KR20220009900A - Transition metal compound and catalyst composition comprising the same - Google Patents

Abstract

The present invention relates to a novel transition metal compound which realizes excellent catalytic activity in polyethylene polymerization and is useful for preparing polyethylene having a high intramolecular short-chain branching content without degradation of physical properties such as molecular weight, melting point, density, and the like, a catalyst composition comprising the same, and a method for manufacturing polyethylene using the same.

Description

Transition metal compound and catalyst composition comprising the same

The present invention relates to a novel transition metal compound and a catalyst composition comprising the same.

Linear low-density polyethylene is widely used in stretch films and overlap films, where it is difficult to apply conventional low-density polyethylene or high-density polyethylene, because it has high breaking strength and elongation, as well as excellent tear strength and falling impact strength, along with the characteristics of general polyethylene.

Low-density polyethylene produced by the high-pressure method has a high melt tension and has good moldability, so it is being used for applications such as films and hollow containers. However, since high-pressure low-density polyethylene has numerous long-chain branching structures, there is a problem in that mechanical strength such as tensile strength, tear strength or impact strength is inferior.

The ethylene-based polymer obtained by using the Ziegler catalyst has excellent mechanical strength such as tensile strength, tear strength or impact resistance compared to high-pressure low-density polyethylene, but has a disadvantage in that the molded article such as a film is sticky.

In order to solve this problem, various ethylene-based polymers using a metallocene catalyst as a homogeneous catalyst (single site catalyst) have been disclosed.

Japanese Patent Laid-Open No. 2005-97481 discloses an ethylene-based polymer obtained by gas phase polymerization in the presence of a catalyst composed of racemic-ethylene bis(1-indenyl)zirconium diphenoxide, and Japanese Patent Application Laid-Open No. 1997-111208 discloses a metal An ethylene-based polymer (Exxon Chemical, trade name EXACT) obtained by using a Rosene compound as a polymerization catalyst is disclosed in Japanese Patent Laid-Open No. 1999-269324 with ethylene-bis(4,5,6,7-tetrahydroindenyl)zirconium. An ethylene-based polymer obtained by high-pressure ionic polymerization in the presence of a catalyst consisting of dichloride and methylalumoxane is disclosed in Japanese Patent Laid-Open No. 2002-3661, bis(n-butylcyclopentadienyl)zirconium dichloride and methylalu An ethylene-based polymer obtained using a catalyst composed of moxane is disclosed.

In addition, U.S. Patent No. 6,180,736 describes a method for producing polyethylene using one type of metallocene catalyst and producing it in a single gas phase reactor or a continuous slurry reactor, so that the manufacturing cost is low, fouling hardly occurs, and the polymerization activity is stable. . In addition, U.S. Patent No. 6,911,508 reports on the preparation of polyethylene with improved rheological properties by polymerization in a single gas phase reactor using a novel metallocene catalyst compound and 1-hexene as a comonomer. However, there is a problem of poor processability due to a narrow molecular weight distribution. In addition, U.S. Patent No. 6,828,394 reports on a method for producing polyethylene having excellent processability and particularly suitable for films by using a mixture of those having good comonomer binding properties and those not having good comonomer binding properties.

On the other hand, U.S. Patent Nos. 6,841,631 and 6,894,128 disclose that at least two types of metal compounds are used as metallocene-based catalysts to produce polyethylene having a bicrystalline or polycrystalline molecular weight distribution, and to be used in films, blow molding, pipes, etc. reported to be applicable. However, these products have improved processability, but the dispersion state for each molecular weight within the unit particle is not uniform, so the extrusion appearance is rough and the physical properties are not stable even under relatively good extrusion conditions.

Against this background, there is a constant demand for the production of better products with a balance between physical properties and processability, and further improvement is required.

An object of the present specification is to provide a novel transition metal compound useful for preparing polyethylene having a high molecular weight and an intramolecular short chain branch (SCB) content along with excellent catalytic activity for ethylene polymerization.

In addition, the present specification is to provide a catalyst composition comprising the transition metal compound.

In addition, the present invention is to provide a method for producing polyethylene using the catalyst composition and polyethylene produced therefrom.

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

[Formula 1]

In Formula 1,

A is a group 14 element,

M is a Group 4 transition metal,

R ¹ and R ² are the same as or different from each other, and each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl , C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

X ¹ , and X ² are the same as or different from each other and are each independently halogen,

Q ¹ , and Q ² are the same as or different from each other _{, and are each independently C 1-20} alkyl.

In addition, the present invention provides a catalyst composition comprising the transition metal compound.

In addition, the present invention provides a method for producing polyethylene, comprising the step of copolymerizing ethylene and alpha-olefin in the presence of the catalyst composition.

In addition, the present invention provides a polyethylene obtained by the above production method.

The terminology used herein is used to describe exemplary embodiments only, and is not intended to limit the present invention.

The singular expression includes the plural expression unless the context clearly dictates otherwise.

In this specification, terms such as "comprises", "comprises" or "have" are used to describe embodied features, numbers, steps, components, or combinations thereof, and include one or more other features, numbers, or steps. , components, combinations or additions thereof are not excluded.

Also in this specification, when it is said that each layer or element is formed "on" or "over" each layer or element, it means that each layer or element is formed directly on each layer or element, or other It means that a layer or element may additionally be formed between each layer, on the object, on the substrate.

In addition, the terms "about," "substantially," and the like, to the extent used throughout this specification are used in or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and are used in the meaning of the present application. It is used to prevent an unscrupulous infringer from using the disclosure in which exact or absolute figures are mentioned for better understanding.

In addition, in the present invention, the (co)polymer is meant to include both a homo-polymer and a copolymer (co-polymer).

Unless otherwise defined herein, "copolymerization" may mean block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization, and "copolymer" means block copolymer, random copolymer, graft copolymer or alternating copolymer. It can mean amalgamation.

Since the present invention may have various changes and may have various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, and should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in detail.

According to one aspect of the present invention, there is provided a transition metal compound represented by the following formula (1).

[Formula 1]

In Formula 1,

A is a group 14 element,

M is a Group 4 transition metal,

R ¹ and R ² are the same as or different from each other, and each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl , C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

X ¹ , and X ² are the same as or different from each other and are each independently halogen,

Q ¹ , and Q ² are the same as or different from each other _{, and are each independently C 1-20} alkyl.

Specifically, the compound represented by Formula 1 is a compound having an asymmetric structure in which an indacene ligand and an indene ligand having a specific substituent are bonded to each other by a specific bridging group, wherein the compound is an indacene ligand and an indene ligand 2 times It is characterized in that the methyl group is substituted at the position and the alkyl group is bonded to the substituted bridging group. In particular, the compound is a compound having a symmetric structure in which the same ligand is bridged, or a compound in which a bulky substituent other than a methyl group is bonded to the ligand, or a compound including a substituent including a hetero atom such as oxygen in the bridging group. While exhibiting excellent process stability and high polymerization activity, it greatly increases the short chain branch (SCB) content in the molecule to change the molecular structure and distribution, so that it has excellent morphology, excellent mechanical properties, and enhanced durability. It can be effectively applied to catalysts.

As used herein, "racemic form" or "racemic form" or "racemic isomer" means that the same substituent on two indenyl and indacenyl moieties is a transition metal represented by M in Formula 1 above, For example, it refers to a shape on opposite sides of a plane including a transition metal such as zirconium (Zr) or hafnium (Hf) and the center of the indenyl and indacenyl portions.

And, as used herein, the term "meso isomer" or "meso isomer" is a stereoisomer of the above-mentioned racemic isomer, and the same substituents on two indenyl and indacenyl moieties are represented by M in Formula 1 above. The indicated transition metal, for example, means a plane including a transition metal such as zirconium (Zr) or hafnium (Hf), and a form on the same side with respect to the center of the indenyl and indacenyl moieties.

In addition, unless there is a special limitation in the present specification, the following terms may be defined as follows.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

Alkyl having 1 to 20 carbon atoms (C _1-20 ) may be a straight chain, branched chain or cyclic alkyl. Specifically, alkyl having 1 to 20 carbon atoms is straight-chain alkyl having 1 to 20 carbon atoms; straight-chain alkyl having 1 to 15 carbon atoms; straight-chain alkyl having 1 to 5 carbon atoms; branched or cyclic alkyl having 3 to 20 carbon atoms; branched or cyclic alkyl having 3 to 15 carbon atoms; Or it may be a branched or cyclic alkyl having 3 to 10 carbon atoms. For example, the alkyl having 1 to 20 carbon atoms (C _1-20 ) is methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl , cyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

The alkenyl having 2 to 20 carbon atoms (C _2-20 ) includes straight-chain or branched alkenyl, and specifically includes allyl, allyl, ethenyl, propenyl, butenyl, pentenyl, and the like. but is not limited.

Examples of alkoxy having 1 to 20 carbon atoms (C _1-20 ) include, but are not limited to, a methoxy group, ethoxy, isopropoxy, n-butoxy, tert-butoxy, and cyclohexyloxy group. .

The alkoxyalkyl group having 2 to 20 (C _2-20 ) is a functional group in which one or more hydrogens of the aforementioned alkyl are substituted with alkoxy, specifically methoxymethyl, methoxyethyl, ethoxymethyl, iso-propoxymethyl, alkoxyalkyl such as iso-propoxyethyl, iso-propoxypropyl, iso-propoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxypropyl, and tert-butoxyhexyl; The present invention is not limited thereto.

The aryloxy having 6 to 40 carbon atoms (C _6-40 ) may include, but is not limited to, phenoxy, biphenoxyl, naphthoxy, and the like.

The aryloxyalkyl group having 7 to 40 (C _7-40 ) is a functional group in which one or more hydrogens of the aforementioned alkyl are substituted with aryloxy, and specifically, phenoxymethyl, phenoxyethyl, phenoxyhexyl, etc. may be mentioned. , but is not limited thereto.

Alkylsilyl having 1 to 20 (C _1-20 ) or an alkoxysilyl group having 1 to 20 (C _1-20 ) is -SiH ₃ 1 to 3 hydrogens are 1 to 3 alkyl or alkoxy as described above. A substituted functional group, specifically, alkylsilyl, such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl group or dimethylpropylsilyl; alkoxysilyl such as methoxysilyl, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl; alkoxyalkylsilyl such as methoxydimethylsilyl, diethoxymethylsilyl, or dimethoxypropylsilyl, but is not limited thereto.

Silylalkyl having 1 to 20 (C _1-20 ) is a functional group in which one or more hydrogens of alkyl as described above are substituted with silyl, specifically -CH ₂ -SiH ₃ , methylsilylmethyl or dimethylethoxysilylpropyl, etc. can be mentioned, but is not limited thereto.

In addition, the alkylene having 1 to 20 carbon atoms (C _1-20 ) is the same as the above-mentioned alkyl except that it is a divalent substituent, specifically methylene, ethylene, propylene, butylene, pentylene, hexylene, hep. tylene, octylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and the like, but is not limited thereto.

Aryl having 6 to 20 carbon atoms (C _6-20 ) may be a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. For example, the aryl having 6 to 20 carbon atoms (C _6-20 ) may include, but is not limited to, phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, and fluorenyl.

_Alkylaryl having 7 to 20 carbon atoms (C 7-20 ) may refer to a substituent in which one or more hydrogens among hydrogens of an aromatic ring are substituted by the aforementioned alkyl. For example, the alkylaryl having 7 to 20 carbon atoms (C _7-20 ) may include, but is not limited to, methylphenyl, ethylphenyl, methylbiphenyl, methylnaphthyl, and the like.

The arylalkyl having 7 to 20 carbon atoms (C _7-20 ) may mean a substituent in which one or more hydrogens of the aforementioned alkyl are substituted by the aforementioned aryl. For example, the arylalkyl having 7 to 20 carbon atoms (C _7-20 ) may include, but is not limited to, phenylmethyl, phenylethyl, biphenylmethyl, naphthylmethyl, and the like.

In addition, arylene having 6 to 20 (C _6-20 ) is the same as the above-described aryl except that it is a divalent substituent, specifically phenylene, biphenylene, naphthylene, anthracenylene, and phenanthrenylene. , fluorenylene, and the like, but are not limited thereto.

And, the Group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf), or rutherpodium (Rf), specifically, titanium (Ti), zirconium (Zr), or hafnium (Hf) may be, and more specifically, may be zirconium (Zr) or hafnium (Hf), but is not limited thereto.

In addition, the group 13 element may be boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), specifically, boron (B), or aluminum (Al). and is not limited thereto.

The above-mentioned substituents are optionally a hydroxyl group within the range of exhibiting the same or similar effect as the desired effect; halogen; alkyl or alkenyl, aryl, alkoxy; alkyl or alkenyl, aryl, alkoxy containing one or more heteroatoms among the heteroatoms of Groups 14 to 16; silyl; alkylsilyl or alkoxysilyl; phosphine group; phosphide group; sulfonate group; And it may be substituted with one or more substituents selected from the group consisting of a sulfone group.

For reference, in the present specification, "part by weight" refers to a relative concept in which the weight of the other material is expressed as a ratio based on the weight of a certain material. For example, in a mixture in which the weight of material A is 50 g, the weight of material B is 20 g, and the weight of material C is 30 g, based on 100 parts by weight of material A, the amounts of material B and material C are each 40 parts by weight and 60 parts by weight.

On the other hand, "wt% (% by weight)" means an absolute concept in which the weight of a certain material is expressed as a percentage among the total weight. In the mixture exemplified above, the content of material A, material B, and material C in 100% of the total weight of the mixture is 50% by weight, 20% by weight, and 30% by weight, respectively.

Specifically, in Formula 1, A may be carbon, silicon, or germanium, preferably silicon.

In Formula 1, M may be zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).

In particular, the transition metal compound exhibits excellent process stability and high polymerization activity when applied as a catalyst to an ethylene polymerization process by substituting a methyl group at a specific position of the indacene ligand and the indene ligand, that is, position 2, while exhibiting a short intramolecular chain By greatly increasing the short chain branch (SCB) content, the molecular structure and distribution are changed, and the resulting polymer is dispersed like grains of sand with excellent mechanical properties, and an excellent morphology can be realized in which the grains maintain their original shape.

^{In addition, the transition metal compound includes substituents R 1} and R ² at a specific position in the indacene ligand and the indene ligand in addition to the methyl group, that is, at the 4th position of the indacene ligand and the indene ligand.

Specifically, R ¹ and R ² may each be hydrogen, phenyl, _{or phenyl substituted with C 1-6} straight or branched chain alkyl. For example, R ¹ and R ² may each be hydrogen, phenyl, or phenyl _{substituted with C 1-4} straight or branched chain alkyl, preferably hydrogen, phenyl, or phenyl substituted with tert-butyl .

For example, the transition metal compound may be represented by the following Chemical Formula 1-1.

[Formula 1-1]

In Formula 1-1, A, M, X ¹ , X ² , Q ¹ , Q ² are as defined in Formula 1,

In Formula 1-1, R' is the same as or different from each other, and each independently represents hydrogen or C _1-6 straight or branched chain alkyl;

a and b are each independently 0 or 1.

In addition, in Formula 1-1, at least one of R' may be C _3-6 branched chain alkyl, and the remaining R' may be hydrogen. Specifically, R' may be hydrogen or tert-butyl.

In addition, when a and b are 0 in Formula 1-1, hydrogen is substituted.

Meanwhile, in Chemical Formulas 1 and 1-1, X ¹ and X ² are each a halogen, specifically chlorine, iodine, or bromine, preferably chlorine.

In addition, in Formulas 1 and 1-1, Q ¹ , Q ² are the same as or different from each other, and each is C _1-6 straight or branched chain alkyl, C _1-4 straight or branched chain alkyl, or C _1-3 It may be a straight chain or branched chain alkyl. In particular, Q ¹ and Q ² may each be C _1-6 straight chain alkyl, C _1-4 straight chain alkyl, or C _1-3 straight chain alkyl. For example, Q ¹ , and Q ² may each be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, preferably methyl, ethyl, or n-propyl have.

In particular, in the transition metal compound of the present invention, the substituents Q ¹ , Q ² included in the bridging group consist of an alkyl group rather than a substituent including a hetero atom such as oxygen. can be obtained

In addition, the compound represented by the formula (1), more preferably, may be any one of the compounds represented by the following structural formula.

.

.

The structural formula is only an example for explaining the present invention, and the present invention is not limited thereto.

And, a series of reactions for preparing the ligand compound and the transition metal compound are shown in Scheme 1 below. However, the following reaction scheme is only an example for explaining the present invention, and the present invention is not necessarily limited thereto.

Hereinafter, referring to Scheme 1, the transition metal compound according to an embodiment of the present invention is a halogenated silane compound in ^{which R 2} substituted 2-methylindenyl compound (Compound 1) and Q ¹ and Q ^{2 are substituted (silane).} ) to prepare a 2-methylindenyl compound (Compound 2) to which a bridging group containing a group 14 element A is linked (Step 1); The 2-methylindenyl compound (Compound 2) having ^{a bridge containing the group 14 element A is reacted with an indacene compound substituted with R 1} , so that 2-methylindenyl and indacenyl are a bridge containing the group 14 element A Preparing a ligand compound (Compound 3) linked to a group (Step 2); The ligand compound (Compound 3) is reacted with a halogen salt of a Group 4 transition metal in ^{which X 1} , X ² is substituted with a halogen element in the Group 4 transition metal M, and the transition metal compound of Formula 1 (Compound 4) ) may be prepared by a method comprising a; (Step 3) for manufacturing.

[Scheme 1]

In Scheme 1, each substituent is as defined above, and X is a halogen element, and may be, for example, chlorine, iodine, or bromine, preferably chlorine. In addition, the reaction in each step may be performed by applying known reactions, and for a more detailed synthesis method, reference may be made to Examples to be described later.

Specifically, in the method for preparing the transition metal compound according to an embodiment of the present invention, a precursor compound having ^{methyl and R 2 as specific substituents at the 2nd and 4th positions, respectively, such as 2-methylindenyl (Compound 1)} reacted with a bridging group-providing compound such as a halogenated silane in the presence of alkyl lithium such as N-butyl lithium (N-Buli), to which a bridge containing a group 14 element A such as silicon is bonded to 2-methyl Preparing an indenyl compound (Compound 2) (Step 1); The 2-methylindenyl compound (Compound 2) to which the silicon bridge is bonded, in the presence of an alkyl lithium such as N-butyl lithium (N-Buli) and a Cucn catalyst, is a specific substituent at the 2nd and 4th positions, respectively. By reacting with an indacenyl compound having methyl and R ¹ , as described above, a ligand compound in which a 2-methyl indenyl structure and a 2-methyl indacenyl structure are linked by a bridging group including a group 14 element A such as silicon (Compound 3 ) to prepare (Step 2); and reacting the ligand compound (Compound 3) with _{a halogen salt of a Group 4 transition metal such as ZrCl 4} to prepare a transition metal compound (Compound 4) of Formula 1 (Step 3); may include

Meanwhile, according to another aspect of the present invention, a catalyst composition comprising the above-described transition metal compound is provided.

Specifically, the catalyst composition according to an embodiment of the present invention may include the transition metal compound of Formula 1 as a single catalyst.

In this case, the catalyst composition may include the transition metal compound as a single catalyst component, for example, may be in the form of a supported metallocene catalyst including the transition metal compound and a carrier. When a supported metallocene catalyst is used, the morphology and physical properties of the polyethylene produced are excellent, and it can be suitably used in the conventional slurry polymerization, bulk polymerization, or gas phase polymerization process.

Specifically, as the carrier, a carrier having a hydroxyl group, a silanol group, or a siloxane group having a high reactivity on the surface may be used. can be used For example, silica prepared by calcining silica gel, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are typically Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ). ₂ and the like oxide, carbonate, sulfate, and nitrate components.

The temperature for calcining or drying the carrier may be from about 200 °C to about 600 °C, or from about 250 °C to about 600 °C. When the calcination or drying temperature for the carrier is low, there is a risk that the surface moisture and the cocatalyst may react because there is too much moisture remaining in the carrier, and the cocatalyst loading rate is relatively low due to the excess hydroxyl groups. It can be increased, but this requires a large amount of co-catalyst. In addition, if the drying or calcination temperature is too high, the surface area decreases as the pores on the surface of the carrier coalesce, a lot of hydroxyl groups or silanol groups disappear on the surface, and only siloxane groups remain, so there is a risk of reducing the reaction site with the promoter. have.

The amount of hydroxyl groups on the surface of the carrier is preferably 0.1 mmol/g to 10 mmol/g, more preferably 0.5 mmol/g to 5 mmol/g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions or drying conditions of the carrier, such as temperature, time, vacuum or spray drying, and the like.

If the amount of the hydroxyl group is less than 0.1 mmol/g, there are few reaction sites with the co-catalyst, and if it exceeds 10 mmol/g, it is not preferable because it may be caused by moisture other than the hydroxyl group present on the surface of the carrier particle. not.

For example, the amount of hydroxyl groups on the surface of the carrier may be 0.1 mmol/g to 10 mmol/g or 0.5 mmol/g to 5 mmol/g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions or drying conditions of the carrier, such as temperature, time, vacuum or spray drying, and the like. If the amount of the hydroxyl group is too low, there are few reaction sites with the promoter, and if it is too large, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle.

Among the above-mentioned carriers, silica, especially silica prepared by calcining silica gel, is supported by chemical bonding between the silica carrier and the functional group of the compound of Formula 1, so the catalyst released from the surface of the carrier in the propylene polymerization process is almost non-existent. As a result, when polyethylene is produced by slurry or gas phase polymerization, it is possible to minimize fouling of the reactor wall or polymer particles agglomerated with each other.

In addition, when supported on a carrier, the compound of Formula 1 is present in an amount of, for example, about 10 μmol or more, or about 30 μmol or more, and about 100 μmol or less, or about 80 μmol or less, based on the weight of the carrier, based on about 1 g of silica. It may be supported in a content range. When supported in the above content range, it may exhibit an appropriate supported catalyst activity, which may be advantageous in terms of maintaining the activity of the catalyst and economic feasibility.

In addition, the catalyst composition may further include one or more cocatalysts together with the above-described transition metal compound and the carrier.

The cocatalyst may be any cocatalyst used for polymerization of olefins under a general metallocene catalyst. This co-catalyst causes a bond to be formed between the hydroxyl group and the Group 13 transition metal on the carrier. In addition, since the cocatalyst exists only on the surface of the carrier, it can contribute to securing the unique characteristics of the specific hybrid catalyst composition of the present application without a fouling phenomenon in which the polymer particles are agglomerated with the reactor wall or each other.

In addition, the catalyst composition may further include one or more cocatalysts selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4.

[Formula 2]

-[Al(R ²¹ )-O] _m -

In Formula 2,

R ²¹ are the same as or different from each other and are each independently halogen, C _1-20 alkyl or C _1-20 haloalkyl;

m is an integer greater than or equal to 2;

[Formula 3]

J(R ³¹ ) ₃

In Formula 3,

R ³¹ are the same as or different from each other and are each independently halogen, C _1-20 alkyl or C _1-20 haloalkyl;

J is aluminum or boron;

[Formula 4]

[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-

In Formula 4,

E is a neutral or cationic Lewis base, [EH] ⁺ and [E] ⁺ are Bronsted acids;

H is a hydrogen atom;

Z is a group 13 element;

Q is the same as or different from each other and is each independently C _6-20 aryl or C _1-20 alkyl, wherein the C _6-20 aryl or C _1-20 alkyl is unsubstituted or halogen, C _1-20 alkyl , C _1-20 alkoxy and C _6-20 substituted with one or more substituents selected from the group consisting of phenoxy.

In the present specification, the hydrocarbyl group is a monovalent functional group in the form of removing a hydrogen atom from hydrocarbon, and an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenyl group It may include an aryl group and an alkynylaryl group. The hydrocarbyl group having 1 to 30 carbon atoms may be a hydrocarbyl group having 1 to 20 carbon atoms or 1 to 10 carbon atoms. For example, the hydrocarbyl group may be a straight chain, branched chain or cyclic alkyl group. More specifically, the hydrocarbyl group having 1 to 30 carbon atoms is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, and a n-hexyl group. straight-chain, branched-chain or cyclic alkyl groups such as a sil group, n-heptyl group, and cyclohexyl group; or an aryl group such as phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, or fluorenyl. In addition, it may be an alkylaryl such as methylphenyl, ethylphenyl, methylbiphenyl, or methylnaphthyl, and may be an arylalkyl such as phenylmethyl, phenylethyl, biphenylmethyl, or naphthylmethyl. In addition, it may be an alkenyl such as allyl, allyl, ethenyl, propenyl, butenyl, pentenyl.

The compound represented by Formula 2 may be, for example, alkylaluminoxane such as modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like.

The alkyl metal compound represented by the above formula (3) is, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethylchloro Aluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolyl aluminum, dimethylaluminummethoxide, dimethylaluminumethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like.

The compound represented by Formula 4 is, for example, triethylammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p- Tolyl) boron, tripropylammonium tetra(p-tolyl) boron, triethylammonium tetra(o,p-dimethylphenyl) boron, trimethylammonium tetra(o,p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributyl Ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra ( o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N ,N-diethylanilinium tetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentafluorophenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphonium Tetraphenylaluminum, triphenylcarboniumtetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenylcarboniumtetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetrapentafluorophenylboron, etc. can

In addition, the catalyst composition may include the cocatalyst and the metallocene compound of Formula 1 in a molar ratio of about 1:1 to about 1:10000, preferably about 1:1 to about 1:1000, respectively. It may be included in a molar ratio of, and more preferably, may be included in a molar ratio of about 1:10 to about 1:100. At this time, if the molar ratio is less than about 1, the metal content of the cocatalyst is too small, so the catalytically active species is not well made, and the activity may be lowered. have.

The supported amount of the cocatalyst may be from about 3 mmol to about 25 mmol, or from about 5 mmol to about 20 mmol based on 1 g of the carrier.

On the other hand, the catalyst composition, the step of supporting a cocatalyst on a carrier; supporting the metallocene compound on the support on which the promoter is supported; and a carrier on which the promoter and the metallocene compound are supported.

In the above method, the supporting conditions are not particularly limited and may be performed within a range well known to those skilled in the art. For example, it can proceed by appropriately using high-temperature loading and low-temperature loading, for example, the loading temperature is ^{possible in the range of about -30 o} C to about 150 ^o C, preferably about 50 ^o C to about 98 ^o C, or from about 55 ^o C to about 95 ^o C. The loading time may be appropriately adjusted according to the amount of the first metallocene compound to be supported. The supported catalyst reacted may be used as it is by removing the reaction solvent by filtration or distillation under reduced pressure, and if necessary, it may be used after Soxhlet filter with an aromatic hydrocarbon such as toluene.

And, the preparation of the supported catalyst may be carried out in the presence of a solvent or non-solvent. When a solvent is used, the usable solvent includes an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, diethyl ether or tetrahydrofuran (THF) ) and most organic solvents such as acetone and ethyl acetate, preferably hexane, heptane, toluene, or dichloromethane.

In addition, the catalyst composition may further include at least one antistatic agent represented by the following formula (5).

[Formula 5]

R ⁵¹ N-(CH ₂ CH ₂ OH) ₂

In Formula 5, R ⁵¹ is C _8-30 straight-chain alkyl.

Specifically, in Formula 5, R ⁵¹ is C _8-30 alkyl, and when R ⁵¹ includes an alkyl group having a carbon number in the above-described range, it exhibits an effect of reducing fine powder through excellent antistatic action without causing unpleasant odor. can

More specifically, the hydroxyethyl-substituted alkylamine may be a compound in which R ⁵¹ in Formula 5 is C _8-22 straight-chain alkyl, C _12-18 straight-chain alkyl, or C _13-15 straight-chain alkyl, , either alone or a mixture of two or more of these compounds may be used. In addition, as a commercially available product, N,N-bis(2-hydroxyethyl)pentadecylamine (N,N-Bis(2-hydroxyethyl)pentadeylamine, Atmer 163 ^TM , manufactured by CRODA) may be used.

In addition, when an antistatic agent is further included, it may be included in an amount of 1 g to 10 g, more specifically 1 g to 5 g, based on 100 g of the carrier.

When the catalyst composition includes all of the above-described carrier, co-catalyst and antistatic agent, the catalyst composition comprises the steps of supporting the co-catalyst on a carrier; supporting the transition metal compound on the support on which the promoter is supported; and adding an antistatic agent in a solution or suspension state to the carrier on which the promoter and the transition metal compound are supported. As described above, the catalyst composition having a structure in which a promoter, a transition metal compound, and an antistatic agent are supported in this order on a carrier may exhibit excellent process stability with high catalytic activity in the polypropylene manufacturing process.

On the other hand, the present invention, in the presence of the catalyst composition, provides a method for producing polyethylene, comprising the step of copolymerizing ethylene and alpha-olefin.

The above-described catalyst composition can exhibit excellent supporting performance, catalytic activity and high co-polymerizability, and even if low-density polyethylene is prepared in a slurry process in the presence of such a catalyst composition, it prevents problems related to conventional productivity deterioration and fouling, and improves process stability can do it

The method for preparing the polyethylene may be carried out by slurry polymerization by applying a conventional apparatus and contacting technique using ethylene and alpha-olefin as raw materials in the presence of the above-described catalyst composition.

The method for preparing the polyethylene may copolymerize ethylene and alpha-olefin using a continuous slurry polymerization reactor, a loop slurry reactor, or the like, but is not limited thereto.

Specifically, in the copolymerization step, based on 1 mole of ethylene, about 0.45 moles or less, or about 0.1 moles to about 0.45 moles, or about 0.4 moles or less, or about 0.2 moles to about 0.4 moles, or about 0.35 moles or less, or from about 0.25 moles to about 0.35 moles.

The method for producing polyethylene has a characteristic that it is not necessary to increase the content of comonomer in order to lower the density of the product, so that the process is stable and the high drop impact strength of the product is reproducible.

In addition, the alpha-olefin is 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, It may be at least one selected from the group consisting of 1-octadecene, 1-eicocene, and mixtures thereof.

Specifically, in the production method of the polyethylene, for example, 1-hexene may be used as the alpha-olefin.

And, the polymerization temperature is about 25 ^o C to about 500 ^o C, or about 25 ^o C to about 300 ^o C, or about 30 ^o C to about 200 ^o C, or about 50 ^o C to about 150 ^o C, or It may be about 60 ^o C to about 120 ^{o C.} In addition, the polymerization pressure may be from about 1 kgf/cm 2 to about 100 kgf/cm 2 , or from about 1 kgf/cm 2 to about 50 kgf/cm 2 , or from about 5 kgf/cm 2 to about 45 kgf/cm 2 , or from about 10 kgf/cm 2 to about 10 kgf/cm 2 about 40 kgf/cm 2 , or about 15 kgf/cm 2 to about 35 kgf/cm 2 .

The catalyst composition including the transition metal compound of Formula 1 according to the present invention is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof, and an aromatic hydrocarbon solvent such as toluene and benzene. , dichloromethane or chlorobenzene can be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom, etc. The solvent used here is preferably used by treating a small amount of alkyl aluminum to remove a small amount of water or air that acts as a catalyst poison, and it is also possible to further use a cocatalyst.

For example, in the polymerization step, hydrogen gas is about 800 ppm or less, or about 0 to about 800 ppm, or about 300 ppm or less, or about 10 ppm to about 300 ppm, or about 100 ppm or less, or about 15 ppm to about, based on the ethylene content. It can be carried out by adding about 100 ppm.

In this ethylene copolymerization process, the catalyst composition including the transition metal compound of the present invention may exhibit high catalytic activity. For example, the catalyst activity during ethylene copolymerization is about 4.0 kg PE /g·cat when calculated as the ratio of the weight (kg PE) of the polyethylene produced per mass (g) of the catalyst composition used based on the unit time (h) hr or more or from about 4.0 kg PE /g.cat.hr to about 50 kg PE /g.cat.hr. Specifically, the activity of the catalyst composition is at least about 4.2 kg PE /g·cat·hr, or at least about 4.3 kg PE /g·cat·hr, or at least about 4.5 kg PE/g·cat·hr, or about 40 kg PE /g·cat·hr or less, or about 30 kg PE /g·cat·hr or less, or about 15 kg PE /g·cat·hr or less.

In particular, when copolymerizing ethylene and alpha-olefin using the catalyst composition containing the transition metal compound of Formula 1 according to the present invention, it exhibits higher comonomer binding properties than before, even when the alpha-olefin comonomer is used in the same amount. Copolymers with higher comonomer content can be produced with higher activity. Accordingly, it is possible to produce a product with a higher comonomer content than a product with an equivalent melting point (Tm) or density, that is, a product with a high Short Chain Branching (SCB) content. In this case, the term short chain branch (SCB) means branches having 2 to 7 carbon atoms attached to the main chain, and is usually a comonomer having 4 or more carbon atoms such as 1-butene, 1-hexene, 1-octene, etc. It refers to the side branches that are formed when olefins are used.

As described above, according to the present invention, polyethylene can be prepared by copolymerizing ethylene and alpha-olefin using the catalyst composition including the transition metal compound of Formula 1 described above.

In this case, the polyethylene to be prepared may be an ethylene 1-hexene copolymer.

The method for producing polyethylene is performed by slurry polymerization in the presence of the above-described catalyst composition, thereby providing polyethylene having excellent mechanical properties.

In particular, the catalyst composition including the transition metal compound of Formula 1 according to the present invention exhibits high activity as described above during copolymerization of ethylene and alpha-olefin, and exhibits high activity without excessively increasing the content of alpha-olefin as a comonomer. It is possible to increase the content of short chain branch (SCB) in the molecule along with the molecular weight.

On the other hand, according to another embodiment of the present invention, the polyethylene prepared by the above-described method, including an alpha-olefin as a comonomer, is provided.

The polyethylene, i.e., the polyethylene copolymer comprising an alpha-olefin as a comonomer, has a weight average molecular weight of from about 380000 g/mol to about 650000 g/mol, or from about 390000 g/mol to about 630000 g/mol, or from about 400000 g/mol to about 580000 g/mol.

For example, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyethylene can be measured using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water).

Specifically, as a gel permeation chromatography (GPC) apparatus, a Waters PL-GPC220 instrument may be used, and a Polymer Laboratories PLgel MIX-B 300 mm long column may be used. At this time, the measurement temperature is 160 ^o C, 1,2,4-trichlorobenzene can be used as a solvent, and the flow rate can be applied at 1 mL/min. Each polyethylene sample was pretreated by dissolving it in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160 ^o C for 10 hours using a GPC analysis device (PL-GP220), and 10 mg/10 mL It can be measured by preparing it at a concentration of , and then supplying it in an amount of 200 μL. In addition, the values of Mw and Mn can be derived using a calibration curve formed using a polystyrene standard specimen. The weight average molecular weight of the polystyrene standard specimen is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 400000 g/mol, 1000000 g Nine types of /mol can be used.

In addition, the polyethylene copolymer may have a melting point (Tm) of about 115 °C or more or about 128 °C or less, or about 117 °C or more or about 126 °C or less.

For example, the melting point (Tm) of the polyethylene copolymer may be determined using a differential scanning calorimeter (DSC).

Specifically, the polyethylene copolymer ^{was heated to 150 o} C, maintained for 5 minutes ^{, lowered to -100 o} C, and then increased again. At this time, the rate of rise and fall of the temperature ^{is adjusted to 10 o} C/min, respectively. The melting temperature is the maximum point of the endothermic peak measured in the section where the second temperature rises.

In addition, the polyethylene copolymer has a short chain branch (SCB) having 2 to 7 carbon atoms per 1000 carbon atoms measured by infrared spectroscopy (FT-IR), 4.0 or more or 10.0 or less, or 4.3. or more, or 4.5 or more, or 8.5 or less, or 7.0 or less.

As an example, the short chain branch (SCB) content in the molecule of the polyethylene copolymer is measured by infrared spectroscopy (FT-IR) by measuring the number of branch short chain branches (SCB) having 2 to 7 carbon atoms per 1000 carbon atoms. can be obtained in a way that

Specifically, the polyethylene copolymer was pretreated by dissolving it in 1,2,4-Trichlorobenzene containing 0.0125% of BHT at 160 °C for 10 hours using PL-SP260VS, and then PerkinElmer Spectrum connected to high-temperature GPC (PL-GPC220). 100 FT-IR was used to measure at 160 °C.

In addition, the polyethylene copolymer is dispersed like grains of sand when observed by the appearance and feel of the finally produced powder, and exhibits an excellent morphology in which the grains maintain a circular shape, and can be effectively applied to the gas phase polymerization reaction for the production of linear low-density polyethylene. .

As described above, the polyethylene obtained according to the present invention may be prepared by copolymerizing ethylene and alpha-olefin using the catalyst composition including the transition metal compound of Formula 1 described above. As a result, the polyethylene realizes high catalytic activity during ethylene copolymerization, and at the same time secures physical properties such as molecular weight, melting point, and density at the same level or higher without increasing the content of alpha-olefin, and at the same time, intramolecular short chain branching (SCB, By greatly increasing the short chain branch) content and changing the molecular structure and distribution, injection products with excellent mechanical properties and excellent durability can be manufactured.

The transition metal compound of the present invention exhibits excellent process stability and high polymerization activity in the ethylene polymerization reaction, and greatly increases the short chain branch (SCB) content in the molecule to change the molecular structure and distribution, thereby providing excellent mechanical properties and has an excellent effect in manufacturing polyethylene with enhanced durability.

Hereinafter, through specific examples of the invention, the operation and effect of the invention will be described in more detail. However, these embodiments are merely presented as an example of the invention, and the scope of the invention is not defined thereby.

<Preparation of metallocene compound>

Synthesis Example 1

Step 1-1. Preparation of ligand compound (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl (2-methyl indene) silane

After 15.24 mmol of 2-methyl indene was added to the reactor, it was dried under reduced pressure for 30 minutes. 70 mL of n-hexane and 10 mL of methyl tert-butyl ether (MTBE) were added and stirred to completely dissolve. After the reactor ^{was cooled to -25 o} C, 6.4 mL (16 mmol) of n-butyllithium (n-BuLi, 2.5 M n-hexane solution) was slowly added dropwise with stirring. After stirring at 25 ^o C for 12 hours, dichloro dimethyl silane (15.24 mmol) was then added thereto.

In another reactor, 2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene) 15.24 After adding mmol to the reactor, it was dried under reduced pressure for 30 minutes. 35 mL of MTBE was added and stirred to completely dissolve. After the reactor ^{was cooled to -25 o} C, 6.4 mL (16 mmol) of n-BuLi (2.5 M n-hexane solution) was slowly added dropwise with stirring. After stirring at 25 ^o C for 12 hours, CuCN was added and reacted for 30 minutes.

After mixing the two reactants prepared in this way, they ^{were reacted at 25 o} C for 12 hours. After adding water and stirring for 1 hour, the reactor was allowed to stand and the water layer was separated. Then, water and toluene were re-injected into the reactor, and after stirring and standing for 5 minutes, the water layer was separated and removed. The organic layer _{was dehydrated with MgSO 4} , filtered again, and put into the reactor and dried.

Step 1-2. Preparation of transition metal compound Dimethyl silanediyl (2-methyl-1H-inden-1-yl) (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) zirconium chloride

The ligand prepared in step 1-1 was dissolved in a mixed solvent (Toluene/Ether, volume ratio 10/1) of _{21 mL of toluene and 2.1 mL of diethylether, Et 2} ^{O, and heated to -25 °} C. After cooling, 12.8 mL (32 mmol) of n-BuLi (2.5 M n-hexane solution) was slowly added dropwise and stirred. After ^{stirring at 25 o} C for 12 hours and cooling ^{to -20 o} _{C, a slurry prepared by mixing ZrCl 4} (15.24 mmol) with toluene (0.17 M) was added. Then, ^{after stirring at 25 o} C for 12 hours, all of the solvent was removed by drying. After filtering and drying using dichloromethane (DCM, dichloromethane), dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried under vacuum to obtain the title metallocene compound as a yellow powder (powder, only racemic) in 20% (molar basis).

For the thus-obtained transition metal compound, NMR data was measured with Bruker AVANCE III HD 500 MHz NMR/PABBO ( ¹ H/ ¹⁹ F/Broad band) probe: ¹ H and solvent: CDCl _{3 .}

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.21(s, 6H), 1.79(S, 6H), 1.95(m, 2H), 2.80(m, 4H), 6.36(s, 2H), 7.18 -7.51 (m, 10H).

Synthesis Example 2

Step 2-1. Preparation of ligand compound (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl (2-methyl-4-phenyl-indene) silane

Synthesis except for using 2-methyl-4-phenyl indene instead of 2-methyl indene as a reactant in step 1-1 of Synthesis Example 1 In the same manner as in step 1-1 of Example 1, the ligand compound (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl (2-methyl-4-phenyl -indene) silane was prepared.

Step 2-2. Transition metal compound Dimethyl silanediyl(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(2-methyl-4-phenyl-1H-inden-1-yl) zirconium production of chloride

In the same manner as in Step 1-2 of Synthesis Example 1 except that the ligand obtained in Step 2-1 was used, the transition metal compound Dimethyl Silanediyl (2-methyl-4-phenyl-1,5,6 having the above structure) ,7-tetrahydro-s-indacen-1-yl)(2-methyl-4-phenyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 2) was prepared.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.22(s, 6H), 1.81(S, 6H), 1.98(m, 2H), 2.81(m, 4H), 6.35(s, 2H), 7.18 -7.49 (m, 13H), 8.29 (d, 1H).

Synthesis Example 3

Step 3-1. Ligand compound (4-(4'-(tert-butyl)phenyl)-2-methyl-inden-1-yl)dimethyl(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene ) production of silane

In step 1-1 of Synthesis Example 1, 4-(4'-(tertbutyl)phenyl)-2methylindene (4-(4'-(tert-) butyl)phenyl)-2-methyl indene) in the same manner as in step 1-1 of Synthesis Example 1, except that the ligand compound (4-(4'-(tert-butyl)phenyl)-2-methyl -inden-1-yl)dimethyl(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene) silane was prepared.

Step 3-2. Transition metal compound Dimethyl silanediyl (4-(4'-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(2-methyl-4-phenyl-1,5,6,7-tetrahydro Preparation of -s-indacen-1-yl) zirconium chloride

In the same manner as in Step 1-2 of Synthesis Example 1 except that the ligand obtained in Step 3-1 was used, the transition metal compound Dimethyl Silanediyl (4-(4'-(tert-butyl)phenyl) having the above structure was used. -2-methyl-1H-inden-1-yl) (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) zirconium chloride (Synthesis Example 3) was prepared .

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.25(s, 6H), 1.33(s, 9H), 1.75(S, 6H), 1.81(m, 2H), 2.81(m, 4H), 6.36 (s, 2H), 7.18-7.39 (m, 12H), 8.21 (d, 1H).

Synthesis Example 4

Step 4-1. Ligand compound (4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(4-(4'-(tert- Preparation of butyl)phenyl)-2-methyl indene)silane

2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene (2-methyl-4-phenyl-1,5,6) as a reactant in step 3-1 of Synthesis Example 3 ,7-tetrahydro-s-indacene) instead of 2-methyl-4-(4'-(tert-butyl)phenyl)-1,5,6,7-tetrahydro-s-indacene (2-methyl-4- The ligand compound ( 4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(4-(4'-(tert-butyl)phenyl )-2-methyl indene) silane was prepared.

Step 4-2. Transition metal compound Dimethyl silanediyl (4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4'-( Preparation of tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride

In the same manner as in Step 3-2 of Synthesis Example 3, except that the ligand obtained in Step 4-1 was used, the transition metal compound Dimethyl silanediyl (4-(4'-(tert-butyl)phenyl) having the structure -2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4'-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 4) was prepared.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.22(s, 6H), 1.29 (s,18H), 1.75(S, 6H), 1.81(m, 2H), 2.81(m, 4H), 6.36 (s, 2H), 7.18-7.39 (m, 11H), 8.21 (d, 1H).

Synthesis Example 5

Step 5-1. Preparation of ligand compound (2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(4-(4'-(tert-butyl)phenyl)-2-methyl indene) silane

2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene (2-methyl-4-phenyl-1,5,6) as a reactant in step 3-1 of Synthesis Example 3 Use 2-methyl-1,5,6,7-tetrahydro-s-indacene (2-methyl-1,5,6,7-tetrahydro-s-indacene) instead of ,7-tetrahydro-s-indacene) In the same manner as in step 3-1 of Synthesis Example 3, except that -(tert-butyl)phenyl)-2-methyl indene) silane was prepared.

Step 5-2. Transition metal compound Dimethyl silanediyl (2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4'-(tert-butyl)phenyl)-2-methyl-1H-inden Preparation of -1-yl) zirconium chloride

In the same manner as in Step 3-2 of Synthesis Example 3, except that the ligand obtained in Step 5-1 was used, the transition metal compound Dimethyl silanediyl (2-methyl-1,5,6,7-tetrahydro having the structure -s-indacen-1-yl)(4-(4'-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 5) was prepared.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.22(s, 6H), 1.23 (s,9H), 1.79(S, 6H), 2.07(m, 2H), 2.85(t,4H), 6.36 (s, 2H), 7.24-7.49 (m, 8H), 8.29 (d, 1H).

Synthesis Example 6

Step 6-1. Preparation of ligand compound (2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl (2-methyl indene) silane

2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene (2-methyl-4-phenyl-1,5,6) as a reactant in step 1-1 of Synthesis Example 1 Use 2-methyl-1,5,6,7-tetrahydro-s-indacene (2-methyl-1,5,6,7-tetrahydro-s-indacene) instead of ,7-tetrahydro-s-indacene) In the same manner as in step 1-1 of Synthesis Example 1, except that silane was prepared.

Step 6-2. Preparation of transition metal compound Dimethyl silanediyl (2-methyl-1H-inden-1-yl) (2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl) zirconium chloride

In the same manner as in Step 1-2 of Synthesis Example 1 except that the ligand obtained in Step 6-1 was used, the transition metal compound Dimethyl silanediyl (2-methyl-1,5,6,7-tetrahydro having the above structure) -s-indacen-1-yl) (2-methyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 6) was prepared.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.24(s, 6H), 1.76(S, 6H), 2.17(m, 2H), 2.89(t,4H), 6.42(s, 2H), 7.24 -7.35 (m,6H).

Synthesis Example 7

Step 7-1. Ligand compound (4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)diethyl(4-(4'-(tert-) Preparation of butyl)phenyl)-2-methyl indene)silane

In the same manner as in Step 3-1 of Synthesis Example 3, except that dichlorodiethyl silane was used instead of dichlorodimethyl silane as a reactant in step 4-1 of Synthesis Example 4 The ligand compound (4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)diethyl(4-(4'-(tert) -butyl)phenyl)-2-methyl indene) silane was prepared.

Step 7-2. Transition metal compound Diethyl silanediyl (4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4'-( Preparation of tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride

In the same manner as in Step 4-2 of Synthesis Example 4 except that the ligand obtained in Step 7-1 was used, the transition metal compound Diethyl silanediyl (4-(4'-(tert-butyl)phenyl) having the above structure was used. -2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4'-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 7) was prepared.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.66 (m, 4H), 0.94 (t, 9H), 1.33 (s, 18H), 1.79 (s, 6H), 1.95 (m, 2H), 2.83 (m, 4H), 3.36(s, 2H), 7.3-7.40 (m, 11H), 8.29(d, 1H).

Synthesis Example 8

Step 8-1. Ligand compound (4-(3',5'-di-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)diethyl(4-(3',5) Preparation of '-di-tert-butylphenyl)-2-methyl indene) silane

As a reactant in step 7-1 of Synthesis Example 7, 2-methyl-4-(4'-(tert-butyl)phenyl)-1,5,6,7-tetrahydro-s-indacene (2-methyl -4-(4'-(tert-butyl)-phenyl) -1,5,6,7-tetrahydro-s-indacene) instead of 4-(3',5'-ditertbutylphenyl)-2-methyl- 1,5,6,7-tetrahydro-s-indacene) ((4-(3',5'-di-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s- indacene) and 4-(3',5 instead of 4-(4'-(tert-butyl)phenyl)-2methyl indene (4-(4'-(tert-butyl)phenyl)-2-methyl indene) '-ditertbutylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene) (4-(3',5'-di-tert-butylphenyl)-2-methyl-1H -indene) in the same manner as in step 7-1 of Synthesis Example 7, except that the ligand compound (4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6, 7-tetrahydro-s-indacen-1-yl)diethyl(4-(4'-(tert-butyl)phenyl)-2-methyl indene)silane was prepared.

Step 8-2. Transition metal compound Diethyl silanediyl (4-(3',5'-di-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(3') Preparation of ,5'-di-tert-butylphenyl)-2-methyl-1H-inden-1-yl) zirconium chloride

In the same manner as in Step 7-2 of Synthesis Example 7 except that the ligand obtained in Step 8-1 was used, the transition metal compound Diethyl silanediyl (4-(3',5'-di-tert-) having the structure butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(3',5'-di-tert-butylphenyl)-2-methyl-1H-inden- 1-yl) zirconium chloride (Synthesis Example 8) was prepared.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.68 (m, 4H), 0.90 (t, 9H), 1.37 (s, 36H), 1.82 (s, 6H), 1.98 (m, 2H), 2.81 (m, 4H), 3.36(s, 2H), 7.35 (m, 4H), 7.73 (s,4H), 8.29(d,1H).

Synthesis Example 9

Step 9-1. Ligand compound (4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)methylpropyl(4-(4'-(tert-) Preparation of butyl)phenyl)-2-methyl indene)silane

The ligand compound ( 4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)methylpropyl(4-(4'-(tert-butyl)phenyl )-2-methyl indene) silane was prepared.

Step 9-2. Transition metal compound Methylpropyl silanediyl (4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4'-( Preparation of tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride

In the same manner as in Step 4-2 of Synthesis Example 4 except that the ligand obtained in Step 9-1 was used, the transition metal compound Methylpropyl silanediyl (4-(4'-(tert-butyl)phenyl) having the structure -2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4'-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride (Synthesis Example 9) was prepared.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.21 (s, 3H), 0.60 (t, 2H), 0.94 (t, 3H), 1.29 (m, 20H), 1.79 (S, 6H), 1.94 (m, 2H), 2.84 (m, 4H), 6.34 (s, 1H), 6.36 (s, 1H), 7.28-7.39 (m, 11H), 7.91 (d, 1H).

Comparative Synthesis Example 1

Step 10-1. Preparation of Ligand Compounds

0.83 g (5 mmol) of fluorene was added to a dried 250 mL schlenk flask, and 30 mL of diethyl ether was injected under reduced pressure. After the ether solution was cooled to -78 °C, the inside of the flask was replaced with argon, and 2.4 mL (6 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly raised to room temperature and stirred until the next day. Another 250 mL schlenk flask was filled with 30 mL of ether, and then 2.4 mL (20 mmol) of dichlorodimethylsilane was injected. After the flask was cooled to -78 °C, a lithiated solution of 2-hexyl-fluorene was injected thereto through a cannula. After the injection was completed, the mixture was slowly raised to room temperature, stirred for about 5 hours, and then ether used as a solvent and excess dichlorodimethylsilane remaining were removed under vacuum under reduced pressure. A dark ocher colored solid chloro(9H-fluoren-9-yl)dimethylsilane was obtained in the flask.

0.83 g (5 mmol) of fluorene was injected into a dried 100 mL schlenk flask and dissolved in 30 mL of ether. Then, 2.4 mL (6 mmol) of a 2.5 M nBuLi hexane solution was slowly added dropwise at -78°C, followed by stirring for one day. After dissolving the previously synthesized chloro(9H-fluoren-9-yl)dimethylsilane in 40 mL of ether, a lithiated solution of fluorene was added dropwise at -78 °C. After reacting overnight (overnight), 50 mL of water was added to the flask to quench (quenching), and the organic layer was separated and dried over MgSO ₄ (drying g). The mixture obtained through filtration was recrystallized with hexane after removing all solvents under vacuum reduced pressure to obtain a ligand compound.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): -0.52 (6H, s), 4.26 (2H, s), 7.29 (4H, m), 7.36 (4H, m), 7.53 (4H, m), 7.89 (4H, m)

Step 10-2. Preparation of transition metal compounds

In a dry 250 mL schlenk flask, 1.94 g (5 mmol) of the ligand compound synthesized in step 10-1 was dissolved in ether, and then 4.4 mL (11 mmol) of a 2.5 M nBuLi hexane solution was added for lithiation. After one day, 1.88 g (5 mmol) of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL schlenk flask to prepare a suspension containing ether. After both flasks were cooled to -78 °C, the lithiated ligand compound was slowly added to the Zr suspension. After injection, the reaction mixture was slowly raised to room temperature. After the reaction was allowed to proceed for one day, the mixture was filtered in a filter system not in contact with external air to obtain a metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 1.46 (6H, s), 6.99 (4H, m), 7.29 (4H, m), 7.68 (4H, m), 7.9 (4H, m).

Comparative Synthesis Example 2

Step 11-1. Preparation of Ligand Compounds

From the reaction between the tert-Bu-O-(CH ₂ ) ₆ Cl compound and Mg(0) in a _{THF solvent, 1.0 mol of a Grignard reagent tert-Bu-O-(CH 2} ) ₆ MgCl solution was obtained. The prepared Grignard compound _{was added to a flask containing methyl-SiCl 3} compound (176.1 mL, 1.5 mol) and THF (2.0 mL) at -30 ° C., stirred at room temperature for at least 8 hours, and then the filtered solution was It was vacuum dried to obtain a compound of tert-Bu-O-(CH ₂ ) ₆ SiMeCl ₂ (yield 92%).

Fluorene (3.33 g, 20 mmol), hexane (100 mL), and MTBE (methyl tert-butyl ether, 1.2 mL, 10 mmol) were put in a reactor at -20 °C, and 8 ml of n-BuLi (2.5 M in Hexane) was added. ) was slowly added and stirred at room temperature for 6 hours to obtain a fluorenyl lithium solution. After the stirring was completed, the reactor temperature was cooled to -30 °C, and tert-Bu-O-(CH ₂ ) ₆ SiMeCl ₂ (2.7 g, 10 mmol) dissolved in hexane (100 mL) at -30 °C was added to the solution. The prepared lithium fluorenyl solution was slowly added over 1 hour. After stirring at room temperature for at least 8 hours, extraction was performed by adding water, and evaporation was performed to obtain (tert-Bu-O-(CH ₂ ) ₆ )MeSi(9-C ₁₃ H ₁₀ ) ₂ compound (5.3 g). , yield 100%).

¹ H-NMR (500 MHz, CDCl ₃ , ppm): -0.35 (MeSi, 3H, s), 0.26 (Si-CH ₂ , 2H, m), 0.58 (CH ₂ , 2H, m), 0.95 (CH _{2 )} , 4H, m), 1.17 (tert-BuO, 9H, s), 1.29 (CH ₂ , 2H, m), 3.21 (tert-BuO-CH ₂ , 2H, t), 4.10 (Flu-9H, 2H, s) ), 7.25 (Flu-H, 4H, m), 7.35 (Flu-H, 4H, m), 7.40 (Flu-H, 4H, m), 7.85 (Flu-H, 4H, d).

Step 11-2. Preparation of transition metal compounds

In the (tert-Bu-O-(CH ₂ ) ₆ )MeSi(9-C1 ₃ H ₁₀ ) ₂ (3.18 g, 6 mmol)/MTBE (20 mL) solution prepared in step 11-1 at -20 ° C. 4.8 mL of n-BuLi (2.5 M in Hexane) was slowly added and reacted for at least 8 hours while raising to room temperature to prepare a slurry solution of dilithium salts. _{The prepared dilithium salt slurry solution was slowly added to the slurry solution of ZrCl 4} (THF) ₂ (2.26 g, 6 mmol)/hexane (20 mL) at -20 °C, and the reaction was further conducted at room temperature for 8 hours. The precipitate was filtered and washed several times with hexane to obtain a red solid (tert-Bu-O-(CH ₂ ) ₆ )MeSi(9-C ₁₃ H ₉ ) ₂ ZrCl ₂ compound (4.3 g, yield 94.5%). ).

¹ H-NMR (500 MHz, C ₆ D ₆ , ppm): 1.15 (tert-BuO, 9H, s), 1.26 (MeSi, 3H, s), 1.58 (Si-CH ₂ , 2H, m), 1.66 ( CH ₂ , 4H, m), 1.91 (CH ₂ , 4H, m), 3.32 (tert-BuO-CH ₂ , 2H, t), 6.86 (Flu-H, 2H, t), 6.90 (Flu-H, 2H) , t), 7.15 (Flu-H, 4H, m), 7.60 (Flu-H, 4H, dd), 7.64 (Flu-H, 2H, d), 7.77 (Flu-H, 2H, d).

Comparative Synthesis Example 3

Step 12-1. Ligand 8-(4-( tert Synthesis of -butyl)phenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene

8-Bromo-6-methyl-1,2,3,5-tetrahydro-s-indacene (35 mmol, 9.8 g), (4-( tert- butyl)phenyl)boronic acid (70 mmol, 12.5 g), sodium carbonate (87.50 mmol, 9.3 g) and tetrakistriphenylphosphine palladium (1.80 mmol, 2 g) were put in 250 mL RBF, and toluene (35 mL), ethanol (18 mL), and water (1 mL) were added. Then, the mixture was stirred in an oil bath preheated to 90° C. for 16 hours. After confirming the degree of reaction by NMR, if the reaction was less advanced, the reaction was further performed for 16 hours, or reactants excluding indacene and solvent were additionally prescribed according to the amount of remaining indacene and reacted for 16 hours. After the reaction was completed, all ethanol was removed from the rotary evaporator, and work up was performed with water and hexane. The organic layers were collected _{, dried over MgSO 4} , and all solvents were removed. The crude mixture from which the solvent was removed was subjected to silica gel short column to remove black impurities. Again, all the solvent was removed and methanol was added to form a solid. The resulting solid was filtered and washed with methanol. The ligand 8-(4-( tert- butyl)phenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene (8.5 g, 80% , a white solid) was obtained.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 7.44~7.31(m, 4H), 7.12(s, 1H), 6.47(s, 1H), 3.19(s, 2H), 2.97(t, 2H) , 2.09 to 2.02 (m, 5H), 1.38 (s, 9H).

Step 12-2. Ligand compound (6-(tert-butoxy)hexyl)(4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4 Synthesis of -(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(methyl)silane

4-(4-( tert- butyl)phenyl)-2-methyl- 1H- indene (19 mmol, 5 g) was placed in a 100 mL Schlenk flask, and an argon state was created. When the argon state was formed, anhydrous hexane (66 mL) and anhydrous MTBE (13 mL) were added, and the mixture was cooled to -25 °C. n- BuLi (2.5 M in Hexane, 21 mmol, 8.4 mL) was slowly injected, and when the injection was finished, the temperature was raised to room temperature and shoban was carried out for 3 hours. After stirring, cool to -25 ℃ again, inject tether silane (15.20 mmol, 4.1 g) into the flask with one shot, filter slowly to room temperature to remove LiCl, and then dry the solvent to (6-(tert-butoxy)hexyl )(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)chloro(methyl)silane was prepared.

Then, in another 100 mL Schlenk flask, 8-(4-( tert- butyl)phenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene (19 mmol, 5.75 g) and CuCN (0.95 mmol, 0.09 g) were added to create an argon state. When the argon state was formed, anhydrous MTBE (48 mL) was added, and the mixture was cooled to -25 °C. n- BuLi (2.5 M in Hexane, 21 mmol, 8.4 mL) was slowly injected, and when the injection was finished, the temperature was raised to room temperature and stirred for 3 hours. After stirring, cool to -25 ℃ again and (6-(tert-butoxy)hexyl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl) synthesized earlier Chloro(methyl)silane was injected into the flask with one shot. Then, the temperature was slowly raised to room temperature and stirred for 16 hours. Purified by silica gel column, the ligand compound of the following structure (6-(tert-butoxy)hexyl)(4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s -indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(methyl)silane was obtained (10.87 mmol, 8.30 g, 57%, light yellow solid).

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 7.78 to 7.41 (m, 6H), 7.34 to 7.31 (m, 3H), 7.28 to 7.12 (m, 2H), 6.84 to 6.80 (m, 1H), 6.56 to 6.54 (m, 1H), 3.77 to 3.60 (m, 2H), 3.27 to 3.23 (t, 2H), 2.97 to 2.81 (m, 4H), 2.20 to 2.09 (m, 6H), 2.04 to 2.02 (m) , 2H), 1.39 to 1.38 (m, 18H), 1.15 (s, 9H), 1.52 to 0.43 (m, 10H), 0.02 to -0.15 (m, 3H).

Step 12-3. Transition metal compound (6-(tert-butoxy)hexyl)(methyl)silanediyl(4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1 Preparation of -yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)zirconium dichloride

(6-(tert-butoxy)hexyl)(4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1 obtained in step 12-2 -yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(methyl)silane ligand (2.62 mmol, 2 g) was placed in a 50 mL Schlenk flask and argon made When the argon state was formed, anhydrous diethyl ether (52.4 mL) was added, and the mixture was cooled to -25 °C. n- BuLi (2.5 M in Hexane, 5.76 mmol, 2.3 mL) was slowly injected, and when the injection was finished, the temperature was raised to room temperature and stirred for 3 hours. After stirring, this solution and _{an argon Schlenk flask containing ZrCl 4} -2 (THF) (2.62 mmol, 1.0 g) were cooled to -78 ℃, and the ligand solution was transferred to a flask containing zirconium at low temperature. . After slowly raising the temperature to room temperature, the mixture was stirred for 16 hours. After stirring, the generated solid was filtered out under argon and the solvent was dried to obtain a crude mixture. This was dissolved in a minimum amount of anhydrous toluene and stored at -25 °C to -30 °C to produce a solid. The resulting solid was collected by filtering after it was released by adding an excess of hexane when it was in a low temperature state. Then, the obtained solid was dried and purified catalyst compound, that is, transition metal compound (6-(tert-butoxy)hexyl)(methyl)silanediyl(4-(4-(tert-butyl)phenyl)-2-methyl-1 ,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)zirconium dichloride (0.49 mmol, 0.45 g, 19%, yellow solid) was obtained.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 7.48~7.46 (m, 3H), 7.42~7.40(m, 5H), 7.25~7.23(m, 2H), 7.18~7.16(m, 2H), 6.69 (s, 1H), 3.38 to 3.35 (t, 2H), 3.01 to 2.79 (m, 4H), 2.35 (s, 3H), 2.21 (s, 3H), 2.03 to 1.94 (m, 2H), 1.88 to 1.35 (m, 10H), 1.15 (s, 9H), 1.33 (s, 18H), 1.19 (s, 9H), 1.16 to 1.12 (m, 3H).

Comparative Synthesis Example 4

Step 13-1. Ligand compound (4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(4-(4'-(tert- Preparation of butyl)-6-tert-butyl-5-methoxy-phenyl)-2-methyl indene) silane

Instead of 4-(4'-(tertbutyl)phenyl)-2methyl indene (4-(4'-(tert-butyl)phenyl)-2-methyl indene) as a reactant in step 4-1 of Synthesis Example 4 4-(4'-(tertbutyl)-6-tertbutyl-5-methoxy-phenyl)-2methyl indene (4-(4'-(tert-butyl)-6-tert-butyl-5-methoxy- phenyl)-2-methyl indene) in the same manner as in step 3-1 of Synthesis Example 3, except that the ligand compound (4-(4'-(tert-butyl)phenyl)-2-methyl-1 ,5,6,7-tetrahydro-s-indacen-1-yl)dimethyl(4-(4'-(tert-butyl)phenyl)-2-methyl indene) silane was prepared.

Step 13-2. Transition metal compound Dimethyl silanediyl (4-(4'-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4'-( Preparation of tert-butyl)-6-tert-butyl-5-methoxy-phenyl)-2-methyl-1H-inden-1-yl) zirconium chloride

In the same manner as in Step 4-2 of Synthesis Example 4 except that the ligand obtained in Step 13-1 was used, the transition metal compound Dimethyl silanediyl (4-(4'-(tert-butyl)phenyl) having the above structure was used. -2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4'-(tert-butyl)-6-tert-butyl-5-methoxy-phenyl)-2 -methyl-1H-inden-1-yl) zirconium chloride (Comparative Synthesis Example 4) was prepared.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.23(s, 6H), 1.29(s,18H), 1.41(s, 9H), 1.76(S, 6H), 1.92(m, 2H), 2.80 (m, 4H), 3.85(s, 3H), 6.36(s, 2H), 7.28-7.36(m,9H), 7.58(s, 1H).

Comparative Synthesis Example 5

Step 14-1. Preparation of ligand compound (4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl indene silane

In step 1-1 of Synthesis Example 1, indene was used instead of 2-methyl indene as a reactant, and 2-methyl-4-phenyl-1,5,6,7-tetrahydro -s-indacene (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacene) instead of 4-phenyl-1,5,6,7-tetrahydro-s-indacene (4 -phenyl-1,5,6,7-tetrahydro-s-indacene) in the same manner as in step 1-1 of Synthesis Example 1, except that the ligand compound (2-methyl-4-phenyl-1 ,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl (2-isopropyl-4-phenyl-indene) silane was prepared.

Step 14-2. Preparation of transition metal compound dimethyl silanediyl (4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) (1H-inden-1-yl) zirconium chloride

In the same manner as in Step 1-2 of Synthesis Example 1, except that the ligand obtained in Step 14-1 was used, the transition metal compound Dimethyl Silanediyl (4-phenyl-1,5,6,7-tetrahydro having the above structure) -s-indacen-1-yl) (1H-inden-1-yl) zirconium chloride (Comparative Synthesis Example 5) was prepared.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.22(s, 6H), 1.96(m, 2H), 2.83(m, 4H), 6.36(d, 2H), 6.58(d, 2H), 7.18 -7.50 (m, 10H).

Comparative Synthesis Example 6

As disclosed in PCT Patent Application Publication No. WO 2006-097497 A1, the transition metal compound having the above structure, 1,1'-dimethylsilylene-bis[2-methyl-4-(4-tert-butylphenyl)-5,6,7- trihydro-s-indacen-1-yl]} zirconium dichloride (Comparative Synthesis Example 6) was prepared.

Comparative Synthesis Example 7

Step 15-1. Preparation of ligand compound (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl cyclopentadienyl silane

Except for using sodium cyclopentadienyl (sodium Cp, Na cyclopentadiene) in THF (1.0 M) instead of 2-methyl indene Li Salt solution as a reactant in step 1-1 of Synthesis Example 1 Then, the ligand compound (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) dimethyl cyclopentadienyl silane was prepared in the same manner as in step 1-1 of Synthesis Example 1. .

Step 15-2. Preparation of transition metal compound Dimethyl silanediyl (2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl) (cyclopentadienyl) zirconium chloride

In the same manner as in Step 1-2 of Synthesis Example 1, except that the ligand obtained in Step 15-1 was used, the transition metal compound Dimethyl Silanediyl (2-methyl-4-phenyl-1,5,6 having the above structure) ,7-tetrahydro-s-indacen-1-yl) (cyclopentadienyl) zirconium chloride (Comparative Synthesis Example 7) was prepared.

¹ H-NMR (500 MHz, CDCl ₃ , ppm): 0.22(s, 6H), 1.80(S, 3H), 1.98(m, 2H), 2.80(m, 4H), 6.35(d, 2H), 6.41 (s, 1H), 6.50 (d, 2H), 7.41-7.46 (m, 6H).

<Preparation of supported catalyst>

Preparation Example 1

After putting 50 mL toluene in a pico reactor, 7 g of silica gel (Silica gel, SYLOPOL 952X, calcinated under 250 ℃) was added under Ar, and 10 mmol of methylaluminoxane (MAO) was slowly injected at room temperature at 95 ℃. The reaction was stirred for 24 hours. After completion of the reaction, cool to room temperature and leave for 15 minutes to decant the solvent using a cannula. Toluene (400 mL) was added, stirred for 1 minute, and left for 15 minutes to decant the solvent using a cannula.

After dissolving 60 μmol of the metallocene compound of Synthesis Example 1 in 30 mL of toluene, it was transferred to the reactor using a cannula. The reaction was stirred at 80 °C for 2 hours. After the reaction was completed and the precipitation was completed, the solvent was decanted using a cannula, cooled to room temperature and left for 15 minutes. The upper layer solution was removed and the remaining reaction product was washed with toluene. After washing again with hexane, N,N-bis(2-hydroxyethyl)pentadecylamine (N,N-Bis(2-hydroxyethyl)pentadeylamine, Atmer 163) as an antistatic agent under hexane based on silica weight (g) After dissolving 2 wt% in 3 mL of hexane, the mixture was stirred at room temperature for 10 minutes. After completion of the reaction and the completion of precipitation, the upper layer was removed and transferred to a glass filter to remove the solvent.

The silica-supported metallocene catalyst in the form of solid particles was obtained by primary drying at room temperature under vacuum for 5 hours, and secondary drying at 45° C. under vacuum for 4 hours.

Preparation Examples 2 to 9

A silica-supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compounds of Synthesis Examples 2 to 9 were used instead of the metallocene compound of Synthesis Example 1, respectively.

Comparative Preparation Examples 1 to 7

A silica-supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compounds of Comparative Synthesis Examples 1 to 7 were used instead of the metallocene compound of Synthesis Example 1, respectively.

<Polyethylene Polymerization>

Example 1

An ethylene-1-hexene copolymer was prepared in the presence of the supported catalyst obtained in Preparation Example 1, and the specific method is as follows.

A 600 mL stainless steel reactor was vacuum dried at 120° C., cooled, and 1 g of trimethylaluminum (TMA) was added to 250 g of hexane at room temperature and stirred for 10 minutes. After removing all of the reacted hexane, 250 g of hexane and 0.5 g of triisobutylaluminum (TIBAL) were added and stirred for 5 minutes. Then, after adding 7 mg of the supported catalyst obtained in Preparation Example 1, the temperature was raised to ^{70 o C and stirred.} After stopping stirring at 70 ^o C, 10 mL of comonomer 1-hexene (1-hexene, C6) was added, and ethylene (ethylene, C2) was filled to 30 bar, and then stirring was started. After polymerization for 30 minutes, unreacted C2 was vented.

Examples 2 to 9

An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalysts of Preparation Examples 2 to 9 were used instead of the supported catalyst of Preparation Example 1, respectively.

Comparative Example 1

An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 1 was used instead of the supported catalyst of Preparation Example 1.

Comparative Examples 2 and 3

In the same manner as in Comparative Example 1, except that the amount of 1-hexene (1-hexene, C6), which is a comonomer, was changed to 20 mL (Comparative Example 2) and 25 mL (Comparative Example 3), respectively. An ethylene-1-hexene copolymer was prepared.

Comparative Example 4

An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 2 was used instead of the supported catalyst of Preparation Example 1.

Comparative Examples 5 and 6

In the same manner as in Comparative Example 4, except that the amount of 1-hexene (1-hexene, C6), which is a comonomer, was changed to 20 mL (Comparative Example 5) and 25 mL (Comparative Example 6), respectively An ethylene-1-hexene copolymer was prepared.

Comparative Example 7

An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 3 was used instead of the supported catalyst of Preparation Example 1.

Comparative Example 8

An ethylene-1-hexene copolymer was prepared in the same manner as in Comparative Example 7, except that the amount of 1-hexene (1-hexene, C6), which is a comonomer, was changed to 20 mL.

Comparative Example 9

An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 4 was used instead of the supported catalyst of Preparation Example 1.

Comparative Example 10

An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation 5 was used instead of the supported catalyst of Preparation Example 1.

Comparative Example 11

An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation Example 6 was used instead of the supported catalyst of Preparation Example 1.

Comparative Example 12

An ethylene-1-hexene copolymer was prepared in the same manner as in Example 1, except that the supported catalyst of Comparative Preparation 7 was used instead of the supported catalyst of Preparation Example 1.

<Test Example: Polymerization process and evaluation of physical properties of polyethylene>

Catalytic activity, process stability, and physical properties of the polyethylene copolymer of Examples and Comparative Examples were measured by the following method, and the results are shown in Table 1 below.

(1) Catalytic activity (activity, kg PE/g cat·hr)

It was calculated as a ratio of the weight (kg PE) of the polyethylene copolymer produced per unit time (h) per the supported catalyst content (g Cat) used.

(2) Melting point (Tm, ℃)

Tm was measured using a differential scanning calorimeter (DSC).

Specifically, as a differential scanning calorimeter (DSC), the melting temperature of the polymer was measured using a DSC 2920 (TA instrument). Specifically, the polymer ^{was heated to 150 o} C and maintained for 5 minutes, and ^{then lowered to -100 o} C and then the temperature was increased again. At this time, the rate of rise and fall of the temperature ^{was adjusted to 10 o} C/min, respectively. The melting temperature was taken as the maximum point of the endothermic peak measured in the section where the second temperature was increased.

(3) weight average molecular weight (Mw, g/mol)

The weight average molecular weight (Mw) of the polyethylene copolymer was measured using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water).

Specifically, as a gel permeation chromatography (GPC) apparatus, a Waters PL-GPC220 instrument was used, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. At this time, the measurement temperature was 160 ^o C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) was used as a solvent, and the flow rate was 1 mL/min. Each polyethylene copolymer sample according to Examples and Comparative Examples was dissolved in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160 ^° C for 10 hours using a GPC analysis device (PL-GP220). It was pretreated, prepared to a concentration of 10 mg/10 mL, and then supplied in an amount of 200 μL. The value of Mw was derived using a calibration curve formed using a polystyrene standard specimen. The weight average molecular weight of the polystyrene standard specimen is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 400000 g/mol, 1000000 g Nine species of /mol were used.

(4) Number of short chain branches (SCB, FT-IR)

For the polyethylene copolymers of Examples and Comparative Examples, the number of short-chain branches (SCB) having 2 to 7 carbon atoms per 1000 carbon atoms was measured by infrared spectroscopy (FT-IR).

Specifically, a polyethylene copolymer sample was pretreated by dissolving it in 1,2,4-Trichlorobenzene containing 0.0125% BHT at 160 °C for 10 hours using PL-SP260VS, and then PerkinElmer Spectrum connected to high temperature GPC (PL-GPC220). Measurements were made at 160 °C using 100 FT-IR.

(5) Evaluation of morphology of polymers

With respect to the polyethylene copolymers of Examples and Comparative Examples, the appearance and touch of the obtained copolymer powder were visually and tactilely checked, and the morphology of the polymer was evaluated.

Specifically, after drying all the obtained powders under the same conditions, if the morphology of the polymer is dispersed like grains of sand and the grains maintain their original shape, it is evaluated as very good, and the morphology of the polymer is determined as grains of sand. If there are particles that are dispersed like a snowman but aggregate like a snowman, it was evaluated as good, and if the morphology of the polymer was tangled in a lump rather than a grain of sand, it was evaluated as bad. In particular, when the morphology of the polyethylene copolymer is poor, it may be difficult to put into the gas phase polymerization reaction for the production of linear low density polyethylene.

compound C6
usage
(mL) activation
(kg PE /g·cat·hr) Mw
(Х10 ³ g/mol) Tm
( ^o C) SCB
(pcs/1000C) Morphology
evaluation Example 1 Synthesis Example 1 10 4.5 530 123.5 5.2 Good Example 2 Synthesis Example 2 10 5.1 400 124.2 5.0 Good Example 3 Synthesis Example 3 10 6.2 480 121.5 5.8 Good Example 4 Synthesis Example 4 10 5.9 450 118.5 6.5 Good Example 5 Synthesis Example 5 10 5.2 480 124.5 5.2 Good Example 6 Synthesis Example 6 10 6.0 460 125.7 4.5 Good Example 7 Synthesis Example 7 10 6.7 450 117.2 6.8 Good Example 8 Synthesis Example 8 10 5.5 580 121.8 5.8 Good Example 9 Synthesis Example 9 10 6.0 480 121.6 5.9 Good Comparative Example 1 Comparative Synthesis Example 1 10 3.2 450 127.7 2.2 usually Comparative Example 2 Comparative Synthesis Example 1 20 2.9 380 124.1 3.9 error Comparative Example 3 Comparative Synthesis Example 1 25 measurement
impossible measurement
impossible measurement
impossible measurement
impossible -
(Fouling) Comparative Example 4 Comparative Synthesis Example 2 10 2.7 400 128.4 1.9 usually Comparative Example 5 Comparative Synthesis Example 2 20 3.0 350 125.8 2.9 error Comparative Example 6 Comparative Synthesis Example 2 25 measurement
impossible measurement
impossible measurement
impossible measurement
impossible -
(Fouling) Comparative Example 7 Comparative Synthesis Example 3 10 2.1 350 126.8 3.5 usually Comparative Example 8 Comparative Synthesis Example 3 20 1.5 300 123.5 4.1 error Comparative Example 9 Comparative Synthesis Example 4 10 0.7 350 124.8 3.8 usually Comparative Example 10 Comparative Synthesis Example 5 10 1.1 150 127.8 1.8 usually Comparative Example 11 Comparative Synthesis Example 6 10 5.1 500 128.1 1.1 error Comparative Example 12 Comparative Synthesis Example 7 10 1.1 330 129.2 1.3 usually

As shown in Table 1, the polyethylene copolymers of Examples 1 to 9 according to the present invention were prepared by using a supported catalyst including a metallocene compound having an asymmetric structure consisting of a specific bridging group and indacene and indene ligands. , It can be seen that the number of short chain branches (SCB) per 1000 carbon atoms is very high, from 4.5/1000C to 6.8/1000C.

On the other hand, in the case of comparative examples in which the copolymerization process was performed by changing the substituent and structure of the catalyst, it is difficult to increase the SCB content even if the input amount of 1-hexene (C6), which is a comonomer, is increased, or the catalyst activity is lowered, or It can be seen that the problem of poor morphology of polyethylene occurs.

Specifically, in Comparative Examples 1 and 4, in which 10 mL of comonomer 1-hexene (C6) was added in the same manner as in Examples, the number of short chain branches (SCB) per 1000 carbon atoms was 2.2/1000C and 1.9/1000C was confirmed to be significantly reduced. Also, in Comparative Examples 2 and 5, in which the comonomer 1-hexene (C6) was increased to 20 mL, the number of short chain branches (SCB) per 1000 carbon atoms was only 3.9/1000C and 2.9/1000C, and the amount was doubled to It was confirmed that not only was it difficult to secure more than 4/1000C, but also the morphology deteriorated. Furthermore, in Comparative Examples 3 and 6, in which the comonomer 1-hexene (C6) was further increased to 25 mL, fouling occurred in the polymerization process, making it impossible to evaluate the physical properties of the polymer.

Meanwhile, in Comparative Example 7 in which 10 mL of comonomer 1-hexene (C6) was added in the same manner as in Examples even when a catalyst including a metallocene compound having an asymmetric parent nucleus structure similar to the catalyst structure used in Examples was used. In the case of , the number of short chain branches (SCB) per 1000 carbon atoms was significantly lowered to 3.5/1000C. In addition, in the case of Comparative Example 8, in which the comonomer 1-hexene (C6) was further increased to 20 mL using the same catalyst as in Comparative Example 7, the number of short chain branches (SCB) per 1000 carbon atoms was increased to 4.1/1000C, In the polymerization process, it can be seen that the catalyst activity is significantly lowered by 4 kg PE/g_cat_h or more, the weight average molecular weight of the obtained polyethylene copolymer is lowered, and the morphology is also poor.

In addition, in the case of Comparative Example 9, in which methoxy at position 5 and tert-butyl at position 6 of indene were included, physical properties similar to those of Examples but the activity was very low, and thus the overall process cost and a disadvantage in that the synthesis cost increases. Similarly, in Comparative Example 10 without a methyl group at the 2-position of indene and indacene, it was confirmed that the activity was not only low, but also the molecular weight was low and the copolymerizability was poor.

In addition, in Comparative Example 11, in which the ligand compound structure was a bis-indacene structure rather than an indene-indacene combination, it was confirmed that the SCB content was very small, although the activity and molecular weight were similar to those of the Example, but the copolymerizability was significantly deteriorated. Moreover, in the case of Comparative Example 12, in which the ligand compound structure was a cyclopentadiene-indacene structure rather than an indene-indacene combination, it was confirmed that not only the activity was low, but also the molecular weight was low and the copolymerizability was poor.

Claims (14)

A transition metal compound represented by the following formula (1):
[Formula 1]

In Formula 1,
A is a group 14 element,
M is a Group 4 transition metal,
R ¹ and R ² are the same as or different from each other, and each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl , C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,
X ¹ and X ² are the same as or different from each other and are each independently halogen,
Q ¹ and Q ² are the same as or different from each other, and are each independently C _1-20 alkyl.
The method of claim 1,
A is silicone,
M is zirconium,
transition metal compounds.
According to claim 1,
R ¹ and R ² are each hydrogen, phenyl, _{phenyl substituted with C 1-6} straight or branched chain alkyl;
transition metal compounds.
The method of claim 1,
Which is represented by the following formula 1-1,
Transition metal compounds:
[Formula 1-1]

In Formula 1-1, A, M, X ¹ , X ² , Q ¹ , Q ² are as defined in claim 1,
R′ is the same as or different from each other, and each independently represents hydrogen or C _1-6 straight or branched chain alkyl;
a and b are each independently 0 or 1.
5. The method of claim 4,
At least one of R' in Formula 1-1 is C _3-6 branched chain alkyl, and the remaining R' is hydrogen,
transition metal compounds.
According to claim 1,
Q ¹ and Q ² are each independently C _1-6 straight or branched chain alkyl;
transition metal compounds.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Transition metal compounds:

.
A catalyst composition comprising the transition metal compound according to claim 1 .
9. The method of claim 8,
Containing the transition metal compound and the carrier,
catalyst composition.
9. The method of claim 8,
Further comprising at least one cocatalyst selected from the group consisting of compounds represented by the following formulas 2 to 4,
Catalyst composition:
[Formula 2]
-[Al(R ²¹ )-O] _m -
In Formula 2,
R ²¹ are the same as or different from each other and are each independently halogen, C _1-20 alkyl or C _1-20 haloalkyl;
m is an integer greater than or equal to 2;
[Formula 3]
J(R ³¹ ) ₃
In Formula 3,
R ³¹ is the same as or different from each other, and each independently represents halogen, C _1-20 alkyl or C _1-20 haloalkyl;
J is aluminum or boron;
[Formula 4]
[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-
In Formula 4,
E is a neutral or cationic Lewis base, [EH] ⁺ and [E] ⁺ are Bronsted acids;
H is a hydrogen atom;
Z is a group 13 element;
Q is the same as or different from each other, and each independently represents C _6-20 aryl or C _1-20 alkyl, wherein the C _6-20 aryl or C _1-20 alkyl is unsubstituted or halogen, C _1-20 alkyl, It is substituted with one or more substituents selected from the group consisting of _{C 1-20} alkoxy and C _{6-20 phenoxy.}
9. The method of claim 8,
Further comprising at least one antistatic agent represented by the following formula (5),
Catalyst composition:
[Formula 5]
R ⁵¹ N-(CH ₂ CH ₂ OH) ₂
In Formula 5,
R ⁵¹ is C _8-30 straight-chain alkyl.
A process for preparing polyethylene comprising copolymerizing ethylene and alpha-olefin in the presence of the catalyst composition of claim 8 .
13. The method of claim 12,
The alpha-olefin is 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- At least one selected from the group consisting of octadecene, 1-eicosene, and mixtures thereof,
Method for producing polyethylene.
13. The method of claim 12,
In the ethylene copolymerization step, the catalytic activity is 4.0 kg PE /g·cat·hr or more, and the catalytic activity is the weight (kg PE) of polyethylene produced per weight (g) of the catalyst composition used based on the unit time (h) is the measured value of
Method for producing polyethylene.