Synthesis Example 2 (Chemical Formula 15) ABCr(THF)3Cl3Comparative Example 3Comparative Synthesis Example 3 (Chemical Formula 16) ABCr(THF)3Cl3Comparative Example 4Comparative Synthesis Example 4 (Chemical Formula 17) ABCr(THF)3Cl3

[0285]

[0286] Experimental example

[0287] The results of the ethylene oligomerization reaction according to the above examples and comparative examples are shown in Table 2 below.

[0288]

[0289] * Catalytic activity (ton / mol·Cr / hr): The catalytic activity was calculated from the total product weight (ton) calculated by adding the weights (ton) of the obtained liquid product and solid product.

[0290]

[0291] * 1-C6, 1-C8, Iso-C6, Iso-C8 selectivity (weight %): The contents of 1-hexene (1-C6), 1-octene (1-C8) and their isomers (Iso-C6 and Iso-C8) were calculated from the results of analyzing the distribution of the liquid product by GC, and the weight % of 1-hexene, 1-octene and their isomers based on the total weight of the product was calculated.

[0292]

[0293] * Solid (weight%): The weight percentage of solid product based on the total weight of the product was calculated. This indicates the extent to which polyethylene with a carbon number of about 40 or more was produced as an insoluble solid that did not dissolve in the solvent.

[0294]

[0295] Catalytic activity 1-C6 and 1-C8 selectivity Iso-C6 Iso-C8 Solid 1-C6 1-C8 Total (ton / mol Cr / hr) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) Example 1 260 36.1 248.3 584.47 3.3 10.2 80.5 8 Example 2 266 37.1 547.3 184.4 63.2 80.3 33 0.4 5 Example 3 240 36.3 246.7 283.0 43.3 20.2 80.6 7 Example 4 246 38.5 546.5 385.0 83.3 50.3 33 0.6 3 Example 522536.3148.8585.163.420.260.35Example 623037.6347.0684.693.340.330.41Example 720936.5246.4482.963.300.300.44Example 821438.7347.2285.953.290.340.32Comparative Example 117628.3354.5882.913.780.390.15Comparative Example 218530.2349.5679.793.560.360.35Comparative Example 317139.2539.0278.273.150.330.67Comparative Example 413940.6238.4279.043.110.420.23

[0296] As shown in Table 2 above, when an ethylene oligomerization reaction is performed using a catalyst composition comprising a ligand compound according to the present invention, it was confirmed that the most appropriate stereogenic group is formed from a ligand compound in which an alkyl group having 21 to 30 carbon atoms is substituted on the nitrogen atom of a diphosphino aminyl moiety, thereby reducing the production ratio of isomers of 1-hexene and / or 1-octene without decreasing the activity of the catalyst, thereby improving the catalytic activity, selectivity, and stability.

[0297]

[0298] From these results, it was confirmed that when ethylene oligomerization is performed using an organic chromium compound and a catalyst composition including the ligand compound of the present invention, linear alpha-olefins can be produced with high 1-hexene and 1-octene selectivity while having excellent productivity due to high catalytic activity.

Claims

A ligand compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R 1 Inland R 4 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or -Si(R 7 )3, m, n, o and p are each independently an integer selected from 0 or 1 to 5, provided that when m, n, o and p are 2 or more, a plurality of R 1 Inland R 4 are identical or different from each other, R 5 is an alkyl group having 21 to 30 carbon atoms, R 7 is an alkyl group having 1 to 20 carbon atoms, and is composed of multiple R 7 are identical or different from each other. In the first paragraph, R 1 Inland R 4 are each independently an alkyl group having 1 to 20 carbon atoms or -Si(R 7 )3-membered ligand compound. In the first paragraph, R 1 Inland R 4 are each independently -Si(R 7 )3, and R 7 is an alkyl group having 1 to 10 carbon atoms, and is composed of multiple R 7 Ligand compounds which are identical or different from each other. In the first paragraph, R 1 Inland R 4 A ligand compound each independently representing a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a tri-n-butylsilyl group, a tri-n-octylsilyl group, or a dimethyl(n-octyl)silyl group. In the first paragraph, Ligand compounds where m, n, o and p are 1. In the first paragraph, R 5 A ligand compound which is a branched alkyl group having 21 to 30 carbon atoms. In the first paragraph, The ligand compound represented by the above chemical formula 1 is a ligand compound represented by the following chemical formula 2 or chemical formula 3: [Chemical formula 2] [Chemical Formula 3] In the above chemical formulas 2 and 3, R 1 Inland R 5 are each identical to those defined in Article 1. In the first paragraph, The ligand compound represented by the above chemical formula 1 is a ligand compound represented by the following chemical formula 4: [Chemical Formula 4] In the above chemical formula 4, R 1 Inland R 4 and m, n, o and p are each the same as defined in Article 1, R 6 and R 7 are each independently an alkyl group having 1 to 27 carbon atoms, and R 6 and R 7 The sum of the carbon atoms is 20 to 29. In the first paragraph, The ligand compound represented by the above chemical formula 1 is a ligand compound represented by the following chemical formula 5 or chemical formula 6: [Chemical Formula 5] [Chemical formula 6] In the above chemical formulas 5 and 6, R 1 Inland R 4 are each identical to those defined in Article 1, R 6 and R 7 are each independently an alkyl group having 1 to 27 carbon atoms, and R 6 and R 7 The sum of the carbon atoms is 20 to 29. In the first paragraph, The ligand compound represented by the above chemical formula 1 is a ligand compound represented by any one of the following chemical formulas 1-1 to 1-12: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6] [Chemical Formula 1-7] [Chemical Formula 1-8] [Chemical Formula 1-9] [Chemical Formula 1-10] [Chemical Formula 1-11] [Chemical Formula 1-12] . An organic chromium compound comprising a ligand compound according to claim 1 and chromium coordinated to the ligand compound. In Article 11, An organic chromium compound in which at least one unshared electron pair among N and two P in the ligand compound represented by the chemical formula 1 is coordinated to chromium. A catalyst composition comprising a ligand compound according to claim 1, chromium and a cocatalyst. In Article 13, The above chromium is derived from a chromium source, A catalyst composition wherein the above chromium source comprises at least one selected from the group consisting of chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III) laurate, chromium (III) tris (2,2,6,6-tetramethyl-3.5-heptanedione), and chromium (III) stearate. In Article 13, The above catalyst is a catalyst composition comprising at least one compound selected from the group consisting of compounds represented by the following chemical formulas 10 to 13: [Chemical Formula 10] <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 the above chemical formula 10, R 13 are each independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, a is an integer greater than or equal to 2, [Chemical Formula 11] E(R 14 )3 In the above chemical formula 11, E is aluminum or boron, R 14 are each independently hydrogen, a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, [Chemical Formula 12] [L-H] + [G(Y)4] - [Chemical Formula 13] [L] + [G(Y)4] - In the above chemical formulas 12 and 13, L is a neutral or cationic Lewis acid, [LH] + is Mount Bronsted, G is a group 13 element, 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 aryl group is substituted, the substituent is a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. A method for producing linear alpha-olefin, comprising a step (S10) of oligomerizing ethylene in the presence of a catalyst composition according to claim 13. In Article 16, A method for producing linear alpha-olefin, wherein the linear alpha-olefin is 1-hexene, 1-octene or a mixture thereof.

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