Ligand compounds, organochromium compounds, and catalyst compositions containing the same

Abstract

The present invention relates to a ligand compound, an organochromium compound, a catalyst composition containing the organochromium compound, and a method for oligomerizing ethylene using the same, which exhibit high catalytic activity and high selectivity for 1-hexene and 1-octene, and which can oligomerize ethylene with excellent efficiency.

Description

[Technical Field]

[0001] This invention claims priority under Korean Patent Application No. 10-2023-0051230, filed on 19 April 2023, and all content disclosed in the said Korean Patent Application is incorporated herein by reference.

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

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

[0004] In the conventional manufacturing process of LLDPE (Linear Low-Density Polyethylene), copolymerization with α-olefins, such as 1-hexene and 1-octene, was carried out to adjust the density by forming branches in the polymer backbone along with ethylene.

[0005] Therefore, in order to produce LLDPE with a high comonomer content, there was a problem in that the price of the comonomer accounted for a large portion of the manufacturing cost. Various attempts have been made to solve this problem.

[0006] Such linear α-olefins were typically produced by the Shell Higher Olefin Process. However, this method had the drawback of requiring a separate separation step to obtain a specific α-olefin, as it simultaneously synthesized α-olefins of various lengths due to the Schultz-Flory distribution.

[0007] To address these problems, methods have been proposed for the selective synthesis of 1-hexene by the trimerization reaction of ethylene, and for the selective synthesis of 1-octene by the tetramerization reaction of ethylene. Furthermore, much research has been conducted on catalytic systems that enable such selective oligomerization of ethylene. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] US5064802B2 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] The problem that the present invention aims to solve is to provide a ligand compound, an organochromium compound, and a catalyst composition containing the same, which exhibit high catalytic activity and high selectivity for 1-hexene and 1-octene, and which can oligomerize ethylene with excellent efficiency. [Means for solving the problem]

[0010] To solve the above problems, the present invention provides a ligand compound, an organochromium compound, a catalyst composition, and a method for oligomerizing ethylene.

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

[0012] [ka]

[0013] In the above Chemical Formula 1, R 1 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may or may not be substituted with a halogen group, an alkoxy group having 1 to 10 carbon atoms which may or may not be substituted with a halogen group, an alkylthio group having 1 to 10 carbon atoms which may or may not be substituted with a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may or may not be substituted with a halogen group, a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently an alkyl group having 1 to 10 carbon atoms), or R 6 combines to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring. When R 6 does not combine with R 1 to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 6 is hydrogen, and R 2 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may or may not be substituted with a halogen group, an alkoxy group having 1 to 10 carbon atoms which may or may not be substituted with a halogen group, an alkylthio group having 1 to 10 carbon atoms which may or may not be substituted with a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may or may not be substituted with a halogen group, a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently an alkyl group having 1 to 10 carbon atoms), or R 7 combines to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring. When R 7 does not combine with R 2 to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, R 7 is hydrogen, and R 3 and R 4Each is independently of hydrogen, a C5-C20 alkyl group, a C5-C20 cycloalkyl group, a C2-C20 alkoxyalkyl group, a C7-C30 arylalkoxyalkyl group, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C10 alkyl group), and R 3 and R 4 It is not possible for both to be hydrogen at the same time, R 5 These are C1-C20 alkyl groups, C1-C20 alkyl groups substituted with C6-C10 aryl groups, C5-C10 cycloalkyl groups, or C5-C10 cycloalkyl groups condensed with C6-C10 aryl groups.

[0014] (2) The present invention is R 1 This is a fluoro, a fluoro-substituted or unsubstituted C1-C5 alkyl group, a fluoro-substituted or unsubstituted C1-C5 alkoxy group, a fluoro-substituted or unsubstituted C1-C5 alkylthio group, a fluoro-substituted or unsubstituted C1-C5 alkylsulfonate group, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C5 alkyl group), or R 6 It is formed by bonding with R to create a monocyclic or polycyclic heterocyclic ring. 2 This is a fluoro, a fluoro-substituted or unsubstituted C1-C5 alkyl group, a fluoro-substituted or unsubstituted C1-C5 alkoxy group, a fluoro-substituted or unsubstituted C1-C5 alkylthio group, a fluoro-substituted or unsubstituted C1-C5 alkylsulfonate group, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C5 alkyl group), or R 7 The present invention provides the ligand compound described in (1) above, which is bonded to form a monocyclic or polycyclic heterocyclic ring.

[0015] (3) The present invention is R 1 is a fluoro group, trifluoromethyl group, methoxy group, methyl group, trifluoromethoxy group, trifluoromethylthio group, methylthio group, methylsulfonate group, or trimethylsilyl group, R 6 It is a compound formed by binding with R to form a furan or dibenzofuran, 2 is a fluoro group, trifluoromethyl group, methoxy group, methyl group, trifluoromethoxy group, trifluoromethylthio group, methylthio group, methylsulfonate group, or trimethylsilyl group, R 7 The present invention provides a ligand compound according to (1) or (2) above, which is formed by binding with to form a furan or dibenzofuran.

[0016] (4) The present invention is R 3 and R 4 Each of these independently provides a ligand compound according to any one of (1) to (3) above, which is an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group, or a tributylsilyl group.

[0017] (5) The present invention is R 3 and R 4 Each of these independently provides a ligand compound according to any one of (1) to (4) above, which is an n-decyl group, a tripropylsilyl group, or a tributylsilyl group.

[0018] (6) The present invention is R 5 The present invention provides a ligand compound according to any one of (1) to (5) above, wherein the ligand is a C3-C5 alkyl group, a C1-C5 alkyl group substituted with a C6-C10 aryl group, a C5-C8 cycloalkyl group, or a C5-C8 cycloalkyl group condensed with a C6-C10 aryl group.

[0019] (7) The present invention provides a ligand compound according to any one of (1) to (6) above, wherein the ligand compound represented by chemical formula 1 is represented by any one of the following chemical formulas 2 to 5.

[0020] [ka]

[0021] [ka]

[0022] [ka]

[0023] [ka]

[0024] In the aforementioned chemical formulas 2 to 5, R 1 ~R 7 These are defined as described in (1) through (6) above.

[0025] (8) The present invention provides a ligand compound according to any one of (1) to (7) above, wherein the ligand compound represented by chemical formula 1 is represented by any one of the following chemical formulas 2-1 to 2-66 and 3-1 to 3-20. [ka] [ka] [ka] [ka]

[0026] (9) The present invention provides an organochromium compound comprising a ligand compound described in any one of (1) to (8) above, and chromium coordinated to the ligand compound.

[0027] (10) The present invention provides the organochromium compound described in (9) above, wherein the ligand compound represented by chemical formula 1 has one or more lone pairs of electrons from N and two P coordinated to chromium.

[0028] (11) The present invention provides a catalyst composition comprising a ligand compound, chromium, and a co-catalyst as described in any one of (1) to (8) above.

[0029] (12) The present invention provides the catalyst composition described in (11), wherein the chromium is derived from a chromium source, and the chromium source comprises one or more selected from the group consisting of chromium(III) acetylacetonate, chromium(III) chloride tetrahydrofuran, chromium(III) 2-ethylhexanoate, chromium(III) acetate, chromium(III) butyrate, chromium(III) pentanoate, chromium(III) laurate, chromium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedione), and chromium(III) stearate.

[0030] (13) The present invention provides a catalyst composition according to (11) or (12), wherein the co-catalyst is one or more compounds selected from the group consisting of compounds represented by the following chemical formulas 6 to 9.

[0031] [Chemical formula 6] -[Al(R 13 )-O] a -

[0032] In the above chemical formula 6, R 13 Each of these is independently a halogen group, a C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with a halogen group, and a is an integer of 2 or more. [Chemical formula 7] E(R 14 )3 In the above chemical formula 7, E is aluminum or boron, and R 14These are, independently, hydrogen, a halogen group, a C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with a halogen group. [Chemical formula 8] [LH] + [G(Y)4] - [Chemical formula 9] [L] + [G(Y)4] - In the chemical formulas 8 and 9, L is a neutral or cationic Lewis acid, and [LH] + is a Brønsted acid, G is a group 13 element, and Y is, independently, a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C6-C20 aryl group, where, if the alkyl group or aryl group is substituted, the substituent is a halogen group, a C1-C20 hydrocarbyl group, a C1-C20 alkoxy group, or a C6-C20 aryloxy group.

[0033] (14) The present invention provides a method for producing a linear α-olefin, comprising the step (S10) of oligomerizing ethylene in the presence of a catalyst composition described in any one of (11) to (13).

[0034] (15) The present invention provides a method for producing the linear α-olefin described in (14), wherein the linear α-olefin is 1-hexene, 1-octene, or a mixture thereof. [Effects of the Invention]

[0035] When oligomerizing ethylene using an organochromium compound and catalyst composition containing the ligand compound of the present invention, high catalytic activity allows for excellent productivity, and linear α-olefins can be produced with high selectivity for 1-hexene and 1-octene. [Modes for carrying out the invention]

[0036] The present invention will now be described in more detail so that it can be easily understood.

[0037] The terms and words used in the description and claims of this invention should not be interpreted in a manner limited to their ordinary or dictionary meanings, but rather should be interpreted in a manner consistent with the technical idea of ​​this invention, in accordance with the principle that inventors may appropriately define the concepts of terms in order to best describe their invention.

[0038] Ligand compounds The present invention provides a ligand compound applicable to catalysts used in the oligomerization reaction of ethylene. When the ligand compound is applied to the oligomerization reaction of ethylene, specifically to a catalyst composition for forming linear α-olefins, it exhibits excellent catalytic activity and high selectivity for linear α-olefins. In particular, compared to conventional PNP-based catalysts, and even catalysts containing symmetric ligand compounds, it produces less solid polyethylene under the same reaction conditions, enabling more efficient production of linear α-olefins.

[0039] According to one embodiment of the present invention, the organochromium compound to which the ligand compound is coordinated can be used in the production of linear α-olefins using ethylene. An oligomerization reaction proceeds under ethylene conditions, and liquid α-olefins, specifically liquid 1-hexene or 1-octene, can be formed with high selectivity. This is because the oligomerization reaction of ethylene involves a transition state that forms a metallacycle, resulting in high selectivity for α-olefins of a specific length.

[0040] According to one embodiment of the present invention, the ligand compound comprises a diphosphino aminyl residue, and an aryl group having a specific substituent is linked to the terminus of the diphosphino aminyl residue, so that the aryl group itself can function as a strong electron-donating group. Due to these structural characteristics, the ligand compound can be applied to an ethylene oligomerization catalyst system and exhibit high activity, and in particular can exhibit high selectivity for 1-hexene, 1-octene, and the like. This is thought to be due to the interaction between adjacent chromium active sites, and in particular, when an aryl group with a specific substituent is linked to the phosphorus (P) atom of the diphosphino aminyl, the electron density increases at the phosphorus (P) and nitrogen (N) atoms contained in the diphosphino aminyl, which changes the electrical and steric properties of the overall ligand compound. This alters the bond between the ligand and the chromium atom, making the catalyst structure more stable. Compared to the conventional metallacycloheptane or metallacyclononane forms, it alters the transition state energy (activation energy), allowing for the formation of α-olefins with higher activity and selectivity, and further reducing the amount of by-products such as large molecular weight solid α-olefins like polyethylene wax (PE Wax).

[0041] According to one embodiment of the present invention, the ligand compound is characterized in that the phenyl group located at the terminus of the diphosphinoaminyl residue has a substituent at the ortho position, which is a halogen group, a C1-C10 alkyl group substituted with or unsubstituted with a halogen group, a C1-C10 alkoxy group substituted with or unsubstituted with a halogen group, a C1-C10 alkylthio group substituted with or unsubstituted with a halogen group, a C1-C10 alkylsulfonate group substituted with or unsubstituted with a halogen group, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C10 alkyl group), or is condensed with phenyl to form a monocyclic or polycyclic aromatic hydrocarbon ring, or a monocyclic or polycyclic heterocycle, and has a substituent at the meta position and the para position, which is an alkyl group of a specific number of carbon atoms, or a silyl group substituted with an alkyl group of a specific number of carbon atoms. The substituent substituted at the ortho position of phenyl can increase the steric strain around the metal atom, thereby increasing the selectivity of 1-hexene. It can also protect the metal atom or directly form a coordination bond, improving the stability of the metal complex compound. In addition, substituents substituted at the meta and para positions of phenyl can increase the solubility of the ligand compound and the metal complex compound in the polymerization solvent, respectively, improving their activity and selectivity. As a result, when using the ligand compound, a chromium catalyst with high stability and excellent activity and selectivity can be produced.

[0042] According to one embodiment of the present invention, the ligand compound has a bulky substituent, such as a cycloalkyl group or a phenyl group, bonded to a nitrogen atom to which two phosphorus atoms are bonded. The bulky substituent bonded to the nitrogen prevents rotation of the nitrogen-phosphorus bond, further improving catalytic stability and activity. In this case, the steric properties of the substituent bonded to the nitrogen atom affect the catalytic activity, stability, and selectivity. If the steric strain of the substituent bonded to the nitrogen atom is too high, the synthesis of the ligand and the formation of the metal complex compound become difficult, and the resulting complex compound becomes unstable. Also, if the steric strain of the substituent bonded to the nitrogen atom is too high, it becomes difficult for raw materials such as ethylene to approach, leading to a decrease in catalytic activity. Furthermore, if the steric strain of the substituent bonded to the nitrogen atom is too low, it is not possible to prevent rotation of the nitrogen-phosphorus bond, and the metal central atom cannot be protected, causing a decrease in catalytic activity and stability. In other words, if the steric strain of the substituent bonded to the nitrogen atom is too high or too low, the catalytic activity decreases, stability decreases, and the amount of by-products such as polyethylene wax increases. Therefore, selecting a substituent bonded to the nitrogen atom that has an appropriate level of steric strain relative to the substituent bonded to the phosphorus atom is extremely important. In the ligand compound according to the present invention, the introduction of a substituent at the ortho position of the phenyl group bonded to the phosphorus atom increases the steric strain around the PNP functional group. Therefore, to prevent an excessive increase in the steric strain of the substituent bonded to the nitrogen atom, the R of Chemical Formula 1 is used. 5 By introducing substituents represented by , the yield and selectivity can be improved when the oligomerization reaction of ethylene is carried out using a catalyst composition containing them. In particular, R of Chemical Formula 1 5 When a substituent in the form of a secondary alkyl group is introduced as the substituent represented by , efficiency is further improved. When a substituent in the form of a primary alkyl group is introduced at the 1st or 2nd carbon position to compensate for the low steric strain, appropriate steric strain can be formed, improving yield and selectivity.

[0043] According to one embodiment of the present invention, the ligand compound may be represented by the following chemical formula 1.

[0044] [ka]

[0045] In the above chemical formula 1, R 1 This is a halogen group, a C1-C10 alkyl group substituted or unsubstituted with a halogen group, a C1-C10 alkoxy group substituted or unsubstituted with a halogen group, a C1-C10 alkylthio group substituted or unsubstituted with a halogen group, a C1-C10 alkylsulfonate group substituted or unsubstituted with a halogen group, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C10 alkyl group), or R 6 It combines with to form a monocyclic or polycyclic aromatic hydrocarbon ring, or a monocyclic or polycyclic heterocycle, R 6 R 1 If it does not bond with to form a monocyclic or polycyclic aromatic hydrocarbon ring, or a monocyclic or polycyclic heterocyclic ring, then R 6 is hydrogen, R 2 This is a halogen group, a C1-C10 alkyl group substituted or unsubstituted with a halogen group, a C1-C10 alkoxy group substituted or unsubstituted with a halogen group, a C1-C10 alkylthio group substituted or unsubstituted with a halogen group, a C1-C10 alkylsulfonate group substituted or unsubstituted with a halogen group, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C10 alkyl group), or R 7 It combines with to form a monocyclic or polycyclic aromatic hydrocarbon ring, or a monocyclic or polycyclic heterocycle, R 7 R 2 If it does not bond with to form a monocyclic or polycyclic aromatic hydrocarbon ring, or a monocyclic or polycyclic heterocyclic ring, then R 7is hydrogen, R 3 and R 4 Each is independently of hydrogen, a C5-C20 alkyl group, a C5-C20 cycloalkyl group, a C2-C20 alkoxyalkyl group, a C7-C30 arylalkoxyalkyl group, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C10 alkyl group), and R 3 and R 4 It is not possible for both to be hydrogen at the same time, R 5 These are C1-C20 alkyl groups, C1-C20 alkyl groups substituted with C6-C10 aryl groups, C5-C10 cycloalkyl groups, or C5-C10 cycloalkyl groups condensed with C6-C10 aryl groups.

[0046] In this invention, "halogen group" means fluorine (-F), chlorine (-Cl), bromine (-Br), and iodine (-I).

[0047] In the present invention, "substituted with a halogen group" means that at least one hydrogen atom bonded to the carbon atom of each substituent is substituted with 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.

[0048] In the present invention, "alkyl group" means a linear or branched hydrocarbon residue, and specific examples may be a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, and hexyl group, depending on the defined number of carbon atoms.

[0049] In the present invention, "alkylthio group" means that at least one substituent is an alkyl group, centered on a sulfide bond, and when the number of carbon atoms is mentioned, it may mean the number of carbon atoms of the alkyl group.

[0050] In the present invention, "alkyl sulfonate group" means a sulfonate in which an alkyl group is substituted for the sulfur atom, and when the number of carbon atoms is mentioned, it may mean the number of carbon atoms of the alkyl group.

[0051] In the present invention, "trialkylsilyl group" is represented as -SiRd3, where each R is an alkyl group substituent, and when the number of carbon atoms of the trialkylsilyl group is mentioned, it may mean the sum of the total number of carbon atoms of all R atoms.

[0052] In the present invention, "monocyclic aromatic hydrocarbon ring" means an aromatic hydrocarbon consisting of one ring, such as a benzene ring, and "polycyclic aromatic hydrocarbon ring" may mean an aromatic hydrocarbon consisting of two or more rings, such as a naphthalene ring.

[0053] In the present invention, "monocyclic heterocycle" means a heterocycle consisting of one ring containing a heteroatom, such as furan, thiophene, pyrrole, and pyridine, and "polycyclic heterocycle" may mean a heterocycle consisting of two or more rings containing heteroatoms, such as benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, benzopyrrole, and dibenzopyrrole. The heterocycle may form an aliphatic or aromatic ring.

[0054] In the present invention, "cycloalkyl group" means a cyclic hydrocarbon residue, and specific examples may include cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, depending on the defined number of carbon atoms.

[0055] In the present invention, "alkoxyalkyl group" means an alkyl group in which an alkoxy group has been substituted, and when the number of carbon atoms of the alkoxyalkyl group is mentioned, it may mean the total number of carbon atoms of the alkoxy group and the alkyl group combined.

[0056] In the present invention, "arylalkoxyalkyl group" means an alkyl group substituted with an alkoxy group containing an aryl group as a substituent, and when the number of carbon atoms of an arylalkoxyalkyl group is mentioned, it may mean the total number of carbon atoms of the alkoxy group and the alkyl group combined.

[0057] In the present invention, unless otherwise specified, "aryl" refers to an optionally substituted benzene ring or a ring system that can be formed by condensing one or more optional substituents. Exemplary substituents include substituted C1-C2 alkyl groups, substituted C2-C3 alkenyl groups, substituted C2-C3 alkynyl groups, heteroaryl groups, heterocyclic groups, aryl groups, alkoxys, aryloxys, aralkoxys, acyls, aroyls, heteroaloyls, acyloxys, aroyloxys, heteroaloyloxys, sulfanyls, sulfinyls, sulfonyls, aminosulfonyls, sulfonylaminos, carboxyamides, aminocarbonyls, carboxys, oxo, hydroxys, mercaptos, aminos, nitros, cyanos, halogens, or ureidos. Such rings or ring systems may be optionally condensed to an aryl ring (e.g., a benzene ring), a carbocyclic ring, or a heterocyclic ring, each having one or more substituents. The following are not limited to phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthrasyl, or phenanthryl, and their substituted derivatives.

[0058] According to one embodiment of the present invention, R 1 This is a fluoro group, a chloro group, a bromo group, a C1-C5 alkyl group that is fluorosubstituted or unsubstituted, a C1-C5 alkoxy group that is fluorosubstituted or unsubstituted, a C1-C5 alkylthio group that is fluorosubstituted or unsubstituted, a C1-C5 alkylsulfonate group that is fluorosubstituted or unsubstituted, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C5 alkyl group), or R 6It may be a monocyclic or polycyclic heterocycle formed by bonding with R. 1 is a fluoro group, trifluoromethyl group, methoxy group, methyl group, trifluoromethoxy group, trifluoromethylthio group, methylthio group, methylsulfonate group, or trimethylsilyl group, R 6 It may be a compound formed by combining with a furan or dibenzofuran.

[0059] According to one embodiment of the present invention, R 2 This is a fluoro group, a chloro group, a bromo group, a C1-C5 alkyl group that is fluorosubstituted or unsubstituted, a C1-C5 alkoxy group that is fluorosubstituted or unsubstituted, a C1-C5 alkylthio group that is fluorosubstituted or unsubstituted, a C1-C5 alkylsulfonate group that is fluorosubstituted or unsubstituted, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C5 alkyl group), or R 7 It may be a monocyclic or polycyclic heterocycle formed by bonding with R. 2 is a fluoro group, trifluoromethyl group, methoxy group, methyl group, trifluoromethoxy group, trifluoromethylthio group, methylthio group, methylsulfonate group, or trimethylsilyl group, R 7 It may be a compound formed by combining with a furan or dibenzofuran.

[0060] According to one embodiment of the present invention, R 1 and R 2 They may be identical to each other.

[0061] According to one embodiment of the present invention, R 3 and R 4Each of these may independently be a C5-C12 alkyl group, a C5-C12 cycloalkyl group, a C6-C12 alkoxyalkyl group, a C10-C20 arylalkoxyalkyl group, or a trialkylsilyl group, in which case the alkyl group of the trialkylsilyl group may independently be a C1-C5 alkyl group. As a specific example, R 3 and R 4 Each of these may independently be an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group, or a tributylsilyl group, and a more specific example is R 3 and R 4 These may each be independently a tripropylsilyl group, a tributylsilyl group, or an n-decyl group. That is, the ligand compound has a phenyl group located at the terminal end of the diphosphinoaminyl residue, with two ortho positions R 1 and R 2 The molecule may have substituents and may have a silyl group substituted with a C10 alkyl group or a C3 or C4 alkyl group at the meta or para position.

[0062] According to one embodiment of the present invention, R 5 This may be a C1-C10 alkyl group, a C1-C10 alkyl group substituted with a C6-C10 aryl group, a C5-C10 cycloalkyl group, or a C5-C10 cycloalkyl group condensed with a C6-C10 aryl group. As a specific example, R 5 This may be a C3-C5 alkyl group, a C1-C5 alkyl group substituted with a C6-C10 aryl group, a C5-C8 cycloalkyl group, or a C5-C8 cycloalkyl group condensed with a C6-C10 aryl group.

[0063] According to one embodiment of the present invention, the ligand compound represented by chemical formula 1 may be represented by any one of the following chemical formulas 2 to 5.

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] In the aforementioned chemical formulas 2 to 5, R 1 ~R 7 These are defined as in Chemical Formula 1.

[0069] According to one embodiment of the present invention, the ligand compound represented by chemical formula 1 may be any one of the following ligand compounds represented by chemical formulas 2-1 to 2-66 and chemical formulas 3-1 to 3-20. [ka] [ka] [ka] [ka]

[0070] According to one embodiment of the present invention, the ligand compound can be realized in a variety of combinations other than the specific examples described above, as long as the above conditions are satisfied, and any compound represented by chemical formula 1 can be applied as the ligand compound of the present invention.

[0071] Organochromium compounds and catalyst compositions The present invention provides a ligand compound represented by the chemical formula 1, and an organochromium compound containing chromium (Cr) coordinated to the ligand compound.

[0072] According to one embodiment of the present invention, the organochromium compound is a chromium complex compound of the ligand compound, and the chromium source may have a form in which one or more lone pairs of electrons from either N or two P atoms in the ligand compound represented by chemical formula 1 form a coordinate bond. That is, a structure in which a phosphorus atom or nitrogen atom of a diphosphinoaminyl residue provides a lone pair of electrons to a chromium atom, and a bidentated state in which two lone pairs of electrons are coordinated is particularly preferred. Such an organochromium compound can be applied to a catalytic system for the oligomerization reaction of ethylene and can exhibit excellent catalytic activity and high selectivity for 1-hexene or 1-octene.

[0073] In the present invention, "catalyst composition" means a state in which three components, including a chromium source, a ligand compound, and a co-catalyst, or two components, a transition metal compound and a co-catalyst, 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, 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 monomers, and may be used in a supported or unsupported state.

[0074] The present invention provides a catalyst composition comprising the ligand compound, chromium, and a co-catalyst. The ligand compound represented by chemical formula 1 and chromium can be coordinated to form an organochromium compound, as described above. That is, the catalyst system may be a three-component catalyst system comprising chromium, the ligand compound represented by chemical formula 1, and a co-catalyst, or a two-component catalyst system comprising the organochromium compound and the co-catalyst. As a specific example, the catalyst composition may comprise the ligand compound, an organochromium compound containing chromium coordinated to the ligand compound, and a co-catalyst. Alternatively, the catalyst composition may comprise a chromium compound in which some components of the co-catalyst are bonded to the organochromium compound.

[0075] According to one embodiment of the present invention, the chromium is derived from a chromium source, which may be an organic or inorganic chromium compound in which the oxidation state of chromium is 0 to 6. Specifically, the chromium source may be a 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, amide, carboxylate radical, etc., having 1 to 20 carbon atoms per radical, and the inorganic radical may be a halide, sulfate, oxide, etc.

[0076] According to one embodiment of the present invention, the chromium source is a compound that exhibits high activity in oligomerization of olefins and is readily available and easy to use, and may be one or more compounds selected from the group consisting of chromium(III) acetylacetonate, chromium(III) chloride tetrahydrofuran, chromium(III) 2-ethylhexanoate, chromium(III) acetate, chromium(III) butyrate, chromium(III) pentanoate, chromium(III) laurate, chromium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedione), and chromium(III) stearate.

[0077] According to one embodiment of the present invention, the co-catalyst may be one or more compounds selected from the group consisting of compounds represented by the following chemical formulas 6 to 9.

[0078] [Chemical formula 6] -[Al(R 13 )-O] a -

[0079] In the above chemical formula 6, R 13 Each of these is independently a halogen group, a C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with a halogen group, and a is an integer of 2 or more.

[0080] [Chemical formula 7] E(R 14 )3

[0081] In the above chemical formula 7, E is aluminum or boron, and R 14 These are, independently, hydrogen, a halogen group, a C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with a halogen group.

[0082] [Chemical formula 8] [LH] + [G(Y)4] -

[0083] [Chemical formula 9] [L] + [G(Y)4] -

[0084] In the chemical formulas 8 and 9, L is a neutral or cationic Lewis acid, and [LH] + is a Brønsted acid, G is a group 13 element, and Y is independently a substituted or unsubstituted C1-C20 alkyl group or a substituted or unsubstituted C6-C20 aryl group, where if the alkyl or aryl group is substituted, the substituent is a halogen group, a C1-C20 hydrocarbyl group, a C1-C20 alkoxy group, or a C6-C20 aryloxy group.

[0085] According to one embodiment of the present invention, the catalyst composition can be produced by a plurality of methods. Specifically, firstly, the catalyst composition can be produced by a step of contacting the organochromium compound with a compound represented by chemical formula 6 or chemical formula 7. Secondly, the catalyst composition can be produced by a step of contacting the organochromium compound with a compound represented by chemical formula 6 or chemical formula 7 to obtain a mixture, and adding a compound represented by chemical formula 8 or chemical formula 9 to the mixture. Thirdly, the catalyst composition can be produced by a step of contacting the organochromium compound with a compound represented by chemical formula 8 or chemical formula 9. Fourthly, the catalyst composition can be produced by a step of contacting the organochromium compound with a compound represented by chemical formula 8 or chemical formula 9 to obtain a mixture, and adding a compound represented by chemical formula 6 or chemical formula 7 to the mixture. Fifth, the catalyst composition can be manufactured by comprising the steps of contacting the chromium source with the compound represented by chemical formula 8 or chemical formula 9 to obtain a reactant, and contacting the reactant with the ligand compound.

[0086] According to one embodiment of the present invention, in the first or third method of producing the catalyst composition, the molar ratio of the compound represented by chemical formula 6 or chemical formula 7 to the organochromium compound may be 1:2 to 5,000, respectively, and as a specific example, it may be 1:100 to 3,000, and as a more specific example, it may be 1:300 to 1,500. When the ratio is within this range, the alkylation of the organochromium compound can be fully carried out, improving the activity of the catalyst composition, preventing a decrease in the activity of the alkylated organochromium compound due to side reactions between residual alkylating agents, and improving economy and the purity of the produced linear α-olefin.

[0087] According to one embodiment of the present invention, in the second method of producing the catalyst composition, the molar ratio of the compound represented by chemical formula 8 or chemical formula 9 to the organochromium compound may be 1:1 to 500, specifically 1:1 to 50, and more specifically 1:1 to 1:25. When the ratio is within this range, the amount of activator is sufficient, the metal compound is fully activated, the activity of the catalyst composition is improved, residual activator is minimized, and economic efficiency and the purity of the produced linear α-olefin can be improved.

[0088] According to one embodiment of the present invention, the compound represented by chemical formula 6 may be an alkylaluminoxane, and specific examples may include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and more specifically, methylaluminoxane.

[0089] 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, etc. Specific examples include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, and tri-p-tolylaluminum; and dialkylaluminum halides such as diethylaluminum chloride.Diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl-n-butyl Dialkylaluminum hydrides such as aluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, or benzyl-n-octylaluminum hydride; alkylaluminum dihydrides such as n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, or n-octylaluminum dihydride; and trialkylborons such as trimethylboron, triethylboron, triisobutylboron, tripropylboron, and tributylboron.

[0090] According to one embodiment of the present invention, the compound represented by chemical formula 8 or chemical formula 9 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, Methyldioctadecylammonium tetrakis(pentafluorophenyl) borate, N,N-Dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-Diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-Dioctadecylanilinium tetrakis(pentafluorophenyl) borate, Trimethylphosphonium tetraphen This may include tetraphenyl borate, triethylphosphonium tetraphenyl borate, tripropylphosphonium tetraphenyl borate, tributylphosphonium tetraphenyl borate, trimethylcarbonium tetraphenyl borate, triethylcarbonium tetraphenyl borate, tripropylcarbonium tetraphenyl borate, tributylcarbonium tetraphenyl borate, 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.

[0091] According to one embodiment of the present invention, the content ratio of the components forming the catalyst composition may be determined considering catalytic activity and selectivity for linear α-olefins. As a specific example, if the catalyst composition is a three-component catalyst composition, the molar ratio of the diphosphinoaminyl residue of the ligand compound to the chromium source to the co-catalyst may be adjusted to about 1:1:1 to about 10:1:10,000, or about 1:1:100 to 5:1:3,000. Also, if the catalyst composition is a two-component catalyst composition, the molar ratio of the diphosphinoaminyl residue of the organochromium compound to the co-catalyst may be adjusted to 1:1 to 1:10,000, or 1:1 to 1:5,000, or 1:1 to 1:3,000.

[0092] According to one embodiment of the present invention, when producing the catalyst composition, hydrocarbon solvents such as pentane, hexane, and heptane; aromatic solvents such as benzene and toluene can be used as the reaction solvent.

[0093] According to one embodiment of the present invention, the components forming the catalyst composition can be added simultaneously or in any order, in the presence or absence of a suitable solvent and monomer, to act as an active catalyst composition. Suitable solvents may include heptane, toluene, cyclohexane, methylcyclohexane, 1-hexene, 1-octene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, and acetone.

[0094] According to one embodiment of the present invention, the organochromium compound and co-catalyst may be used in a form supported on a carrier, in which case the carrier may be silica or alumina.

[0095] According to one embodiment of the present invention, the catalyst composition may further include a support. Specifically, the ligand compound represented by chemical formula 1 may be applied to the oligomerization reaction of ethylene in a form supported on a support. The support may be a metal, metal salt, or metal oxide applied to the supported catalyst, and specifically, the support may be silica, silica-alumina, silica-magnesia, etc., and may include metal oxides, carbonates, sulfates, and nitrates such as Na2O, K2CO3, BaSO4, and Mg(NO3)2.

[0096] According to one embodiment of the present invention, the catalyst composition can be used for the trimerization or tetramerization reaction of ethylene, and as described above, it can produce 1-hexene or 1-octene with high selectivity.

[0097] Method for oligomerizing ethylene The present invention provides a method for oligomerizing ethylene, comprising the step (S10) of oligomerizing ethylene in the presence of the catalyst composition, to produce a linear α-olefin.

[0098] In this invention, "oligomerization" means the polymerization of an olefin into a multimer. Depending on the number of olefin molecules polymerized, this is called trimerization or tetramerization, and these are collectively referred to as multimerization. In particular, in this specification, it may mean the selective production of 1-hexene and 1-octene, which are the main comonomers of LLDPE, from ethylene.

[0099] 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 reaction product, and the linear α-olefin may be 1-hexene, 1-octene, or a mixture thereof.

[0100] According to one embodiment of the present invention, the method for oligomerizing ethylene may be carried out using ethylene as a raw material and applying the aforementioned catalyst composition, conventional apparatus, and contact technology. Specifically, the oligomerization reaction of ethylene may be carried out in the presence or absence of an inert solvent by a homogeneous liquid-phase reaction, a slurry reaction in which some or all of the catalyst composition is not dissolved, a bulk reaction in which the product α-olefin acts as the main medium, or a gas-phase reaction.

[0101] According to one embodiment of the present invention, the oligomerization reaction of ethylene may be carried out under an inert solvent. Specific examples of the inert solvent include benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, and 2,2,4-trimethylpentane.

[0102] 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, or 0°C to 150°C, or 30°C to 100°C, or 50°C to 100°C. The reaction may also be carried out at a pressure of 15 psig to 3000 psig, or 15 psig to 1500 psig, or 15 psig to 1000 psig.

[0103] Hereinafter, embodiments of the present invention will be described in detail so that those with ordinary skill in the art to which the present invention pertains can easily implement it. However, the present invention can be realized in various different forms and is not limited to the embodiments described herein.

[0104] Examples of synthesis and comparative synthesis Synthesis Examples 1 to 66: Synthesis of ligand compounds represented by chemical formulas 2-1 to 2-66 20 mmol (2 eq) of p-bromo-(tri-n-butylsilyl)-C6H4 was dissolved in 20 ml of tetrahydrofuran and then cooled to -78 °C. While maintaining the temperature, 20 mmol (2 eq) of n-butyllithium was added dropwise and then stirred for 3 hours. Next, 10 mmol (1 eq) of dichloro(diethylamino)phosphine dissolved in 10 ml of tetrahydrofuran was added dropwise, and then the temperature was raised to room temperature and stirred overnight. Then, the solvent was removed using a vacuum, and the resulting intermediate was dissolved in 30 ml of hexane. After adding HCl (in ether, 2 eq), it was stirred for 15 minutes and filtered. The filtrate was dried under vacuum to obtain (p-(tri-n-butylsilyl)-C6H4)2PCl. In a well-dried flask, 11 mmol (2.2 eq) of R 5 -NH2 and 10 ml of dichloromethane were introduced under a nitrogen atmosphere and stirring was started. 5 mmol (1 eq) of (p-(tri-n-butylsilyl)-C6H4)2PCl was diluted with 10 ml of dichloromethane and slowly introduced into the flask. After stirring for 4 hours until the reaction was completed, the solid precipitated by a filter was removed, the solvent was removed under reduced pressure, and (p-(tri-n-butylsilyl)-C6H4)2P-NHR 5 was obtained.

[0105] 5 mmol (1 eq) of PCl3 was dissolved in 10 ml of ether and cooled to 0°C. Next, 10 mmol (2 eq) of HNEt2 dissolved in 10 ml of ether was slowly added and stirred overnight. The solid was removed by filtration, and ArMgBr (2 eq) prepared from Ar and shaved Mg (Mg turning) was slowly added and stirred overnight at room temperature. Then, HCl (in ether, 2 eq) was added and stirred at room temperature for 30 minutes. The solid was removed by filtration and the mixture was reduced in pressure to obtain Ar2PCl. 5 mmol (1 eq) of Ar2PCl was dissolved in 10 ml of dichloromethane, and then 15 mmol (3 eq) of triethylamine was added. Next, 5 mmol (1 eq) of (p-(tri-n-butylsilyl)-C6H4)2P-NHR 5 The compound was dissolved in dichloromethane and slowly added, then stirred overnight at room temperature. After removing the solvent under vacuum, it was dissolved in hexane, and the ligand compounds represented by chemical formulas 2-1 to 2-66 were obtained by column chromatography.

[0106] R is a substituent of the reactants used in Synthesis Examples 1 to 66. 5 The structures of the ligand compounds produced in each synthesis example and Ar are shown in Table 1 below. 1 The 1H NMR data is shown below.

[0107] [Table 1A] [Table 1B] [Table 1C] [Table 1D] [Table 1E] [Table 1F]

Table 1G

Table 1I

Table 1J

[0108] Synthesis Example 1 (Chemical Formula 2-1)

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[0109] Synthesis Example 2 (Chemical Formula 2-2)

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[0110] Synthesis Example 3 (Chemical Formula 2-3)

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[0111] Synthesis Example 4 (Chemical Formula 2-4)

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[0112] Synthesis Example 5 (Chemical Formula 2-5)

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[0113] Synthesis Example 6 (Chemical Formula 2-6)

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[0114] Synthesis Example 7 (Chemical Formula 2-7)

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[0115] Synthesis Example 8 (Chemical Formula 2-8)

Chem.

[0116] Synthesis Example 9 (Chemical Formula 2-9)

Chem.

[0117] Synthesis Example 10 (Chemical Formula 2-10)

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[0118] Synthesis Example 11 (Chemical Formula 2-11)

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[0119] Synthesis Example 12 (Chemical Formula 2-12)

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[0120] Synthesis Example 13 (Chemical Formula 2-13)

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[0121] Synthesis Example 14 (Chemical Formula 2-14)

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[0122] Synthesis Example 15 (Chemical Formula 2-15)

Chem.

[0123] Synthesis Example 16 (Chemical Formula 2-16)

Chem.

[0124] Synthesis Example 17 (Chemical Formula 2-17)

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[0125] Synthesis Example 18 (Chemical Formula 2-18)

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[0126] Synthesis Example 19 (Chemical Formula 2-19)

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[0127] Synthesis Example 20 (Chemical Formula 2-20)

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[0128] Synthesis Example 21 (Chemical Formula 2-21)

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[0129] Synthesis Example 22 (Chemical Formula 2-22)

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[0130] Synthesis Example 23 (Chemical Formula 2-23)

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[0131] Synthesis Example 24 (Chemical Formula 2-24)

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[0132] Synthesis Example 25 (Chemical Formula 2-25)

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[0133] Synthesis Example 26 (Chemical Formula 2-26)

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[0134] Synthesis Example 27 (Chemical Formula 2-27)

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[0135] Synthesis Example 28 (Chemical Formula 2-28)

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[0136] Synthesis Example 29 (Chemical Formula 2-29)

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[0137] Synthesis Example 30 (Chemical Formula 2-30)

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[0138] Synthesis Example 31 (Chemical Formula 2-31)

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[0139] Synthesis Example 32 (Chemical Formula 2-32)

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[0140] Synthesis Example 33 (Chemical Formula 2-33)

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[0141] Synthesis Example 34 (Chemical Formula 2-34)

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[0142] Synthesis Example 35 (Chemical Formula 2-35)

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[0143] Synthesis Example 36 (Chemical Formula 2-36)

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[0144] Synthesis Example 37 (Chemical Formula 2-37)

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[0145] Synthesis Example 38 (Chemical Formula 2-38)

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[0146] Synthesis Example 39 (Chemical Formula 2-39)

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[0147] Synthesis Example 40 (Chemical Formula 2-40)

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[0148] Synthesis Example 41 (Chemical Formula 2-41)

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[0149] Synthesis Example 42 (Chemical Formula 2-42)

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[0150] Synthesis Example 43 (Chemical Formula 2-43)

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[0151] Synthesis Example 44 (Chemical Formula 2-44)

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[0152] Synthesis Example 45 (Chemical Formula 2-45)

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[0153] Synthesis Example 46 (Chemical Formula 2-46)

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[0154] Synthesis Example 47 (Chemical Formula 2-47)

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[0155] Synthesis Example 48 (Chemical Formula 2-48)

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[0156] Synthesis Example 49 (Chemical Formula 2-49)

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[0157] Synthesis Example 50 (Chemical Formula 2-50)

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[0158] Synthesis Example 51 (Chemical Formula 2-51)

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[0159] Synthesis Example 52 (Chemical Formula 2-52)

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[0160] Synthesis Example 53 (Chemical Formula 2-53)

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[0161] Synthesis Example 54 (Chemical Formula 2-54)

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[0162] Synthesis Example 55 (Chemical Formula 2-55)

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[0163] Synthesis Example 56 (Chemical Formula 2-56)

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[0164] Synthesis Example 57 (Chemical Formula 2-57)

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[0165] Synthesis Example 58 (Chemical Formula 2-58)

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[0166] Synthesis Example 59 (Chemical Formula 2-59)

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[0167] Synthesis Example 60 (Chemical Formula 2-60)

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[0168] Synthesis Example 61 (Chemical Formula 2-61)

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[0169] Synthesis Example 62 (Chemical Formula 2-62)

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[0170] Synthesis Example 63 (Chemical Formula 2-63)

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[0171] Synthesis Example 64 (Chemical Formula 2-64)

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[0172] Synthesis Example 65 (Chemical Formula 2-65)

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[0173] Synthesis Example 66 (Chemical Formula 2-66)

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[0174] Synthesis Examples 67-86: Synthesis of Ligand Compounds Represented by Chemical Formulas 3-1-3-20 20 mmol (2 eq) of m-bromo-(tri-n-butylsilyl)-C6H4 was dissolved in 20 ml of tetrahydrofuran and 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. Next, 10 mmol (1 eq) of dichloro(diethylamino)phosphine, dissolved in 10 ml of tetrahydrofuran, was added dropwise, and the mixture was raised to room temperature and stirred overnight. The solvent was then removed under vacuum, and the resulting intermediate was dissolved in 30 ml of hexane. HCl (in ether, 2 eq) was added, the mixture was stirred for 15 minutes, and the solution was filtered. The filtrate was dried under vacuum to obtain (m-(tri-n-butylsilyl)-C6H4)2PCl. In a well-dried flask, 11 mmol (2.2 eq) of R4 was added. 5 -NH2 and 10 ml of dichloromethane were added under a nitrogen atmosphere and stirring was started. 5 mmol (1 eq) of (m-(tri-n-butylsilyl)-C6H4)2PCl, diluted with 10 ml of dichloromethane, was slowly added to the flask. After stirring for 4 hours to complete the reaction, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and (m-(tri-n-butylsilyl)-C6H4)2P-NHR was obtained by column chromatography. 5 I obtained it.

[0175] 5 mmol (1 eq) of PCl3 was dissolved in 10 ml of ether and cooled to 0°C. Next, 10 mmol (2 eq) of HNEt2 dissolved in 10 ml of ether was slowly added and stirred overnight. The solid was removed by filtration, and ArMgBr (2 eq) prepared from Ar and shaved Mg (Mg turning) was slowly added and stirred overnight at room temperature. Then, HCl (in ether, 2 eq) was added and stirred at room temperature for 30 minutes. The solid was removed by filtration and the mixture was reduced in pressure to obtain Ar2PCl. 5 mmol (1 eq) of Ar2PCl was dissolved in 10 ml of dichloromethane, and then 15 mmol (3 eq) of triethylamine was added. Next, 5 mmol (1 eq) of (m-(tri-n-butylsilyl)-C6H4)2P-NHR 5 The compound was dissolved in dichloromethane and slowly added, then stirred overnight at room temperature. After removing the solvent under vacuum, it was dissolved in hexane, and the ligand compounds represented by chemical formulas 3-1 to 3-20 were obtained by column chromatography.

[0176] R is a substituent of the reactants used in the above synthesis examples 67 to 86. 5 The structures of the ligand compounds produced in each synthesis example and Ar are shown in Table 2 below. 1 The 1H NMR data is shown below.

[0177] [Table 2A] [Table 2B] [Table 2C]

[0178] Synthesis Example 67 (Chemical Formula 3-1) [ka] N-(bis(2-fluorophenyl)phosphaneyl)-N-methyl-1,1-bis(3-(tributylsilyl)phenyl)phosphanamine 1 1H NMR (500 MHz, CDCl3): δ 7.60(m, 2H), 7.43(m, 2H), 7.35(m, 2H), 7.31(m, 2H), 7.24(m, 2H), 7.12(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)

[0179] Synthesis Example 68 (Chemical Formula 3-2)

Chem.

[0180] Synthesis Example 69 (Chemical Formula 3-3)

Chem.

[0181] Synthesis Example 70 (Chemical Formula 3-4)

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[0182] Synthesis Example 71 (Chemical Formula 3-5)

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[0183] Synthesis Example 72 (Chemical Formula 3-6)

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[0184] Synthesis Example 73 (Chemical Formula 3-7)

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[0185] Synthesis Example 74 (Chemical Formula 3-8)

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[0186] Synthesis Example 75 (Chemical Formula 3-9)

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[0187] Synthesis Example 76 (Chemical Formula 3-10)

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[0188] Synthesis Example 77 (Chemical Formula 3-11)

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[0189] Synthesis Example 78 (Chemical Formula 3-12)

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[0190] Synthesis Example 79 (Chemical Formula 3-13)

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[0191] Synthesis Example 80 (Chemical Formula 3-14)

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[0192] Synthesis Example 81 (Chemical Formula 3-15)

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[0193] Synthesis Example 82 (Chemical Formula 3-16)

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[0194] Synthesis Example 83 (Chemical Formula 3-17)

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[0195] Synthesis Example 84 (Chemical Formula 3-18)

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[0196] Synthesis Example 85 (Chemical Formula 3-19)

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[0197] Synthesis Example 86 (Chemical Formula 3-20)

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[0198] Comparative Synthesis Example 1: Synthesis of the chemical compound shown in Chemical Formula 10 In a dry flask, 5.5 mmol (0.5 eq) of 3-methyl-2-butanamine, 22 mmol (2 eq) of triethylamine, and 10 ml of dichloromethane were added under a nitrogen atmosphere, and stirring was started. After cooling to 0°C, 11 mmol (1 eq) of chlorobis(4-(tributylsilyl)phenyl)phosphane was slowly added. After the reaction was complete, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and the compound represented by chemical formula 10 was obtained by column chromatography.

[0199] [ka] N-(bis(4-(tributylsilyl)phenyl)phosphaneyl)-N-(3-methylbutan-2-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphanamine 1 H NMR(500 MHz, C6D6): δ 7.96-7.34(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)

[0200] Comparative Synthesis Example 2: Synthesis of Ligand Compound Represented by Chemical Formula 11 In a dry flask, 5.5 mmol (0.5 eq) of cyclohexylamine, 22 mmol (2 eq) of triethylamine, and 10 ml of dichloromethane were added under a nitrogen atmosphere, and stirring was started. After cooling to 0°C, 11 mmol (1 eq) of chlorobis(4-cyclohexylphenyl)phosphane was slowly added. After the reaction was complete, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and the compound represented by chemical formula 11 was obtained by column chromatography.

[0201] [ka] N-(bis(4-cyclohexylphenyl)phosphaneyl)-N-cyclohexyl-1,1-bis(4-cyclohexylphenyl)phosphanamine 1 H NMR(500 MHz, C6D6): δ 7.58(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)

[0202] Comparative Synthesis Example 3: Synthesis of Ligand Compound Represented by Chemical Formula 12 In a dry flask, 5.5 mmol (0.5 eq) of cyclohexylamine, 22 mmol (2 eq) of triethylamine, and 10 ml of dichloromethane were added under a nitrogen atmosphere, and stirring was started. After cooling to 0°C, 11 mmol (1 eq) of chlorobis(4-phenylphenyl)phosphane was slowly added. After the reaction was complete, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and the compound represented by chemical formula 12 was obtained by column chromatography.

[0203] [ka] 1,1-di([1,1'-biphenyl]-4-yl)-N-cyclohexyl-N-(di([1,1'-biphenyl]-4-yl)phosphaneyl)phosphanamine 1 H NMR(500 MHz, C6D6): δ 7.92-7.42(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)

[0204] Comparative Synthesis Example 4: Synthesis of a ligand compound represented by chemical formula 13 In a dry flask, 5.5 mmol (0.5 eq) of cyclohexylamine, 22 mmol (2 eq) of triethylamine, and 10 ml of dichloromethane were added under a nitrogen atmosphere, and stirring was started. After cooling to 0°C, 11 mmol (1 eq) of chlorobis(3,5-dimethylphenyl)phosphane was slowly added. After the reaction was complete, the precipitated solid was removed by filtration, the solvent was removed under reduced pressure, and the compound represented by chemical formula 13 was obtained by column chromatography.

[0205] [ka] N-(bis(3,5-dimethylphenyl)phosphanyl)-N-cyclohexyl-1,1-bis(3,5-dimethylphenyl)phosphanamine 1 H NMR(500 MHz, C6D6): δ 7.38(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)

[0206] Examples and Comparative Examples Example 1 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 chemical formula 2-1 in Synthesis Example 1, and 0.5 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) as a co-catalyst were placed in a flask, 30 ml of dichloromethane was added, and the mixture was stirred for 1 hour. The solvent was then removed under vacuum. Subsequently, the solution was dissolved in methylcyclohexane and filtered, and the solvent was removed again under vacuum. The solution was then dissolved in methylcyclohexane to prepare a 0.15 mM (Cr-based) catalyst solution.

[0207] A 600 ml Parr reactor was prepared, vacuumed at 120 °C for 2 hours, then the interior was replaced with argon and the temperature was lowered to 70 °C. Then, 180 ml of methylcyclohexane and 2 ml of 725 μmol of diisobutylaluminum hydride as an activator were added, followed by the addition of 5 ml (0.75 μmol Cr) of the catalyst solution. After stirring at 1,000 rpm for 2 minutes, the ethylene line valve, adjusted to 40 bar, was opened to fill the reactor with ethylene, and the mixture 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, and the unreacted ethylene was slowly vented before adding 0.5 ml of nonane (GC internal standard). After stirring for 10 seconds, 2 ml of the liquid portion of the reactor was taken and quenched with water. The resulting organic portion was filtered through a PTFE syringe filter to prepare a GC-FID sample. The distribution of the liquid product was then analyzed by GC (Agilent, 6890N, Alltech AT-5 (30m x 0.32mm ID x 0.25μm; series no. 12446)). Additionally, 400 ml of ethanol / HCl (10 vol% of aqueous 12M HCl solution) was added to the remaining reaction mixture, stirred, filtered, and the amount of solid product was analyzed. The resulting polymer was dried overnight in a vacuum oven at 80°C.

[0208] Examples 2-86 and Comparative Examples 1-4 The procedure was carried out in the same manner as in Example 1-1, except that the type of catalyst was changed as shown in Table 3 below.

[0209] [Table 3A] [Table 3B] [Table 3C]

[0210] Experimental example The results of the ethylene oligomerization reaction in the above examples and comparative examples are shown in Table 4 below.

[0211] *Catalytic activity (ton / mol·Cr / hr): The catalytic activity was calculated from the total weight (tons) of the products obtained, which is the sum of the weights (tons) of the liquid and solid products.

[0212] *1-C6 and 1-C8 selectivity (weight %): The content of 1-hexene (1-C6) and 1-octene (1-C8) was calculated from the distribution of the liquid product analyzed by GC, and the weight % of 1-hexene or 1-octene was calculated based on the total weight of the product.

[0213] *Solid (weight %): The weight percentage of the solid product was calculated based on the total weight of the product. This represents the extent to which polyethylene with approximately 40 or more carbon atoms was produced, which is an insoluble solid not dissolved in the solvent.

[0214] [Table 4A] [Table 4B] [Table 4C]

[0215] As shown in Table 4 above, when performing an oligomerization reaction of ethylene using a catalyst composition containing the ligand compound according to the present invention, it was confirmed that catalytic activity, selectivity, and stability are all improved by adjusting the steric strain around the PNP functional group from substituents such as alkyl groups of specific carbon atoms or alkyl groups of specific carbon atoms substituted on the phenyl group located at the terminus of the diphosphinoaminyl residue, which has a specific substituent at the ortho position and alkyl groups of specific carbon atoms at the meta and para positions, respectively.

[0216] These results confirm that when oligomerizing ethylene using an organochromium compound and catalyst composition containing the ligand compound of the present invention, high catalytic activity results in excellent productivity, and linear α-olefins can be produced with high selectivity for 1-hexene and 1-octene.

Claims

1. A ligand compound represented by the following chemical formula 1. 【Chemistry 1】 (In the above chemical formula 1, R １ This is a halogen group, a C1-C10 alkyl group substituted or unsubstituted with a halogen group, a C1-C10 alkoxy group substituted or unsubstituted with a halogen group, a C1-C10 alkylthio group substituted or unsubstituted with a halogen group, a C1-C10 alkylsulfonate group substituted or unsubstituted with a halogen group, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C10 alkyl group), or R ６ It combines with to form a monocyclic or polycyclic aromatic hydrocarbon ring, or a monocyclic or polycyclic heterocycle, R ６ R １ If it does not bond with to form a monocyclic or polycyclic aromatic hydrocarbon ring, or a monocyclic or polycyclic heterocyclic ring, then R ６ It is hydrogen, R ２ is a halogen group, an alkyl group having 1 to 10 carbon atoms which may or may not be substituted with a halogen group, an alkoxy group having 1 to 10 carbon atoms which may or may not be substituted with a halogen group, an alkylthio group having 1 to 10 carbon atoms which may or may not be substituted with a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may or may not be substituted with 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 ７ combines with to form a monocyclic or polycyclic aromatic hydrocarbon ring, or a monocyclic or polycyclic heterocyclic ring, and R ７ is R ２ when it does not combine with 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 Each is independently of hydrogen, a C5-C20 alkyl group, a C5-C20 cycloalkyl group, a C2-C20 alkoxyalkyl group, a C7-C30 arylalkoxyalkyl group, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C10 alkyl group), and R ３ and R ４ They cannot be hydrogen at the same time. R ５ This refers to an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with 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 condensed with an aryl group having 6 to 10 carbon atoms.

2. R １ This is a fluoro, a fluoro-substituted or unsubstituted C1-C5 alkyl group, a fluoro-substituted or unsubstituted C1-C5 alkoxy group, a fluoro-substituted or unsubstituted C1-C5 alkylthio group, a fluoro-substituted or unsubstituted C1-C5 alkylsulfonate group, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C5 alkyl group), or R ６ It is formed by bonding with a monocyclic or polycyclic heterocyclic ring. R ２ This is a fluoro, a fluoro-substituted or unsubstituted C1-C5 alkyl group, a fluoro-substituted or unsubstituted C1-C5 alkoxy group, a fluoro-substituted or unsubstituted C1-C5 alkylthio group, a fluoro-substituted or unsubstituted C1-C5 alkylsulfonate group, or a trialkylsilyl group (each alkyl group of the trialkylsilyl group is independently a C1-C5 alkyl group), or R ７ The ligand compound according to claim 1, wherein it is bonded to form a monocyclic or polycyclic heterocyclic ring.

3. R １ is a fluoro group, trifluoromethyl group, methoxy group, methyl group, trifluoromethoxy group, trifluoromethylthio group, methylthio group, methylsulfonate group, or trimethylsilyl group, R ６ It combines with to form furan or dibenzofuran, R ２ is a fluoro group, trifluoromethyl group, methoxy group, methyl group, trifluoromethoxy group, trifluoromethylthio group, methylthio group, methylsulfonate group, or trimethylsilyl group, R ７ The ligand compound according to claim 1, which is bonded to a furan or dibenzofuran to form a furan or dibenzofuran.

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

5. R ３ and R ４ The ligand compound according to claim 1, wherein each of the groups is independently an n-decyl group, a tripropylsilyl group, or a tributylsilyl group.

6. R ５ The ligand compound according to claim 1, wherein is a C3-C5 alkyl group, a C1-C5 alkyl group substituted with a C6-C10 aryl group, a C5-C8 cycloalkyl group, or a C5-C8 cycloalkyl group condensed with a C6-C10 aryl group.

7. The ligand compound according to claim 1, wherein the ligand compound represented by chemical formula 1 is represented by any one of the following chemical formulas 2 to 5. 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 (In the above chemical formulas 2 to 5, R １ ~R ７ These are defined as in Claim 1, respectively.

8. The ligand compound represented by chemical formula 1 is one of the following chemical formulas 2-1 to 2-66 and 3-1 to 3-20, according to claim 1. 【Chemical Engineering 6A】 【Chemistry 6B】 【Chemical 6C】 【6D Transformation】

9. An organochromium compound comprising the ligand compound described in claim 1, and chromium coordinated to the ligand compound.

10. The organochromium compound according to claim 9, wherein the ligand compound represented by the chemical formula 1 is in a form in which one or more lone pairs of electrons from N and two P are coordinated to chromium.

11. A catalyst composition comprising the ligand compound, chromium, and co-catalyst described in claim 1.

12. The aforementioned chromium is derived from a chromium source. The catalyst composition according to claim 11, wherein the chromium source comprises one or more selected from the group consisting of chromium(III) acetylacetonate, chromium(III) chloride tetrahydrofuran, chromium(III) 2-ethylhexanoate, chromium(III) acetate, chromium(III) butyrate, chromium(III) pentanoate, chromium(III) laurate, chromium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedione), and chromium(III) stearate.

13. The catalyst composition according to claim 11, wherein the co-catalyst is one or more compounds selected from the group consisting of compounds represented by the following chemical formulas 6 to 9. [Chemical formula 6] -[Al(R １３ )-O] ａ - In the aforementioned chemical formula 6, R １３ These are, independently, a halogen group, a C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with a halogen group. a is an integer greater than or equal to 2, [Chemical formula 7] E(R １４ ) ３ In the aforementioned chemical formula 7, E is aluminum or boron, R １４ These are, independently, hydrogen, a halogen group, a C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with a halogen group. [Chemical formula 8] [L-H] ＋ [G(Y) ４ ] － [Chemical formula 9] [L] ＋ [G(Y) ４ ] － In the aforementioned chemical formulas 8 and 9, L is a neutral or cationic Lewis acid. [L-H] ＋ It is a Brønsted acid, G is a group 13 element, Each Y is independently a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C6-C20 aryl group, where, if the alkyl group or aryl group is substituted, the substituent is a halogen group, a C1-C20 hydrocarbyl group, a C1-C20 alkoxy group, or a C6-C20 aryloxy group.

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

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

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