Transition metal compound and catalyst composition comprising same

Abstract

The present invention relates to a transition metal compound having a novel structure and a catalyst composition comprising same, wherein use of the catalyst composition comprising the transition metal compound of the present invention enables production of an olefin polymer with high productivity.

Description

Transition metal compounds and catalyst compositions containing the same

[0001] Cross-citation with related applications

[0002] The present application claims the benefit of priority based on Korean patent applications No. 10-2024-0152102, No. 10-2024-0152106 and No. 10-2024-0152101 filed on October 31, 2024, and Korean patent application No. 10-2025-0158960 filed on October 29, 2025, and all contents disclosed in the documents of said Korean patent applications are incorporated herein as part of the specification.

[0003] Technology field

[0004] The present invention relates to a transition metal compound of a novel structure and a catalyst composition containing the same.

[0005]

[0006] Generally, olefin polymers such as ethylene copolymers are useful polymer materials used as materials for blow molded products, extruded products, films, sheets, etc., and have been manufactured in the presence of a Ziegler-Natta catalyst system.

[0007] The above-mentioned Ziegler-Natta catalyst is a heterogeneous catalyst used in systems where the phase of the reactant and the phase of the catalyst are not identical, such as liquid-phase reactant-solid catalyst systems. Such a Ziegler-Natta catalyst is composed of two components, typically consisting of transition metals such as titanium (Ti), vanadium (V), chromium (Cr), molybdenum (Mo), zirconium (Zr), halogen compounds (e.g., TiCl4), alkyllithium, and alkylaluminum.

[0008] However, the above-mentioned Ziegler-Natta catalyst has a disadvantage in that it fails to overcome the limitations of a heterogeneous catalyst, as the concentration of active species relative to transition metal atoms is only a few percent to several tens of percent, and most transition metal atoms do not perform their functions.

[0009] Recently, metallocene compounds have been attracting attention as next-generation catalysts capable of overcoming these disadvantages. The metallocene compounds are known to exhibit desirable polymerization activity in olefin polymerization as homogeneous catalysts containing group 4 metals.

[0010] Most metallocene catalysts used in polymerization have group 4 metal elements such as titanium, zirconium, and hafnium (Hf) and supporting ligands as precursors, and consist of two aromatic pentatomic rings and two halogen compounds acting as leaving groups. Among these, the supporting ligands coordinating to the central metal are typically aromatic cyclopentadienyl groups.

[0011] Although these metallocene catalysts are applied in various ways, such as in olefin polymerization processes, they have shown some limitations in catalytic activity (particularly in solution processes at temperatures above 100°C). For example, due to relatively fast end-terminating reactions (or chain-linking reactions) such as the beta-hydride elimination reaction, it is generally known that low molecular weight olefin polymers with a molecular weight (Mn) of 20,000 or less can be produced at temperatures above 100°C. Furthermore, it is known that the active species of metallocene catalysts tend to become deactivated at temperatures above 100°C. Therefore, in order to increase the applicability of metallocene catalysts, it is necessary to find a way to overcome the aforementioned limitations.

[0012]

[0013] The present invention aims to provide a novel transition metal oxide capable of producing olefin polymers with high productivity by exhibiting excellent copolymerization, and a catalyst composition containing the same.

[0014]

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

[0016] [Chemical Formula 1]

[0017]

[0018] In the above chemical formula 1,

[0019] M is Hf or Zr, and

[0020] L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and

[0021] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0022] Z1 and Z2 are each independently a silyl-substituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, and

[0023] R1 to R 24 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms.

[0024] (2) The present invention provides a transition metal compound in which Z1 and Z2 are each independently represented by any one of the following chemical formulas a to c.

[0025] [Chemical formula a]

[0026]

[0027] [Chemical formula b]

[0028]

[0029] [Chemical formula c]

[0030]

[0031] In the above chemical formulas a to c,

[0032] R25 to R 29 Each is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms, and R 25 to R 29 One or more of them are alkylsilyl groups having 1 to 20 carbon atoms, and

[0033] R 30 to R 36 Each is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms, and

[0034] R 37 to R 41 Each is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0035] (3) The present invention provides a transition metal compound in which, in (1) or (2) above, the transition metal compound represented by Chemical Formula 1 is represented by Chemical Formula 1A below.

[0036] [Chemical Formula 1A]

[0037]

[0038] In the above chemical formula 1A,

[0039] M is Hf or Zr, and

[0040] L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and

[0041] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0042] R1 to R 24Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and

[0043] R 42 to R 45 Each is independently hydrogen or an alkylsilyl group having 1 to 20 carbon atoms, and R 42 and R 43 One or more of and R 44 and R 45 One or more of them are alkylsilyl groups having 1 to 20 carbon atoms.

[0044] (4) The present invention provides a transition metal compound according to (3) above, wherein the transition metal compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1A-1 to 1A-5.

[0045] [Chemical Formula 1A-1]

[0046]

[0047] [Chemical Formula 1A-2]

[0048]

[0049] [Chemical Formula 1A-3]

[0050]

[0051] [Chemical Formula 1A-4]

[0052]

[0053] [Chemical Formula 1A-5]

[0054]

[0055] (5) The present invention provides a transition metal compound in which, in (1) or (2) above, the transition metal compound represented by Chemical Formula 1 is represented by Chemical Formula 1B below.

[0056] [Chemical Formula 1B]

[0057]

[0058] In the above chemical formula 1B,

[0059] M is Hf or Zr, and

[0060] L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and

[0061] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0062] R1 to R 24 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and

[0063] R 46 and R 47 Each is independently hydrogen or an alkyl group having 1 to 20 carbon atoms.

[0064] (6) The present invention provides a transition metal compound in which the transition metal compound represented by the above formula 1 is represented by any one of the following formulas 1B-1 to 1B-4.

[0065] [Chemical Formula 1B-1]

[0066]

[0067] [Chemical Formula 1B-2]

[0068]

[0069] [Chemical Formula 1B-3]

[0070]

[0071] [Chemical Formula 1B-4]

[0072]

[0073] (7) The present invention provides a transition metal compound in which, in (1) or (2) above, the transition metal compound represented by Chemical Formula 1 is represented by Chemical Formula 1C below.

[0074] [Chemical Formula 1C]

[0075]

[0076] In the above chemical formula 1C,

[0077] M is Hf or Zr, and

[0078] L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and

[0079] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0080] R1 to R 24 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and

[0081] R 48 and R 49 Each is independently hydrogen or an alkyl group having 1 to 20 carbon atoms.

[0082] (8) The present invention provides a transition metal compound according to (7) above, wherein the transition metal compound represented by the formula 1 is represented by any one of the following formulas 1C-1 to 1C-6.

[0083] [Chemical Formula 1C-1]

[0084]

[0085] [Chemical Formula 1C-2]

[0086]

[0087] [Chemical Formula 1C-3]

[0088]

[0089] [Chemical Formula 1C-4]

[0090]

[0091] [Chemical Formula 1C-5]

[0092]

[0093] [Chemical Formula 1C-6]

[0094]

[0095] (9) The present invention provides a catalyst composition comprising a transition metal compound and a co-catalyst according to any one of (1) to (8) above.

[0096] (10) The present invention provides a catalyst composition according to (9) above, wherein the co-catalyst comprises one or more selected from the group consisting of compounds represented by the following chemical formulas 2 to 5.

[0097] [Chemical Formula 2]

[0098] -[Al(R 50 )-O] a -

[0099] In the above chemical formula 2,

[0100] R 50 Each is 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

[0101] a is an integer greater than or equal to 2, and

[0102] [Chemical Formula 3]

[0103] E(R 51 ) 3

[0104] In the above chemical formula 3,

[0105] E is aluminum or boron, and

[0106] R 51 Each is 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, and

[0107] [Chemical Formula 4]

[0108] [Le-H] + [G(A)4] -

[0109] [Chemical Formula 5]

[0110] [Le] + [G(A)4] -

[0111] In the above chemical formulas 4 and 5,

[0112] Le is a neutral or cationic Lewis acid, and

[0113] [Le-H] + is Mount Brønsted, and

[0114] G is a Group 13 element, and

[0115] A 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.

[0116] (11) The present invention provides a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of a catalyst composition according to (9) or (10) above.

[0117] (12) The present invention provides a method for manufacturing an olefin polymer, wherein the olefin polymer is an ethylene / alpha-olefin copolymer, in accordance with (11) above.

[0118] (13) The present invention provides a method for producing an olefin polymer according to (12), wherein the alpha-olefin comprises one or more selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene, norbornene, norvonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

[0119]

[0120] By using a catalyst containing the transition metal compound of the present invention, olefin polymers can be manufactured with high productivity.

[0121]

[0122] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0123]

[0124] Terms and words used in the description and claims of the present invention shall not be interpreted as being limited to their ordinary or dictionary meanings, and shall be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0125] The term “alkyl” as used herein means a straight-chain, cyclic, or branched hydrocarbon residue unless otherwise noted, and includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, and hexyl.

[0126] As used herein, the term “cycloalkyl” refers to a non-aromatic cyclic hydrocarbon radical composed of carbon atoms unless otherwise noted. “Cycloalkyl” includes, by non-limiting example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

[0127] As used herein, the term “aryl” refers, unless otherwise noted, to an optionally substituted benzene ring or to a ring system that may be formed by fusing one or more optional substituents. Exemplary optional substituents include a substituted C1-3 alkyl, substituted C2-3 alkenyl, substituted C2-3 alkynyl, heteroaryl, heterocyclic, aryl, alkoxy, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonylamino, carboxyamide, aminocarbonyl, carboxy, oxo, hydroxy, mercapto, amino, nitro, cyano, halogen, or ureido. Such rings or ring systems may optionally be fused to aryl rings (e.g., benzene rings), carbon ring rings, or heterocyclic rings having one or more optional substituents. Examples of 'aryl' groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl, or phenanthyl, and their substituted derivatives.

[0128] In the present invention, “alkylaryl” means an aryl group substituted by the alkyl group.

[0129] In the present invention, “arylalkyl” means an alkyl group substituted by the aryl group.

[0130] In the present invention, “hydrocarbyl” means a monovalent hydrocarbon group having 1 to 20 carbon atoms, consisting only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl, or arylalkyl, unless otherwise noted.

[0131] In the present invention, “alkylene group” may refer to divalent aliphatic saturated hydrocarbons such as methylene, ethylene, propylene, and butylene.

[0132] In the present invention, the term “alkoxy group” may include all functional groups, atomic groups, or compounds in which the hydrogen at the terminal end of an alkyl group is substituted with an oxygen atom, such as methoxy, ethoxy, propoxy, and butoxy.

[0133] In this specification, the term “substitution” means that a hydrogen atom bonded to a carbon atom of a compound is replaced by another substituent (e.g., hydrogen, halogen, amine group, nitrile group, alkyl group, cycloalkyl group, alkoxy group, aryloxy group, aryl group, heterocyclic group, etc.), and the substitution site is not limited to the site where the hydrogen atom is substituted, that is, as long as the substituent is a site where the hydrogen atom can be substituted, and in the case of two or more substitutions, the two or more substituents may be the same or different from each other.

[0134] Unless otherwise stated, the term “substituted or unsubstituted” in this specification means that it is substituted or unsubstituted with one or more substituents selected from the group including hydrogen, halogen, amine group, nitrile group, alkyl group, cycloalkyl group, alkoxy group, aryloxy group, aryl group, and heterocyclic group, or is substituted or unsubstituted with a substituent in which two or more of the exemplified substituents are connected.

[0135] In this specification, where the terms “substituted” or “substituted or unsubstituted” are not modified before a functional group, unless otherwise noted, it means an unsubstituted functional group.

[0136]

[0137] The present invention relates to a transition metal compound represented by the following chemical formula 1.

[0138] [Chemical Formula 1]

[0139]

[0140] In the above chemical formula 1,

[0141] M is Hf or Zr, and

[0142] L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and

[0143] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0144] Z1 and Z2 are each independently a silyl-substituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, and

[0145] R1 to R 24 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms.

[0146]

[0147] The transition metal compound of the present invention has a structure in which a silyl-substituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted cycloalkyl group is bonded to a phenolate, and exhibits catalytic activity equivalent to or higher than that of conventional compounds, and can show improved copolymerization and solubility. When using the transition metal compound of the present invention, polymers with excellent processability can be prepared by having high processability and a broad molecular weight distribution, and exhibiting an improved MFRR. This is a unique feature that can be achieved by the novel structure of the compound newly developed in the present invention.

[0148] In the transition metal compound of the present invention, when the Leaving group (L in Formula 1) directly bonded to the central metal is an alkyl group, the solubility of the catalyst in polar or non-polar solvents can be further improved as the number of carbon atoms in the alkyl group increases.

[0149] In addition, when an alkyl group is substituted on the carbazole in the transition metal compound of the present invention, the solubility of the catalyst in polar or non-polar solvents can be further improved.

[0150]

[0151] In the above chemical formula 1, M is Hf or Zr.

[0152] In the above chemical formula 1, L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen. Specifically, it may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and, for example, a methyl group.

[0153] In the above chemical formula 1, Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms. Specifically, it may be an alkylene group having 2 to 30 carbon atoms, an alkylene group having 2 to 10 carbon atoms, an alkylene group having 2 to 6 carbon atoms, and, for example, a propylene group.

[0154] In the above chemical formula 1, Z1 and Z2 are each independently a silyl-substituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms.

[0155] The silyl group that is a substituent in the above silyl-substituted phenyl group may be substituted or unsubstituted. When the silyl group substituted on the above naphthyl group, cycloalkyl group, and phenyl group is substituted, the substituent may be hydrogen, halogen, cyanide group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, or alcohol group having 1 to 20 carbon atoms.

[0156]

[0157] More specifically, Z1 and Z2 may each independently be a structure represented by any one of the following chemical formulas a to c.

[0158] [Chemical formula a]

[0159]

[0160] [Chemical formula b]

[0161]

[0162] [Chemical formula c]

[0163]

[0164] In the above chemical formulas a to c, R 25 to R 29 Each is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms, and R 25 to R 29 One or more of them are alkylsilyl groups having 1 to 20 carbon atoms. More specifically, R 25 and R 29 is hydrogen, and R 26 to R 28 One or more of them may be an alkylsilyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 15 carbon atoms, or an alkylsilyl group having 1 to 10 carbon atoms, for example, a trimethylsilyl group, a triisopropylsilyl group, or an octyldimethylsilyl group.

[0165] In the above chemical formulas a to c, R 30 to R 36 Each is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms. Specifically, it may be hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and may be, for example, a methyl group. More specifically, R 32 is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, e.g., a methyl group, and R 30 , R 31 and R 33 to R 36 It can be hydrogen.

[0166] In the above chemical formulas a to c, R 37 to R 41 Each is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Specifically, it may be hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and may be, for example, a methyl group, an ethyl group, a propyl group, or a butyl group. More specifically, R 37 , R 36 , R 40 and R 41 is hydrogen, and R 39 It may be an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and, for example, may be a methyl group, an ethyl group, a propyl group, or a butyl group.

[0167]

[0168] In the above Chemical Formula 1, R1 to R 24Each is independently hydrogen, a halogen, a cyano group, an amine group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Specifically, it may be hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. For example, it may be hydrogen, F, or a tert-butyl group. More specifically, R1 to R 17 , R 19 to R 22 and R 24 is hydrogen, and R 18 and R 23 It may be a halogen, e.g., F. Or, R1, R2, R4, R5, R7 to R 10 , R 12 , R 13 , R 15 to R 17 , R 19 to R 22 and R 24 is hydrogen, and R3, R6, R 11 and R 14 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, for example, a tert-butyl group, and R 18 and R 23 It can be a halogen group, such as F.

[0169]

[0170] The transition metal compound represented by the above chemical formula 1 may be represented by the following chemical formula 1A.

[0171] [Chemical Formula 1A]

[0172]

[0173] In the above chemical formula 1A,

[0174] M is Hf or Zr, and

[0175] L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and

[0176] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0177] R1 to R 24 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and

[0178] R 42 to R 45 Each is independently hydrogen or an alkylsilyl group having 1 to 20 carbon atoms, and R 42 and R 43 One or more of and R 44 and R 45 One or more of them are alkylsilyl groups having 1 to 20 carbon atoms.

[0179]

[0180] Specifically, in the above chemical formula 1A, M is Hf, L is an alkyl group having 1 to 20 carbon atoms, Y is an alkylene group having 2 to 40 carbon atoms, and R1 to R 17 , R 19 to R 22 and R 24 is hydrogen, and R 18 and R 23 is a halogen, and R 42 and R 44 Each may independently be hydrogen or an alkylsilyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 15 carbon atoms, or an alkylsilyl group having 1 to 10 carbon atoms.

[0181] Additionally, specifically, in the above formula 1A, M is Hf or Zr, L is an alkyl group having 1 to 20 carbon atoms, Y is an alkylene group having 2 to 40 carbon atoms, and R1, R2, R4, R5, R7 to R 10 , R 12 , R 13 , R 15 to R 17 , R 19 to R 22 and R 24 is hydrogen, and R3, R6, R 11 and R 14 is an alkyl group having 1 to 20 carbon atoms, and R 18 and R 23 is a halogen, and R 42 and R 44 Each may independently be hydrogen or an alkylsilyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 15 carbon atoms, or an alkylsilyl group having 1 to 10 carbon atoms.

[0182]

[0183] For example, the transition metal compound represented by the above chemical formula 1 may be represented by any one of the following chemical formulas 1A-1 to 1A-5.

[0184] [Chemical Formula 1A-1]

[0185]

[0186] [Chemical Formula 1A-2]

[0187]

[0188] [Chemical Formula 1A-3]

[0189]

[0190] [Chemical Formula 1A-4]

[0191]

[0192] [Chemical Formula 1A-5]

[0193]

[0194]

[0195] The transition metal compound represented by the above chemical formula 1 may be represented by the following chemical formula 1B.

[0196] [Chemical Formula 1B]

[0197]

[0198] In the above chemical formula 1B,

[0199] M is Hf or Zr, and

[0200] L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and

[0201] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0202] R1 to R 24 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and

[0203] R 46 and R 47 Each is independently hydrogen or an alkyl group having 1 to 20 carbon atoms.

[0204]

[0205] Specifically, in the above chemical formula 1B, M is Hf, L is an alkyl group having 1 to 20 carbon atoms, Y is an alkylene group having 2 to 40 carbon atoms, and R1, R2, R4, R5, R7 to R 10 , R 12 , R 13 , R 15 to R 17 , R 19 to R 22 and R 24 is hydrogen, and R3, R6, R 11 and R14 is an alkyl group having 1 to 20 carbon atoms, and R 18 and R 23 is a halogen, and R 46 and R 47 Each can independently be hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.

[0206]

[0207] For example, the transition metal compound represented by the above chemical formula 1 may be represented by any one of the following chemical formulas 1B-1 to 1B-4.

[0208] [Chemical Formula 1B-1]

[0209]

[0210] [Chemical Formula 1B-2]

[0211]

[0212] [Chemical Formula 1B-3]

[0213]

[0214] [Chemical Formula 1B-4]

[0215]

[0216]

[0217] The transition metal compound represented by the above chemical formula 1 may be represented by the following chemical formula 1C.

[0218] [Chemical Formula 1C]

[0219]

[0220] In the above chemical formula 1C,

[0221] M is Hf or Zr, and

[0222] L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and

[0223] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0224] R1 to R 24 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and

[0225] R 48 and R 49 Each is independently hydrogen or an alkyl group having 1 to 20 carbon atoms.

[0226]

[0227] Specifically, in the above chemical formula 1C, M is Hf or Zr, L is an alkyl group having 1 to 20 carbon atoms, Y is an alkylene group having 2 to 40 carbon atoms, and R1 to R 17 , R 19 to R 22 and R 24 is hydrogen, and R 18 and R 23 is a halogen group, and R 48 and R 49 Each can independently be an alkyl group having 1 to 20 carbon atoms.

[0228] Additionally, specifically, in the above chemical formula 1C, M is Hf, L is an alkyl group having 1 to 20 carbon atoms, Y is an alkylene group having 2 to 40 carbon atoms, and R1, R2, R4, R5, R7 to R 10 , R 12 , R 13 , R 15 to R 17 , R 19 to R 22 and R 24 is hydrogen, and R3, R6, R 11 and R 14 is an alkyl group having 1 to 20 carbon atoms, and R 18and R 23 is a halogen group, and R 48 and R 49 Each can independently be an alkyl group having 1 to 20 carbon atoms.

[0229]

[0230] For example, the transition metal compound represented by the above chemical formula 1 may be represented by any one of the following chemical formulas 1C-1 to 1C-6.

[0231] [Chemical Formula 1C-1]

[0232]

[0233] [Chemical Formula 1C-2]

[0234]

[0235] [Chemical Formula 1C-3]

[0236]

[0237] [Chemical Formula 1C-4]

[0238]

[0239] [Chemical Formula 1C-5]

[0240]

[0241] [Chemical Formula 1C-6]

[0242]

[0243]

[0244] In addition, the present invention relates to a catalyst composition comprising the aforementioned transition metal compound.

[0245] In the present invention, the “composition” includes reaction products and decomposition products formed from the materials of the composition, as well as a mixture of materials comprising the composition.

[0246] The catalyst composition of the present invention may further include a co-catalyst.

[0247] The above co-catalyst may be one known in the relevant technical field, and for example, the co-catalyst may include one or more selected from the group consisting of compounds represented by the following chemical formulas 2 to 5.

[0248] [Chemical Formula 2]

[0249] -[Al(R 50 )-O] a -

[0250] In the above chemical formula 2,

[0251] R 50 Each is 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

[0252] a is an integer greater than or equal to 2, and

[0253] [Chemical Formula 3]

[0254] E(R 51 ) 3

[0255] In the above chemical formula 3,

[0256] E is aluminum or boron, and

[0257] R 51 Each is 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, and

[0258] [Chemical Formula 4]

[0259] [Le-H] + [G(A)4] -

[0260] [Chemical Formula 5]

[0261] [Le] + [G(A)4] -

[0262] In the above chemical formulas 4 and 5,

[0263] Le is a neutral or cationic Lewis acid, and

[0264] [Le-H]+ is Mount Brønsted, and

[0265] G is a Group 13 element, and

[0266] A 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.

[0267] The compound represented by the above chemical formula 2 is not particularly limited as long as it is an alkylaluminoxan. Preferred examples include methylaluminoxan, ethylaluminoxan, isobutylaluminoxan, butylaluminoxan, etc., and a particularly preferred compound is methylaluminoxan.

[0268] The compound represented by the above chemical formula 3 is not particularly limited, but preferred examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc., and particularly preferred compounds are selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[0269] Examples of compounds represented by the above chemical formula 4 or 5 include, when G is boron, for example, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] -, Dioctadecylmethylammonium tetrakis(phenyl)borate, Dioctadecylmethylammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, Triethylammonium tetraphenylborate, Tributylammonium tetraphenylborate, Trimethylammonium tetraphenylborate, Tripropylammonium tetraphenylborate, Trimethylammonium tetra(p-tolyl)borate, Trimethylammonium tetra(o,p-dimethylphenyl)borate, Tributylammonium tetra(p-trifluoromethylphenyl)borate, Trimethylammonium tetra(p-trifluoromethylphenyl)borate, Tributylammonium tetrapentafluorophenylborate, N,N-Diethylanilinium tetrapentylborate, N,N-Diethylanilinium tetrapentafluorophenylborate, Diethylammonium tetrapentafluorophenylborate, Triphenylphosphonium tetraphenylborate, It may be trimethylphosphonium tetraphenylborate, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, triphenylcarbonium tetra(p-trifluoromethylphenyl)borate, triphenylcarbonium tetrapentafluorophenylborate, or a combination thereof, and where Z is aluminum, e.g., triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, It may be trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentafluorophenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, or a combination thereof, but is not limited thereto.

[0270] In particular, the co-catalyst used in the present invention may be a compound represented by the above chemical formula 4 or 5, and specifically may be dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate.

[0271] In addition, the transition metal compound represented by Chemical Formula 1 and the co-catalyst can also be used in a form supported on a carrier. A person skilled in the art can appropriately select and use a carrier, and for example, silica or alumina can be used.

[0272]

[0273] The present invention relates to a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the aforementioned catalyst composition.

[0274] In the present invention, the term “polymer” refers to a polymer compound produced by polymerizing monomers of the same or different types. Thus, the general term “polymer” encompasses “homopolymer,” a term commonly used to refer to a polymer produced from only one type of monomer, and “interpolymer,” a term defined below.

[0275] In the present invention, the term “copolymer” refers to a polymer produced by the polymerization of at least two different monomers. Thus, the general term “copolymer” includes “copolymer,” which is a term commonly used to refer to a polymer produced from two different monomers, and a polymer produced from two or more different monomers.

[0276] The olefin polymer of the present invention may be an olefin homopolymer or an olefin / alpha-olefin copolymer depending on the type of olefin monomer, and preferably an ethylene / alpha-olefin copolymer. In this case, the content of the alpha-olefin monomer, which is the comonomer, can be appropriately selected by a person skilled in the art according to the use, purpose, etc. of the olefin polymer, and may be, for example, about 1 mol% or more and 99 mol% or less.

[0277] The above alpha-olefin monomer may include one or more selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene, norbornene, norvonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

[0278] In the method for producing an olefin polymer according to the present invention, the catalyst composition may be dissolved or diluted and injected in an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of an olefin monomer, such as pentane, hexane, heptane, nonane, decane, and their isomers, an aromatic hydrocarbon solvent such as toluene and benzene, or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene. It is preferable to use a solvent in which a small amount of water or air, which acts as a poison to the catalyst, is removed by treating it with a small amount of alkylaluminum, and it is also possible to carry out the process by further using a co-catalyst.

[0279] In the method for manufacturing an olefin polymer according to the present invention, the most preferred manufacturing process using the catalyst composition is a solution process, and the composition can also be applied to a slurry or gas phase process when used with an inorganic carrier such as silica.

[0280] The above polymerization can be carried out by homopolymerizing with one olefin monomer or copolymerizing with two or more olefin monomers using a single continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

[0281] In addition, during the above polymerization reaction, an organoaluminum compound is further added to remove moisture within the reactor, and the polymerization reaction can proceed in its presence. Specific examples of such organoaluminum compounds include trialkylaluminum, dialkyl aluminum halides, alkyl aluminum dihalides, aluminum dialkyl hydrides, or alkyl aluminum sesquihalides, and more specific examples include Al(C2H5)3, Al(C2H5)2H, Al(C3H7)3, Al(C3H7)2H, Al(i-C4H9)2H, and Al(C8H 17 )3, Al(C 12 H 25 )3, Al(C2H5)(C 12 H 25 )2, Al(i-C4H9)(C 12 H 25 Examples include )2, Al(i-C4H9)2H, Al(i-C4H9)3, (C2H5)2AlCl, (i-C3H9)2AlCl, or (C2H5)3Al2Cl3. These organoaluminum compounds can be continuously fed into the reactor and can be fed at a ratio of about 0.1 to 10 moles per 1 kg of reaction medium fed into the reactor for proper moisture removal.

[0282] According to one embodiment of the present invention, the polymerization of the olefin polymer can be carried out by reacting for about 4 minutes to 2 hours, specifically about 4 minutes to 1 hour, or about 4 minutes to 30 minutes, under conditions of a temperature of about 80 to 200°C, specifically about 90 to 200°C, about 130 to 200°C, or about 150 to 170°C, and a pressure of about 20 to 100 bar, specifically about 20 to 50 bar, or about 20 to 40 bar.

[0283]

[0284] Examples

[0285] The present invention will be explained in more detail below through examples. However, the following examples are intended to illustrate the present invention and do not limit the scope of the present invention.

[0286]

[0287] Preparation of Transition Metal Compounds

[0288] Preparation Example 1

[0289] [Chemical Formula 1A-1]

[0290]

[0291] The above compound was prepared as follows.

[0292]

[0293] A flask connected to a reflux apparatus was prepared. Under an argon atmosphere, 12 g (46.67 mmol) of PL-1, 9.51 g (48.99 mmol) of PL-2, 12.90 g (93.34 mmol) of K2CO3, and 0.27 g (0.23 mmol) of Pd(PPh3)4 were added to the flask. Subsequently, 62 mL of toluene, 62 mL of EtOH, and 31 mL of H2O were added in sequence, and the mixture was stirred under reflux for 16 hours. After the reaction was complete, 62 mL of water was added at room temperature and stirred, followed by extraction with ethyl acetate. The extracted organic layer was dehydrated using MgSO4, and the organic solvent was removed under reduced pressure. PL-3 was washed with EtOH and vacuum dried to obtain 12.5 g (38.28 mmol, 82%) of white solid PL-3.

[0294] 1 H NMR (500 MHz, CDCl3) δ 7.60-7.50 (6H), 7.12 (2H), 5.47 (1H), 3.94 (1H), 3.62 (1H), 2.03 (1H), 1.89 (2H), 1.76-1.59 (3H), 0.30 (9H).

[0295]

[0296] Under an argon atmosphere, 312.49 g (38.25 mmol) of PL- was placed into a Schrank flask, 77 mL of THF was added, and the mixture was stirred at -78°C using a dry ice bath. 21.4 mL (53.5 mmol) of 2.5 M n-BuLi(in hexane) was added, and the mixture was stirred at -10°C for 4 hours. After cooling to -78°C, 54 mL of THF containing 13.6 g (53.58 mmol) of I2 was slowly added. After removing the dry ice bath, the mixture was stirred overnight at room temperature. After the reaction was complete, a saturated aqueous solution of Na2S2O3 was added and the mixture was stirred. The organic layer was extracted using ethyl acetate, and water was removed using MgSO4. Brown oil PL-416.78 g (37.09 mmol, 97%) was obtained by vacuum distillation.

[0297] 1 H NMR (500 MHz, CDCl3) δ 8.01 (1H), 7.59-7.48 (5H), 7.13 (1H), 5,66 (1H), 3.90 (1H), 3.63 (1H), 2.22-1.60 (6H), 0.30 (9H).

[0298]

[0299] Prepare a flask connected to a reflux apparatus. In an argon atmosphere, PL-48.41 g (18.59 mmol), TCBZ5.71 g (20.43 mmol), K3PO47.9 g (37.22 mmol) , CuI ,0.51 g (3.69 mmol), 46 mL of toluene, and 0.6 mL of DMEDA (5.58 mmol) were added in that order. The mixture was stirred under reflux for 48 hours. After the reaction was complete, the base was removed using a filter filled with Celite and THF, and the organic layer was collected. Brine was added to extract the organic layer, and the remaining water was removed using MgSO4. The oil obtained after vacuum distillation was purified by silica chromatography (hexane:ethyl acetate = 40:1). 10.68 g (17.68 mmol, 95%) of white solid PL-5 was obtained.

[0300] 1 H NMR (500 MHz, CDCl3) δ 8.13 (2H), 7.75 (1H), 7.66 (1H), 7.58 (4H), 7.47 (1H), 7.42 (2H), 7.22 (1H), 7.15 (1H), 5.32 (1H), 3.74 (1H), 3.52 (1H), 1.76-1.00 (24H), 0.29 (9H).

[0301]

[0302] 510.68 g (17.68 mmol) of PL- was placed into a Schrank flask under an argon atmosphere, 87 mL of THF was added, and the mixture was stirred at -78°C using a dry ice base. 8.5 mL (21.25 mmol) of 2.5 M n-BuLi(in hexane) was added, and the mixture was stirred at -10°C for 4 hours. The temperature was lowered to -78°C, and 9 mL (44.12 mmol) of 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. After removing the dry ice base, the mixture was slowly stirred overnight at room temperature. After adding a saturated aqueous solution of NaHCO3 and stirring, the organic layer was extracted using ethyl acetate, and the moisture was removed using MgSO4. The obtained oil was precipitated using acetonitrile and vacuum dried to obtain 69.34 g (12.80 mmol) of white solid PL-.

[0303] 1 H NMR (500 MHz, CDCl3) δ 8.10 (2H), 8.07 (1H), 7.72 (1H), 7.56 (4H), 7.42 (2H), 7.23 (2H), 4.96 (1H), 2.87 (1H), 2.73 (1H), 1.69-1.00 (6H), 1.45 (18H), 1.39 (12H), 0.28 (9H).

[0304]

[0305] Under an argon atmosphere, 65.00 g (6.85 mmol) of PL, 71.25 g (2.96 mmol) of PL, 1.23 g (8.90 mmol) of K2CO3, and 40.172 g (0.15 mmol) of Pd(PPh3) were added to a flask connected to a reflux tube, 20 mL of dioxane and 9 mL of H2O were added, and the mixture was refluxed for 48 hours. After the reaction was complete, a saturated aqueous solution of NaHCO3 was added, followed by extraction with EA. The organic layer was dehydrated using MgSO4, and then subjected to vacuum distillation to obtain a brown solid. The obtained brown solid, along with 0.06 g (0.30 mmol) of p-toluenesulfonic acid monohydrate, 15 mL of MeOH, and 15 mL of THF, were added to a flask and refluxed overnight. After the reaction was complete, water was added and stirred, and the organic layer was extracted with MTBE. The organic layer was dehydrated using MgSO4, and then vacuum distilled to obtain pale oil. Silica chorionic villus chromatography (hexane:ethyl acetate = 50:1) was performed, and 12.97 g (2.28 mmol, 77%) of white solid L- was obtained.

[0306] 1 H NMR (500 MHz, CDCl3) δ 8.21 (4H), 7.64 (2H), 7.55-7.48 (10H), 7.42 (4H), 7.10 (4H), 7.02 (2H), 6.43 (2H), 6.00 (2H), 5.53 (2H), 3.84 (4H), 2.04 (2H), 1.46 (38H), 0.28 (18H).

[0307]

[0308] 0.3 mL (0.9 mmol) of HfCl4, 2 mL cold toluene, and 3 M methylmagnesium bromide in diethyl ether was added to a vial under an argon atmosphere and stirred for 5 minutes. 10.284 g (0.22 mmol) of L was dissolved in 3.5 mL of toluene, added to the vial, and stirred overnight at room temperature. After removing the organic solvent by vacuum drying, a filter filled with celite was prepared, and the organic layer was collected using 40 mL of tol:hexane (1:3). After removing the organic solvent by vacuum drying, a white solid S10.3 g (0.2 mmol, 91%) was obtained.

[0309] 1 H NMR (500 MHz, CDCl3) δ 8.32 (2H), 8.10 (2H), 7.90 (2H), 7.56 (8H), 7.52 (2H), 7.44-7.38 (6H), 7.30 (2H), 7.05 (2H), 6.33 (2H), 4.64 (2H), 3.90 (2H), 3.50 (2H), 1.58 (2H), 1.53 (18H), 1.39 (18H), 0.27 (18H), -1.66 (6H).

[0310]

[0311] Preparation Example 2

[0312] [Chemical Formula 1A-2]

[0313]

[0314] The above compound was prepared as follows.

[0315]

[0316] Prepare a flask connected to a reflux apparatus. In an argon atmosphere, PL-48.37 g (18.50 mmol), CBZ3.40 g (20.33 mmol), K3PO47.86 g (37.03 mmol) , CuI ,0.51 g (3.69 mmol), 46 mL of toluene, and 0.6 mL of DMEDA (5.56 mmol) were added in that order. The mixture was stirred under reflux for 48 hours. After the reaction was complete, the base was removed using a filter filled with Celite and THF, and the organic layer was collected. Brine was added to extract the organic layer, and the remaining water was removed using MgSO4. The oil obtained after vacuum distillation was purified by silica chromatography (hexane:ethyl acetate = 40:1). 6.0 g (12.20 mmol, 66%) of white solid PL-8 was obtained.

[0317] 1 H NMR (500 MHz, CDCl3) δ 8.40 (2H), 7.76 (1H), 7.70 (1H), 7.60 (4H), 7.54 (1H), 7.49 1H), 7.38 (2H), 7.29 (2H), 7.22 (1H), 5.35 (1H), 3.64 (1H), 3.47 (1H), 1.70-1.00 (6H), 0.292 (9H).

[0318]

[0319] 86.00 g (12.20 mmol) of PL- was placed into a Schrank flask under an argon atmosphere, 62 mL of THF was added, and the mixture was stirred at -78°C using a dry ice base. 5.9 mL (14.75 mmol) of 2.5 M n-BuLi(in hexane) was added, and the mixture was stirred at -10°C for 4 hours. The temperature was lowered to -78°C, and 6.23 mL (14.75 mmol) of 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. After removing the dry ice base, the mixture was slowly stirred overnight at room temperature. After adding a saturated aqueous solution of NaHCO3 and stirring, the organic layer was extracted using ethyl acetate, and the moisture was removed using MgSO4. The obtained solid was washed with acetonitrile and vacuum dried to obtain a white solid of 5.72 g (9.26 mmol) of PL-9.

[0320] 1 H NMR (500 MHz, CDCl3) δ 8.11 (3H), 7.75 (1H), 7.58 (4H), 7.43-7.23 (6H), 5.0 (1H), 2.66-2.55 (2H), 1.72 (1H), 1.39 (12H), 1.37-1.10 (4H), 0.95 (1H), 0.28 (9H).

[0321]

[0322] Under an argon atmosphere, 92.50 g (4.05 mmol) of PL, 70.74 g (1.75 mmol) of PL, 0.99 g (7.16 mmol) of K2CO3, and 40.103 g (0.09 mmol) of Pd(PPh3) were added to a flask connected to a reflux tube, 12 mL of Dioxane and 6 mL of H2O were added, and the mixture was refluxed for 48 hours. After the reaction was complete, a saturated aqueous solution of NaHCO3 was added, followed by extraction with EA. The organic layer was dehydrated using MgSO4, and then subjected to vacuum distillation to obtain a brown solid. The obtained brown solid, along with 0.034 g (0.18 mmol) of p-toluenesulfonic acid monohydrate, 10 mL of MeOH, and 10 mL of THF, were added to a flask and refluxed overnight. After the reaction was complete, water was added and stirred, and the organic layer was extracted with MTBE. After removing moisture from the organic layer using MgSO4, a white solid was obtained by vacuum distillation. Silica chorionic villus chromatography (hexane:ethyl acetate = 50:1) was performed, and 21.50 g (1.39 mmol, 80%) of white solid L- was obtained.

[0323] 1 H NMR (500 MHz, CDCl3) δ 8.19 (2H), 7.67 (2H), 7.54 (10H), 7.36-7.27 (8H), 7.17 (4H), 6.55 (2H), 6.15 (2H), 5.67 (2H), 3.87 (4H), 2.05 (2H), 0.28 (18H).

[0324]

[0325] 40.07 g (0.22 mmol) of HfCl, 2 mL of cold toluene, and 0.3 mL (0.9 mmol) of 3 M methylmagnesium bromide in diethyl ether were added to a vial under an argon atmosphere and stirred for 5 minutes. 20.235 g (0.22 mmol) of L was dissolved in 3.5 mL of toluene, added to the vial, and stirred overnight at room temperature. After removing the organic solvent by vacuum drying, a filter filled with celite was prepared, and the organic layer was collected using 40 mL of toluene. After removing the organic solvent by vacuum drying, a white solid S20.25 g (0.2 mmol, 89%) was obtained.

[0326] 1 H NMR (500 MHz, CDCl3) δ 8.34 (2H), 8.14 (2H), 7.92 (2H), 7.57 (8H), 7.55 (2H), 7.50 (2H), 7.45-7.35 (8H), 7.20 (2H), 7.05 (2H), 6.37 (2H), 4.46 (2H), 3.90 (2H), 3.52 (2H), 1.60 (2H), 0.28 (18H), -1.70 (6H).

[0327]

[0328] Preparation Example 3

[0329] [Chemical Formula 1A-3]

[0330]

[0331] The above compound was prepared as follows.

[0332]

[0333] In an argon atmosphere, 0.05 g (0.16 mmol) of HfCl 4, 10.203 g (0.16 mmol) of L, and 4 mL of cold toluene were added to a vial, followed by the addition of 0.32 mL (0.64 mmol) of 2 M butylmagnesium chloride in diethyl ether, and the mixture was stirred overnight at room temperature. After removing the organic solvent by vacuum drying, a filter filled with celite was prepared, and the organic layer was collected using 20 mL of toluene. After removing the organic solvent by vacuum drying, a white solid S 20.20 g (0.13 mmol, 81%) was obtained.

[0334] 1 H NMR (500 MHz, CDCl3) δ 8.32 (2H), 8.08 (2H), 7.88 (2H), 7.53 (8H), 7.48-7.38 (10H), 7.27 (2H), 7.05 (2H), 6.30 (2H), 4.62 (2H), 3.90 (2H), 3.50 (2H), 1.60-1.40 (36H), 1.40-0.60 (14H) 0.31 (18H), -1.20 (2H), -1.50 (2H).

[0335]

[0336] Preparation Example 4

[0337] [Chemical Formula 1A-4]

[0338]

[0339] The above compound was prepared as follows.

[0340]

[0341] Synthesis was carried out in the same manner as S1, except that L10.15g was used as the starting material (yield 65%).

[0342] 1H NMR (500 MHz, CDCl3) δ-1.426, 0.273, 1.373, 1.531, 3.457, 3.837, 4.618, 6.30, 7.05, 7.44, 7.56,7.87, 8.08, 8.31.

[0343]

[0344] Preparation Example 5

[0345] [Chemical Formula 1A-5]

[0346]

[0347] The above compound was prepared as follows.

[0348]

[0349] Prepare a flask connected to a reflux apparatus. Under an argon atmosphere, 7.00 g (30.54 mmol) of PL-10, 7.10 g (31.97 mmol) of PL-11, 8.44 g (61.07 mmol) of K2CO3, and 0.18 g (0.16 mmol) of Pd(PPh3)4 were added to the flask. Subsequently, 40 mL of toluene, 40 mL of EtOH, and 20 mL of H2O were added in sequence, followed by stirring under reflux for 16 hours. After the reaction was complete, water was added at room temperature and stirred, followed by extraction with ethyl acetate. The extracted organic layer was dehydrated using MgSO4, and the organic solvent was removed under reduced pressure. PL-12 was obtained in oil form and used in the following reaction without purification. 9.98 g (30.57 mmol, Quant.)

[0350] 1 H NMR (500 MHz, CDCl3) δ 7.50 (1H), 7.35-7.22 (5H), 6.95 (2H), 5.30 (1H), 3.78 (1H), 3.42 (1H), 1.88-1.40 (6H), 0.11 (9H).

[0351]

[0352] Under an argon atmosphere, 129.98 g (30.57 mmol) of PL-1 was placed into a Schrank flask, 76 mL of THF was added, and the mixture was stirred at -78°C using a dry ice bath. 17.1 mL (42.75 mmol) of 2.5 M n-BuLi(in hexane) was added, and the mixture was stirred at -10°C for 4 hours. After cooling to -78°C, 43 mL of THF containing 10.86 g (42.79 mmol) of I2 was slowly added. After removing the dry ice bath, the mixture was stirred overnight at room temperature. After the reaction was complete, a saturated aqueous solution of Na2S2O3 was added and the mixture was stirred. The organic layer was extracted using ethyl acetate, and water was removed using MgSO4. Brown oil PL-1313.73 g (30.57 mmol, quant.) was obtained by vacuum distillation.

[0353] 1 H NMR (500 MHz, CDCl3) δ 8.00 (1H), 7.65-7.40 (5H), 7.14 (1H), 5,60 (1H), 3.90 (1H), 3.63 (1H), 2.24-1.60 (6H), 0.33 (9H).

[0354]

[0355] Prepare a flask connected to a reflux apparatus. In an argon atmosphere, PL-13 13.83 g (30.57 mmol), TCBZ 8.54 g (30.56 mmol), K3PO 4 13.0 g (61.24 mmol) , CuI ,1.74 g (9.14 mmol), 150 mL of toluene, and 1.35 mL (15.35 mmol) of DMEDA were added in that order. The mixture was stirred under reflux for 48 hours. After the reaction was complete, the base was removed using a filter filled with Celite and THF, and the organic layer was collected. Brine was added to extract the organic layer, and the remaining water was removed using MgSO4. The oil obtained after vacuum distillation was purified by silica chromatography (hexane:ethyl acetate = 40:1). 17.0 g (28.15 mmol, 92%) of white solid PL-14 was obtained.

[0356] 1 H NMR (500 MHz, CDCl3) δ 8.14 (2H), 7.74-7.15 (11H), 5.25 (1H), 3.74 (1H), 3.50 (1H), 1.80-1.00 (24H), 0.29 (9H).

[0357]

[0358] In an argon atmosphere, 15.40 g (25.50 mmol) of PL-14 was added to a Schrank flask, 130 mL of THF was added, and the mixture was stirred at -78°C using a dry ice base. 12.3 mL (30.75 mmol) of 2.5 M n-BuLi (in hexane) was added, and the mixture was stirred at -10°C for 4 hours. The temperature was then lowered to -78°C, and 10.4 mL (51.06 mmol) of 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. After removing the dry ice base, the mixture was slowly stirred overnight at room temperature. After adding a saturated aqueous NaHCO3 solution and stirring, the organic layer was extracted using ethyl acetate, and the moisture was removed using MgSO4. The obtained oil was precipitated using acetonitrile and then vacuum dried to obtain a white solid PL-1510.34 g (14.22 mmol, 56%).

[0359] 1 H NMR (500 MHz, CDCl3) δ 8.10 (2H), 8.02 (1H), 7.68-7.24 (9H), 4.96 (1H), 2.87 (1H), 2.75 (1H), 1.69-1.00 (6H), 1.45 (18H), 1.39 (12H), 0.31 (9H).

[0360]

[0361] Under an argon atmosphere, 152.00 g (2.74 mmol) of PL-, 70.40 g (0.95 mmol) of PL-, 0.79 g (5.72 mmol) of K2CO3, and 40.055 g (0.05 mmol) of Pd(PPh3) were added to a flask connected to a reflux tube. Then, 4.7 mL of dioxane and 2.8 mL of H2O were added, and the mixture was refluxed overnight. After the reaction was complete, a saturated aqueous solution of NaHCO3 was added, followed by extraction with EA. The organic layer was dehydrated using MgSO4, and a brown solid was obtained by vacuum distillation. The obtained brown solid, along with 0.02 g (0.1 mmol) of p-toluenesulfonic acid monohydrate, 3 mL of MeOH, and 3 mL of THF, were added to a flask and refluxed overnight. After the reaction was complete, water was added and stirred, followed by extraction of the organic layer with MTBE. The organic layer was dehydrated using MgSO4, and a pale oil was obtained by vacuum distillation. Silica chorionic villus sampling (hexane: ethyl acetate = 50:1) was performed, and 30.5 g (0.38 mmol, 41%) of white solid L- was obtained.

[0362] 1 H NMR (500 MHz, CDCl3) δ 8.24 (4H), 7.65 (4H), 7.55-7.42 (12H), 7.10 (4H), 7.02 (2H), 6.44 (2H), 5.92 (2H), 5.53 (2H), 3.82 (4H), 2.02 (2H), 1.41 (38H), 0.26 (18H).

[0363]

[0364] Synthesis was carried out in the same manner as S1, except that 0.1208g of L3 was used as the starting material (yield 75.8%).

[0365] 1 H NMR (500 MHz, CDCl3) δ-1.435, 0.267, 1.38, 1.521, 3.47, 3.85, 4.60, 6.30, 7.05, 7.42, 7.67,7.85, 8.08, 8.31.

[0366]

[0367] Preparation Example 6

[0368] [Chemical Formula 1B-1]

[0369]

[0370] The above compound was prepared as follows.

[0371]

[0372] Prepare a flask connected to a reflux apparatus. Under an argon atmosphere, 6.92 g (31.30 mmol) of 1-bromo-4-methylnaphthalene, 10.00 g (32.87 mmol) of Borate Compound, 8.65 g (62.59 mmol) of K2CO3, and 0.36 g (0.31 mmol) of Pd(PPh3)4 were added to the flask. Subsequently, 42 mL of toluene, 42 mL of EtOH, and 21 mL of H2O were added in sequence, and the mixture was stirred under reflux for 16 hours. After the reaction was complete, water was added at room temperature and stirred, followed by extraction with ethyl acetate. The extracted organic layer was dehydrated using MgSO4, and the organic solvent was removed under reduced pressure. Silica chromatography was performed (Hexane : EA = 20:1), and vacuum drying was carried out to obtain 19.39 g (29.49 mmol, 94%) of a white solid.

[0373] 1H NMR (500 MHz, CDCl3) δ 8.05 (1H), 7.95 (1H), 7.52 (1H), 7.44-7.30 (5H), 7.16 (2H), 5.50 (1H), 4.00 (1H), 3.66 (1H), 2.73 (3H). 2.02-1.60 (6H)

[0374]

[0375] Under an argon atmosphere, 1-19.39 g (29.49 mmol) was placed into a Schrank flask, 59 mL of THF was added, and the mixture was stirred at -78°C using a dry ice bath. 16.5 mL (41.25 mmol) of 2.5 M n-BuLi(in hexane) was added, and the mixture was stirred at -10°C for 4 hours. After cooling to -78°C, 38 mL of THF containing dissolved I215.3 g (38.25 mmol) was slowly added. After removing the dry ice bath, the mixture was stirred overnight at room temperature. After the reaction was complete, a saturated aqueous solution of Na2S2O3 was added and the mixture was stirred. The organic layer was extracted using ethyl acetate, and water was removed using MgSO4. Brown oil 1-213.11 g (quant.) was obtained by vacuum distillation.

[0376] 1 H NMR (500 MHz, CDCl3) δ 8.05 (1H), 7.99-7.89 (2H), 7.58-7.27 (5H), 7.18 (1H), 5.62 (1H), 3.95 (1H), 3.68 (1H), 2.74 (3H), 2.28-1.60 (6H).

[0377]

[0378] Prepare a flask connected to a reflux apparatus. Under an argon atmosphere, 1-26.34 g (14.27 mmol), TCBZ 4.20 g (15.03 mmol), K3PO 46.06 g (28.55 mmol) , CuI ,0.40 g (2.10 mmol), 47 mL of toluene, and 0.46 mL (4.28 mmol) of DMEDA were added in that order. The mixture was stirred under reflux for 48 hours. After the reaction was complete, the base was removed using a filter filled with Celite and THF, and the organic layer was collected. Brine was added to extract the organic layer, and the remaining water was removed using MgSO4. The oil obtained after vacuum distillation was purified by silica chromatography (hexane:ethyl acetate = 40:1). 5.76 g (9.67 mmol, 68%) of white solid 1-3 was obtained.

[0379] 1 H NMR (500 MHz, CDCl3) δ 8.02-8.12 (4H), 7.62-7.20 (11H), 5.38 (1H), 3.80 (1H), 3.56 (1H), 2.70 (3H), 1.51-1.11 (24H).

[0380]

[0381] Under an argon atmosphere, 1-35.75 g (9.65 mmol) was placed into a Schrank flask, 48 mL of THF was added, and the mixture was stirred at -78°C using a dry ice base. 4.7 mL (11.75 mmol) of 2.5 M n-BuLi(in hexane) was added, and the mixture was stirred at -10°C for 4 hours. The temperature was lowered to -78°C, and 9.93 mL (24.19 mmol) of 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. After removing the dry ice base, the mixture was slowly stirred overnight at room temperature. After adding a saturated aqueous NaHCO3 solution and stirring, the organic layer was extracted using ethyl acetate, and the moisture was removed using MgSO4. The obtained oil was precipitated using MeOH and vacuum dried to obtain a white solid 1-46.43 g (12.80 mmol, 92%).

[0382] 1 H NMR (500 MHz, CDCl3) δ 8.12-7.95 (5H), 7.65-7.24 (9H), 5.15 (1H), 2.98 (1H), 2.80 (1H), 2.71 (3H), 1.50-1.11 (42H).

[0383]

[0384] Under an argon atmosphere, 43.00 g (4.16 mmol) of 1-, 0.76 g (1.80 mmol) of phenyl compound, 1.00 g (7.24 mmol) of k2CO3, and 40.105 g (0.09 mmol) of Pd(PPh3) were added to a flask connected to a reflux tube, 12 mL of dioxane and 6 mL of H2O were added, and the mixture was refluxed for 48 hours. After the reaction was complete, a saturated aqueous solution of NaHCO3 was added, followed by extraction with EA. The organic layer was dehydrated using MgSO4, and then subjected to vacuum distillation to obtain a brown solid. The obtained brown solid, along with 0.04 g (0.18 mmol) of p-toluenesulfonic acid monohydrate, 15 mL of MeOH, and 15 mL of THF, were added to a flask and refluxed overnight. After the reaction was complete, water was added and stirred, and the organic layer was extracted with MTBE. The organic layer was dehydrated using MgSO4, and then vacuum distilled to obtain pale oil. Silica chorionic villus chromatography (hexane:ethyl acetate = 50:1) was performed, and a white solid 1-51.5 g (1.17 mmol, 65%) was obtained.

[0385] 1 H NMR (500 MHz, CDCl3) δ 8.19 (4H), 8.02 (4H), 7.55-7.32 (20H), 7.19-7.05 (6H), 6.50 (2H), 6.02 (2H), 5.67 (2H), 3.90 (4H), 2.71 (6H), 2.13 (2H), 1.45 (38H).

[0386] 40.07 g (0.22 mmol) of HfCl, 2 ml of cold toluene, and 0.3 mL (0.9 mmol) of 3 M methylmagnesium bromide in diethyl ether were added to a vial under an argon atmosphere and stirred for 5 minutes. 50.281 g (0.22 mmol) of I-50 was dissolved in 3 mL of toluene, added to the vial, and stirred overnight at room temperature. After removing the organic solvent by vacuum drying, a filter filled with celite was prepared, and the organic layer was collected using 40 mL of tol:hexane (1:3). After removing the organic solvent by vacuum drying, a white solid S10.3 g (0.2 mmol, 91%) was obtained.

[0387] 1 H NMR (500 MHz, CDCl3) δ 8.30 (2H), 8.10-8.05 (6H), 7.80 (2H), 7.56-7.30 (20H), 7.11 (2H), 6.30 (2H), 4.68 (2H), 4.05 (2H), 3.60 (2H), 2.68 (6H), 1.47 (36H), -1.58 (6H).

[0388]

[0389] Preparation Example 7

[0390] [Chemical Formula 1B-2]

[0391]

[0392] The above compound was prepared as follows.

[0393]

[0394] Prepare a flask connected to a reflux apparatus. Under an argon atmosphere, 1-26.34 g (15.24 mmol), CBZ 2.67 g (15.97 mmol), K3PO 46.47 g (30.48 mmol) , CuI ,(0.2 eq.), 47 mL of toluene, and 0.49 mL (4.57 mmol) of DMEDA were added in that order. The mixture was stirred under reflux for 72 hours. After the reaction was complete, the base was removed using a filter filled with Celite and THF, and the organic layer was collected. Brine was added to extract the organic layer, and the remaining water was removed using MgSO4. The oil obtained after vacuum distillation was purified by silica chromatography (hexane:ethyl acetate = 40:1). 4.59 g (9.49 mmol, 62%) of white solid 2-1 was obtained.

[0395] 1 H NMR (500 MHz, CDCl3) δ 8.19-8.05 (6H), 7.68 (1H), 7.62-7.25 (10H), 5.43 (1H) 3.74 (1H), 3.56 (1H), 2.77 (3H), 1.98-1.00 (6H).

[0396]

[0397] Under an argon atmosphere, 2-14.59 g (9.49 mmol) was placed into a Schrank flask, 38 mL of THF was added, and the mixture was stirred at -78°C using a dry ice base. 4.2 mL (10.5 mmol) of 2.5 M n-BuLi(in hexane) was added, and the mixture was stirred at -10°C for 4 hours. The temperature was lowered to -78°C, and 4.8 mL (23.65 mmol) of 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. After removing the dry ice base, the mixture was slowly stirred overnight at room temperature. After adding a saturated aqueous NaHCO3 solution and stirring, the organic layer was extracted using ethyl acetate, and the moisture was removed using MgSO4. The obtained oil was precipitated using MeOH and vacuum dried to obtain a white solid 2-24.89 g (8.02 mmol, 85%).

[0398] 1H NMR (500 MHz, CDCl3) δ 8.18-8.00 (5H), 7.65 (1H) 7.58-7.24 (8H), 7.28-7.25 (2H), 5.08 (1H), 2.98 (1H), 2.80 (1H), 2.78 (3H), 2.68 (2H), 1.75 (1H), 1.48(12H), 1.46-1.00 (6H).

[0399]

[0400] Under an argon atmosphere, 22.17 g (3.56 mmol), 0.63 g (1.49 mmol), 0.62 g (4.49 mmol), and 40.870 g (0.08 mmol) of Pd(PPh3) were added to a flask connected to a reflux tube, followed by the addition of 7 mL of Dioxane and 4.5 mL of H2O, and the mixture was refluxed for 48 hours. After the reaction was complete, a saturated aqueous solution of NaHCO3 was added, and the mixture was extracted with EA. The organic layer was dehydrated using MgSO4, and then subjected to vacuum distillation to obtain a brown solid. The obtained brown solid, along with 0.03 g (0.16 mmol) of p-toluenesulfonic acid monohydrate, 8 mL of MeOH, and 8 mL of THF, was added to a flask and refluxed overnight. After the reaction was complete, water was added and stirred, and the organic layer was extracted with MTBE. The organic layer was dehydrated using MgSO4, and then vacuum distilled to obtain pale oil. Silica chorionic villus chromatography (hexane:ethyl acetate = 50:1) was performed, and a white solid 2-31.5 g (1.17 mmol, 65%) was obtained.

[0401] 1 H NMR (500 MHz, CDCl3) δ 8.19 (4H), 8.02 (4H), 7.55-7.22 (24H), 7.05 (2H), 6.59 (2H), 6.08 (2H), 5.60 (2H), 3.95 (4H), 2.71 (6H), 2.15 (2H).

[0402] 40.07 g (0.22 mmol) of HfCl, 2 ml of cold toluene, and 0.3 mL (0.9 mmol) of 3 M methylmagnesium bromide in diethyl ether were added to a vial under an argon atmosphere and stirred for 5 minutes. 2-30.232 g (0.22 mmol) was dissolved in 3 mL of toluene, added to the vial, and stirred overnight at room temperature. After removing the organic solvent by vacuum drying, a filter filled with celite was prepared, and the organic layer was collected using 40 mL of tol:hexane (1:3). After removing the organic solvent by vacuum drying, a white solid S20.3 g (0.2 mmol, 91%) was obtained.

[0403] 1 H NMR (500 MHz, CDCl3) δ 8.30 (2H), 8.30-7.05 (34H), 6.35 (2H), 4.50 (2H), 4.00 (2H), 3.60 (2H), 2.70 (6H), 1.75 (2H), -1.65 (6H).

[0404]

[0405] Preparation Example 8

[0406] [Chemical Formula 1B-3]

[0407]

[0408] The above compound was prepared as follows.

[0409]

[0410] Prepare a flask connected to a reflux apparatus. Under an argon atmosphere, add 10.00 g (31.30 mmol) of 2-(4-bromophenoxy)tetrahydro-2H-pyran, 7.00 g (40.70 mmol) of 1-naphthaleneboronic acid, 10.80 g (78.14 mmol) of K2CO3, and 0.23 g (0.005 mmol) of Pd(PPh3)4 to the flask. Subsequently, add 52 mL of toluene, 52 mL of EtOH, and 26 mL of H2O in sequence, and stir under reflux for 16 hours. After the reaction is complete, add additional water at room temperature and stir, then extract with ethyl acetate. Remove moisture from the extracted organic layer using MgSO4, and then remove the organic solvent under reduced pressure. Silica chromatography was performed (Hexane : EA = 20: 1), and vacuum drying was performed to obtain a white solid 3-110.22 g (32.10 mmol, 83%).

[0411] 1 H NMR (500 MHz, CDCl3) δ 7.95-7.60 (3H), 7.52-7.40 (6H), 7.16 (2H), 5.51 (1H), 4.00 (1H), 3.65 (1H), 4.00 (1H), 3.66 (1H), 2.10-1.60 (6H).

[0412]

[0413] Under an argon atmosphere, 3-110.22 g (33.58 mmol) was placed into a Schrank flask, 40 mL of THF was added, and the mixture was stirred at -78°C using a dry ice bath. 18.8 mL (47.00 mmol) of 2.5 M n-BuLi(in hexane) was added, and the mixture was stirred at -10°C for 4 hours. After cooling to -78°C, 40 mL of THF containing dissolved I211.0 g (43.34 mmol) was slowly added. After removing the dry ice bath, the mixture was stirred overnight at room temperature. After the reaction was complete, a saturated aqueous solution of Na2S2O3 was added and the mixture was stirred. The organic layer was extracted using ethyl acetate, and water was removed using MgSO4. By vacuum distillation, 3-213.30 g (30.91 mmol, 92%) of white solid was obtained.

[0414] 1 H NMR (500 MHz, CDCl3) δ 8.05 (1H), 7.90-7.85 (4H), 7.50-7.35 (5H), 7.18 (1H), 5.62 (1H), 3.95 (1H), 3.68 (1H), 2.28-1.60 (6H).

[0415]

[0416] Prepare a flask connected to a reflux apparatus. Under an argon atmosphere, 3-26.60 g (15.34 mmol), TCBZ 4.71 g (16.86 mmol), K3PO 46.50 g (30.62 mmol) , CuI ,0.42 g (2.21 mmol), 38 mL of toluene, and 0.49 mL (4.61 mmol) of DMEDA were added in that order. The mixture was stirred under reflux for 48 hours. After the reaction was complete, the base was removed using a filter filled with Celite and THF, and the organic layer was collected. Brine was added to extract the organic layer, and the remaining water was removed using MgSO4. The oil obtained after vacuum distillation was purified by silica chromatography (hexane:ethyl acetate = 40:1). 7.17 g (12.32 mmol, 80%) of white solid 1-3 was obtained.

[0417] 1 H NMR (500 MHz, CDCl3) δ 8.12-8.02 (3H), 7.80-7.65 (2H), 7.63 (1H), 7.55-7.40 (8H), 7.27 (1H), 7.23 (1H), 5.38 (1H), 3.80 (1H), 3.56 (1H), 1.48-1.11 (24H).

[0418]

[0419] Under an argon atmosphere, 3-37.15 g (12.29 mmol) was placed into a Schrank flask, 60 mL of THF was added, and the mixture was stirred at -78°C using a dry ice base. 5.4 mL (13.50 mmol) of 2.5 M n-BuLi(in hexane) was added, and the mixture was stirred at -10°C for 4 hours. The temperature was lowered to -78°C, and 6.26 mL (30.69 mmol) of 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. After removing the dry ice base, the mixture was slowly stirred overnight at room temperature. After adding a saturated aqueous NaHCO3 solution and stirring, the organic layer was extracted using ethyl acetate, and the moisture was removed using MgSO4. The obtained oil was precipitated using MeOH and vacuum dried to obtain a white solid 3-46.17 g (8.72 mmol, 71%).

[0420] 1 H NMR (500 MHz, CDCl3) δ 8.10-7.82 (6H), 7.65 (1H), 7.51-7.26 (8H), 5.15 (1H), 2.98 (1H), 2.80 (1H), 1.50-1.11 (42H).

[0421]

[0422] Under an argon atmosphere, 3-42.00 g (4.83 mmol), 0.50 g (1.18 mmol), 0.66 g (4.78 mmol), and 40.07 g (0.06 mmol) of Pd(PPh3) were added to a flask connected to a reflux tube, followed by the addition of 8 mL of Dioxane and 4 mL of H2O, and the mixture was refluxed for 48 hours. After the reaction was complete, a saturated aqueous solution of NaHCO3 was added, and the mixture was extracted with EA. The organic layer was dehydrated using MgSO4, and a brown solid was obtained by vacuum distillation. The obtained brown solid, along with 0.03 g (0.16 mmol) of p-toluenesulfonic acid monohydrate, 6 mL of MeOH, and 6 mL of THF, was added to a flask and refluxed overnight. After the reaction was complete, water was added and stirred, and the organic layer was extracted with MTBE. The organic layer was dehydrated using MgSO4, and a white solid was obtained by vacuum distillation. Silica chorionic villus sampling (hexane: ethyl acetate = 50:1) was performed, and 50.70 g (0.56 mmol, 47%) of a white solid was obtained.

[0423] 1 H NMR (500 MHz, CDCl3) δ 8.19 (4H), 8.02-7.82 (6H), 7.55-7.22 (22H), 6.44 (2H), 6.00 (2H), 5.60 (2H), 3.95 (4H), 2.15 (2H), 1.42 (38H).

[0424] 40.07 g (0.22 mmol) of HfCl, 2 ml of cold toluene, and 0.3 mL (0.9 mmol) of 3 M methylmagnesium bromide in diethyl ether were added to a vial under an argon atmosphere and stirred for 5 minutes. 30.275 g (0.22 mmol) of 3-50.275 g (0.22 mmol) was dissolved in 3 mL of toluene, added to the vial, and stirred overnight at room temperature. After removing the organic solvent by vacuum drying, a filter filled with celite was prepared, and the organic layer was collected using 40 mL of tol:hexane (1:3). After removing the organic solvent by vacuum drying, a white solid S30.3 g (0.2 mmol, 91%) was obtained.

[0425] 1 H NMR (500 MHz, CDCl3) δ 8.30 (2H), 8.10-8.05 (4H), 7.80-7.60 (6H), 7.50-7.40 (18H), 7.05 (2H), 6.30 (2H), 4.68 (2H), 4.05 (2H), 3.60 (2H), 1.78 (2H), 1.47 (36H), -1.60 (6H).

[0426]

[0427] Preparation Example 9

[0428] [Chemical Formula 1B-4]

[0429]

[0430] The above compound was prepared as follows.

[0431]

[0432] 40.05 g (0.16 mmol) of HfCl, 2 ml of cold toluene, and 0.32 mL (0.64 mmol) of 2 M butylmagnesium chloride in diethyl ether were added to a vial under an argon atmosphere and stirred for 5 minutes. 30.196 g (0.16 mmol) of 3-50.196 g (0.16 mmol) was dissolved in 3 mL of toluene, added to the vial, and stirred overnight at room temperature. After removing the organic solvent by vacuum drying, a filter filled with celite was prepared, and the organic layer was collected using 40 mL of tol:hexane (1:3). After removing the organic solvent by vacuum drying, a white solid S40.2 g (0.2 mmol, 83%) was obtained.

[0433] 1 H NMR (500 MHz, CDCl3) δ 8.10-7.11 (34H), 6.05 (2H), 4.47 (2H), 3.75 (2H), 3.40 (2H), 1.51 (2H), 1.28 (36H), 1.47 (36H), 1.43-0.83 (14H), -1.43 (2H), -1.71(2H).

[0434]

[0435] Preparation Example 10

[0436] [Chemical Formula 1C-1]

[0437]

[0438] The above compound was prepared as follows.

[0439]

[0440] 1 eq. of 4-(trans-4-ethylcyclohexyl)phenol, 8 mol% of PPTS, and 2 eq. of DHP dissolved in 1 M dichloromethane were added to a 100 ml round flask. The reaction was carried out overnight at 35°C. After the reaction was complete, the mixture was cooled to room temperature, followed by extraction with distilled water and DCM (dichloromethane), and the product was obtained by column analysis.

[0441] 1 H NMR (500 MHz, CDCl3): 7.08(2H, d), 6.97(2H, d), 5.4(1H, m), 3.85(1H,m), 3.60(1H,m), 2.4(1H, t), 2.0(1H, d), 1.9(7H, m), 1.61(3H, m), 1.41(2H, m), 1.21(1H, m), 1.12(2H, m), 0.88(3H, t)

[0442]

[0443] 1 eq. of 2-(4-((1s,4r)-4-ethylcyclohexyl)phenoxy)tetrahydro-2H-pyran) was added to 0.3 M THF in a 100 ml Schrenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 21.3 eq. of I was slowly added. The reaction was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, a sat. sodium thiosulfate solution was added and stirred for 10 minutes. After extraction with EA (Ethyl Acetate), the mixture was vacuum dried. The resulting solid was column-coated to obtain the product.

[0444] 1H NMR (500 MHz, CDCl3): 7.55(1H, d), 7.12(1H, m), 6.98(1H, d), 5.47(1H, m), 3.91(1H,m), 3.62(1H, m), 2.36(1H, t), 2.15(1H, t), 1.96(1H, m), 1.87(4H, m), 1.76-1.56(4H, m), 1.39(2H, q), 1.25(2H, m), 1.17(1H, m), 1.02(2H, m), 0.88(3H, t)

[0445]

[0446] 1 eq. of 2-(4-((1s,4r)-4-ethylcyclohexyl)phenoxy)tetrahydro-2H-pyran, 1.1 eq. of carbazole, 20 mol% of CuI, 3.8 eq. of K3PO, and 50 mol% of DMEDA were added to a 100 ml flask in 0.2 M toluene. The reaction was carried out at 115°C for two nights. After the reaction was complete, the mixture was cooled to room temperature, extracted with EA (Ethyl Acetate), and vacuum dried. The resulting solid was dissolved in hexane and processed through a column to obtain the product.

[0447] 1 H NMR (500 MHz, CDCl3):8.13(2H, d), 7.38(2H, q), 7.33(2H, d), 7.26(4H, m), 7.18(1H, d), 5.216(1H, m), 3.61(1H, m), 3.43(1H, m), 2.50(1H, m), 1.95-1.86(4H, dd), 1.46-1.34(4H, m), 1.25(3H, m), 1.2-1.11(4H, m), 1.06(3H, m), 0.9(3H, t)

[0448]

[0449] 1 eq. of 9-(5-((1r,4r)-4-ethylcyclohexyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole was added to 0.2 M THF in a 100 ml Schrenk flask. At -10°C, 1.25 eq. of n-BuLi was added, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of methyl borate was slowly added. The process was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, the product was obtained by EA (Ethyl Acetate) extraction followed by vacuum drying.

[0450] 1 H NMR (500 MHz, CDCl3): 8.19(2H, s), 8.10(2H, d), 7.47(2H, dd), 7.40(2H, dd), 7.13(2H, d), 2.61(1H, t), 2.03-1.91(4H, dd), 1.46-1.34(4H, m), 1.25(3H, m), 1.2-1.11(4H, m), 1.06(3H, m), 0.9(3H, t)

[0451]

[0452] In a 100 ml Schlenk flask, 1 eq. of 1,3-bis(2-bromo-4-fluorophenoxy)propane and 2.5 eq. of (3-(9H-carbazol-9-yl)-5-((1s,4s)-4-ethylcyclohexyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)boronic acid), 6 eq. of K2CO3, and 45 mol% of Pd(PPh3) were mixed with 0.2 M 1,4-dioxane and 0.5 M It was added to H2O. The reaction was carried out overnight at 95°C. During the reaction, if the amount of 9-(5-((1r,4r)-4-ethylcyclohexyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-yl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole was insufficient, additional amounts were added. After the reaction was complete, it was cooled to room temperature, extracted with EA, and vacuum dried. The product was obtained by dissolving it in hexane and running it through a column.

[0453] 1H NMR (500 MHz, CDCl3): 8.18(4H, d), 7.33(4H, t), 7.28-7.23(6H, m), 7.13(2H, s), 7.11(4H, d), 7.03(2H, dd), 6.63(2H, td), 6.2(2H, dd), 5.6(2H, s), 3.86(4H, t), 2.47(2H, td), 2.02(2H, t), 1.95-1.84(8H, dd), 1.43(4H, qd), 1.26(4H, m), 1.14(2H, m), 1.13(4H, m), 0.88(6H, t)

[0454]

[0455] 1 eq of HfCl4 was added to a cold (-25°C) slurry state with 0.05 M toluene, and 4.1 eq. of 3.0 M MeMgBr was added. The mixture was stirred for 2 minutes, 1 eq. of ligand was added as a solid, and washed with toluene. The temperature was gradually increased, and the reaction mixture was stirred overnight at room temperature. The black mixture was concentrated under high vacuum, and hexane was added to the dried solid and stirred for about 10 minutes. The solid was filtered and collected, and the colorless filtrate was concentrated under high vacuum to obtain a white product.

[0456] 1 H NMR (500 MHz, C6D6): 8.32(2H, d), 8.12(2H, d), 7.44(6H, m), 7.34(6H, d), 7.12(4H, t), 7.09(2H, m), 6.99(2H, d), 6.34(2H, t), 4.34(2H, dd), 3.82(2H, m), 3.42(2H, m), 2.49(2H, t), 1.96-1.83(8H, dd), 1.50(2H, t), 1.41(4H, m), 1.27-1.20(14H, m), 1.03(4H, m), 0.90(6H, s)

[0457]

[0458] Preparation Example 11

[0459] [Chemical Formula 1C-2]

[0460]

[0461] The above compound was prepared as follows.

[0462]

[0463] 1 eq. of 4-(trans-4-ethylcyclohexyl)phenol, 8 mol% of PPTS, and 2 eq. of DHP dissolved in 1 M dichloromethane were added to a 100 ml round flask. The reaction was carried out overnight at 35°C. After the reaction was complete, the mixture was cooled to room temperature, extracted with distilled water and MC (Dimethyl Chloride), and the product was obtained by column analysis.

[0464] 1 H NMR (500 MHz, CDCl3): 7.08(2H, d), 6.97(2H, d), 5.4(1H, m), 3.85(1H,m), 3.60(1H, m), 2.4(1H, t), 2.0(1H, d), 1.9(7H, m), 1.61(3H, m), 1.41(2H, m), 1.21(1H, m), 1.12(2H, m), 0.88(3H, t)

[0465]

[0466] 1 eq. of 2-(4-((1s,4r)-4-ethylcyclohexyl)phenoxy)tetrahydro-2H-pyran) was added to 0.3 M THF in a 100 ml Schrenk flask. At -10°C, 1.25 eq. of n-BuLi was added, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of I2 was slowly added. The reaction was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, a sat. sodium thiosulfate solution was added and stirred for 10 minutes. After EA extraction, the mixture was vacuum dried. The resulting solid was column-coated to obtain the product.

[0467] 1 H NMR (500 MHz, CDCl3): 7.55(1H, d), 7.12(1H, m), 6.98(1H, d), 5.47(1H, m), 3.91(1H,m), 3.62(1H, m), 2.36(1H, t), 2.15(1H, t), 1.96(1H, m), 1.87(4H, m), 1.76-1.56(4H, m), 1.39(2H, q), 1.25(2H, m), 1.17(1H, m), 1.02(2H, m), 0.88(3H, t)

[0468]

[0469] 1 eq. of 2-(4-((1r,4r)-4-ethylcyclohexyl)-2-iodophenoxy)tetrahydro-2H-pyran, 1.1 eq. of 3,6-di-tert-butylcarbazole, 20 mol% of CuI, 3.8 eq. of K3PO4, and 50 mol% of N-methylimidazole were added to a 100 ml flask in 0.2 M toluene. The reaction was carried out at 115°C for two nights. After the reaction was complete, the mixture was cooled to room temperature, extracted with EA (Ethyl Acetate), and vacuum dried. The resulting solid was dissolved in hexane and processed through a column to obtain the product.

[0470] 1 H NMR (500 MHz, CDCl3): 8.12(2H, d), 7.41(2H, t), 7.32(2H, m), 7.24(1H, dd), 7.18(1H, d), 7.12(1H, d), 5.19(1H, m), 3.74(1H, m), 3.46(1H, m), 2.48(1H, m), 1.93-1.86(4H, dd), 1.46-1.34(22H, m), 1.25(3H, m), 1.2-1.11(4H, m), 1.06(3H, m), 0.9(3H, t)

[0471]

[0472] 1 eq. of 3,6-di-tert-butyl-9-(5-((1r,4r)-4-ethylcyclohexyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole was added to 0.2 M THF in a 100 ml Schrenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature and stirred for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of dissolved methyl borate was slowly added. The process was carried out overnight at room temperature while slowly raising the temperature. After the reaction was completed, the product was obtained by vacuum drying after EA (Ethyl Acetate) extraction.

[0473]

[0474] In a 100 ml Schlenk flask, 1 eq. of 1,3-bis(2-bromo-4-fluorophenoxy)propane and 2.5 eq. of (3-(3,6-di-tert-butyl-9H-carba-zol-9-yl)-5-((1r,4r)-4-ethylcyclohexyl)-2-hydroxyphenyl)-boronic acid), 6 eq. of K2CO3, and 45 mol% of Pd(PPh3) were mixed with 0.2 M 1,4-dioxane and 0.5 M H2O. The reaction was carried out overnight at 95°C. During the reaction, if the amount of 9-(5-((1r,4r)-4-ethylcyclohexyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-yl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole was insufficient, additional amounts were added. After the reaction was complete, the mixture was cooled to room temperature, extracted with EA (Ethyl Acetate), and vacuum dried. The product was obtained by dissolving it in hexane and running it through a column.

[0475] 1H NMR (500 MHz, CDCl3): 8.19(4H, d), 7.4(4H, dd), 7.21(2H, d), 7.08(2H, d), 7.00(4H, d), 6.99(2H, dd), 6.54(2H, td), 6.06(2H, dd), 5.44(2H, s), 3.82(4H, t), 2.43(2H, t), 2.01(2H, m), 1.89-1.81(8H, dd), 1.46(36H, s), 1.45(8H, m), 1.25(10H, m), 1.14(2H, m), 0.99(4H, m), 0.87(6H, t)

[0476]

[0477] 1 eq of HfCl4 was added to a cold (-25°C) slurry state with 0.05 M toluene, and 4.1 eq. of 3.0 M MeMgBr was added. The mixture was stirred for 2 minutes, 1 eq. of ligand was added as a solid, and washed with toluene. The temperature was gradually increased, and the reaction mixture was stirred overnight at room temperature. The black mixture was concentrated under high vacuum, and hexane was added to the dried solid, followed by stirring for about 10 minutes. The solid was filtered and collected, and the colorless filtrate was concentrated under high vacuum to obtain a white product.

[0478] 1 H NMR (500 MHz, CDCl3): 8.3(2H, d), 8.06(2H, d), 7.45(2H, dd), 7.41(2H, dd), 7.35(2H, dd), 7.31(2H, d), 7.24(2H, d), 7.06(2H, d), 6.99(2H, dd), 6.28(2H, td), 4.56(2H, dd), 3.81(2H, q), 3.38(2H, q), 2.46(2H, td), 1.94-1.83(8H, dd), 1.53(18H, s), 1.36(18H, s), 1.45(8H, m), 1.25(10H, m), 1.14(2H, m), 0.99(4H, m), 0.87(6H, t), -1.78(6H, s)

[0479]

[0480] Preparation Example 12

[0481] [Chemical Formula 1C-3]

[0482]

[0483] The above compound was prepared as follows.

[0484]

[0485] 1 eq. of 4-(trans-4-butylcyclohexyl)phenol, 8 mol% of PPTS, and 2 eq. of DHP dissolved in 1 M dichloromethane were added to a 100 ml round flask. The reaction was carried out overnight at 35°C. After the reaction was complete, the mixture was cooled to room temperature, distilled water, and MC (Dimethyl Chloride) extraction were performed, followed by hexane slurrying to obtain the product.

[0486] 1 H NMR (500 MHz, CDCl3): 7.16(2H, d), 6.98(2H, d), 5.4(1H, t), 3.98(1H, m), 3.61(1H, m), 2.42(1H, t), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0487]

[0488] 1 eq. of 2-(4-((1s,4r)-4-butylcyclohexyl)phenoxy)tetrahydro-2H-pyran) was added to 0.3 M THF in a 100 ml Schrenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of I2 was slowly added. The reaction was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, a sat. sodium thiosulfate solution was added and stirred for 10 minutes. After EA extraction, the mixture was vacuum dried. The resulting solid was dissolved in hexane, filtered via a celite filter, and dried with hexane to obtain the product.

[0489] 1 H NMR (500 MHz, CDCl3): 7.60(1H, s), 7.11(2H, d), 6.99(2H, d), 5.48(1H, t), 3.90(1H, t), 3.60(1H, m), 2.37(1H, t), 2.15(1H, m), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0490]

[0491] 1 eq. of 2-(4-((1r,4r)-4-butylcyclohexyl)-2-iodophenoxy)tetrahydro-2H-pyran, 1.1 eq. of 3,6-di-tert-butylcarbazole, 20 mol% of CuI, 3.8 eq. of K3PO4, and 50 mol% of N-methylimidazole were added to a 100 ml flask in 0.2 M toluene. The reaction was carried out overnight at 115°C. After the reaction was complete, the mixture was cooled to room temperature, extracted with EA, and vacuum dried. The resulting solid was dissolved in hexane and processed through a column to obtain the product.

[0492] 1 H NMR (500 MHz, CDCl3): 8.11(2H, s), 7.41(2H, td), 7.32(1H, d), 7.24(2H, td), 7.18(1H, d), 7.11(1H, m), 5.2(1H, t), 3.71(1H, td), 3.48(1H, dt), 2.48(1H, tt), 1.95-1.85(4H, dd), 1.70(2H, m), 1.46(18H, s), 1.36(2H, m), 1.25(11H, m), 1.02(2H, m), 0.90(3H, t)

[0493]

[0494] 1 eq. of 3,6-di-tert-butyl-9-(5-((1r,4r)-4-butylcyclohexyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole was added to 0.2 M THF in a 100 ml Schrenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature and stirred for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of methyl borate was slowly added. The process was carried out overnight at room temperature while slowly raising the temperature. After the reaction was completed, EA was extracted and vacuum dried, the resulting solid was mixed with methanol slurry and filtered, and the obtained solid was dried to obtain the product.

[0495] 1 H NMR (500 MHz, CDCl3): 8.19(2H, s), 8.10(2H, d), 7.47(2H, d), 7.40(2H, dd), 7.13(2H, d), 2.61(1H, t), 2.03-1.91(4H, dd), 1.46-1.34(22H, m), 1.24(2H, m), 1.2-1.11(3H, m), 1.05(2H, m), 0.9(3H, t)

[0496]

[0497] 1,3-bis(2-bromo-4-fluorophenoxy)propane 1 eq., (3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-((1r,4r)-4-butylcyclohexyl)-2-hydroxyphenyl)-boronic acid 2.5 eq., K2CO3 6 eq., and Pd(PPh3)45 mol% were added to a 50 ml vial in 0.2 M 1,4-dioxane and 0.5 M H2O. The reaction was carried out overnight at 95°C. After the reaction was complete The product was cooled to room temperature, vacuum dried after EA extraction, dissolved in hexane, and processed through a column to obtain the product.

[0498] 1 H NMR (500 MHz, CDCl3): 8.19(4H, s), 7.40(4H, d), 7.2(2H, m), 7.04(6H,t), 7.00(2H, d), 6.55(2H, t), 6.07(2H, m), 5.43(2H, s), 3.82(4H, t), 2.43(2H, t), 2.02(2H, t), 1.92-1.81(8H, dd), 1.70(4H, m), 1.46(36H, s), 1.36(4H, m), 1.25-1.19(22H, m), 1.02(4H, m), 0.90(6H, t)

[0499]

[0500] 1 eq of HfCl4 was added to a cold (-25°C) slurry state with 0.05 M toluene, and 4.1 eq. of 3.0 M MeMgBr was added. The mixture was stirred for 2 minutes, 1 eq. of ligand was added as a solid, and washed with toluene. The temperature was gradually increased, and the reaction mixture was stirred overnight at room temperature. The black mixture was concentrated under high vacuum, and hexane was added to the dried solid, followed by stirring for about 10 minutes. The solid was filtered and collected, and the colorless filtrate was concentrated under high vacuum to obtain a white product.

[0501] 1 H NMR (500 MHz, CDCl3): 8.29(2H, d), 8.06(2H, d), 7.45(2H, dd), 7.41(2H, dd), 7.36(2H, dd), 7.33(2H, d), 7.236(2H, d), 7.05(2H, d), 6.99(2H, dd), 6.28(2H, m), 4.56(2H, dd), 3.80(2H, m), 3.38(2H, m), 2.45(2H, tt), 1.93-1.82(8H, dd), 1.70(4H, m), 1.46(36H, s), 1.36(4H, m), 1.25-1.19(22H, m), 1.02(4H, m), 0.90(6H, t), -1.75(6H, s)

[0502]

[0503] Preparation Example 13

[0504] [Chemical Formula 1C-4]

[0505]

[0506] The above compound was prepared as follows.

[0507]

[0508] 1 eq. of 4-(trans-4-butylcyclohexyl)phenol, 8 mol% of PPTS, and 2 eq. of DHP dissolved in 1 M dichloromethane were added to a 100 ml round flask. The reaction was carried out overnight at 35°C. After the reaction was complete, the mixture was cooled to room temperature, distilled water, and MC (Dimethyl Chloride) extraction were performed, followed by hexane slurrying to obtain the product.

[0509] 1 H NMR (500 MHz, CDCl3): 7.16(2H, d), 6.98(2H, d), 5.4(1H, t), 3.98(1H, m), 3.61(1H, m), 2.42(1H, t), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0510]

[0511] 1 eq. of 2-(4-((1s,4r)-4-butylcyclohexyl)phenoxy)tetrahydro-2H-pyran) was added to 0.3 M THF in a 100 ml Schrenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of I2 was slowly added. The reaction was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, a sat. sodium thiosulfate solution was added and stirred for 10 minutes. After EA extraction, the mixture was vacuum dried. The resulting solid was dissolved in hexane, filtered via a celite filter, and dried with hexane to obtain the product.

[0512] 1H NMR (500 MHz, CDCl3): 7.60(1H, s), 7.11(2H, d), 6.99(2H, d), 5.48(1H, t), 3.90(1H, t), 3.60(1H, m), 2.37(1H, t), 2.15(1H, m), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0513]

[0514] 1 eq. of 2-(4-((1r,4r)-4-butylcyclohexyl)-2-iodophenoxy)tetrahydro-2H-pyran, 1.1 eq. of carbazole, 20 mol% of CuI, 3.8 eq. of K3PO4, and 50 mol% of N-methylimidazole were added to a 100 ml flask in 0.2 M toluene. The reaction was carried out at 115°C for two nights. After the reaction was complete, the mixture was cooled to room temperature, extracted with EA (Ethyl Acetate), and vacuum dried. The resulting solid was dissolved in hexane and processed through a column to obtain the product.

[0515] 1 H NMR (500 MHz, CDCl3): 8.16(2H, d), 7.41(2H, m), 7.36(2H, m), 7.27(4H, m), 7.20(1H, d), 5.24(1H, m), 3.63(1H, m), 3.46(1H, m), 2.55(1H, t), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0516]

[0517] 1 eq. of 9-(5-((1s,4r)-4-butylcyclohexyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole was added to 0.2 M THF in a 100 ml Schrenk flask. At -10°C, 1.25 eq. of n-BuLi was added, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of dissolved methyl borate was slowly added. The process was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, the product was obtained by EA (Ethyl Acetate) extraction followed by vacuum drying.

[0518] 1 H NMR (500 MHz, CDCl3): 8.23(1H, d), 8.13(1H, d), 7.82(1H, d), 7.45(1H, t), 7.35(2H, m), 7.25(3H, m), 7.10(1H, d), 3.5(1H, s), 2.68(1H, t), 1.95-1.81(4H, d), 1.65(2H, m), 1.29(2H, m), 1.20(11H, m), 1.02(2H, m), 0.89(3H, t)

[0519]

[0520] 1,3-bis(2-bromo-4-fluorophenoxy)propane 1 eq., (5-((1s,4r)-4-butylcyclohexyl)-3-(9H-carbazol-9-yl)-2-hydroxyphenyl)boronic acid 2.5 eq., K2CO3 6 eq., and 45 mol% Pd(PPh3) were added to a 50 ml vial in 0.2 M 1,4-dioxane and 0.5 M H2O. The reaction was carried out at 95°C overnight. After the reaction was completed, the mixture was cooled to room temperature, vacuum dried after EA extraction, and the resulting solid was dissolved in hexane and passed through a column, and the resulting solution was vacuum dried. The dried solid was slurried with hexane to obtain the product.

[0521] 1 H NMR (500 MHz, CDCl3): 8.18(4H, d), 7.33(3H, t), 7.26(3H, t), 7.16(4H, d), 7.08(4H, d), 6.76(4H, d), 6.62(2H, t), 6.2(2H, m), 5.57(2H, s), 3.83(4H, t), 2.46(2H, t), 2.39(2H, t), 1.94-1.86(8H, dd), 1.41(10H, m), 1.34-1.04(12H, m), 1.04(6H, t)

[0522]

[0523] 1 eq of HfCl4 was added to a cold (-25°C) slurry state with 0.05 M toluene, and 4.1 eq. of 3.0 M MeMgBr was added. The mixture was stirred for 2 minutes, 1 eq. of ligand was added as a solid, and washed with toluene. The temperature was gradually increased, and the reaction mixture was stirred overnight at room temperature. The black mixture was concentrated under high vacuum, and toluene was added to the dried solid, followed by stirring for about 10 minutes. The solid was filtered and collected, and the colorless filtrate was concentrated under high vacuum to obtain a white product.

[0524] 1 H NMR (500 MHz, CDCl3): 8.37(2H, d), 8.16(2H, d), 7.49(6H, d), 7.34(6H, m), 7.17(4H, m), 7.09(2H, s), 6.99(2H, d), 6.37(2H, t), 4.41(2H, t), 3.81(2H, m), 3.41(2H, m), 2.48(2H, t), 1.96-1.93(8H, dd), 1.41(5H, m), 1.34(12H, m), 1.04(4H, m), 1.04(6H, t), -1.78(6H, s)

[0525]

[0526] Preparation Example 14

[0527] [Chemical Formula 1C-5]

[0528]

[0529] The above compound was prepared as follows.

[0530]

[0531] 1 eq. of 4-(trans-4-butylcyclohexyl)phenol, 8 mol% of PPTS, and 2 eq. of DHP dissolved in 1 M dichloromethane were added to a 100 ml round flask. The reaction was carried out overnight at 35°C. After the reaction was complete, the mixture was cooled to room temperature, distilled water, and MC (Dimethyl Chloride) extraction were performed, followed by hexane slurrying to obtain the product.

[0532] 1 H NMR (500 MHz, CDCl3): 7.16(2H, d), 6.98(2H, d), 5.4(1H, t), 3.98(1H, m), 3.61(1H, m), 2.42(1H, t), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0533]

[0534] 1 eq. of 2-(4-((1s,4r)-4-butylcyclohexyl)phenoxy)tetrahydro-2H-pyran) was added to 0.3 M THF in a 100 ml Schrenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of I2 was slowly added. The reaction was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, a sat. sodium thiosulfate solution was added and stirred for 10 minutes. After EA extraction, the mixture was vacuum dried. The resulting solid was dissolved in hexane, filtered via a celite filter, and dried with hexane to obtain the product.

[0535] 1H NMR (500 MHz, CDCl3): 7.60(1H, s), 7.11(2H, d), 6.99(2H, d), 5.48(1H, t), 3.90(1H, t), 3.60(1H, m), 2.37(1H, t), 2.15(1H, m), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0536]

[0537] 1 eq. of 2-(4-((1r,4r)-4-butylcyclohexyl)-2-iodophenoxy)tetrahydro-2H-pyran, 1.1 eq. of 3,6-di-tert-butylcarbazole, 20 mol% of CuI, 3.8 eq. of K3PO4, and 50 mol% of N-methylimidazole were added to a 100 ml flask in 0.2 M toluene. The reaction was carried out overnight at 115°C. After the reaction was complete, the mixture was cooled to room temperature, extracted with EA, and vacuum dried. The resulting solid was dissolved in hexane and processed through a column to obtain the product.

[0538] 1 H NMR (500 MHz, CDCl3): 8.11(2H, s), 7.41(2H, td), 7.32(1H, d), 7.24(2H, td), 7.18(1H, d), 7.11(1H, m), 5.2(1H, t), 3.71(1H, td), 3.48(1H, dt), 2.48(1H, tt), 1.95-1.85(4H, dd), 1.70(2H, m), 1.46(18H, s), 1.36(2H, m), 1.25(11H, m), 1.02(2H, m), 0.90(3H, t)

[0539]

[0540] 1 eq. of 3,6-di-tert-butyl-9-(5-((1r,4r)-4-butylcyclohexyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole was added to 0.2 M THF in a 100 ml Schrenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature and stirred for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of methyl borate was slowly added. The process was carried out overnight at room temperature while slowly raising the temperature. After the reaction was completed, EA was extracted and vacuum dried, the resulting solid was mixed with methanol slurry and filtered, and the obtained solid was dried to obtain the product.

[0541] 1 H NMR (500 MHz, CDCl3): 8.19(2H, s), 8.10(2H, d), 7.47(2H, d), 7.40(2H, dd), 7.13(2H, d), 2.61(1H, t), 2.03-1.91(4H, dd), 1.46-1.34(22H, m), 1.24(2H, m), 1.2-1.11(3H, m), 1.05(2H, m), 0.9(3H, t)

[0542]

[0543] 1,3-bis(2-bromo-4-fluorophenoxy)propane 1 eq., (3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-((1r,4r)-4-butylcyclohexyl)-2-hydroxyphenyl)-boronic acid 2.5 eq., K2CO3 6 eq., and Pd(PPh3)45 mol% were added to a 50 ml vial in 0.2 M 1,4-dioxane and 0.5 M H2O. The reaction was carried out overnight at 95°C. After the reaction was complete The product was cooled to room temperature, vacuum dried after EA extraction, dissolved in hexane, and processed through a column to obtain the product.

[0544] 1 H NMR (500 MHz, CDCl3): 8.19(4H, s), 7.40(4H, d), 7.2(2H, m), 7.04(6H,t), 7.00(2H, d), 6.55(2H, t), 6.07(2H, m), 5.43(2H, s), 3.82(4H, t), 2.43(2H, t), 2.02(2H, t), 1.92-1.81(8H, dd), 1.70(4H, m), 1.46(36H, s), 1.36(4H, m), 1.25-1.19(22H, m), 1.02(4H, m), 0.90(6H, t)

[0545]

[0546] 1 eq of ZrCl4 was added to a cold (-25°C) slurry state with 0.05 M toluene, and 4.1 eq. of 3.0 M MeMgBr was added. The mixture was stirred for 2 minutes, 1 eq. of ligand was added as a solid, and washed with toluene. The temperature was gradually increased, and the reaction mixture was stirred overnight at room temperature. The black mixture was concentrated under high vacuum, and hexane was added to the dried solid and stirred for about 10 minutes. The solid was filtered and collected, and the colorless filtrate was concentrated under high vacuum to obtain a white product.

[0547] 1 H NMR (500 MHz, CDCl3): 8.29(2H, d), 8.06(2H, d), 7.45(2H, dd), 7.41(2H, dd), 7.36(2H, dd), 7.33(2H, d), 7.236(2H, d), 7.05(2H, d), 6.99(2H, dd), 6.28(2H, m), 4.56(2H, dd), 3.80(2H, m), 3.38(2H, m), 2.45(2H, tt), 1.93-1.82(8H, dd), 1.70(4H, m), 1.46(36H, s), 1.36(4H, m), 1.25-1.19(22H, m), 1.02(4H, m), 0.90(6H, t), -1.75(6H, s)

[0548]

[0549] Preparation Example 15

[0550] [Chemical Formula 1C-6]

[0551]

[0552] The above compound was prepared as follows.

[0553]

[0554] 1 eq. of 4-(trans-4-butylcyclohexyl)phenol, 8 mol% of PPTS, and 2 eq. of DHP dissolved in 1 M dichloromethane were added to a 100 ml round flask. The reaction was carried out overnight at 35°C. After the reaction was complete, the mixture was cooled to room temperature, distilled water, and MC (Dimethyl Chloride) extraction were performed, followed by hexane slurrying to obtain the product.

[0555] 1 H NMR (500 MHz, CDCl3): 7.16(2H, d), 6.98(2H, d), 5.4(1H, t), 3.98(1H, m), 3.61(1H, m), 2.42(1H, t), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0556]

[0557] 1 eq. of 2-(4-((1s,4r)-4-butylcyclohexyl)phenoxy)tetrahydro-2H-pyran) was added to 0.3 M THF in a 100 ml Schrenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of I2 was slowly added. The reaction was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, a sat. sodium thiosulfate solution was added and stirred for 10 minutes. After EA extraction, the mixture was vacuum dried. The resulting solid was dissolved in hexane, filtered via a celite filter, and dried with hexane to obtain the product.

[0558] 1H NMR (500 MHz, CDCl3): 7.60(1H, s), 7.11(2H, d), 6.99(2H, d), 5.48(1H, t), 3.90(1H, t), 3.60(1H, m), 2.37(1H, t), 2.15(1H, m), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0559]

[0560] 1 eq. of 2-(4-((1r,4r)-4-butylcyclohexyl)-2-iodophenoxy)tetrahydro-2H-pyran, 1.1 eq. of carbazole, 20 mol% of CuI, 3.8 eq. of K3PO4, and 50 mol% of N-methylimidazole were added to a 100 ml flask in 0.2 M toluene. The reaction was carried out at 115°C for two nights. After the reaction was complete, the mixture was cooled to room temperature, extracted with EA (Ethyl Acetate), and vacuum dried. The resulting solid was dissolved in hexane and processed through a column to obtain the product.

[0561] 1 H NMR (500 MHz, CDCl3): 8.16(2H, d), 7.41(2H, m), 7.36(2H, m), 7.27(4H, m), 7.20(1H, d), 5.24(1H, m), 3.63(1H, m), 3.46(1H, m), 2.55(1H, t), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0562]

[0563] 1 eq. of 9-(5-((1s,4r)-4-butylcyclohexyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole was added to 0.2 M THF in a 100 ml Schrenk flask. At -10°C, 1.25 eq. of n-BuLi was added, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of dissolved methyl borate was slowly added. The process was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, the product was obtained by EA (Ethyl Acetate) extraction followed by vacuum drying.

[0564] 1 H NMR (500 MHz, CDCl3): 8.23(1H, d), 8.13(1H, d), 7.82(1H, d), 7.45(1H, t), 7.35(2H, m), 7.25(3H, m), 7.10(1H, d), 3.5(1H, s), 2.68(1H, t), 1.95-1.81(4H, d), 1.65(2H, m), 1.29(2H, m), 1.20(11H, m), 1.02(2H, m), 0.89(3H, t)

[0565]

[0566] 1,3-bis(2-bromo-4-fluorophenoxy)propane 1 eq., (5-((1s,4r)-4-butylcyclohexyl)-3-(9H-carbazol-9-yl)-2-hydroxyphenyl)boronic acid 2.5 eq., K2CO3 6 eq., and 45 mol% Pd(PPh3) were added to a 50 ml vial in 0.2 M 1,4-dioxane and 0.5 M H2O. The reaction was carried out at 95°C overnight. After the reaction was completed, the mixture was cooled to room temperature, vacuum dried after EA extraction, and the resulting solid was dissolved in hexane and passed through a column, and the resulting solution was vacuum dried. The dried solid was slurried with hexane to obtain the product.

[0567] 1 H NMR (500 MHz, CDCl3): 8.18(4H, d), 7.33(3H, t), 7.26(3H, t), 7.16(4H, d), 7.08(4H, d), 6.76(4H, d), 6.62(2H, t), 6.2(2H, m), 5.57(2H, s), 3.83(4H, t), 2.46(2H, t), 2.39(2H, t), 1.94-1.86(8H, dd), 1.41(10H, m), 1.34-1.04(12H, m), 1.04(6H, t)

[0568]

[0569] 1 eq of ZrCl4 was added to a cold (-25°C) slurry state with 0.05 M toluene, and 4.1 eq. of 3.0 M MeMgBr was added. The mixture was stirred for 2 minutes, 1 eq. of ligand was added as a solid, and washed with toluene. The temperature was gradually increased, and the reaction mixture was stirred overnight at room temperature. The black mixture was concentrated under high vacuum, and hexane was added to the dried solid and stirred for about 10 minutes. The solid was filtered and collected, and the colorless filtrate was concentrated under high vacuum to obtain a white product.

[0570] 1 H NMR (500 MHz, CDCl3): 8.37(2H, d), 8.16(2H, d), 7.49(6H, d), 7.34(6H, m), 7.17(4H, m), 7.09(2H, s), 6.99(2H, d), 6.37(2H, t), 4.41(2H, t), 3.81(2H, m), 3.41(2H, m), 2.48(2H, t), 1.96-1.93(8H, dd), 1.41(5H, m), 1.34(12H, m), 1.04(4H, m), 1.04(6H, t), -1.78(6H, s)

[0571]

[0572] Comparative Manufacturing Example 1

[0573]

[0574] It was prepared by manufacturing according to the method disclosed in patent document US 2017-0267796 A1 and KR 10-2100142 B1.

[0575]

[0576] Comparative Manufacturing Example 2

[0577]

[0578] It was prepared by manufacturing according to the method disclosed in patent document US 2017-0267796 A1.

[0579]

[0580] Comparative Manufacturing Example 3

[0581]

[0582] It was prepared by manufacturing according to the method disclosed in Patent Document KR 10-2019-0123345 A.

[0583]

[0584] Comparative Manufacturing Example 4

[0585]

[0586] It was prepared by manufacturing according to the method disclosed in patent document US 2017-0267796 A1 and KR 10-2100142 B1.

[0587]

[0588] Comparative Manufacturing Example 5

[0589]

[0590] It was prepared by manufacturing according to the method disclosed in Patent Document WO 2012-027448 A1.

[0591]

[0592] Comparative Manufacturing Example 6

[0593]

[0594] It was prepared by manufacturing by referring to the method disclosed in patent document US 2017-0267796 A1.

[0595]

[0596] Polymerization of Ethylene / Alpha-Olefin Copolymers

[0597] Example 1

[0598] n-hexane solvent (800–900 mL) and 1-octene (200–300 mL) were added to a 2L autoclave reactor (ZIPPERCLAVE-Autoclave Engineers, Parker Hannifin), and the reactor temperature was preheated to 150°C. At the same time, the reactor pressure was pre-filled with ethylene (35 bar). 0.8–1.0 μmol of the catalyst from Preparation Example 1, 10 equivalents of the catalyst, dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (AB), and 5 mmol of Tibal as a scavenger were sequentially introduced into the reactor under high argon pressure, and 400–500 mL of hydrogen (H2) was added to carry out the copolymerization reaction for 8 minutes. Next, the remaining ethylene gas was removed, and the polymer solution was added to an excess amount of ethanol to induce precipitation. The precipitated polymer was washed with ethanol 2 to 3 times, and then dried in a vacuum oven at 90°C for more than 12 hours.

[0599]

[0600] Examples 2 to 15 and Comparative Examples 1 to 6

[0601] An ethylene / alpha-olefin copolymer was prepared in the same manner as in Example 1, except that the type of catalyst was changed according to Table 1 below.

[0602]

[0603] Classification Catalyst Type Example 1 Preparation Example 1 Example 2 Preparation Example 2 Example 3 Preparation Example 3 Example 4 Preparation Example 4 Example 5 Preparation Example 5 Example 6 Preparation Example 6 Example 7 Preparation Example 7 Example 8 Preparation Example 8 Example 9 Preparation Example 9 Example 10 Preparation Example 10 Example 11 Preparation Example 11 Example 12 Preparation Example 12 Example 13 Preparation Example 13 Example 14 Preparation Example 14 Example 15 Preparation Example 15 Comparative Example 1 Comparative Preparation Example 1 Comparative Example 2 Comparative Preparation Example 2 Comparative Example 3 Comparative Preparation Example 3 Comparative Example 4 Comparative Preparation Example 4 Comparative Example 5 Comparative Preparation Example 5 Comparative Example 6 Comparative Preparation Example 6

[0604]

[0605]

[0606] <Analysis of Manufacturing Results for Ethylene / Alpha-Olefin Copolymers>

[0607] Experimental Example 1

[0608] The physical properties of each copolymer prepared in the above examples and comparative examples were compared and analyzed and are shown in Table 2. The measurement conditions and methods are as follows.

[0609]

[0610] (1) Catalytic activity (kgPE / mmol)

[0611] The obtained polymer was vacuum-dried to measure the yield, and the value was calculated by dividing the polymer (kg) by the catalyst (mmol).

[0612]

[0613] (2) Density

[0614] According to ASTM D-792, a sheet with a thickness of 3 mm and a radius of 2 cm was prepared using a 180°C press mold and cooled at 10°C / min and measured on a Mettler balance.

[0615]

[0616] (3) Melt Index (MI) and Melt Flow Ratio (MFR)

[0617] MI according to ASTM D-1238 (condition E, 190℃, 2.16 kg load) 2.16 was measured, and MI was measured according to ASTM D-1238 (condition E, 190℃, 10 kg load). 10 The ratio of the measured melt indices (MI) was measured. 10 / MI 2.16 The melt flow index was calculated by )

[0618]

[0619] (4) Weight-average molecular weight (Mw, g / mol) and molecular weight distribution (MWD)

[0620] Number average molecular weight (Mn) and weight average molecular weight (Mw) were measured using gel permeation chromatography (GPC), and the molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.

[0621] - Column: PL Olexis

[0622] - Solvent: TCB (Trichlorobenzene)

[0623] - Flow rate: 1.0 ml / min

[0624] - Sample concentration: 1.0 mg / ml

[0625] - Injection volume: 200 µl

[0626] - Column temperature: 160℃

[0627] - Detector: Agilent High Temperature RI detector

[0628] - Standard: Polystyrene (corrected by a cubic function)

[0629]

[0630] Catalytic Activity (kgPE / mmol) Density (g / mL) MI 2.16 (g / 10min)MI 10(g / 10min)MFRRMWD Example 1850.8610.3955.63114.3 - Example 21250.8530.5408.37015.5 - Example 3830.8570.475.1310.9 - Example 42260.87720.9165.47.9 - Example 52260.87915.6116.67.5 - Example 6850.8630.5797.41712.81 - Example 71010.8550.4906.80113.88 - Example 81030.8631.39120.0714.43 - Example 9950.8600.1742.25012.9-Example 101230.8530.314.2113.52.47Example 111240.8570.363.910.82.60Example 121280.8550.324.1212.92.53Example 131300.8570.394.6211.82.58Example 142310.87712.8130.210.22.42Example 152450.87913.1135.710.42.50Comparative Example 1730.8560.323.1529.92.09Comparative Example 2710.8610.393.569.132.12 Comparative Example 3470.8650.2843.4612.2 Comparative Example 4860.87910.880.127.40 Comparative Example 5900.8660.523.6717.06 Comparative Example 6530.8682.5517.316.79

[0631]

[0632] Referring to Table 2 above, it can be confirmed that when a transition metal compound according to the present invention is used as a catalyst, as in the embodiments of the present invention, olefin copolymers can be produced with excellent yield due to high catalytic activity. In addition, it can be confirmed that the processability of the produced olefin copolymers, namely the copolymers of Examples 1 to 15 of the present invention, has improved MFRR to an equivalent superior level compared to Comparative Examples 1 to 6.

[0633] Specifically, the transition metal compound according to the present invention has a structure in which a silyl-substituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted cycloalkyl group is bonded to a phenolate, and it can be confirmed that the catalytic activity is further enhanced compared to the transition metal compound having a structure in which an unsubstituted alkyl group or a silyl-substituted alkyl group is bonded to a phenolate, which is the catalyst used in the comparative example.

Claims

Transition metal compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, M is Hf or Zr, and L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and Z1 and Z2 are each independently a silyl-substituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, and R1 to R 24 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms. In claim 1, Z1 and Z2 are transition metal compounds, each having a structure independently represented by any one of the following chemical formulas a to c: [Chemical formula a] [Chemical formula b] [Chemical formula c] In the above chemical formulas a to c, R 25 to R 29 Each is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms, and R 25 to R 29 One or more of them are alkylsilyl groups having 1 to 20 carbon atoms, and R 30 to R 36 Each is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms, and R 37 to R 41 Each is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. In claim 1, The transition metal compound represented by the above chemical formula 1 is a transition metal compound represented by the following chemical formula 1A: [Chemical Formula 1A] In the above chemical formula 1A, M is Hf or Zr, and L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R1 to R 24 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and R 42 to R 45 Each is independently hydrogen or an alkylsilyl group having 1 to 20 carbon atoms, and R 42 and R 43 One or more of and R 44 and R 45 One or more of them are alkylsilyl groups having 1 to 20 carbon atoms. In claim 3, A transition metal compound represented by the above chemical formula 1 is a transition metal compound represented by any one of the following chemical formulas 1A-1 to 1A-5: [Chemical Formula 1A-1] [Chemical Formula 1A-2] [Chemical Formula 1A-3] [Chemical Formula 1A-4] [Chemical Formula 1A-5] . In claim 1, The transition metal compound represented by the above chemical formula 1 is a transition metal compound represented by the following chemical formula 1B: [Chemical Formula 1B] In the above chemical formula 1B, M is Hf or Zr, and L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R1 to R 24 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and R 46 and R 47 Each is independently hydrogen or an alkyl group having 1 to 20 carbon atoms. In claim 5, A transition metal compound represented by the above chemical formula 1 is a transition metal compound represented by any one of the following chemical formulas 1B-1 to 1B-4: [Chemical Formula 1B-1] [Chemical Formula 1B-2] [Chemical Formula 1B-3] [Chemical Formula 1B-4] . In claim 1, The transition metal compound represented by the above chemical formula 1 is a transition metal compound represented by the following chemical formula 1C: [Chemical Formula 1C] In the above chemical formula 1C, M is Hf or Zr, and L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R1 to R 24 Each is independently hydrogen, halogen, cyano group, amine group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and R 48 and R 49 Each is independently hydrogen or an alkyl group having 1 to 20 carbon atoms. In claim 7, A transition metal compound represented by the above chemical formula 1 is a transition metal compound represented by any one of the following chemical formulas 1C-1 to 1C-6: [Chemical Formula 1C-1] [Chemical Formula 1C-2] [Chemical Formula 1C-3] [Chemical Formula 1C-4] [Chemical Formula 1C-5] [Chemical Formula 1C-6] . A catalyst composition comprising the transition metal compound and co-catalyst of claim 1. In claim 9, A catalyst composition comprising one or more selected from the group consisting of compounds represented by the following chemical formulas 2 to 5, wherein the above co-catalyst: [Chemical Formula 2] -[Al(R 50 )-O] a - In the above chemical formula 2, R 50 Each is 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 greater than or equal to 2, and [Chemical Formula 3] E(R 51 ) 3 In the above chemical formula 3, E is aluminum or boron, and R 51 Each is 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, and [Chemical Formula 4] [Le-H] + [G(A)4] - [Chemical Formula 5] [And] + [G(A)4 - In the above chemical formulas 4 and 5, Le is a neutral or cationic Lewis acid, and [Le-H] + is Mount Brønsted, and G is a Group 13 element, and A 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 an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition of claim 9 or 10. In claim 11, A method for manufacturing an olefin polymer, wherein the above olefin polymer is an ethylene / alpha-olefin copolymer. In claim 12, A method for preparing an olefin polymer, wherein the alpha-olefin comprises one or more selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene, norbornene, norvonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

Images