RU2783262C2 - Metal-ligand complex, ethylene-base catalytic composition for polymerization, including specified complex, and method for production of ethylene-based polymer, using specified complex - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a metal-ligand complex selected from compounds represented by following chemical formulas:

(WC03 precatalyst),

(WC04 precatalyst).

An ethylene-based catalytic composition for polymerization and a method for the production of ethylene-based polymer, using the specified complex, are also proposed.

EFFECT: proposed complexes provide polymerization even at a high temperature, do not reduce catalyst activity, and allow for production of copolymers with high molecular weight.

6 cl, 2 tbl, 15 ex

Description

[Technical field]

The present invention relates to a metal ligand complex, an ethylene-based polymerization catalyst composition comprising said complex, and a process for producing an ethylene-based polymer using said complex.

[Prior Art]

Usually, in the preparation of an ethylene-α-olefin copolymer or an ethylene-olefin-diene copolymer, a so-called Ziegler-Natta catalyst is used, which includes a titanium or vanadium compound as the main catalytic component and an aluminum alkyl compound as a cocatalyst component.

US Pat. Nos. 3,594,330 and 3,676,415 disclose an improved Ziegler-Natta catalyst. The Ziegler-Natta catalyst system has a high activity for polymerization of ethylene, but due to the heterogeneous catalytic active site, there is a disadvantage of a wide molecular weight distribution of the polymer usually produced and, in particular, a non-uniform distribution of the composition of the ethylene-α-olefin copolymer.

Subsequently, various studies have been carried out on a metallocene catalyst system consisting of a metallocene compound of a group 4 transition metal such as zirconium and hafnium and methylalumoxane as a cocatalyst, which is a homogeneous catalyst with one type of catalytic active site and can produce polyethylene having narrow molecular weight distribution and uniform composition distribution compared to a conventional Ziegler-Natta catalyst.

For example, European Patent Publication Nos. 320762 and 372632 or Japanese Patent Laid-Open Publication Nos. (Sho) 63-092621, (Hei) 02-84405 or (Hei) 03-2347 disclose that a metallocene compound is activated by a methylalumoxane cocatalyst in Cp ₂ TiCl ₂ , Cp ₂ ZrCl ₂ , Cp ₂ ZrMeCl, Cp ₂ ZrMe ₂ , ethylene(IndH ₄ ) ₂ ZrCl ₂ etc. with polymerization of ethylene with high activity, which leads to the production of polyethylene with a molecular weight distribution (Mw/Mn) in the range of 1.5-2.0.

However, it is difficult to obtain a high molecular weight polymer with this catalyst system.

That is, it is known that when this catalyst system is applied to a solution polymerization process carried out at a high temperature, the polymerization activity rapidly decreases and the β-dehydrogenation reaction is predominant, which makes the catalyst system unsuitable for producing a high molecular weight polymer.

Meanwhile, various studies have been carried out to improve the solubility of the catalyst in the aliphatic hydrocarbon so that the catalytic efficiency in the commercial process is maximized and the transportation volume of the catalyst is reduced, which greatly increases the cost of storage and transportation in such a process. In addition, since the concentration of the catalyst is limited, deterioration of the catalyst due to the natural presence of impurities in the solvent becomes an even greater problem.

Accordingly, there is currently a need for a catalyst and a catalyst precursor having improved performance, which continues to be required in the chemical industry.

[Prior art document]

[Patent document]

(Patent Document 1) US Patent No. 3594330

(Patent Document 2) US Patent No. 3676415

(Patent Document 3) European Patent Publication No. 320762.

(Patent Document 4) European Patent Publication No. 372632.

(Patent Document 5) Japanese Patent Laid-Open No. (Sho) 63-092621

(Patent Document 6) Japanese Patent Laid-Open Publication No. (Hei) 02-84405

(Patent Document 7) Japanese Patent Laid-Open Publication No. (Hei) 03-2347

[Disclosure]

[Technical problem]

The aim of the present invention is to provide a metal ligand complex with a specific substituent and an ethylene-based polymerization catalyst composition comprising said complex.

Another object of the present invention is to provide a method for producing an ethylene-based polymer using an ethylene-based polymerization catalyst composition.

[Technical solution]

In one general aspect, a metal ligand complex with significantly improved solubility in an organic solvent, in particular an aliphatic hydrocarbon, is represented by the following chemical formula 1:

[Chemical formula 1]

where

M is a transition metal of group 4 of the periodic table;

R' and R" are independently (C1-C20) alkyl;

R ₁ and R ₂ are independently halo, (C1-C20) alkyl, (C1-C20) alkoxy or halo(C1-C20) alkyl;

R ₃ is (C8-C20) straight chain alkyl; and

m is an integer from 2 to 4.

Preferably, in chemical formula 1 according to an exemplary embodiment of the present invention, R ₃ may be straight chain (C8-C20) alkyl.

More preferably, in the chemical formula 1 according to an exemplary embodiment of the present invention, R ₃ may be (C8-C20) straight chain alkyl, M may be titanium, zirconium or hafnium, R' and R" may be independently of each other be (C1-C5) alkyl, R ₁ and R ₂ may be identical to each other halogen, (C1-C8) alkyl or (C1-C8) alkoxy, and m may be the integer 3.

Preferably, the chemical formula 1 according to an exemplary embodiment of the present invention may be represented by the following chemical formula 2:

[Chemical formula 2]

where

M is titanium, zirconium or hafnium;

R' and R" are independently (C1-C5) alkyl;

R ₁ and R ₂ are independently halogen, (C1-C8)alkyl or (C1-C8)alkoxy; and

R ₃ is (C8-C12) straight chain alkyl.

In another general aspect, an ethylene-based polymerization catalyst composition includes a metal ligand complex of the present invention and a co-catalyst.

Preferably, the cocatalyst according to an exemplary embodiment of the present invention may be an aluminum compound cocatalyst, a boron compound cocatalyst, or a mixture thereof, and may be used in an amount of 0.5 to 10,000 mol per 1 mol of metal ligand complex.

In yet another general aspect, a process for producing an ethylene-based polymer comprises: polymerizing ethylene or ethylene and an α-olefin in the presence of an ethylene-based polymerization catalyst composition to form an ethylene-based polymer.

Preferably, the polymerization in accordance with a typical embodiment of the present invention can be carried out at 170-250°C.

[Useful effects]

The metal ligand complex according to an exemplary embodiment of the present invention has greatly improved solvent solubility due to the introduction of a specific functional group with a controlled carbon number and a controlled shape, which more effectively improves the polymerization process.

In addition, the metal ligand complex according to an exemplary embodiment of the present invention has an excellent catalyst activity due to the introduction of a certain functional group at a certain position, and furthermore allows polymerization even at a high polymerization temperature and does not decrease the catalyst activity.

In addition, the metal ligand complex according to an exemplary embodiment of the present invention has good olefin reactivity for easy polymerization of olefins, and can produce a high molecular weight ethylene-based polymer at a high polymerization temperature.

Accordingly, a metal ligand complex according to an exemplary embodiment of the present invention and a catalyst composition comprising said complex can be very useful in producing an ethylene-based polymer having excellent physical properties.

[Best Mode for Carrying Out the Invention]

The following describes the metal ligand complex of the present invention, the ethylene-based polymerization catalyst composition including said complex, and the process for producing an ethylene-based polymer using said complex, with the technical terms and scientific terms used herein having the usual meaning, understood by those skilled in the art to which the present invention pertains, unless otherwise specified, and descriptions of known functions and configurations that might obscure the present invention are omitted from the following description.

"Alkyl", "alkoxy", and other substituents containing an "alkyl" moiety described herein include both straight and branched chain forms, and unless otherwise indicated, contain from 1 to 20 carbon atoms, preferably 1 to 15, more preferably 1 to 10 carbon atoms.

In addition, "(C8-C20)alkyl containing one or more nitrogen atoms, oxygen atoms, sulfur atoms and phosphorus atoms" is a substituent containing one or more nitrogen atoms, oxygen atoms, sulfur atoms and phosphorus atoms in an alkyl group, containing from 8 to 20 carbon atoms, and a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom may be present between the carbon atoms of the alkyl group or as a substituent of the alkyl group. By way of example, mention may be made of, but not limited to, alkoxy, aminoalkyl, secondary amines, ether compounds, and the like.

The haloalkyl described herein is an alkyl group in which one or more hydrogen atoms are replaced by a halogen, and may contain one or more halogen atoms in the alkyl group.

The present invention provides a metal ligand complex represented by the following chemical formula 1, which has improved solubility, excellent thermal stability, and high catalytic activity at a high polymerization temperature by introducing a substituent having a controlled shape and a controlled number of carbon atoms at a certain position, and thus , can be very useful for high molecular weight ethylene-based polymerization.

[Chemical formula 1]

where

M is a transition metal of group 4 of the periodic table;

R' and R" are independently (C1-C20) alkyl;

R ₁ and R ₂ are independently halo, (C1-C20) alkyl, (C1-C20) alkoxy or halo(C1-C20) alkyl;

R ₃ is (C8-C20) straight chain alkyl; and

m is an integer from 2 to 4.

The metal ligand complex according to an exemplary embodiment of the present invention is represented by the chemical formula 1 above, and due to the introduction of (C8-C20) straight chain alkyl, which is intended as a controlled substituent, in R ₃ in the chemical formula 1, the solubility in the organic solvent is particularly aliphatic hydrocarbon is greatly improved, and the catalytic activity is very high even at high polymerization temperature.

Accordingly, the metal ligand complex according to an exemplary embodiment of the present invention has excellent thermal stability to maintain high catalytic activity even at high temperature, and also has good polymerization reactivity with other olefins, and can produce a high molecular weight polymer in high yield, and therefore , has a high commercial practicality in comparison with the already known metallocene and non-metallocene catalysts having a single active site.

Preferably, in the chemical formula 1 according to an exemplary embodiment of the present invention, R ₃ may be (C8-C20) straight chain alkyl, more preferably (C8-C12) straight chain alkyl.

Preferably, in the chemical formula 1 according to an exemplary embodiment of the present invention, R ₃ may be (C8-C20) straight chain alkyl, M may be titanium, zirconium or hafnium, R' and R" may independently represent is (C1-C5)alkyl, R ₁ and R ₂ may be identical to each other halogen, (C1-C8) alkyl or (C1-C8) alkoxy, and m may be the integer 3.

From the viewpoint of improving solubility, catalytic activity and olefin reactivity, the chemical formula 1 according to an exemplary embodiment of the present invention may be preferably represented by the following chemical formula 2:

[Chemical formula 2]

where

M is titanium, zirconium or hafnium;

R' and R" are independently (C1-C5) alkyl;

R ₁ and R ₂ are independently halogen, (C1-C8)alkyl or (C1-C8)alkoxy; and

R ₃ is (C8-C12) straight chain alkyl.

In terms of higher solubility, catalytic activity and olefin reactivity, R ₃ in the chemical formula 2 according to an exemplary embodiment of the present invention may preferably be (C8-C12) straight chain alkyl and more preferably n -octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

In particular, the metal ligand complex according to an exemplary embodiment of the present invention may be compounds selected from the group consisting of, but not limited to, the following structures:

where M represents titanium, zirconium or hafnium; and PrO-, BuO-, PentylO-, HexylO-, HeptylO-, OctylO-, Pr-, Butyl-, Pentyl-, Hexyl-, Heptyl- and Octyl- include both straight and branched chain forms.

In addition, the present invention provides an ethylene-based polymerization catalyst composition comprising the metal ligand complex of the present invention and a co-catalyst.

The cocatalyst according to an exemplary embodiment of the present invention may be a boron compound cocatalyst, an aluminum compound cocatalyst, and a mixture thereof.

The cocatalyst according to an exemplary embodiment of the present invention may be included in a molar ratio of 0.5 to 10,000 per mole of the metal ligand complex.

A boron compound that can be used as a cocatalyst in the present invention may include boron compounds known from US Pat.

[Chemical formula 11]

B(R ²¹ ) ₃

[Chemical Formula 12]

[R ²² ] ⁺ [B(R ²¹ ) ₄ ] ^-

[Chemical formula 13]

[(R ²³ ) _p ZH] ⁺ [B(R ²¹ ) ₄ ] ^-

where B is a boron atom; R ²¹ represents a phenyl group, and the phenyl group may be further substituted with 3-5 substituents selected from the group consisting of a fluorine atom, a (C1-C20) alkyl group, a (C1-C20) alkyl group substituted with a fluorine atom, (C1 -C20 alkoxy or (C1-C20) alkoxy substituted with a fluorine atom; R ²² is a (C5-C7) aromatic radical or a (C1-C20) alkyl (C6-C20) aryl radical, (C6-C20) aryl (C1-C20) alkyl radical, for example a triphenylmethyl radical; Z represents a nitrogen or phosphorus atom; R ²³ is a (C1-C20) alkyl radical or an anilinium radical substituted with two (C1-C20) alkyl groups together with a nitrogen atom; and p is the integer 2 or 3.

Preferred examples of a boron-based cocatalyst include trityltetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris (3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenylbis(pentafluorophenyl)borane, tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis (2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(2,2,4-trifluorophenyl)borate, phenylbis(pentafluorophenyl)borate or tetrakis(3,5-bistrifluoromethylphenyl) )borate. In addition, some examples of their combinations may include ferrocenium tetrakis(pentafluorophenyl)borate, 1,1'-dimethylferrocenium tetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, triphenylmethyl tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(3,5 -bistrifluoromethylphenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-bistrifluoromethylphenyl)borate, N , N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bistrifluoromethylphenyl) )borate, diisopropylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, or tri(dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate , and most preferred among them are any one or two or more selected from the group consisting of triphenylmethyl tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakispentafluorophenylborate, triphenylmethyl tetrakispentafluorophenylborate and trispentafluoroborane.

An example of an aluminum compound that can be used as a cocatalyst in a catalyst composition according to an exemplary embodiment of the present invention may include an aluminoxane compound of chemical formula 14 or 15, an organoaluminum compound of chemical formula 16, or an organoaluminum alkyl oxide or organoaluminum aryl oxide compound of chemical formula 17 or 18:

[Chemical formula 14]

(-Al(R ²⁴ )-O-) _m

[Chemical Formula 15]

(R ²⁴ ) ₂ Al-(-O(R ²⁴ )-) _q -(R ²⁴ ) ₂

[Chemical Formula 16]

(R ²⁵ ) _r Al(E) _3-r

[Chemical Formula 17]

(R ²⁶ ) ₂ AlOR ²⁷

[Chemical Formula 18]

R ²⁶ Al(OR ²⁷ ) ₂

where R ₂₄ represents a (C1-C20)alkyl group, preferably a methyl group or an isobutyl group; m and q are independently an integer from 5 to 20; R ₂₅ and R ₂₆ independently of each other represent a (C1-C20)alkyl group; E represents a hydrogen atom or a halogen atom; r is an integer from 1 to 3; and R ₂₇ is a (C1-C20) alkyl group or (C6-C30) aryl group.

Specific examples of a compound that can be used as the aluminum compound may include alumoxane compounds such as methylalumoxane, modified methylalumoxane, and tetraisobutylaluminumoxane; organoaluminum compounds, for example trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropropylaluminum, triisobutylaluminum and trihexylaluminum; dialkylaluminum chloride such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminum dichloride such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride; a dialkylaluminum hydride such as dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride; алкилалкоксиалюминий, такой как метилдиметоксиалюминий, диметилметоксиалюминий, этилдиэтоксиалюминий, диэтилэтоксиалюминий, изобутилдибутоксиалюминий, диизобутилбутоксиалюминий, гексилдиметоксиалюминий, дигексилметоксиалюминий и диоктилметоксиалюминий, предпочтительно соединение, выбранное из группы, состоящей из метилалюмоксана, модифицированного метилалюмоксана, тетраизобутилалюмоксана, триалкилалюминия, триэтилалюминия и триизобутилалюминия по отдельности или в их комбинации, more preferably trialkylaluminum, even more preferably triethylaluminum and triisobutylaluminum.

Preferably, in the catalyst composition according to an exemplary embodiment of the present invention, when an aluminum compound is used as the cocatalyst, the preferred range of the ratio between the metal ligand complex of the present invention and the cocatalyst may be a transition metal (M):aluminum (Al) atom of 1:50 up to 1:5000 in terms of the molar ratio.

Preferably, in a catalyst composition according to an exemplary embodiment of the present invention, when both an aluminum compound and a boron compound are used as the cocatalyst, the preferred range of the ratio between the metal ligand complex of the present invention and the cocatalyst may be transition metal (M):boron atom: aluminum atom 1:0.1-100:10-1000, more preferably 1:0.5-5:25-500, calculated on a mole ratio.

As another aspect, in accordance with an exemplary embodiment of the present invention, a process for producing an ethylene polymer using an ethylene-based polymerization catalyst composition can be carried out by bringing the metal ligand complex, the co-catalyst and ethylene and, if necessary, the vinyl-based comonomer, into contact in the presence of an appropriate organic solvent. Meanwhile, the precatalyst component, which is a metal ligand complex, and the cocatalyst component may be separately added to the reactor, or each component may be premixed and added to the reactor, and the mixing conditions such as the order of addition, temperature, or concentration, are not specifically limited.

Preferred organic solvents that can be used in the preparation process may be C3-C20 hydrocarbons and specific examples thereof may include butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, etc.

In particular, when preparing an ethylene-α-olefin copolymer, C3-C18 α-olefins together with ethylene can be used as comonomer, and preferably, α-olefins can be selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene and 1-octadecene. More preferably, 1-butene, 1-hexene, 1-octene or 1-decene and ethylene can be copolymerized. In this case, the preferred ethylene pressure and polymerization reaction temperature may be 1-1000 atm, more preferably 10-150 atm, and for efficient polymerization reaction, the polymerization reaction temperature is 170-250°C, preferably 180-200°C.

In addition, the copolymer obtained in accordance with the method of the present invention usually contains 50 wt.% or more, preferably 60 wt.% or more, and more preferably 60-99 wt.% ethylene.

As described above, linear low density polyethylene (LLDPE) made using C4-C10 α-olefins as comonomer has a density range of 0.940 g/cm ³ or less, expandable into the range of very low density polyethylene (VLDPE) or ultra low density polyethylene density (ULDPE) with a density of 0.900 g/cm ³ or olefin elastomer. Further, in the preparation of the ethylene copolymer according to the present invention, hydrogen can be used as a molecular weight regulator to adjust the molecular weight, and the copolymer generally has a weight average molecular weight (Mw) of 80,000 to 500,000.

The ethylene-propylene-diene copolymer as a specific example of the olefin-diene copolymer obtained by the catalyst composition according to a typical embodiment of the present invention may have an ethylene content of 30 to 80 wt.%, a propylene content of 20 to 70 wt.% , and the content of the diene from 0 to 15 wt.%. The diene monomer that can be used in the present invention has two or more double bonds, and examples thereof may include 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,6- octadiene, 1,7-octadiene, 1,7-nonadiene, 1,8-nonadiene, 1,8-decadiene, 1,9-decadiene, 1,12-tetradecadiene, 1,13-tetradecadiene, 3-methyl-1, 4-hexadiene, 3-methyl-1,5-hexadiene, 3-ethyl-1,4-hexadiene, 3-ethyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,3- dimethyl-1,5-hexadiene, 5-vinyl-2-norbornene, 2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5-norbornadiene, 7-propyl-2,5- norbornadiene, 7-butyl-2,5-norbornadiene, 7-phenyl-2,5-norbornadiene, 7-hexyl-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene, 7-methyl-7- ethyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene, 7-bromo-2,5-norbornadiene, 7-fluoro-2,5-norbornadiene, 7,7-dichloro-2,5-norbornadiene, 1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene, 1-propyl-2,5-norbornadiene, 1-butyl-2,5-norbornadiene, 1-chloro-2,5-norbornadiene, 1-bromo-2,5-norbornadiene, 5-isopropyl-2-norborn ene, 1,4-cyclohexadiene, bicyclo(2,2,1)hepta-2,5-diene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, bicyclo(2,2,2)octa- 2,5-diene, 4-vinylcyclohexa-1-ene, bicyclo(2,2,2)octa-2,6-diene, 1,7,7-trimethylbicyclo-(2,2,1)hepta-2,5 -diene, dicyclopentadiene, methyltetrahydroindene, 5-arylbicyclo(2,2,1)hepta-2-ene, 1,5-cyclooctadiene, 1,4-diarylbenzene, butadiene, isoprene, 2,3-dimethyl-1,3-butadiene , 1,2-butadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3-ethyl-1 ,3-pentadiene and the like, and most preferably the diene monomer may be 5-ethylidene-2-norbornene and dicyclopentadiene. The diene monomer may be selected depending on the processing characteristics of the ethylene-propylene-diene copolymer, and if necessary, two or more diene monomers may be mixed.

In this case, the preferred pressure and temperature in the reactor may be a pressure of 1-1000 atm, more preferably 5-100 atm, and, for an efficient polymerization reaction, a polymerization reaction temperature of 170-250°C, preferably 180-200°C.

The ethylene-olefin-diene copolymer obtained in accordance with an exemplary embodiment of the present invention may have an ethylene content of 30 to 80 wt.%, an olefin content of 20 to 70 wt.%, and a diene content of 0 to 15 wt.%.

In general, in the case of producing an ethylene-propylene-diene copolymer, the molecular weight of the copolymer decreases with increasing propylene content, however, in the case of the ethylene-propylene-diene copolymer according to the present invention, a product with a relatively high molecular weight can be obtained without reducing the molecular weight even if reduction of propylene content up to 50%.

Since the catalyst composition provided in the present invention is provided in a homogeneous form in a polymerization reactor, it is preferable to apply the catalyst composition to a solution polymerization process that is carried out at a temperature equal to or above the melting point of the polymer. However, as disclosed in US Pat. No. 4,752,597, the catalyst composition can be used in a slurry polymerization or gas phase polymerization process in the form of a heterogeneous catalyst composition obtained by supporting a metal ligand complex precatalyst and a cocatalyst on a porous metal oxide support.

Hereinafter, the present invention is described in detail with the help of the following examples, however, the scope of the present invention is not limited to them.

Unless otherwise noted, all experiments on the synthesis of ligands and catalysts were carried out using standard Schlenk or glove box technology under nitrogen atmosphere, and the organic solvent used in the reaction was used after heating the solvent under reflux over sodium metal and benzophenone to remove moisture and distill solvent immediately before use. ¹ H-NMR analysis of the synthesized ligand and catalyst was performed using a Bruker 400 or 500 MHz at room temperature.

IR analysis was performed with 5 mg of the compound in solid state using a Bruker ATR-IR.

Cyclohexane was used as a polymerization solvent after sufficient removal of moisture, oxygen, and other catalyst poisoning materials from it by passing the cyclohexane through a 5 Å molecular sieve and a tube filled with active alumina, and bubbling the cyclohexane with high purity nitrogen. Polymerized polymer using the methods described below:

1. Melt flow index (MI)

measured at 190° C. under a load of 2.16 kg using ASTM D1238 analysis method.

2. Density

measured using ASTM D792 analysis method.

3. Molecular weight and molecular weight distribution

was measured using size exclusion chromatography with a three-stage stirred column.

The solvent used in the present invention was 1,2,4-trichlorobenzene, and the measurement temperature was 120°C.

[Production Example 1] Synthesis of 1,3-bis(4-fluoro-2-iodophenoxy)propane (compound A)

Synthesis of 4-fluoro-2-iodophenol (compound a-1)

4-Fluorophenol (40 mmol, 4.9 g), NaI and NaOH were added according to equivalents to a round bottom flask, MeOH (60 ml) was added thereto, and the temperature was brought to 0° C. using an ice bath. NaOCl (1 eq) was added over 1 hour using a syringe pump. After adding all of the NaOCl, the reactants were stirred at the same temperature for 3 hours. Thereafter, 10% sodium thiosulfate solution (30 ml) was added thereto, the pH was again adjusted to 5-6 with 5% HCl solution, and extraction was performed with diethyl ether. The extracted filtrate was separated and purified by column chromatography (eluent EA/n-Hex=1/30 v/v) to give compound a-1 as a light yellow solid (5.2 g, 54%).

¹ H NMR (CDCl ₃ ): δ 7.39 (d, 1H), 7.01 (m, 1H), 6.98 (m, 1H), 5.10 (s, 1H).

Synthesis of 1,3-bis(4-fluoro-2-iodophenoxy)propane (compound A)

Propane-1,3-diylbis(4-methylbenzenesulfonate) (2.5 mmol, 961 mg) and compound a-1 (5 mmol, 1.2 g) were added to a round bottom flask, K ₂ CO ₃ (1.5 eq.) and acetone (20 ml), and the reactants were heated under reflux for 24 hours. After completion of the reaction, the reactants were cooled to room temperature, the acetone was removed by distillation under reduced pressure, and extraction was carried out with MC (methylene chloride) and water. The extracted filtrate was separated and purified by column chromatography (eluent EA/n-Hex=1/10 v/v) to give Compound A as a yellow solid (1.03 g, 80%).

¹ H NMR (CDCl ₃ ): δ 7.49 (d, 2H), 7.02 (m, 2H), 6.80 (m, 2H), 4.25 (t, 4H), 2.34 (q , 2H).

[Example 1] Synthesis of WC03 precatalyst

Synthesis of 2-iodo-4-octylphenol (compound 3-1)

4-n-Octylphenol (20 mmol, 4.13 g), NaI (1.1 eq) and NaOH (1.2 eq) were added to a round bottom flask, MeOH (120 ml) was added and the temperature was brought to 0 ° using an ice bath. NaOCl (1 eq.) was slowly added thereto over 1 hour using a syringe pump, and the reactants were further stirred at the same temperature for 3 hours. After 10% sodium thiosulfate solution (30 ml) was added thereto, the pH was adjusted to 5-6 using 5% HCl solution, and extraction was performed with diethyl ether. The solvent was removed from the extracted filtrate, and column chromatography was used (eluent EA/n-Hex=1/30 v/v) to obtain compound 3-1 as a colorless liquid (2.9 g, 65%).

Synthesis of 2-(2-iodo-4-octylphenoxy)tetrahydro-2H-pyran (compound 3-2)

Compound 3-1 and p-TsOH (0.1 eq.) were added to a round bottom flask, DCM (50 ml) was added, DHP (dihydropyran, 3 eq.) was added thereto, and then the reactants were stirred at room temperature for 30 minutes. After that, extraction was performed with a 1 M K ₂ CO ₃ solution, and column chromatography was performed (eluent EA/n-Hex=1/30 v/v) to obtain compound 3-2 as a colorless liquid (9.2 g, 85%) .

¹ H NMR (CDCl ₃ ): δ 7.46 (s, 1H), 7.05 (d, 1H), 6.90 (d, 1H), 5.13 (s, 1H), 2.49 (t , 3H), 1.55 (m, 2H), 1.28 (m, 10H), 0.88 (t, 3H).

Synthesis of 3,6-di-tert-butyl-9-(5-octyl-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole (compound 3-3)

3,6-Di-tert-butyl-9H-carbazole (5 mmol, 1.4 g) and compound 3-2 (1.8 eq.) were added to a two-necked round bottom flask, CuI (3 mol%), N , N-dimethylethylenediamine (3 mol%) and K ₃ PO ₄ (3.8 eq.), and used the Schlenk line to create conditions with nitrogen. Thereafter, toluene (25 ml) was added thereto, and the reactants were heated under reflux at 125° C. for 4 days. After completion of the reaction, the product was cooled to room temperature, and the catalyst was removed from there using a silica gel filter. In this case, THF was used as the wash solution. The solvent was removed by distillation under reduced pressure and the product was recrystallized using acetonitrile (5 ml) to give compound 3-3 as a colorless solid (0.94 g, 51%).

¹ H NMR (CDCl ₃ ): δ 8.13 (s, 2H), 7.43 (m, 2H), 7.31 (m, 2H), 7.29 (m, 1H), 7.17 (m , 1H), 7.13 (m, 1H), 5.21 (m, 1H), 4.15 (m, 1H), 3.74 (m, 1H), 3.70 (m, 1H), 2 .62(m, 2H), 1.62(m, 2H), 1.47(s, 20H), 1.38~1.25(m, 18H), 0.88(m, 3H).

Synthesis of 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (compound 3-4)

Compound 3-3 (4 mmol, 2.3 g) was added under nitrogen atmosphere to a round bottom flask, THF (45 ml) was added thereto, n-BuLi (1.1 eq.) was added very slowly at -10°C, and then the reactants were stirred for 4 hours. After 4 hours, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (i-PrO-B(pin), 2.5 eq.) was added there very slowly, and then the temperature was raised to room temperature, and the reactants were stirred for 12 hours. After completion of the reaction, cold sat. NaHCO ₃ (aq.) solution (35 ml), the reactants were stirred for 10 minutes, and extraction was carried out using DCM. After extraction, the resulting solid was filtered through a short column of silica gel with ethyl acetate, and then the solvent was evaporated to give a white solid, which was added to acetonitrile (10 ml) and stirred for 1 hour. After stirring, the compound obtained by filtration was dried to give compound 3-4 as a colorless solid (1.1 g, 41%).

¹ H NMR (CDCl ₃ ): δ 8.13 (s, 2H), 7.94 (s, 1H), 7.55 (s, 1H), 7.45 (d, 2H), 7.35 (s , 1H), 7.17(m, 1H), 7.13(d, 2H), 2.58(t, 2H), 1.61(m, 3H), 1.44~1.37(m, 20H), 1.35(s, 12H), 1.27(m, 10H), 0.87(m, 3H).

Synthesis of the ligand WC03L

Under nitrogen atmosphere, compound 3-4 (2 mmol), compound A (0.5 eq.), Pd(PPh ₃ ) ₄ (0.3 mol%) and NaOH (3 eq.) were added to a two-necked round bottom flask, added DME (40 ml), THF (20 ml) and H ₂ O (10 ml) in that order, and the reactants were heated under reflux at 100°C for 48 hours. After completion of the reaction, the product was cooled to room temperature, and the catalyst was removed from there using a silica gel filter. The solvent was removed by distillation under reduced pressure, and the remaining solvent was removed using vacuum.

The residue from which the solvent was removed was added to a round bottom flask, p-TsOH (1 mol%) was added thereto, then 100 ml of MeOH and THF were added there, and the reactants were heated under reflux at 80°C for 8 hours. After completion of the reaction, the product was cooled to room temperature, and extraction was carried out with water. The extracted filtrate was separated and purified by column chromatography (eluent EA/n-Hex=1/50 v/v), and then the product was recrystallized using EA (5 ml) to give ligand WC03L (0.7 g, 29% ).

1H NMR (CDCl3): δ 8.22 (s, 4H), 7.43 (m, 4H), 7.36 (s, 2H), 7.32(s, 2H), 7.12(m, 6H ), 7.03(s, 2H), 6.54(m, 2H), 6.05(m, 2H), 5.47(s, 2H), 3.83(m, 4H), 2.59 (m, 4H), 2.08 (m, 2H), 1.35 ~ 1.27 (m, 66H), 0.90 (m, 6H); 13C-{1H}-NMR: 156.2, 151.2, 148.2, 142.9, 139.9, 135.7, 131.1, 128.9, 128.0, 127.9, 126, 7, 124.9, 123.6, 123.5, 118.4, 118.2, 116.4, 115.5, 115.3, 113.1, 113.0, 109.5, 65.2, 35.1, 34.8, 32.2, 32.0, 31.6, 29.5, 29.44, 29.41, 29.0, 22.8, 14.2.

Synthesis of WC03 precatalyst

The reaction was carried out in a glove box under a nitrogen atmosphere. ZrCl ₄ (0.45 g, 1.93 mmol) and toluene (80 ml) were added to a 100 ml flask to obtain a suspension. The suspension was cooled to -20°C for 30 minutes in a refrigerator with a glove box. To the suspension was added 3.0 M methylmagnesium bromide (2.6 ml, 10.2 mmol) in diethyl ether at low temperature with stirring. The mixture was intensively stirred for 30 minutes. The solid dissolved, but the reaction solution turned cloudy yellow. The ligand WC03L (2.0 g, 1.6 mmol) was slowly added to the mixture as a solid. After completion of the reaction, the flask was heated to room temperature, the reactants were stirred for 12 hours, and the reaction mixture was filtered through a syringe connected to a membrane filter. The filtered solution was dried under vacuum to give the WC03 precatalyst as a brown solid (2.04 g, yield: 93.2%).

¹ H NMR (CDCl ₃ ): δ 8.31 (s, 2H), 8.02 s, 2H), 7.56 (s, 2H), 7.50 (s, 2H), 7.41(d, 2H), 7.25(d, 2H), 7.23(s, 2H), 6.95(m, 2H), 6.25(t, 2H), 4.61(t, 2H), 3, 84(t, 2H), 3.32(t, 2H), 2.0~1.3(m, 34H), 1.78(s, 2H), 1.72(s, 18H), -1, 62(s, 6H).

[Example 2] Synthesis of WC04 precatalyst

Synthesis of 2-iodo-4-dodecylphenol (compound 4-1)

4-n-Dodecylphenol (40 mmol, 10.5 g), NaI (1.1 eq) and NaOH (1.2 eq) were added to a round bottom flask, MeOH (120 ml) was added thereto and the temperature was brought to 0 °C using an ice bath. NaOCl (1 eq.) was slowly added thereto over 1 hour using a syringe pump, and then the reactants were further stirred at the same temperature for 3 hours. Thereafter, 10% sodium thiosulfate solution (30 ml) was added thereto, the pH was again adjusted to 5-6 using 6.5% HCl solution, and extraction was performed with diethyl ether. The extracted filtrate was separated and purified by column chromatography (eluent EA/n-Hex=1/30 v/v) to give compound 4-1 as a colorless liquid (8 g, 65%).

Synthesis of 2-(2-iodo-4-dodecylphenoxy)tetrahydro-2H-pyran (compound 4-2)

Compound 4-1 and p-TsOH (0.1 eq) were added to a round bottom flask and DCM (50 ml) was added thereto. After adding DHP (3 equiv.) the reactants were stirred at room temperature for 30 minutes. After completion of the reaction, extraction was performed with a 1 M K ₂ CO ₃ solution, and the product was separated and purified by column chromatography (eluent EA/n-Hex=1/60 v/v) to obtain compound 4-2 as a colorless liquid (9, 4 g, 95%).

Synthesis of 3,6-di-tert-butyl-9-(5-dodecyl-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole (compound 4-3)

3,6-Di-tert-butyl-9H-carbazole (5 mmol, 1.4 g) and compound 4-2 (1.8 eq.) were added to a two-necked round bottom flask, CuI (3 mol%), N , N-dimethylethylenediamine (3 mol%) and K ₃ PO ₄ (3.8 eq.), and used the Schlenk line to create conditions with nitrogen. After toluene (25 ml) was added thereto, the reactants were heated under reflux at 125° C. for 4 days. After completion of the reaction, the product was cooled to room temperature, and the catalyst was removed from there using a silica gel filter. In this case, THF was used as the wash solution. After the solvent was removed by distillation under reduced pressure, the product was recrystallized using acetonitrile (5 ml) to give compound 4-3 as a colorless solid (0.94 g, 30%).

Synthesis of 3,6-di-tert-butyl-9-(5-dodecyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole (compound 4-4)

Compound 4-3 (4 mmol, 2.3 g) was added under nitrogen atmosphere to a round bottom flask, THF (45 ml) was added thereto, n-BuLi (1.1 eq.) was added very slowly at -10°C, and then the reactants were stirred for 4 hours. After 4 hours, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.5 eq.) was added there very slowly, and then the temperature was raised to room temperature, and the reactants were stirred for 12 hours. After completion of the reaction, cold sat. NaHCO ₃ (aq.) solution (35 ml), the reactants were stirred for 10 minutes, and extraction was carried out using DCM. Thereafter, the product was used in the crude mixture state in the next reaction.

Synthesis of the ligand WC04L

Under nitrogen atmosphere, compound 4-4 (2 mmol), compound A (0.5 eq.), Pd(PPh ₃ ) ₄ (0.3 mol%) and NaOH (3 eq.) were added to a two-necked round bottom flask, added DME (40 ml), THF (20 ml) and H ₂ O (10 ml) in that order, and the reactants were heated under reflux at 100°C for 48 hours. After completion of the reaction, the product was cooled to room temperature, the catalyst was removed therefrom using a silica gel filter, the solvent was removed by distillation under reduced pressure, and the remaining solvent was removed using vacuum.

The residue from which the solvent was removed was added to a round bottom flask, and p-TsOH (1 mol%) was added thereto. Again, 100 ml of MeOH and THF were added there, and then the reactants were heated under reflux at 80°C for 8 hours. After completion of the reaction, the product was cooled to room temperature, and extraction was carried out with water. Thereafter, the product was separated and purified by column chromatography (eluent EA/n-Hex=1/50 v/v), and then the product was recrystallized again using EA (5 ml) to give ligand WC04L (0.5 g) .

¹ H NMR (CDCl ₃ ): δ 8.17 (s, 4H), 7.49 ~ 6.92 (m, 18H), 6.54 (m, 2H), 6.05 (m, 2H), 5 .47(s, 2H), 1.50~0.65(m, 88H).

Synthesis of WC04 precatalyst

The WC04 precatalyst was prepared in the same manner as in Example 1, except that the WC04L ligand was used instead of the WC03L ligand.

¹ H NMR (CDCl ₃ ): δ 8.35 (s, 2H), 8.03 s, 2H), 7.54 ~ 6.95 (m, 18H), 6.54 (m, 2H), 6, 05(m, 2H), 5.47(s, 2H), 1.50~0.65(m, 88H), -1.63(s, 6H).

[Comparative Example 1] Synthesis of Precatalyst WC01

Preparation of 2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenol (compound 1-1)

4-(2,4,4-trimethylpentan-2-yl)phenol (50 mmol, 10.32 g), NaI (1.1 eq) and NaOH (1.2 eq) were added to a round bottom flask. MeOH (120 ml) was added there, the temperature was brought to 0°C using an ice bath, and NaOCl (1 eq) was slowly added there over 1 hour using a syringe pump. Thereafter, the reactants were stirred at the same temperature for 3 hours, and 10% sodium thiosulfate solution (30 ml) was added thereto. The pH was again adjusted to 5-6 using 5% HCl solution, extraction was performed with diethyl ether, and then the product was separated and purified by column chromatography (eluent: EA/n-Hex=1/30 v/v) to obtain compound 1- 1 as a colorless liquid (8.64 g, 52%).

Preparation of 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran (compound 1-2)

Compound 1-1 and p-TsOH (0.1 eq) were added to a round bottom flask and dissolved in DCM (50 ml). After DHP (3 eq.) was added thereto, p-TsOH (0.1 eq.) was added and the reactants were stirred at room temperature for 30 minutes. After that, the reaction mixture was extracted with 1 M K ₂ CO ₃ solution, and the product was separated and purified by column chromatography (eluent EA/n-Hex=1/30 v/v) to obtain compound 1-2 as a colorless liquid (9, 2 g, 85%).

Synthesis of 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9 -carbazole (compound 1-3)

3,6-Di-tert-butyl-9H-carbazole (9.5 mmol, 2.7 g) and compound 1-2 (1.8 eq.) were added to a two-necked round bottom flask, CuI (3 mol%) was added thereto , N, N-Dimethylethylenediamine (3 mol%) and K ₃ PO ₄ (3.8 eq.), and used the Schlenk line to create conditions with nitrogen. After further addition of toluene (50 ml) thereto, the reactants were heated under reflux at 125° C. for 4 days. After completion of the reaction, the product was cooled to room temperature, and the catalyst was removed from there using a silica gel filter. In this case, THF was used as the wash solution. The solvent was removed by evaporation, the product was filtered through a short column of silica gel with ethyl acetate, and recrystallized with acetonitrile (10 ml) to give compound 1-3 as a colorless solid (3.7 g, 80%).

¹ H NMR (CDCl ₃ ): δ 8.13 (s, 2H), 7.47 (s, 1H), 7.42 (m, 3H), 7.31 (d, 1H), 7.15 (d , 1H), 7.09 (d, 1H), 5.22 (s, 1H), 3.74 (m, 1H), 3.49 (m, 1H), 1.74 (s, 2H), 1 .47 (s, 18H), 1.38 (s, 6H), 0.8 (s, 9H)

Synthesis of 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (compound 1-4)

In the presence of nitrogen, compound 1-3 (6.5 mmol, 3.6 g) was added to a round bottom flask, THF (45 ml) was added thereto, n-BuLi (1.1 eq.) was added very slowly at -10°C , and then the reactants were stirred for 4 hours. Thereafter, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.5 eq.) was very slowly added thereto, and then the temperature was raised to room temperature, and the reactants were stirred for 12 hours . After completion of the reaction, cold sat. NaHCO ₃ (aq.) solution (35 ml), the reactants were stirred for 10 minutes, and extraction was carried out using DCM. The resulting solid was filtered through a short column of silica gel with ethyl acetate, and then the solvent was evaporated to give a white solid, which was added to acetonitrile (10 ml) and stirred for 1 hour. After stirring, the compound obtained by filtration was dried to give compound 1-4 as a colorless solid (4.3 g, 83%).

¹ H NMR (CDCl ₃ ): δ 8.15 (s, 1H), 8.09 (s, 2H), 8.0 (s, 1H), 7.71~7.55(dd, 1H), 7 .45 (m, 4H), 7.14 (d, 1H), 7.10 (d, 1H), 4.84 (s, 1H), 2.74 (m, 1H), 2.60 (m, 1H), 1.65 (s, 3H), 1.60 (s, 2H), 1.55 (s, 5H), 1.45 (s, 27H), 1.38 (m, 27H), 0, 81 (s, 5H), 0.77 (s, 9H)

Synthesis of 4-fluoro-2-iodo-6-methylphenol (compound 1-5)

4-Fluoro-2-methylphenol (20 mmol, 2.5 g), NaI and NaOH were added in equivalent to a round bottom flask. MeOH (60 ml) was added there, the temperature was brought to 0°C using an ice bath, and NaOCl (1 eq.) was slowly added there over 1 hour using a syringe pump. After adding all of the NaOCl, the reactants were stirred at the same temperature for 3 hours. Thereafter, 10% sodium thiosulfate solution (30 ml) was added thereto, the pH was again adjusted to 5-6 with 5% HCl solution, and extraction was performed with diethyl ether. The extracted filtrate was separated and purified by column chromatography (eluent EA/n-Hex=1/30 v/v) to give compound 1-5 as a light yellow solid (4.3 g, 80%).

Synthesis of propane-13-diylbis(4-methylbenzenesulfonate) (compound 1-6)

Propan-1,3-diol (25 mmol, 1.9 g) and 4-methylbenzene-1-sulfonyl chloride (55 mmol, 10.5 g) were added to a round bottom flask, and then DCM (200 ml) was added thereto, and the temperature brought to 0°C using an ice bath. After triethylamine (75 mmol, 7.6 g) was added thereto, the reactants were stirred at room temperature for 12 hours after triethylamine was added. After completion of the reaction, extraction was carried out using DCM, and the product was filtered through a short column of silica gel with ethyl acetate, and then recrystallized using acetone, and a white solid was filtered off, while obtaining compound 1-6 (7.7 g, 80%).

Synthesis of 1,3-bis(4-fluoro-2-iodo-6-methylphenoxy)propane (compound 1-7)

Compound 1-6 (2.5 mmol, 961 mg) and compound 1-5 (5 mmol, 1.3 g) were added to a round bottom flask, and then K ₂ CO ₃ (1.5 eq.) and acetone ( 20 ml), and the reactants were heated under reflux for 24 hours. After completion of the reaction, the product was cooled to room temperature, the acetone was removed by distillation under reduced pressure, and extraction was performed with MC and water. The filtrate was separated and purified by column chromatography (eluent: EA/n-Hex=1/10 v/v) to give compound 1-7 as a yellow solid (1.4 g, 84%).

Synthesis of the ligand WC01L

Under nitrogen compound 1-4 (2.5 mmol), compound 1-7 (0.5 eq.), Pd(PPh ₃ ) ₄ (0.3 mol%) and NaOH (3 eq.) were added to a two-necked round bottom flask , and then added there DME (40 ml), THF (20 ml) and H ₂ O (10 ml) in that order, and the reactants were heated under reflux at 100°C for 48 hours. After completion of the reaction, the product was cooled to room temperature, and the catalyst was removed from there using a silica gel filter. The filtrate was removed by distillation under reduced pressure, and the remaining solvent was removed under vacuum.

The residue from which the solvent was removed was added to a round bottom flask, and p-TsOH (1 mol%) was added thereto. Again, 100 ml of MeOH and THF were added there, and then the reactants were heated under reflux at 80°C for 8 hours. After completion of the reaction, the product was cooled to room temperature, and extraction was carried out with water. After that, the extracted filtrate was separated and purified by column chromatography (eluent EA/n-Hex=1/50 v/v), and then recrystallized using EA (5 ml), while obtaining the ligand WC01L (0.88 g, 68 %).

¹ H NMR (CDCl ₃ ): δ 8.14 (s, 1H), 7.43 (s, 2H), 7.37 (m, 6H), 7.02(d, 4H), 6.95 (dd , 2H), 6.85 (dd, 2H), 6.47 (s, 2H), 3.64 (t, 4H), 2.03 (s, 6H), 1.73 (s, 6H), 1 .55 (s, 18H), 1.43 (s, 36H), 1.34 (s, 12H), 0.76 (s, 18H); ¹³ C-{ ¹ H}-NMR: 159.97, 158.03, 149.88, 147.55, 143.17, 142.57, 139.69, 128.69, 127.49, 126.45, 125.58, 123.53, 123.32, 117.15, 116.38, 116.22, 109.20, 70.9, 57.06, 38.24, 34.72, 32.44, 32, 05, 31.86, 31.63, 30.61, 16.45.

Synthesis of the WC01 precatalyst

The WC01 precatalyst was prepared in the same manner as in Example 1, except that the WC01L ligand was used instead of the WC03L ligand.

¹ H NMR (CDCl ₃ ): δ 8.31 (s, 2H), 8.02 s, 2H), 7.56 (s, 2H), 7.50 (s, 2H), 7.41(d, 2H), 7.25(d, 2H), 7.23(s, 2H), 6.95(m, 2H), 6.25(t, 2H), 4.61(t, 2H), 3, 76 (t, 2H), 3.38 (t, 2H), 2.35 (s, 12H), 1.85 (s, 4H), 1.83 (s, 36H), 1.52(s, 18H ), 1.45(s, 3H), 0.98(s, 12H), -1.65(s, 3H)

[Comparative Example 2] Synthesis of WC02 Precatalyst

Synthesis of the ligand WC02L

Compound 1-4 (2.5 mmol), Compound A (0.5 eq.), Pd(PPh ₃ ) ₄ (0.3 mol%) and NaOH (3 eq.) were added to a two-necked round bottom flask under nitrogen atmosphere, was added there DME (40 ml), THF (20 ml) and H ₂ O (10 ml) in that order, and the reactants were heated under reflux at 100°C for 48 hours. After completion of the reaction, the product was cooled to room temperature, the catalyst was removed therefrom using a silica gel filter, the product was distilled under reduced pressure to remove the solvent, and the remaining solvent was removed using vacuum.

The residue from which the solvent was removed was added to a round bottom flask, p-TsOH (1 mol%) was added thereto, then 100 ml of MeOH and THF were added there, and the reactants were heated under reflux at 80°C for 8 hours. After completion of the reaction, the product was cooled to room temperature, extracted with water, and the product was separated and purified by column chromatography (eluent EA/n-Hex=1/50 v/v), and then recrystallized using EA (5 ml) , thus obtaining the WC02L ligand (1.1 g, 70%).

1H NMR (CDCl3): δ 8.23 (s, 4H), 7.45 (d, 4H), 7.43 (s, 2H), 7.39(d, 2H), 7.25 (d, 4H ), 6.95 (d, 2H), 6.53 (m, 2H), 5.95 (m, 2H), 5.40 (s, 2H), 3.80 (t, 4H), 1.99 (m, 2H), 1.71 (s, 4H), 1.49 (s, 36H), 1.36 (s, 12H), 0.80 (s, 18H); 13C-{1H}-NMR: 158.0, 156.1, 151.2, 147.8, 139.9, 129.1, 128.1, 128.0, 127.2, 126.0, 124, 2, 123.6, 123.3, 118.2, 118.0, 116.3, 115.3, 115.2, 112.8, 112.8, 109.2, 64.9, 57.1, 38.2, 34.7, 32.4, 32.1, 31.8, 31.5, 29.0.

Synthesis of WC02 precatalyst

The WC02 precatalyst was prepared in the same manner as in Example 1, except that the WC02L ligand was used instead of the WC03L ligand.

¹ H NMR (CDCl ₃ ): δ 8.31 (s, 2H), 8.02 s, 2H), 7.56 (s, 2H), 7.50 (s, 2H), 7.41(d, 2H), 7.25(d, 2H), 7.23(s, 2H), 6.95(m, 2H), 6.25(t, 2H), 4.61(t, 2H), 3, 76 (t, 2H), 3.38 (t, 2H), 2.35 (s, 4H), 1.85 (s, 4H), 1.83 (s, 36H), 1.52(s, 18H ), 1.45(s, 3H), 0.98(s, 12H), -1.65(s, 3H)

[Comparative Example 3] Synthesis of Precatalyst WB02

Synthesis of the WB02L ligand

(1) Suzuki Combination

2,7-Di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane -2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (2.5 mmol), compound 1-7 (0.5 eq.), Pd(PPh ₃ ) ₄ (0.3 mol%) and NaOH (3 equiv.) were added to a two-necked round bottom flask, and conditions were created with nitrogen. Added there DME (40 ml), THF (20 ml) and H ₂ O (10 ml) in that order, and heated the reactants under reflux at 100°C for 48 hours. After completion of the reaction, the product was cooled to room temperature, the catalyst was removed therefrom using a silica gel filter, the product was distilled under reduced pressure to remove the solvent, and the remaining solvent was removed using vacuum.

(2) THP protection

To the residue obtained by removal of the solvent, p-TsOH (1 mol%) was added, 100 ml of MeOH and THF were added thereto, and the reactants were heated under reflux at 80°C for 8 hours. After the completion of the reaction, the product was cooled to room temperature, extraction was performed with water to remove the solvent, and then the product was separated and purified by column chromatography (eluent: EA/n-Hex=1/50 v/v), thereby obtaining WB02L ligand as a colorless solid (2.2 g, 70%).

¹ H NMR (CDCl ₃ ): δ 8.02 (d, 4H), 7.41 (d, 4H), 7.31 (s, 4H), 7.26(s, 4H), 7.06 (d , 2H), 6.85 (d, 2H), 6.21 (s, 2H), 3.61 (t, 4H), 2.05 (s, 6H), 1.92 (m, 6H), 1 .42 (s, 12H), 1.27 (s, 38H), 0.79 (s, 18H); ¹³ C-{ ¹ H}-NMR: 159.8, 157.8, 150.14, 150.12, 149.7, 149.1, 147.8, 142.8, 141.7, 129.1, 127.5, 126.3, 124.9, 121.0, 119.6, 119.5, 118.2, 117.7, 117.3, 117.1, 106.3, 106.2, 70, 87, 57.1, 38.2, 35.2, 35.0, 32.5, 32.4, 31.9, 31.8, 31.7, 31.6, 30.7, 29.7, 16.4.

Synthesis of precatalyst WB02

The WB02 precatalyst was prepared in the same manner as in Example 1, except that the WC02L ligand was used instead of the WC03L ligand.

¹ H NMR (C ₆ D ₆ ): δ 8.25 (s, 2H), 8.03 s, 2H), 7.96 (s, 2H), 7.85 (s, 2H), 7.64 ( s, 2H), 7.51(d, 2H), 7.36(d, 2H), 7.31(s, 2H), 6.87(m, 2H), 6.05(m, 2H), 3.58 (t, 2H), 3.23 (t, 2H), 1.78 (s, 2H), 1.58 (s, 18H), 1.33 (s, 18H), 1.25 (s , 3H), 1.01(s, 3H), 0.85(s, 12H).

[Comparative Example 4] Synthesis of Precatalyst WD01

Synthesis of the ligand WD01L

Ligand WD01L was obtained in the same manner as in example 1, except that 2-iodo-4-n-butylphenol was used instead of 2-iodo-4-octylphenol (compound 3-1).

¹ H NMR (CDCl ₃ ): δ 8.20 (s, 4H), 7.41 (d, 4H), 7.26 (s, 2H), 7.06(d, 6H), 7.04 (d , 2H), 6.52 (m, 2H), 5.95 (m, 2H), 5.98 (m, 2H), 3.81 (t, 4H), 2.57 (t, 4H), 2 .03 (d, 2H), 1.58 (m, 4H), 1.46 (s, 36H), 1.36 (m, 4H), 0.91 (m, 6H); ¹³ C-{ ¹ H}-NMR: 158.16, 156.25, 151.24, 151.22, 148.19, 142.94, 139.93, 135.73, 131.15, 128.93, 127.99, 126.69, 124.9, 123.67, 123.52, 118.4, 118.21, 116.43, 115.52, 115.35, 113.06, 113.0, 109, 51, 65.21, 34.89, 34.82, 33.79, 32.2, 28.89, 22.5, 14.01.

Synthesis of the WD01 precatalyst

The WD01 precatalyst was prepared in the same manner as in Example 1, except that the WC01L ligand was used instead of the WC03L ligand.

¹ H NMR (CDCl ₃ ): δ 8.15 (s, 2H), 8.02 s, 2H), 7.56 (s, 2H), 7.50 (s, 2H), 7.23(d, 2H), 7.21(d, 2H), 7.19(s, 2H), 6.95(m, 2H), 6.21(t, 2H), 4.61(t, 2H), 3, 84(t, 2H), 3.32(t, 2H), 2.0~1.3(m, 42H), 1.36(s, 4H), 0.92(m, 6H), -1, 62(s, 6H).

[Comparative Example 5] Synthesis of WD02 Precatalyst

Synthesis of the ligand WD02L

Ligand WD02L was obtained in the same manner as in example 1, except that 2-iodo-4-n-hexylphenol was used instead of 2-iodo-4-octylphenol (compound 3-1).

¹ H NMR (CDCl ₃ ): δ 8.20 (s, 4H), 7.43 (d, 4H), 7.28 (s, 2H), 7.08(d, 6H), 7.04 (d , 2H), 6.52 (m, 2H), 6.02 (m, 2H), 5.45 (s, 2H), 3.84 (t, 4H), 2.59 (t, 4H), 2 .04 (d, 2H), 1.62 (m, 4H), 1.49 (s, 36H), 1.31 (m, 12H), 0.90 (m, 6H); ¹³ C-{ ¹ H}-NMR: 158.16, 156.25, 151.24, 148.21, 142.94, 139.93, 135.78, 131.14, 128.94, 126.70, 124.89, 123.67, 123.53, 118.39, 118.21, 116.43, 115.53, 115.35, 113.07, 113.0, 109.52, 65.21, 35, 14, 34.89, 32.2, 31.79, 31.59, 29.11, 29.00, 22.73, 14.21.

Synthesis of the WD02 precatalyst

The WD02 precatalyst was prepared in the same manner as in Example 1, except that the WC02L ligand was used instead of the WC03L ligand.

¹ H NMR (CDCl ₃ ): δ 8.15 (s, 2H), 8.00 (s, 2H), 7.32 (s, 2H), 7.21 (s, 2H), 7.07 (d , 2H), 7.04 (d, 2H), 7.00(s, 2H), 6.95 (s, 2H), 6.51 (m, 2H), 6.21 (t, 2H), 4 .61(t, 2H), 3.84(t, 2H), 3.32(t, 2H), 1.61(m, 4H), 1.5~1.3(m, 48H), 0, 92 (m, 6H), -1.62 (s, 6H).

[Example 3] Copolymerization of ethylene and 1-octene

The polymerization was carried out in a temperature controlled continuous polymerization reactor equipped with a mechanical stirrer. Into a 1.0 L reactor with continuous stirring, preheated to a temperature of 130-200°C, was fed the solvent methylcyclohexane, 1-octene and ethylene monomer at a pressure of 40 bar. The copolymerization reaction was carried out by feeding the reactor WC03 (Example 1) as a polymerization catalyst and TTB (trityl tetrakis-pentafluorophenylborate) as a co-catalyst from a catalyst storage tank and TiBAO (tetraisobutylaluminumoxane) as a scavenger. Methylcyclohexane as a reaction solvent was introduced into the reactor in an amount of 5 kg per hour with a residence time in the reactor of approximately 8 minutes, and ethylene was introduced into the reactor with a C2/MCH ratio set to 10 in an amount in the range of approximately 400-600 g per hour. The polymerization was carried out at a relatively high temperature of 180°C, 190°C and 200°C, the catalyst was introduced into the reactor, adjusting the amount of catalyst introduced by the amount to maintain the temperature difference between the supply temperature and the reactor temperature, and the pressure of the polymer solution formed by the copolymerization reaction , was reduced to 3 bar at the rear of the reactor and then passed to the solvent separator, thereby removing most of the solvent during the solvent separation process.

The polymerization reaction conditions and the results of the polymerization carried out as described above are shown in Table 1 below.

[Example 4]

The process was carried out in the same manner as in Example 3, except that the WC04 precatalyst synthesized in Example 2 was used for polymerization. and the polymerization reaction conditions and polymerization results are shown in Table 1 below.

[Comparative Example 6]

The method was carried out in the same manner as in Example 3, except that WB02 synthesized in Comparative Example 3 was used as a pre-catalyst. The polymerization reaction conditions and results are shown in Table 2 below.

[Comparative Example 7]

The method was carried out in the same manner as in Example 3, except that WC01 synthesized in Comparative Example 1 was used as the pre-catalyst. The polymerization reaction conditions and results are shown in Table 2 below.

[Comparative Example 8]

The method was carried out in the same manner as in Example 3, except that WC02 synthesized in Comparative Example 2 was used as a pre-catalyst. The polymerization reaction conditions and results are shown in Table 2 below.

[Comparative Example 9]

The method was carried out in the same manner as in Example 3, except that WD01 synthesized in Comparative Example 4 was used as the pre-catalyst. The polymerization reaction conditions and results are shown in Table 2 below.

[Comparative Example 10]

The method was carried out in the same manner as in Example 3, except that WD02 synthesized in Comparative Example 5 was used as the pre-catalyst. The polymerization reaction conditions and results are shown in Table 2 below.

[Table 1]

Example 3 Example 4 Catalyst WC03 (example 1) WC04 (example 2) Pace. polymerization ( ^o C) 190 200 180 190 180 190 Serving temperature ( ^o C) 85 95 85 95 85 95 delta T 105 105 95 95 95 95 TSR (kg/h) 3.2 3.2 3.2 3.2 3.2 3.2 Retention time (min) 8.4 8.4 8.4 8.4 8.4 8.4 C2 (%) ten ten ten ten ten ten Ratio C8/C2 1.0 1.0 1.0 1.0 1.0 1.0 TTB (µmol/kg) fifty fifty fifty fifty fifty fifty TiBAO (µmol/kg) 200 200 200 200 200 200 Consumable cat-r (µmol/kg) 1.6 1.7 0.9 1.2 0.9 1.3 MI 0.515 1.017 0.29 0.715 0.31 0.73 Density 0.891 0.8895 0.893 0.881 0.891 0.880 Mw (×10 ³ ) - - 131 122 135 121 PDI - - 2.4 2.3 2.3 2.4

[Table 2]

Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Catalyst WB02
(Comparative example 3) WC01
(Comparative example 1) WC02
(Comparative example 2) WD01
(Comparative example 4) WD02
(Comparative example 5) Pace. polymerization ( ^o C) 190 180 180 190 190 200 190 200 Serving temperature ( ^o C) 85 85 85 95 85 95 85 85 delta T 95 95 95 95 105 105 105 105 TSR (kg/h) 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 Retention time (min) 8.4 8.4 8.4 8.4 8.4 8.4 8.4 8.4 C2 (%) ten ten ten ten ten ten ten ten Ratio C8/C2 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 TTB (µmol/kg) fifty fifty fifty fifty fifty fifty fifty fifty TiBAO (µmol/kg) 200 200 200 200 200 200 200 200 Consumable cat-r (µmol/kg) 1.4 6.8 1.6 3.4 1.5 2.2 2.0 2.3 MI 6.969 32.2 0.694 1.128 0.44 0.736 0.457 1.025 Density 0.9255 0.908 0.892 0.882 0.901 0.901 0.8977 0.9 Mw (×10 ³ ) 69 37 95 67 - - - - PDI 2.3 2.7 2.3 2.3 - - - -

As described in the polymerization results in Tables 1 and 2, it was unexpectedly found that the precatalysts of the present invention (WC03 and WC04) in which a substituent having a controlled number of carbon atoms and a specific shape is introduced into R ₃ in the chemical formula 1 have excellent catalytic activity. and comonomer reactivity compared to conventional catalysts WB02, WC01, WC02, WD01 and WD02, which are comparative examples. In particular, it was found that even at high temperature polymerization at 180° C. or more, the precatalysts of the examples of the present invention can produce a high molecular weight ethylene-1-octene copolymer compared to the precatalyst of the comparative examples.

That is, in the case of WC01 and WC02, the molecular weight of the copolymers obtained by copolymerization of ethylene and 1-octene at 180°C was 37,000 g/mol and 95,000 g/mol, respectively, while the molecular weight of the copolymers obtained by polymerization using WC03 and WC04 of the present of the invention as a precatalyst was 131,000 g/mol and 135,000 g/mol, respectively, and thus a copolymer with a significantly higher molecular weight compared to the comparative examples can be obtained.

In addition, when polymerized at 190°C, which is higher than 180°C, the WB02 and WC02 catalysts of Comparative Examples also produced copolymers with a molecular weight of 69,000 g/mol and 67,000 g/mol, respectively, while the copolymers obtained using the precatalysts of the present invention (WC03 and WC04) had a high molecular weight of 100,000 g/mol or more.

In addition, under the same polymerization conditions, when comparing the results of polymerization using WD01 (Comparative Example 9) and WD02 (Comparative Example 10) as the precatalyst, in which the number of carbon atoms at the R ₃ position is less than 8, with the results of polymerization using as a pre-catalyst of WC03 (Example 3), which is substituted with straight chain n-octyl with 8 carbon atoms at the R ₃ position, the WC03 of the present invention had higher catalytic activity and comonomer reactivity at 200°C, which is a high polymerization temperature , thereby demonstrating excellent performance in the production of a low density product. That is, for the catalyst consumption reflecting catalytic activity, WD01 and WD02 showed values of 2.2 and 2.3 at 200°C, while WC03 of the present invention showed a value of 1.7, which is a relatively lower catalyst consumption, and, thus reflecting excellent catalytic activity. In addition, it was found that the polymer obtained at a polymerization temperature of 200°C using WD01 and WD02 as a precatalyst had a density of 0.901 g/cm ³ and 0.900 g/cm ³ respectively, while the polymer obtained under the same polymerization conditions using the WD03 of the present invention as a pre-catalyst had a lower density of 0.8895 g/cm ³ .

As shown in the above examples and comparative examples, when a metal ligand complex which is a compound with a certain functional group introduced at a certain position is used as a pre-catalyst, excellent activity is surprisingly exhibited even at a high temperature. In addition, when the metal ligand complex of the present invention is used as a precatalyst, olefin reactivity is excellent, and a polymer with high molecular weight and low density can be obtained easily compared to the metal ligand precatalyst of the comparative example.

As described above, although examples of the present invention have been described in detail, various changes can be made to the present invention by a person skilled in the art without departing from the scope of the present invention as defined in the claims that follow. Accordingly, any future modification of the examples of the present invention cannot deviate from the methodology of the present invention.

Claims (13)

1. Metal ligand complex selected from compounds represented by the following chemical formulas:

(precatalyst WC03);

(precatalyst WC04). 2. An ethylene-based polymerization catalyst composition comprising: metal ligand complex according to claim 1 and cocatalyst. 3. The catalyst composition of claim 2, wherein the cocatalyst is an aluminum compound cocatalyst, a boron compound cocatalyst, or a mixture thereof. 4. Catalyst composition according to claim 2, in which the co-catalyst is used in an amount of from 0.5 to 10,000 mol per 1 mol of the metal ligand complex. 5. A method for producing an ethylene-based polymer, including: polymerizing ethylene or ethylene and an α-olefin in the presence of the ethylene-based polymerization catalyst composition of claim 2 to form an ethylene-based polymer. 6. The method according to p. 5, in which the polymerization is carried out at 170-250°C.