Olefin-based polymer

Abstract

An olefin-based polymer according to an embodiment of the present invention may have (a) a melt index (MI, 190 °C, 2.16 kg load conditions) of 0.1-30 g / 10 min and (b) a density of 0.855-0.880 g / cc, and satisfy (c) expression 1. [Expression 1] F(30) ≥ 2462.2 x density -2094, wherein F(30) is the total amount of calories required to melt the crystalline phase at 30 °C or higher, as determined by successive self-nucleation and annealing (SSA) analysis using a differential scanning calorimeter.

Description

Olefin polymers

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority based on Korean patent application 10-2024-0152304 filed on October 31, 2024, and all contents disclosed in the literature of said Korean patent applications are incorporated herein as part of this specification.

[0003]

[0004] [Technology Field]

[0005] The present invention relates to an olefin-based polymer, and specifically to an olefin-based polymer having excellent blocking characteristics through improved crystallinity.

[0006] Polyolefins are widely used for extrusion, blow molding, and injection molding products due to their excellent moldability, heat resistance, mechanical properties, hygienic quality, water vapor permeability, and appearance characteristics of the molded articles. However, polyolefins, particularly polyethylene, lack polar groups within their molecules, resulting in low compatibility with polar resins such as nylon and poor adhesion to polar resins and metals. Consequently, it has been difficult to blend polyolefins with polar resins or metals, or to laminate them with these materials. Furthermore, polyolefin molded articles suffer from low surface hydrophilicity and antistatic properties.

[0007] To solve these problems and increase affinity for polar materials, a method of grafting a polar group-containing monomer onto a polyolefin via radical polymerization has been widely used. However, this method had a problem of low miscibility due to poor viscosity balance between the graft polymer and the polar resin caused by intramolecular crosslinking and molecular chain cleavage of the polyolefin during the graft reaction. In addition, there was a problem of poor appearance characteristics of the molded product due to gel components generated by intramolecular crosslinking or foreign substances generated by molecular chain cleavage.

[0008] In addition, as a method for producing olefin polymers such as ethylene homopolymers, ethylene / α-olefin copolymers, propylene homopolymers, or propylene / α-olefin copolymers, a method of copolymerizing polar monomers under a metal catalyst, such as a titanium catalyst or a vanadium catalyst, has been used. However, when copolymerizing polar monomers using such metal catalysts, there is a problem that the molecular weight distribution or composition distribution is wide and the polymerization activity is low.

[0009] Another method is known to be polymerization in the presence of a metallocene catalyst consisting of a transition metal compound such as zirconocene dichloride and an organoaluminum oxy compound (aluminoxane). When a metallocene catalyst is used, high molecular weight olefin polymers are obtained with high activity, and the resulting olefin polymers have a narrow molecular weight distribution and a narrow compositional distribution.

[0010] In addition, a method for producing polyolefins containing polar groups using a metallocene catalyst is also known, which uses a metallocene compound having a ligand of a non-crosslinked cyclopentadienyl group, a crosslinked or non-crosslinked bis indenyl group, or an ethylene-crosslinked unsubstituted indenyl / fluorenyl group. However, these methods have the disadvantage of very low polymerization activity. For this reason, a method of protecting polar groups with a protecting group is being implemented, but when a protecting group is introduced, the process becomes complicated because this protecting group must be removed again after the reaction.

[0011] Ansa-metallocene compounds are organometallic compounds containing two ligands connected to each other by a bridge group, wherein rotation of the ligands is prevented by the bridge group and the activity and structure of the metal center are determined.

[0012] Such anssa-metallocene compounds are used as catalysts in the production of olefinic homopolymers or copolymers. In particular, it is known that anssa-metallocene compounds containing cyclopentadienyl-fluorenyl ligands can produce high molecular weight polyethylene, thereby enabling control of the microstructure of polypropylene.

[0013] In addition, anssa-metallocene compounds containing indenyl ligands are known to be capable of producing polyolefins with excellent activity and improved stereoregularity.

[0014] As such, various studies are being conducted on ansah-metallocene compounds that possess higher activity and can control the microstructure of olefinic polymers, but the extent of such research is still insufficient.

[0015] [Prior Art Literature]

[0016] [Patent Literature]

[0017] (Patent Document 0001) Korean Registered Patent No. 10-288272

[0018] The present invention aims to provide an olefin-based polymer having improved crystallinity, excellent blocking characteristics, and a melt flow rate ratio (MFRR).

[0019] (1) The present invention provides an olefin-based polymer that satisfies the requirements of (a) to (c) below: (a) a melt index (MI, 190°C 2.16 kg load condition) of 0.1 g / 10 min or more and 30 g / 10 min or less, (b) a density of 0.855 g / cc or more and 0.880 g / cc or less, and (c) satisfies the following mathematical formula 1.

[0020] [Mathematical Formula 1]

[0021] F(30) ≥ 2462.2 x density - 2094

[0022] Here, the above F (30) is the total amount of heat required to melt the crystalline phase at 30°C or higher, as confirmed by differential scanning calorimetry (SSA) analysis.

[0023] (2) The present invention provides an olefin-based polymer that additionally satisfies the requirement that F (30) is 10 or more and 80 or less when measured by the differential scanning calorimetry (SSA) method in (1).

[0024] (3) The present invention provides an olefinic polymer that further satisfies the requirement of (1) or (2) above, wherein (e) the weight-average molecular weight (Mw) is 10,000 g / mol or more and 800,000 g / mol or less.

[0025] (4) The present invention provides an olefinic polymer that additionally satisfies the requirement of (f) having a molecular weight density (MWD) of 1.5 or more and 2.4 or less in any one of (1) to (3).

[0026] (5) The present invention provides an olefin polymer in any one of (1) to (4), wherein the olefin polymer has a melt flow rate ratio (MFRR) of 6 or more and 8 or less.

[0027] (6) The present invention provides an olefin polymer in any one of (1) to (5), wherein the olefin polymer is a copolymer of ethylene and an alpha-olefin comonomer having 3 to 12 carbon atoms.

[0028] (7) The present invention provides an olefin-based polymer in any one of (1) to (6), wherein the alpha-olefin comonomer comprises one or more mixtures 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-itocene, norbornene, norvonadiene, ethylidenenovodene, phenylnovodene, vinylnovodene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

[0029] (8) The present invention provides an olefin polymer in any one of (1) to (7), wherein the olefin polymer is a copolymer of ethylene and 1-butene.

[0030] The olefin-based polymer according to the present invention has improved crystallinity and exhibits excellent blocking characteristics and melt flow rate ratio (MFRR).

[0031] Figure 1 is a graph showing the results of differential scanning calorimetry (SSA) measurements for the olefin-based polymers of Example 4 and Comparative Example 6.

[0032] FIG. 2 is a graph showing the F (30) values ​​according to density for the olefin-based polymers of Examples 1 to 5 and Comparative Examples 1, 4 to 7.

[0033] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0034] Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0035] 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.

[0036] 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.

[0037] As used herein, the term “aryl” refers to an optionally substituted benzene ring unless otherwise noted, 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.

[0038] In the present invention, “alkylaryl” means an aryl group substituted by the alkyl group.

[0039] In the present invention, “arylalkyl” means an alkyl group substituted by the aryl group.

[0040] 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.

[0041] In the present invention, “alkylene group” may refer to divalent aliphatic saturated hydrocarbons such as methylene, ethylene, propylene, and butylene.

[0042] 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.

[0043] 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., deuterium, halogen 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, the site where the substituent 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.

[0044] In this specification, the term "polymer" means a polymer compound produced by the polymerization of the same or different types of monomers. The general term "polymer" includes the terms "homopolymer," "copolymer," "terpolymer," as well as "copolymer." Furthermore, the term "copolymer" means a polymer produced by the polymerization of two or more different types of monomers. The general term "copolymer" includes the term "copolymer" (commonly used to refer to a polymer produced from two different monomers) as well as the term "terpolymer" (commonly used to refer to a polymer produced from three different types of monomers). This includes a polymer produced by the polymerization of four or more types of monomers.

[0045]

[0046] An olefin-based polymer according to one embodiment of the present invention satisfies the requirements of (a) to (c) below.

[0047] (a) The melt index (MI, 190℃ 2.16 kg load condition) is 0.1 g / 10 min or more and 30 g / 10 min or less, (b) the density is 0.855 g / cc or more and 0.880 g / cc or less, and (c) the following mathematical formula 1 is satisfied.

[0048] [Mathematical Formula 1]

[0049] F(30) ≥ 2462.2 x density - 2094

[0050] Here, the above F (30) is the total amount of heat required to melt the crystalline phase at 30°C or higher, as confirmed by differential scanning calorimetry (SSA) analysis.

[0051]

[0052] An olefin-based polymer according to one embodiment of the present invention has low density and improved crystallinity compared to conventional olefin-based polymers, so that when having the same level of density and melt index (Melt Index, MI, 190°C, 2.16 kg load condition), it can exhibit a superior melt flow rate ratio (MFRR) and blocking characteristics.

[0053]

[0054] The density of the olefin-based polymer according to one embodiment of the present invention may be 0.855 g / cc or more and 0.880 g / cc or less, and as a specific example, it may be 0.856 g / cc or more, 0.857 g / cc or more, 0.858 g / cc or more, 0.859 g / cc or more, or 0.860 g / cc or more, and may also be 0.879 g / cc or less, 0.878 g / cc or less, 0.877 g / cc or less, 0.876 g / cc or less, or 0.875 g / cc or less.

[0055] Typically, the density of olefinic polymers is influenced by the type and content of monomers used during polymerization and the degree of polymerization, while in the case of copolymers, it is significantly influenced by the content of comonomers. The olefinic polymer of the present invention is polymerized using a catalyst composition containing a transition metal compound having a characteristic structure, which enables the introduction of a large amount of comonomers; thus, the olefinic polymer of the present invention can have a low density within the range described above.

[0056]

[0057] The melt index (MI) of an olefin-based polymer according to one embodiment of the present invention can be controlled by adjusting the amount of comonomer of the catalyst used in the process of polymerizing the olefin-based polymer, and can affect the mechanical properties, impact strength, and moldability of the olefin-based polymer.

[0058] According to one embodiment of the present invention, the melt index is measured according to ASTM D1238 at 190°C and a load of 2.16 kg under low density conditions of 0.855 g / cc to 0.880 g / cc, and is 0.1 g / 10 min or more and 30 g / 10 min or less. Specifically, it may be 0.2 g / 10 min or more, 0.4 g / 10 min or more, 0.6 g / 10 min or more, 0.8 g / 10 min or more, or 1.0 g / 10 min or more. Additionally, it may be 25 g / 10 min or less, 20 g / 10 min or less, 15 g / 10 min or less, 10 g / 10 min or less, or 6 g / 10 min or less.

[0059]

[0060] An olefinic polymer according to one embodiment of the present invention can satisfy the following mathematical formula 1 in relation to density and F (30), which is the total amount of heat required to melt the crystalline phase at 30°C or higher as confirmed by differential scanning calorimetry (SSA) analysis.

[0061] [Mathematical Formula 1]

[0062] F(30) ≥ 2462.2 x density - 2094

[0063] Generally, the method for obtaining crystal information using differential scanning calorimetry (DSC) involves obtaining a standard melting temperature (Tm) peak in the second cycle after the first cycle, which involves heating at a constant rate to a temperature approximately 30°C higher than the melting temperature (Tm) and then cooling at a constant rate to a temperature approximately 30°C lower than the glass transition temperature (Tg). The above differential scanning calorimetry precision measurement (SSA) method is a method for obtaining more precise crystal information by using differential scanning calorimetry (DSC) to undergo a process of heating and cooling to a temperature just before the melting temperature (Tm) peak after the first cycle, and then repeatedly performing a process of heating and cooling to a temperature approximately 10°C lower (Eur. Polym. J. 2015, 65, 132).

[0064] An olefin-based polymer according to one embodiment of the present invention is polymerized using a catalyst composition containing a transition metal compound having a characteristic structure, and the crystallinity is improved, which is manifested as an increase in the distribution of high crystallinity. When F (30) satisfies the above mathematical formula 1 during differential scanning calorimetry (SSA) measurement, the total amount of heat required to melt the crystalline phase at 30°C or higher is high, so the crystallinity is increased and the distribution of crystallinity is increased, and the increase in high crystallinity improves the heat resistance of the olefin-based polymer and can improve blocking characteristics.

[0065]

[0066] An olefin-based polymer according to one embodiment of the present invention may further satisfy the requirement that (d) F (30) is 10 or more and 80 or less when measured by differential scanning calorimetry (SSA). Specifically, F (30) may be 15 or more, 20 or more, 25 or more, or 30 or more, and may also be 75 or less, 70 or less, 65 or less, or 60 or less. When the above range is satisfied, the heat resistance of the olefin-based polymer may be improved and the blocking characteristics may be improved.

[0067]

[0068] An olefin-based polymer according to one embodiment of the present invention may further satisfy the requirement that (e) the weight-average molecular weight (Mw) is 10,000 g / mol or more and 800,000 g / mol or less, and specifically, the weight-average molecular weight (Mw) may be 20,000 g / mol or more, 30,000 g / mol or more, 40,000 g / mol or more, 50,000 g / mol or more, or 60,000 g / mol or more. In the present invention, the weight-average molecular weight (Mw) is the polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).

[0069]

[0070] An olefinic polymer according to one embodiment of the present invention may additionally satisfy the requirement that the molecular weight distribution (MWD) (f), which is the ratio (Mw / Mn) of the weight-average molecular weight (Mw) and the number-average molecular weight (Mn), is 1.5 or higher and 2.2 or lower. Specifically, the molecular weight distribution (MWD) may be 1.52 or higher, 1.54 or higher, 1.56 or higher, 1.58 or higher, or 1.6 or higher, and may also be 2.35 or lower, 2.3 or lower, 2.25 or lower, or 2.2 or lower.

[0071]

[0072] An olefin copolymer according to one embodiment of the present invention can exhibit excellent blocking characteristics and a melt flow rate ratio by satisfying the above-described requirements.

[0073] An olefin-based copolymer according to one embodiment of the present invention may have a melt flow rate ratio (MFRR) of 6 or more and 8 or less. As a specific example, the melt flow rate ratio may be 6.1 or more, 6.2 or more, 6.3 or more, 6.4 or more, or 6.5 or more, and may also be 7.9 or less, 7.8 or less, 7.7 or less, 7.6 or less, or 7.5 or less. The melt flow rate ratio is MI 10 (Melting Index under a load of 10 kg and 190°C) is MI 2.16 It refers to the ratio divided by (melt index under a load of 2.16 kg and 190°C), and as the number of long chains (LCB) of the polymer decreases, the above MFRR may show a low value and the mechanical properties of the polymer may be improved.

[0074] According to one embodiment of the present invention, the olefin polymer may be a homopolymer selected from olefin monomers, specifically alpha-olefin monomers, cyclic olefin monomers, diene olefin monomers, triene olefin monomers, and styrene monomers, or a copolymer of two or more types. More specifically, the olefin polymer may be a copolymer of ethylene and an alpha-olefin having 3 to 12 carbon atoms or a copolymer of ethylene and an alpha-olefin having 3 to 10 carbon atoms.

[0075] According to one embodiment of the present invention, the alpha-olefin comonomer may comprise any one or more mixtures 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, ethylidenenovodene, phenylnovodene, vinylnovodene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene, and specific examples include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, It may include any one or more mixtures selected from the group consisting of 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicocene.

[0076] More specifically, the olefin copolymer according to one embodiment of the present invention may be a copolymer of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, or ethylene and 1-octene, and even more specifically, the olefin copolymer according to one example of the present invention may be a copolymer of ethylene and 1-butene.

[0077] According to one embodiment of the present invention, when the olefin-based polymer is a copolymer of ethylene and an alpha-olefin, the amount of the alpha-olefin may be 90 weight% or less, more specifically 70 weight% or less, more specifically 5 weight% to 60 weight%, and even more specifically 20 weight% to 50 weight% with respect to the total weight of the copolymer. When the alpha-olefin is included within the above range, it is easy to realize the aforementioned physical properties.

[0078] An olefin-based polymer according to one embodiment of the present invention having the physical properties and compositional characteristics described above can be prepared through a continuous solution polymerization reaction in which hydrogen gas is introduced and olefin monomers are polymerized in a single reactor in the presence of a metallocene catalyst composition containing one or more transition metal compounds. Accordingly, in the olefin-based polymer according to one embodiment of the present invention, a block is not formed in which two or more repeating units derived from any one of the monomers constituting the polymer are connected linearly. That is, the olefin-based polymer according to the present invention does not include a block copolymer and may be selected from the group consisting of a random copolymer, an alternative copolymer, and a graft copolymer, and more specifically, may be a random copolymer.

[0079]

[0080] Specifically, the olefin copolymer of the present invention can be obtained by a manufacturing method comprising the step of polymerizing an olefin monomer while introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of the following chemical formula 1.

[0081] According to one embodiment of the present invention, the amount of hydrogen gas input may be 25 Sccm or more and 120 Sccm or less. Specifically, the amount of hydrogen gas input may be 26 Sccm or more, 28 Sccm or more, 30 Sccm or more, 32 Sccm or more, 34 Sccm or more, 36 Sccm or more, 38 Sccm or more, or 40 Sccm or more, and may also be 118 Sccm or less, 116 Sccm or less, 114 Sccm or less, 112 Sccm or less, 110 Sccm or less, 108 Sccm or less, 106 Sccm or less, 104 Sccm or less, 102 Sccm or less, or 100 Sccm or less. If the amount of hydrogen gas introduced during the step of polymerizing the olefin monomer satisfies the above range, an olefin-based polymer satisfying the requirements of (a) to (c) of the present invention can be produced.

[0082]

[0083] However, in the preparation of an olefin-based polymer according to one embodiment of the present invention, the range of the structure of the transition metal compound of Formula 1 below is not limited to a specific disclosed form, and it should be understood that it includes all modifications, equivalents, and substitutions that fall within the spirit and technical scope of the present invention.

[0084] [Chemical Formula 1]

[0085]

[0086] In the above chemical formula 1,

[0087] M is Hf or Zr, and

[0088] 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

[0089] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0090] Cy1 and Cy2 are each independently a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted amine group, and the substituents of Cy1 and Cy2 are selected from the group consisting of 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, and an alkoxy group having 1 to 10 carbon atoms.

[0091] R1 to R 24 Each is independently hydrogen, halogen, cyano group, amino 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.

[0092] The transition metal compound of the present invention has a structure in which a substituted / unsubstituted cycloalkyl group, a substituted / unsubstituted aryl group, or a substituted / unsubstituted amine group is bonded to a phenolate, and can produce a polymer having high catalytic activity compared to conventional compounds, excellent blocking characteristics, and a melt flow rate ratio.

[0093]

[0094] In the above chemical formula 1, M can be Hf or Zr, and as a specific example, it can be Hf.

[0095] 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.

[0096] 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.

[0097] In the above chemical formula 1, Cy1 and Cy2 are each independently a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted amine group.

[0098] When Cy1 and Cy2 are substituted, the substituents of Cy1 and Cy2 are selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, and specifically, they may be alkyl groups having 1 to 15 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or alkyl groups having 1 to 6 carbon atoms, and for example, may be methyl groups, ethyl groups, propyl groups, or butyl groups.

[0099]

[0100] More specifically, Cy1 and Cy2 may each independently have a structure represented by the following chemical formula A.

[0101] [Chemical Formula A]

[0102]

[0103] In the above chemical formula A,

[0104] R 25 to R 29 Each is independently hydrogen or an alkyl group having 1 to 20 carbon atoms.

[0105] More specifically, R 25 , R 26 , R 28 and R 29 is hydrogen, and R 27It 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, a methyl group, an ethyl group, a propyl group, or a butyl group.

[0106]

[0107] In addition, Cy1 and Cy2 may each independently have a structure represented by the following chemical formula B.

[0108] [Chemical Formula B]

[0109]

[0110] In the above chemical formula B,

[0111] Ar may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and specific examples may refer to a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted anthracenyl group. When the above Ar is substituted, the substituent of Ar is selected from the group consisting of 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, and an alkoxy group having 1 to 10 carbon atoms, and specifically, it may be 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, it may be a methyl group, an ethyl group, a propyl group, or a butyl group.

[0112]

[0113] In addition, Cy1 and Cy2 may each independently have a structure represented by the following chemical formula C.

[0114] [Chemical Formula C]

[0115]

[0116] In the above chemical formula C,

[0117] R 30 to R 31 Each is independently hydrogen or an alkyl group having 1 to 20 carbon atoms.

[0118] More specifically, R 30 and R 31 Each of the following may independently be hydrogen, 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 may be, for example, a methyl group, an ethyl group, a propyl group, or a butyl group. In the above formula 1, R1 to R 24 Each is independently hydrogen, a halogen, a cyano group, an amino 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 group, 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.

[0119]

[0120] The transition metal compound represented by the above chemical formula 1 may be represented by the following chemical formula 1A.

[0121] [Chemical Formula 1A]

[0122]

[0123] In the above chemical formula 1A,

[0124] M is Hf or Zr, and

[0125] 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

[0126] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0127] R1 to R 24 Each is independently hydrogen, halogen, cyano group, amino 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

[0128] R 32 and R 33 Each is independently hydrogen or an alkyl group having 1 to 20 carbon atoms.

[0129]

[0130] Specifically, in the above chemical 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 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 30 and R 31 Each can independently be an alkyl group having 1 to 20 carbon atoms.

[0131] Additionally, 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, 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 group, and R 30 and R 31 Each can independently be an alkyl group having 1 to 20 carbon atoms.

[0132] For example, the transition metal compound represented by the above chemical formula 1A may be one selected from the group comprising the following chemical formulas 1-1 to 1-6.

[0133] [Chemical Formula 1-1]

[0134]

[0135] [Chemical Formula 1-2]

[0136]

[0137] [Chemical Formula 1-3]

[0138]

[0139] [Chemical Formula 1-4]

[0140]

[0141] [Chemical Formula 1-5]

[0142]

[0143] [Chemical Formula 1-6]

[0144]

[0145]

[0146] The transition metal compound represented by the above chemical formula 1 may be represented by the following chemical formula 1B.

[0147] [Chemical Formula 1B]

[0148]

[0149] In the above chemical formula 1B,

[0150] M is Hf or Zr, and

[0151] 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

[0152] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0153] R1 to R 23 Each is independently hydrogen, halogen, cyano group, amino 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.

[0154]

[0155] Specifically, in the above 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 to R8 may each independently be hydrogen or a halogen, and more specifically, at least one of R1 to R8 may be a halogen. In addition, R9 to R 23 Each can independently be hydrogen or an alkyl group having 1 to 20 carbon atoms, and more specifically, R9 to R 23 R 17 to R 23 It can be hydrogen.

[0156] For example, the transition metal compound represented by the above chemical formula 1B may be one selected from the group comprising the following chemical formulas 1-7 to 1-10.

[0157] [Chemical Formula 1-7]

[0158]

[0159] [Chemical Formula 1-8]

[0160]

[0161] [Chemical Formula 1-9]

[0162]

[0163] [Chemical Formula 1-10]

[0164]

[0165]

[0166] The transition metal compound represented by the above chemical formula 1 may be represented by the following chemical formula 1C.

[0167] [Chemical Formula 1C]

[0168]

[0169] In the above chemical formula 1C,

[0170] M is Hf or Zr, and

[0171] L is a substituted or unsubstituted 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

[0172] Y is a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0173] X1 and X2 are each independently hydrogen, a halogen, an alkyl group having 1 to 4 carbon atoms, or are connected to each other to form an aromatic ring, and

[0174] R1 to R 12Each is independently hydrogen, halogen, cyano group, amino 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.

[0175] The transition metal compound of the present invention has a structure in which a carbazole group substituted or unsubstituted in the bisphenolate structure within the compound is bonded to the ortho position and an amine group is bonded to the para position, and when the compound is used as a catalyst, an olefin polymer having a higher melting temperature (Tm) and improved mechanical properties compared to conventional compounds can be produced.

[0176]

[0177] In the above chemical formula 1C, M can be Hf or Zr, and as a specific example, it can be Hf.

[0178] In the above chemical formula 1C, 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.

[0179] In the above chemical formula 1C, Y is a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms. Specifically, it may be a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms, and more specifically, it may be an unsubstituted alkylene group having 1 to 40 carbon atoms.

[0180] In the above chemical formula 1C, X1 and X2 are each independently hydrogen, a halogen, an alkyl group having 1 to 4 carbon atoms, or connected to each other to form an aromatic ring. Specifically, X1 may be a halogen, and more specifically, F. Additionally, X2 may be hydrogen or an alkyl group having 1 to 4 carbon atoms, and more specifically, hydrogen.

[0181] In the above chemical formula 1C, R1 to R 12 Each is independently hydrogen, halogen, cyano group, amino 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, R1 to R4 may each independently be an alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 7 to 40 carbon atoms, more specifically may be an alkyl group having 1 to 20 carbon atoms, and even more specifically may be an alkyl group having 4 to 20 carbon atoms.

[0182] According to one embodiment of the present invention, when R1 to R4 are long-chain alkyl groups having 4 or more carbon atoms, the solubility for hexane, which was rarely observed in conventional catalyst compounds, can be significantly increased. In addition, the long chain and the amine group at the para position play a role in raising the melting temperature, thereby improving the mechanical strength of the olefin polymer produced using the said compound as a catalyst. Specifically, R5 to R 12 Each may independently be hydrogen or an alkyl group having 1 to 20 carbon atoms. According to one embodiment of the present invention, the transition metal compound represented by Formula 1C may be one selected from the group comprising Formulas 1-11 to 1-14 below.

[0183] [Chemical Formula 1-11]

[0184]

[0185] [Chemical Formula 1-12]

[0186]

[0187] [Chemical Formula 1-13]

[0188]

[0189] [Chemical Formula 1-14]

[0190]

[0191]

[0192] According to one embodiment of the present invention, the transition metal compound of Formula 1 may be used as a catalyst for a polymerization reaction in the form of a catalyst composition comprising, in addition, a compound represented by Formulas 2 to 5 below as a co-catalyst.

[0193] [Chemical Formula 2]

[0194] -[Al(R 38 )-O] a -

[0195] In the above chemical formula 2,

[0196] R 38 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

[0197] a is an integer greater than or equal to 2, and

[0198] [Chemical Formula 3]

[0199] E(R 39 ) 3

[0200] In the above chemical formula 3,

[0201] E is aluminum or boron, and

[0202] R 39 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

[0203] [Chemical Formula 4]

[0204] [Le-H] + [G(A)4] -

[0205] [Chemical Formula 5]

[0206] [Le] + [G(A)4] -

[0207] In the above chemical formulas 4 and 5,

[0208] Le is a neutral or cationic Lewis acid, and

[0209] [Le-H] + is Mount Brønsted, and

[0210] G is a Group 13 element, and

[0211] 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.

[0212]

[0213] 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.

[0214] 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.

[0215] 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.

[0216]

[0217] According to one embodiment of the present invention, the co-catalyst may be a compound represented by the chemical formula 4 or 5, and specifically, may be dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate.

[0218] 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.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] According to one embodiment of the present invention, the input temperature of the raw material (including monomer, catalyst composition, and solvent) input for polymerizing the olefin-based polymer may have a temperature range of 10°C or higher and 30°C or lower. Specifically, the raw material input for polymerizing the olefin-based polymer may be 11°C or higher, 12°C or higher, 13°C or higher, 14°C or higher, or 15°C or higher, and may also be 29°C or lower, 28°C or lower, 27°C or lower, 26°C or lower, or 25°C or lower.

[0224] According to one embodiment of the present invention, the temperature inside the reactor for polymerizing the olefin-based polymer may have a temperature range of 160°C or higher and 200°C or lower. Specifically, the temperature inside the reactor for polymerizing the olefin-based polymer may be introduced at a temperature of 162°C or higher, 164°C or higher, 166°C or higher, 168°C or higher, or 170°C or higher, and may also be introduced at a temperature of 196°C or lower, 192°C or lower, 188°C or lower, 184°C or lower, or 180°C or lower.

[0225] According to one embodiment of the present invention, the temperature of the outer jacket of the reactor for polymerizing the olefin-based polymer may have a temperature range of 150°C or higher and 170°C or lower. Specifically, the temperature of the outer jacket of the reactor for polymerizing the olefin-based polymer may be 152°C or higher, 154°C or higher, 156°C or higher, 158°C or higher, or 160°C or higher, and may also be 169°C or lower, 168°C or lower, 167°C or lower, 166°C or lower, or 165°C or lower.

[0226] According to one embodiment of the present invention, the polymerization of the olefin-based 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 pressure conditions of about 20 to 100 bar, specifically about 20 to 50 bar, or about 20 to 40 bar.

[0227]

[0228] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0229]

[0230] Transition metal compound A

[0231] [Chemical Formula 1-1]

[0232]

[0233] The above compound was prepared as follows.

[0234]

[0235] 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.

[0236] 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)

[0237]

[0238] 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.

[0239] 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)

[0240]

[0241] 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.

[0242] 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)

[0243]

[0244] 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.

[0245] 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)

[0246]

[0247]

[0248] 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.

[0249] 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)

[0250]

[0251] 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.

[0252] 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)

[0253]

[0254] Transition metal compound B

[0255] [Chemical Formula 1-7]

[0256]

[0257] The above compound was prepared as follows.

[0258]

[0259] 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 are added to the flask. Subsequently, 42 mL of Toluene, 42 mL of EtOH, and 21 mL of H2O are added in sequence, and the mixture is stirred under reflux for 16 hours. After the reaction is complete, water is added at room temperature and stirred, followed by extraction with ethyl acetate. The extracted organic layer is dehydrated using MgSO4, and the organic solvent is removed under reduced pressure. Silica chromatography was performed (Hexane : EA = 20: 1), and vacuum drying was performed to obtain 9.39 g (29.49 mmol, 94%) of a white solid (compound 1-1).

[0260] 1 H 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)

[0261]

[0262] Under an argon atmosphere, 19.39 g (29.49 mmol) of Compound 1-2 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 15.3 g (38.25 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 (Compound 1-2) 13.11 g (quant.) was obtained by vacuum distillation.

[0263] 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).

[0264]

[0265] Prepare a flask connected to a reflux apparatus. Under an argon atmosphere, compound 1-2 6.34 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 (Compound 1-3) was obtained.

[0266] 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).

[0267]

[0268] In an argon atmosphere, 1-35.75 g (9.65 mmol) of the compound 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 reduced 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 then vacuum dried to obtain 6.43 g (12.80 mmol, 92%) of a white solid (compound 1-4).

[0269] 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).

[0270]

[0271] Under an argon atmosphere, 43.00 g (4.16 mmol) of compound 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. After removing moisture from the organic layer using MgSO4, a pale oil was obtained by vacuum distillation. Silica chorionic chromatography (hexane:ethyl acetate = 50:1) was performed, and 1.5 g (1.17 mmol, 65%) of a white solid (compound 1-5) was obtained.

[0272] 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).

[0273] 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 Compound 1 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, 0.3 g (0.2 mmol, 91%) of a white solid (transition metal compound B) was obtained.

[0274] 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).

[0275]

[0276]

[0277] Transition metal compound C

[0278] [Chemical Formula 1-2]

[0279]

[0280] The above compound was prepared as follows.

[0281]

[0282] 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.

[0283] 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)

[0284]

[0285] 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.

[0286] 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)

[0287]

[0288] 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.

[0289] 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)

[0290]

[0291] 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 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 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.

[0292] 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)

[0293]

[0294] 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.

[0295] 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)

[0296]

[0297] 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.

[0298] 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)

[0299]

[0300] Transition metal compound D

[0301] [Chemical Formula 1-12]

[0302]

[0303] (a) Preparation of ligand compound (2-bromo-4-(didodecylamino)phenol)

[0304] 12 g (63.82 mmol) of 4-amino-2-bromophenol reagent, 31.813 g (127.64 mmol) of 1-bromododecane, 43.35 mL (255.28 mmol) of DiPEA, and 160 mL of DMF were weighed into a 250 mL two-neck flask, and the mixture was refluxed overnight at 150 °C. After confirming the NMR, the mixture was worked up with water, EA, and magnesium sulfate, and the organic layer was concentrated to obtain a red liquid product of 18 g with a yield of 53.8%.

[0305] 1 H-NMR (in CDCl3500 MHz): 6.88 (d, 1H), 6.74 (d, 1H), 6.57 (d, 1H), 4.88 (s, 1H), 3.14 (t, 4H), 1.50-1.52 (m, 4H), 1.32-1.27 (m, 40H), 0.88 (s, 6H)

[0306] (b) Preparation of ligand compound (3-bromo-N,N-didodecyl-4(methoxymethoxy)aniline)

[0307] 5 g (9.53 mmol) of the product obtained above was weighed into a 100 mL one-neck container, and 19.06 mL of DMF was added. 457.4 mg (11.406 mmol) of NaH was added gradually at RT and reacted for 30 minutes, after which 860.5 μl (11.436 mmol) of chloromethylmethylether was added and reacted overnight. After confirming the NMR, workup was performed with water and EA / magnesium sulfate. 5.3 g of red liquid was obtained with a yield of 97.8%.

[0308] 1H-NMR (in CDCl3 500 MHz): 6.99(d, 1H), 6.79(d, 1H), 6.51(d,1H), 5.10(s, 2H), 3.54(s, 3H), 3.17(t, 4H), 1.54-1.51(m, 4H), 1.30-1.26(m, 40H), 0.88(t, 6H)

[0309] (c) Preparation of ligand compound (3-(9H-carbazol-9-yl)-N,N-didodecyl-4-(methoxymethoxy)aniline)

[0310] 4.66 mg (8.2 mmol) of the product obtained above, 1.25 mg (7.45 mmol), 1.42 g (7.45 mmol) of CuI, 1.78 mL (22.35 mmol) of methylimidazole, and 6 g (28.31 mmol) of K3PO4 were weighed into a 250 mL two-neck container, 37.25 mL of toluene was added, and the mixture was refluxed overnight at 120°C. Workup was performed with water and EA to obtain 4.81 g of a white solid product with a yield of 94%.

[0311] 1 H-NMR (in CDCl3500 MHz): 8.13(d, 2H), 7.40(t, 2H), 7.29-7.24(m, 4H), 6.72(d, 1H), 6.69(d, 1H), 4.71(s, 2H), 3.21(t, 4H), 3.02(s, 3H), 1.60-1.56(m, 4H), 1.30-1.25(m, 40H), 0.89(t, 6H)

[0312] (d) Preparation of ligand compound (3-(9H-carbazol-9-yl)-N,N-didodecyl-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline)

[0313] 4.81 g (7.34 mmol) of the product obtained above and 9.6 mL of THF were weighed into a 100 mL one-neck container, followed by the dropwise addition of 5.87 mL (14.67 mmol) of 2.5 M n-BuLi in hexane and an overnight reaction at RT. 3.74 mL (18.35 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise and an overnight reaction was performed at RT; after workup with EA and water, a yellow liquid product was obtained.

[0314] 1 H-NMR (in CDCl3500 MHz): 8.10(d, 2H), 7.39(t, 2H), 7.31(d, 2H), 7.23(t, 2H), 7.19(s, 1H), 6.73(d, 1H), 4.59(s, 2H), 3.23(t, 4H), 2.25(s, 3H), 1.56(s, 4H), 1.36(s, 12H), 1.25(m, 12H), 1.88(t, 6H)

[0315] (e) Preparation of ligand compound (6',6'''-(propane-1,3-diylbis(oxy))bis(3-(9H-carbazol-9-yl)-5-(didodecylamino)-3'-fluoro-[1,1'-biphenyl]-2-ol)

[0316] In a 50 mL vial, 1.34 g (1.72 mmol) of the product obtained above, 299.2 mg (0.68 mmol) of 1,3-bis(2-bromo-4-fluorophenoxy)propane, 6.9 mL of dioxane, and 758.5 ​​mg of K3PO4 in 11 mL of H2O were quantified and heated to 100 °C. 40 mg of Tetrakix (triphenylphosphine) palladium was added and heated overnight. After working up with water and EA, 20 mL of MeOH + 5 mL of concentrated HCl was added, and the mixture was heated to 70 °C for 4 hours to obtain a yellow liquid.

[0317] 1 H-NMR (in CDCl3500 MHz): 8.17(d, 4H), 7.33(t, 4H), 7.26(t, 4H), 7.19(d, 4H), 7.04(d,2H), 6.70(s, 2H), 6.61(m, 2H), 6.57(s, 2H), 6.17-6.15(m, 2H), 5.19(s, 1H), 3.87(t, 4H), 3.18(t, 8H), 2.05-2.02(m, 2H), 1.55(m, 8H), 1.23(s, 80H), 0.89(t, 12H)

[0318] (f) ((3-(9H-carbazol-9-yl)-5-(didodecylamino)-5'-fluoro-2'-hydroxy-[1,1'-biphenyl]-2-yl)oxy)((3-(9H -carbazol-9-yl)-5-(didodecylamino)-5'-fluoro-2'-propoxy-[1,1'-biphenyl]-2-yl)oxy)dimethylhafnium manufacturing

[0319] After quantifying HfCl4 in a 10 mL vial, toluene was added, and MMB was added dropwise. After reacting for 5 minutes, 204 mg (0.138 mmol) of the ligand obtained above was dissolved in toluene and added dropwise to the reaction solution. After reacting overnight at RT, the toluene was completely evaporated, and the mixture was extracted with hexane to obtain 216 mg of a bright yellow solid product with a yield of 92.7%.

[0320] 1H-NMR (in CDCl3500 MHz): 8.32(d, 2H), 8.11(d, 2H), 7.52(d, 2H), 7.40-7.32(m, 8H), 7.18(t, 2H), 6.97(d, 2H), 6.92(d, 2H), 6.56(s, 2H), 6.32(t, 2H), 4.40-4.37(m, 2H), 3.90-3.86(m, 2H), 3.46-3.43(m, 2H), 3.28(t, 8H), 1.59-1.54(m, 8H), 1.22(s, 80H), 0.88(t, 12H), -1.83(s, 6H)

[0321]

[0322] Transition metal compound E

[0323]

[0324] It was prepared by manufacturing according to the method disclosed in US Patent 2017-0267796 A1 and KR 10-2100142 B1.

[0325]

[0326] Transition metal compound F

[0327]

[0328] 2 g of 9H-carbazole-4-ol, 1 eq of 1-iodohexane, and 2 eq of K2CO3 were added to 0.3 M acetone and reluxed overnight at 80°C. The reaction was then terminated by adding an additional 0.5 eq of 1-iodohexane. After the reaction was complete, all acetone was vacuum-dried, and extraction with EA was performed. Slurrying with MeOH yielded 2 g of 4-(hexyloxy)-9H-carbazole with a 68% yield.

[0329] 1H NMR (500 MHz, DMSO): 11.23(1H,s), 8.13(1H,d), 7.45(1H, d), 7.32(1H, t), 7.28(1H, t), 7.13(1H, t), 7.06(1H, d), 6.67(1H, d), 4.19(2H, t), 3.33(12H, s), 1.9(2H, m), 1.57(2H, m), 1.37(2H, m), 0.9(3H, t)

[0330] Subsequently, regarding the 4-(hexyloxy)-9H-carbazole obtained by the above-described manufacturing method, a catalyst was synthesized and prepared according to the manufacturing method disclosed in US Patent 2004 / 0014950 A1.

[0331]

[0332] Transition metal compound G

[0333]

[0334] It was prepared by manufacturing according to the method disclosed in Patent KR 10-2021-038235 A.

[0335]

[0336] Transition metal compound H

[0337]

[0338] It was prepared by manufacturing according to the method disclosed in Patent KR 10-2021-038235 A.

[0339]

[0340] Transition metal compound I

[0341]

[0342] It was prepared by manufacturing according to the method disclosed in Patent KR 10-2023-078560 A.

[0343]

[0344] Example 1

[0345] After filling a 1.5 L continuous process reactor with hexane solvent (7 kg / h) and 1-butene (0.68 kg / h), a triisobutylaluminum compound (TiBAl, 200 μmol / min), a transition metal compound obtained in Preparation Example 1 (0.20 μmol / min), and an N,N-Dimethylanilinium teterakis(pentafluorophenyl)borate co-catalyst (1.50 μmol / min) were simultaneously introduced into the reactor at an input temperature of 18.5°C. Subsequently, hydrogen gas (49 Sccm) and ethylene (0.68 kg / h) were introduced into the reactor, and a copolymerization reaction was carried out in a continuous process at a pressure of 70 bar, maintaining the temperature of the outer jacket of the reactor at 160°C and the temperature inside the reactor at 178.5°C for at least 10 minutes to obtain an olefinic polymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0346]

[0347] Examples 2 to 5, Comparative Examples 1 to 7

[0348] A copolymerization reaction was carried out in the same manner as in Example 1, and an olefinic polymer was obtained by varying the amount of transition metal compound, the amount of catalyst and co-catalyst, the internal temperature of the reactor (RT), the temperature of the jacket on the outer wall of the reactor (JT), the amount of hydrogen input, the type and amount of comonomer, and the input temperature of the raw material (FT), respectively, as shown in Tables 1 and 2 below.

[0349]

[0350] Example 1 2 3 4 5 Catalyst Type ABCDC Input Amount (μmol / min) 0.20 0.11 0.14 0.10 0.10 Catalyst Input Amount (μmol / min) 1.50 1.38 0.42 0.25 0.25 TiBAl Input Amount (μmol / min) 200 100 60 60 60 Ethylene Input Amount (kg / h) 0.68 0.87 0.87 0.87 0.87 Hexane Input Amount (kg / h) 77 77 1-Butene Input Amount (kg / h) 0.68 0.60 0.60 0.82 0.82 Hydrogen Input Amount (Sccm) 495757100100FT(°C) 18.519.018.920.521.2JT(°C) 160160160160160RT(°C) 178.5175.1174.2170.8170.0

[0351] Comparative Example 1 234567 Catalyst Type EFGH, IHHJ Input Amount (μmol / min) 0.10 0.10 0.11 0.66 0.40 0.60 0.45 Co-catalyst Input Amount (μmol / min) 1.38 0.22 0.66 1.98 1.20 1.80 1.60 TiBAl Input Amount (μmol / min) 100 50 70 50 60 60 50 Ethylene Input Amount (kg / h) 0.87 0.87 0.87 0.87 0.87 0.87 0.87 Hexane Input Amount (kg / h) 77 75 55 71-Butene Input Amount (kg / h) 0.71 1.00 0.85 -0.95 0.85 1.081-Octene Input Amount (kg / h) ---1.92 ---Hydrogen Input Amount (Sccm) 147 15 100 --- 12 FT (°C) 39.4 59.5 63.1 24.2 30.5 30.4 25.6 JT (°C) 160 150 170 140 160 160 160 RT (°C) 177.1 159.4 176.4 146.0 169.5 170.0 160.5 * Comparative Example 4 Catalyst: H:I = 1:2.5 (Molar Ratio)

[0352] Experimental Example 1

[0353] The physical properties of each olefin-based polymer prepared in the above examples and comparative examples were compared and analyzed and are shown in Table 3 below. The measurement conditions and methods are as follows.

[0354]

[0355] * Density: 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.

[0356]

[0357] * Melt Index (MI) and Melt Flow Rate Ratio (MFRR): MI according to ASTM D-1238 10 MI was measured by (Condition E, 190℃, 10Kg load) and MI2 (Condition E, 190℃, 2.16Kg load). 10 / MI 2.16 It was calculated as.

[0358]

[0359] * Weight-average molecular weight (Mw, g / mol) and molecular weight distribution (MWD): 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.

[0360] - Column: PL Olexis

[0361] - Solvent: TCB (Trichlorobenzene)

[0362] - Flow rate: 1.0 ml / min

[0363] - Sample concentration: 1.0 mg / ml

[0364] - Injection volume: 200 µl

[0365] - Column temperature: 160℃

[0366] - Detector: Agilent High Temperature RI detector

[0367] - Standard: Polystyrene (corrected by a cubic function)

[0368]

[0369] * F(30): Obtained using the SSA (Successive self-nucleation / annealing) measurement method with a Differential Scanning Calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments.

[0370] Specifically, in the first cycle, the temperature was increased to 150°C, maintained at that temperature for 1 minute, and then cooled to -100°C. In the second cycle, the temperature was increased to 120°C, maintained at that temperature for 30 minutes, and then cooled to -100°C. In the third cycle, the temperature was increased to 110°C, maintained at that temperature for 30 minutes, and then cooled to -100°C. This process of raising the temperature in 10°C increments and cooling to -100°C was repeated down to -60°C to allow crystallization to occur in each temperature range. During this process, the rate of temperature increase and decrease were each controlled to 10°C / min. In the final cycle, the heat capacity was determined while increasing the temperature to 150°C.

[0371] The temperature-heat capacity curve obtained in this way was integrated for each section to fractionate the heat capacity of each section relative to the total heat capacity. In addition, the melting enthal ratio (ΔH) at 30°C or higher during SSA measurement was summed, and the total sum was defined as F (30).

[0372] Figure 1 shows a graph representing the results of differential scanning calorimetry (SSA) measurements for the olefin-based polymers of Example 4 and Comparative Example 6.

[0373]

[0374] * De-Blocking Force: 50g of each copolymer prepared in the above examples and comparative examples was placed in a 9*8 size zipper bag to prepare a sample. The sample was placed in a constant temperature and humidity chamber (Espec PSL-2J) and a weight was placed on top. Subsequently, the temperature was raised to 35°C over 30 minutes, maintained at 35°C for 7 hours, lowered to -5°C over 30 minutes, maintained at -5°C for 5 hours, raised to 0°C over 30 minutes, and maintained at 0°C for 5 hours to induce blocking of the sample. Afterward, pressure was applied to the center of the thinnest surface of the blocked sample using a tensile compressor (IMADA MV-1000N2) to measure the De-Blocking Force.

[0375]

[0376] Density (g / cc) Melt Index (g / 10 min) GPCSSA De-Blocking Force (N) MFRRM w (g / mol) MWDF (30) Example 1 0.863 44.376,626 2.08 33.73 5.77.81 Example 20.864 95.972,864 2.18 38.52 5.98 Example 30.8667 4.26 77,597 2.17 42.419.37.7 Example 40.8659 4.95 73,575 2.13 39.42 27.16 Example 50.86565.44 73,556 2.13 9.12 6.27.1 Comparative Example 10.862085.6273,6422.1729.735.4 Unmeasurable Comparative Example 20.86785.3666,4942.237.142.710.47 Comparative Example 30.86214.5275,2662.1724.651.38.84 Comparative Example 40.85900.99111,1632.3917.340.29.15 Comparative Example 50.86211.298,0882.122643.99.18 Comparative Example 60.86545.0470,5372.3334.255.98.89 Comparative Example 70.871033.843,4742.1447.637.55.64

[0377] Experimental Example 2

[0378] The F (30) and density values ​​of each olefin-based polymer prepared in Examples 1 to 5 and Comparative Examples 1, 4 to 7 are shown as a graph in FIG. 2, and the degree of increase in F (30) value with increasing density is shown as a trend line.

[0379] The following mathematical formula 1 represents the relationship between the trend line and the F (30) value, and Table 4 shows whether each olefin-based polymer prepared in Examples 1 to 5 and Comparative Examples 1 to 7 satisfies the following mathematical formula 1.

[0380] [Mathematical Formula 1]

[0381] F(30) ≥ 2462.2 x density - 2094

[0382]

[0383] SSA2462.2 x Density - 2094 Satisfaction of Equation 1 F(30) Example 1 33.731.86348 ○ Example 2 38.535.55678 ○ Example 3 42.439.98874 ○ Example 4 39.438.01898 ○ Example 5 39.137.28032 ○ Comparative Example 1 29.728.4164 ○ Comparative Example 2 37.142.6971X Comparative Example 3 24.628.6626X Comparative Example 4 17.321.0298X Comparative Example 5 2628.66262X Comparative Example 6 34.236.78788X Comparative Example 7 47.650.5762X

[0384] Referring to Tables 3 and 4 above, it can be seen that the olefinic polymers of Examples 1 to 5 have relatively lower melt index values ​​compared to Comparative Examples 1 to 7, which have an equivalent level of density, and that the F (30) value and density satisfy Equation 1. Thus, it can be seen that the olefinic polymers of Examples 1 to 5 have an increased distribution of high crystallinity compared to the olefinic polymers of Comparative Examples 1 to 7, which have an equivalent level of density.

[0385] As such, it can be confirmed that the olefin polymers of Examples 1 to 5, which have a high crystallinity distribution compared to the olefin polymers of Comparative Examples 1 to 7, have an excellent melt flow rate ratio and, at the same time, exhibit excellent blocking characteristics with improved heat resistance.

Claims

Olefin-based polymers satisfying the requirements of (a) to (c) below: (a) The melt index (MI, 190℃ 2.16 kg load condition) is 0.1 g / 10 min or more and 30 g / 10 min or less, and (b) Density of 0.855 g / cc or more and 0.880 g / cc or less, and (c) Satisfies the following mathematical formula 1. [Mathematical Formula 1] F(30) ≥ 2462.2 x density - 2094 Here, the above F (30) is the total amount of heat required to melt the crystalline phase at 30°C or higher, as confirmed by differential scanning calorimetry (SSA) analysis. In paragraph 1, (d) An olefinic polymer that additionally satisfies the requirement that F (30) is 10 or more and 80 or less when measured by the differential scanning calorimetry (SSA) method. In paragraph 1, (e) An olefinic polymer that additionally satisfies the requirement of having a weight-average molecular weight (Mw) of 10,000 g / mol or more and 800,000 g / mol or less. In paragraph 1, (f) An olefinic polymer that additionally satisfies the requirement that the molecular weight density (MWD) is 1.5 or greater and 2.4 or less. In paragraph 1, The above olefin-based polymer is an olefin-based polymer having a melt flow rate ratio (MFRR) of 6 or more and 8 or less. In paragraph 1, The above olefin polymer is an olefin polymer that is a copolymer of ethylene and an alpha-olefin comonomer having 3 to 12 carbon atoms. In paragraph 6, The above alpha-olefin comonomer is an olefin-based polymer comprising any one or more mixtures 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, and 1-eicocene. In paragraph 6, The above olefinic polymer is an olefinic polymer that is a copolymer of ethylene and 1-butene.

Images