KR102564398B1 - Hybride supported metallocene catalyst and method for preparing polyethylene copolymer using the same - Google Patents

Abstract

The present invention provides a supported hybrid metallocene catalyst useful for preparing a polyethylene copolymer having excellent process stability and high polymerization activity in an ethylene polymerization reaction and excellent mechanical properties due to high copolymerizability.

Description

Hybrid Supported Metallocene Catalyst and Method for Preparing Polyethylene Copolymer Using the Same {HYBRIDE SUPPORTED METALLOCENE CATALYST AND METHOD FOR PREPARING POLYETHYLENE COPOLYMER USING THE SAME}

The present invention relates to a hybrid supported metallocene catalyst and a method for preparing a polyethylene copolymer using the same.

The olefin polymerization catalyst system can be classified into a Ziegler-Natta system and a metallocene catalyst system. These two highly active catalyst systems have been developed according to their respective characteristics.

Ziegler-Natta catalyst has been widely applied to existing commercial processes since its invention in the 1950s, but since it is a multi-site catalyst in which several active sites are mixed, it is characterized by a wide molecular weight distribution of the polymer and comonomer There is a problem that there is a limit to securing desired physical properties because the composition distribution of is not uniform.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst containing a transition metal compound as a main component and a cocatalyst containing an organometallic compound containing aluminum as a main component. Such a catalyst is a homogeneous complex catalyst and exhibits the characteristics of a single site catalyst. According to the characteristics of a single site, a polymer with a narrow molecular weight distribution and a uniform comonomer composition distribution is obtained. It has properties that can change the tacticity, copolymerization characteristics, molecular weight, crystallinity, etc. of a polymer according to the modification of the ligand structure and polymerization conditions.

Due to recent changes in environmental awareness, many product groups are seeking to reduce the generation of volatile organic compounds (VOCs). However, in the case of Ziegler-Natta catalysts (Z/N, ziegler-natta) used in the manufacture of polyethylene, there was a problem of generating high volatile organic compounds (TVOCs, total volatile organic compounds). In particular, in the case of various commercially available polyethylene, Ziegler-Natta catalyst-applied products form the mainstream, but recently, the conversion to metallocene catalyst-applied products with low odor and low elution characteristics is accelerating.

On the other hand, linear low density polyethylene (LLDPE) is prepared by copolymerizing ethylene and alpha-olefin at low pressure using a polymerization catalyst. However, there is a problem in that it is difficult to increase the impact strength of the film due to the low comonomer incorporation characteristics of the known catalyst itself, due to the low comonomer concentration at high molecular weight. In particular, when the concentration of comonomers such as alpha-olefins is increased in the copolymerization process, there is a problem in that the morphology of the produced polymer is lowered. In addition, as the density of LLDPE decreases, the impact strength of the film increases, but fouling occurs frequently during low-density production, resulting in poor process stability.

Accordingly, a catalyst for producing low density polyethylene capable of producing a low density polyethylene resin product having excellent morphology and excellent drop impact strength as a catalyst having excellent comonomer incorporation characteristics of high molecular weight while having a stable process during polyethylene production is required. .

The present invention is intended to provide a mixed supported metallocene catalyst useful for producing a polyethylene copolymer having excellent mechanical properties due to high comonomer incorporation characteristics while exhibiting excellent process stability and high polymerization activity in an ethylene polymerization reaction. .

In addition, the present invention is to provide a method for preparing a polyethylene copolymer using the hybrid supported metallocene catalyst.

The present invention relates to at least one first metallocene compound selected from compounds represented by Formula 1 below; at least one second metallocene compound selected from compounds represented by Formula 2 below; and a carrier supporting the first and second metallocene compounds.

[Formula 1]

(Cp ¹ R ^a ) _n (Cp ² R ^b )M ¹ Q ¹ _3-n

In Formula 1,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. one, which is unsubstituted or substituted with a C _1-20 hydrocarbon;

R ^a and R ^b are the same as or different from each other, and are each independently hydrogen, C _1-20 alkyl, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-20 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl, provided that R at least one of ^a and R ^b is not hydrogen;

Q ¹ is halogen, C _1-20 alkyl, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkylidene, substituted or unsubstituted amino group, C _2-20 alkoxyalkyl, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;

n is 1 or 0;

[Formula 2]

In Formula 2,

M ² is a Group 4 transition metal;

A is carbon (C), silicon (Si), or germanium (Ge);

X ¹ and X ² are the same as or different from each other, and each independently represents halogen or C _1-20 alkyl;

L ¹ and L ² are the same as or different from each other, and each independently represent C _1-20 alkylidene;

D ¹ and D ² are oxygen (O);

R ¹ and R ² are the same as or different from each other, and are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-40 alkylaryl, C _7-40 arylalkyl;

R ³ and R ⁴ are the same as or different from each other, and each independently represent C _1-20 alkyl.

In addition, the present invention provides a method for producing a polyethylene copolymer comprising the step of copolymerizing ethylene and an alpha-olefin in the presence of the above-described mixed supported metallocene catalyst.

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

Terms used in this specification are only used to describe exemplary embodiments, and are not intended to limit the present invention.

Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this specification, terms such as "comprise", "comprise" or "having" are used to describe an implemented feature, number, step, component, or combination thereof, and one or more other features, numbers, or steps. , components, combinations or additions thereof are not excluded.

Also, as used throughout this specification, the terms "about", "substantially" and the like are used at or approximating that value when manufacturing and material tolerances inherent in the stated meaning are given, and Exact or absolute figures are used as an aid to understanding and to prevent exploitation by unscrupulous infringers of the disclosed disclosure.

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. can mean synthesis.

Also, in this specification, when each layer or element is referred to as being formed “on” or “above” each layer or element, it means that each layer or element is formed directly on each layer or element, or other This means that layers or elements may be additionally formed between each layer or on the object or substrate.

Since the present invention can have various changes and various forms, specific embodiments will be exemplified and described in detail below. However, it should be understood that this does not limit the present invention to the specific disclosed form, and includes all modifications, equivalents, and substitutes included in the spirit and technical scope of the present invention.

Hereinafter, the present invention will be described in detail.

According to one aspect of the present invention, at least one first metallocene compound selected from compounds represented by Formula 1 below; at least one second metallocene compound selected from compounds represented by Formula 2 below; and a carrier supporting the first and second metallocene compounds.

[Formula 1]

(Cp ¹ R ^a ) _n (Cp ² R ^b )M ¹ Q ¹ _3-n

In Formula 1,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. one, which is unsubstituted or substituted with a C _1-20 hydrocarbon;

R ^a and R ^b are the same as or different from each other, and are each independently hydrogen, C _1-20 alkyl, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-20 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl, provided that R at least one of ^a and R ^b is not hydrogen;

Q ¹ is halogen, C _1-20 alkyl, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkylidene, substituted or unsubstituted amino group, C _2-20 alkoxyalkyl, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;

n is 1 or 0;

[Formula 2]

In Formula 2,

M ² is a Group 4 transition metal;

A is carbon (C), silicon (Si), or germanium (Ge);

X ¹ and X ² are the same as or different from each other, and each independently represents halogen or C _1-20 alkyl;

L ¹ and L ² are the same as or different from each other, and each independently represent C _1-20 alkylidene;

D ¹ and D ² are oxygen (O);

R ¹ and R ² are the same as or different from each other, and are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-40 alkylaryl, C _7-40 arylalkyl;

R ³ and R ⁴ are the same as or different from each other, and each independently represent C _1-20 alkyl.

In the present specification, the following terms may be defined as follows unless otherwise specified.

A hydrocarbyl group is a monovalent functional group obtained by removing a hydrogen atom from a hydrocarbon, and includes 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 alkenylaryl group, and an alkynyl group. It may contain a nyl aryl group and the like. And, the C _1-30 hydrocarbyl group may be a C _1-20 or C _1-10 hydrocarbyl group. For example, a hydrocarbyl group can be a straight-chain, branched-chain or cyclic alkyl. More specifically, the C _1-30 hydrocarbyl group is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group straight-chain, branched-chain or cyclic alkyl groups such as a real group, an n-heptyl group, and a cyclohexyl group; or an aryl group such as phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, or fluorenyl. It may also be an alkyl aryl such as methylphenyl, ethylphenyl, methylbiphenyl, or methylnaphthyl, or an arylalkyl such as phenylmethyl, phenylethyl, biphenylmethyl, or naphthylmethyl. It may also be alkenyl such as allyl, allyl, ethenyl, propenyl, butenyl, and pentenyl.

A hydrocarbyloxy group is a functional group in which a hydrocarbyl group is bonded to oxygen. Specifically, the C _1-30 hydrocarbyloxy group may be a C _1-20 or C _1-10 hydrocarbyloxy group. For example, the hydrocarbyloxy group can be a straight-chain, branched-chain or cyclic alkyl. More specifically, the C _1-30 hydrocarbyloxy group is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a tert-butoxy group, and an n-pentoxy group. , straight-chain, branched-chain or cyclic alkoxy groups such as n-hexoxy group, n-heptoxy group, and cyclohexoxy group; or an aryloxy group such as a phenoxy group or a naphthalenoxy group.

A hydrocarbyloxyhydrocarbyl group is a functional group in which one or more hydrogens of the hydrocarbyl group are substituted with one or more hydrocarbyloxy groups. Specifically, the C _2-30 hydrocarbyloxyhydrocarbyl group may be a C _2-20 or C _2-15 hydrocarbyloxyhydrocarbyl group. For example, the hydrocarbyloxyhydrocarbyl group may be a straight-chain, branched-chain or cyclic alkyl. More specifically, the C _2-30 hydrocarbyloxyhydrocarbyl group is a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-part alkoxyalkyl groups such as a oxymethyl group, a tert-butoxyethyl group, and a tert-butoxyhexyl group; or an aryloxyalkyl group such as a phenoxyhexyl group.

A hydrocarbyl (oxy)silyl group is a functional group in which 1 to 3 hydrogens of -SiH ₃ are substituted with 1 to 3 hydrocarbyl groups or hydrocarbyloxy groups. Specifically, the C _1-30 hydrocarbyl (oxy)silyl group may be a C _1-20 , C _1-15 , C _1-10 , or C _1-5 hydrocarbyl (oxy)silyl group. More specifically, the C _1-30 hydrocarbyl (oxy) silyl group is an alkyl such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group, or a dimethylpropylsilyl group. silyl group; an alkoxysilyl group such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group, or a dimethoxyethoxysilyl group; and an alkoxyalkylsilyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, or a dimethoxypropylsilyl group.

In addition, a silyl hydrocarbyl group having 1 to 20 carbon atoms (C _1-20 ) is a functional group in which one or more hydrogens of the hydrocarbyl group are substituted with a silyl group. The silyl group may be -SiH ₃ or a hydrocarbyl (oxy)silyl group. Specifically, the C _1-20 silylhydrocarbyl group may be a C _1-15 or C _1-10 silylhydrocarbyl group. More specifically, a C _1-20 silylhydrocarbyl group is a silylalkyl group such as -CH ₂ -SiH ₃ ; an alkylsilylalkyl group such as a methylsilylmethyl group, a methylsilylethyl group, a dimethylsilylmethyl group, a trimethylsilylmethyl group, a dimethylethylsilylmethyl group, a diethylmethylsilylmethyl group, or a dimethylpropylsilylmethyl group; or an alkoxysilylalkyl group such as a dimethylethoxysilylpropyl group.

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 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 of 1 to 15 carbon atoms; straight-chain alkyl of 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 are not limited thereto.

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

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

An alkoxyalkyl group having 2 to 20 carbon atoms (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; It is not limited to this.

Examples of aryloxy having 6 to 40 carbon atoms (C _6-40 ) include phenoxy, biphenoxyl, naphthoxy, and the like, but are not limited thereto.

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

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

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

In addition, alkylene or alkylidene 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 , heptylene, octylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like, but is not limited thereto.

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

Alkylaryl having 7 to 20 carbon atoms (C _7-20 ) may mean a substituent in which one or more hydrogens of an aromatic ring are substituted with the above-mentioned alkyl. As an example, the alkylaryl having 7 to 20 carbon atoms (C _7-20 ) includes methylphenyl, ethylphenyl, methylbiphenyl, methylnaphthyl, etc., but is not limited thereto

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

In addition, arylene or arylidene having 6 to 20 carbon atoms (C _6-20 ) is the same as the above-mentioned aryl except for being a divalent substituent, specifically phenylene, biphenylene, naphthylene, anthracenylene , 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 rutherfordium (Rf), specifically titanium (Ti), zirconium (Zr), or hafnium (Hf) It may be, more specifically, 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), and specifically may be boron (B) or aluminum (Al). and is not limited thereto.

The above-mentioned substituents are optionally hydroxy groups within the range of exhibiting the same or similar effects to the desired effect; halogen; alkyl or alkenyl, aryl, alkoxy; Alkyl or alkenyl, aryl, alkoxy containing at least one heteroatom 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 sulfone groups.

On the other hand, the hybrid supported catalyst of the present invention is mixed supported with a low copolymerizable first metallocene compound and a second metallocene compound having a high molecular weight during ethylene polymerization, thereby providing excellent process stability and high activity in ethylene polymerization. It exhibits a high copolymerizability (comonomer incorporation) and has a useful feature for preparing a polyethylene copolymer having excellent mechanical properties.

In particular, in the hybrid supported metallocene catalyst according to the embodiment, the first metallocene compound represented by Formula 1 contributes to making a low molecular weight linear copolymer, and the second metal represented by Formula 2 Strong compounds can contribute to making high molecular weight linear copolymers. The hybrid supported metallocene catalyst has excellent supported performance, catalytic activity and high synthesis can be represented. In particular, when low-density polyethylene is produced in a slurry process using such a mixed supported metallocene catalyst, the process stability is improved and the fouling problem that has occurred in the past can be prevented. In addition, polyethylene with excellent physical properties, for example, low density polyethylene, can be provided using the hybrid supported metallocene catalyst.

Specifically, the first metallocene compound has a form in which cyclopentadienyl, indenyl, or fluorenylyl ligands in Formula 1 are bridged with a Group 4 transition metal, and these ligands are at least one other than hydrogen. It is characterized by having a substituent. For example, a cyclopentadienyl, indenyl, or fluorenylyl ligand is unsubstituted or substituted with a C _1-20 hydrocarbon or a C _1-12 hydrocarbon. In particular, the cyclopentadienyl, indenyl, or fluorenylyl ligand is substituted with at least one or more alkyl, alkenyl, alkoxyalkyl, or arylalkyl. As cyclopentadienyl, indenyl, or fluorenylyl ligands of this specific structure are applied, catalytic activity and copolymerizability can be improved, the resulting polymer molecular structure is improved, and reactivity control is excellent.

Specifically, in Chemical Formula 1, M ¹ may be zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).

In Formula 1, Cp ¹ and Cp ² may each be cyclopentadienyl, indenyl, or fluorenyl, and preferably, at least one of Cp ¹ and Cp ² is cyclopentadienyl or indenyl. . More preferably, both Cp ¹ and Cp ² may be cyclopentadienyl.

The Cp ¹ and Cp ² may be unsubstituted or substituted with at least one C _1-20 hydrocarbon. For example, the Cp ¹ and Cp ² may be substituted with one or more of a C _1-10 hydrocarbyl group, a C _1-10 hydrocarbyloxy group, or a C _1-10 hydrocarbyloxyhydrocarbyl group, Specifically, it may be substituted with one or more of methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, tert-butoxyhexyl, butenyl, phenylpropyl, phenylhexyl, or phenyl. there is.

More specifically, in the first metallocene compound, Cp ¹ and Cp ² are identical to or different from each other, and preferably, a symmetrical structure may be formed by including the same substituents in which Cp ¹ and Cp ² are identical to each other.

And, R ^a and R ^b are each hydrogen, C _1-6 straight chain or branched alkyl, C _2-6 alkynyl, C _1-6 alkoxy-substituted C _1-6 alkyl, C _6-12 of aryl-substituted C _1-6 alkyl, or C _6-12 aryl, provided that at least one of R ^a and R ^b is not hydrogen. In particular, R ^a and R ^b may be the same as or different from each other, for example, the same as each other, and Formula 1 may have a symmetrical structure. For example, R ^a and R ^b are hydrogen, methyl (Me), ethyl (Et), n-propyl (n-Pr), iso-propyl (i-Pr), n-butyl (n-Bu), tert-butyl (t-Bu), n-pentyl (n-Pt), n-hexyl (n-Hex), tert-butoxy (t-Bu-O) hexyl, butenyl, phenylpropyl, phenylhexyl, or It may be phenyl (Ph).

And, in Chemical Formula 1, each Q ¹ may be halogen, and specifically may be chlorine.

And, in Formula 1, n is 1 or 0, preferably n is 1.

Meanwhile, the first metallocene compound may be represented by any one of Chemical Formulas 1-1 to 1-5.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Formulas 1-1 to 1-5, M ¹ and Q ¹ are as defined in Formula 1,

R' and R" are the same as or different from each other, and are each independently hydrogen, C _1-20 alkyl, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-20 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl, provided that R at least one of ' and R" is not hydrogen;

m1 is each independently an integer of 1 to 8;

m2 is each independently an integer of 1 to 6;

More preferably, the first metallocene compound may be represented by Chemical Formula 1-1.

And, in Formulas 1-1 to 1-5, R' and R" are each hydrogen, C _1-6 straight-chain or branched alkyl, C _2-6 alkynyl, C _1-6 alkoxy-substituted C It may be _1-6 alkyl, C _6-12 aryl-substituted C _1-6 alkyl, or C _6-12 aryl, provided that at least one of R' and R" is not hydrogen. Preferably, at least one of R' and R" is methyl (Me), ethyl (Et), n-propyl (n-Pr), iso-propyl (i-Pr), n-butyl (n-Bu ), tert-butyl (t-Bu), n-pentyl (n-Pt), n-hexyl (n-Hex), tert-butoxy (t-Bu-O) hexyl, butenyl, phenylpropyl, phenylhexyl , or phenyl (Ph), the remainder being hydrogen.

And, in Formulas 1-1 to 1-5, m1 and m2 are each an integer of 1 to 4, preferably 1 or 2, respectively.

Specifically, the first metallocene compound may be represented by one of the following structural formulas.

.

.

The first metallocene compound represented by the above structural formulas may be synthesized by applying known reactions, and a more detailed synthesis method may refer to Examples.

Meanwhile, the supported hybrid catalyst of the present invention is characterized in that it includes the second metallocene compound represented by Chemical Formula 2 together with the first metallocene compound described above.

Specifically, the second metallocene compound has a form in which two indenyl ligands in Chemical Formula 2 are bonded to a Group 4 transition metal through a carbon or silicon bridge, and methyl at position 2 of the indenyl ligand, 4 It is characterized in that two indenyl ligands having a specific substituent have the same symmetrical structure as each aryl substituted with a hydrocarbyloxyhydrocarbyl group is substituted at position No. As the bis-indenyl ligand of this specific structure is applied, the process stability is increased by reducing the ratio of ethylene and comonomer in the reaction system due to high copolymerizability, and high comonomer copolymerization (comonomer) in the polymer area of the resulting polyethylene molecular weight distribution graph Incorporation), it is possible to produce linear low-density polyethylene products with excellent morphology and high impact strength.

Specifically, in Chemical Formula 2, M ² may be zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).

And, in Chemical Formula 2, A may be silicon (Si).

And, in Chemical Formula 2, X ¹ and X ² may each be halogen, and specifically, may be chlorine.

And, in Formula 2, L ¹ and L ² may each be a C _1-3 alkylidene, and specifically, may be methylidene, ethylidene, or propylidene.

And, in Chemical Formula 2, D ¹ and D ² are oxygen (O).

And, in Formula 2, R ¹ and R ² may each be C _1-6 straight-chain or branched alkyl or C _6-12 aryl, and specifically, R ¹ and R ² are the same as each other and methyl ( Me), ethyl (Et), n-propyl (n-Pr), iso-propyl (i-Pr), n-butyl (n-Bu), tert-butyl (t-Bu), or phenyl (Ph)yl can

And, in Formula 2, R ³ and R ⁴ may each independently be a straight-chain or branched C _1-6 alkyl, specifically, R ³ and R ⁴ are the same as each other and represent a straight-chain C _1-6 may be an alkyl. For example, R ³ and R ⁴ are each methyl (Me), ethyl (Et), n-propyl (n-Pr), n-butyl (n-Bu), n-pentyl (n-Pt), or n- It may be hexyl (n-Hex).

Meanwhile, the second metallocene compound may be represented by Chemical Formula 2-1 below.

[Formula 2-1]

In Formula 2-1, M ² , A, X ¹ , X ² , R ¹ , R ² , R ³ , and R ⁴ are as defined in Formula 2 above.

Specifically, the second metallocene compound may be represented by one of the following structural formulas.

.

.

The second metallocene compound represented by the above structural formulas may be synthesized by applying known reactions, and a more detailed synthesis method may refer to the Examples.

In the method for preparing the metallocene compound, hybrid supported catalyst, or catalyst composition of the present invention, equivalent weight (eq) means molar equivalent weight (eq/mol).

Meanwhile, in the hybrid supported metallocene catalyst of the present invention, the first metallocene compound is represented by any one of Chemical Formulas 1-1 to 1-5, and the second metallocene compound is represented by Chemical Formula 2-1 may be represented by:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Formulas 1-1 to 1-5, M ¹ and Q ¹ are as defined in Formula 1,

R' and R" are the same as or different from each other, and are each independently hydrogen, C _1-20 alkyl, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-20 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl, provided that R at least one of ' and R" is not hydrogen;

m1 is each independently an integer of 1 to 8;

m2 is each independently an integer from 1 to 6;

[Formula 2-1]

In Formula 2-1, M ² , A, X ¹ , X ² , R ¹ , R ² , R ³ , and R ⁴ are as defined in Formula 2 above.

In addition, the hybrid supported metallocene catalyst of the present invention is more specifically, in Formulas 1-1 to 1-5, M ¹ is Zr; all Q ¹ are Cl; At least one of R' and R" is methyl (Me), ethyl (Et), n-propyl (n-Pr), iso-propyl (i-Pr), n-butyl (n-Bu), tert-butyl (t-Bu), n-pentyl (n-Pt), n-hexyl (n-Hex), tert-butoxy (t-Bu-O) hexyl, butenyl, phenylpropyl, phenylhexyl, or phenyl (Ph ), and the rest are hydrogen In addition, in Formula 2-1, M ² is Zr; X ¹ and X ² are Cl; R ¹ and R ² are the same as each other, and methyl (Me), ethyl (Et), n-propyl (n-Pr), iso-propyl (i-Pr), n-butyl (n-Bu), tert-butyl (t-Bu), or phenyl (Ph); R ³ and R ⁴ are the same and methyl (Me), ethyl (Et), n-propyl (n-Pr), n-butyl (n-Bu), n-pentyl (n-Pt), or n-hexyl (n-Hex).

Meanwhile, in the present invention, the first metallocene compound and the first metallocene compound may be meso isomers, racemic isomers, or a mixture thereof.

As used herein, "racemic form" or "racemic form" or "racemic isomer" means that the same substituent on two cyclopentadienyl moieties is M ₁ or M ₂ in Formula 1 or Formula 2 above. It means a form on the opposite side to the center of the cyclopentadienyl moiety and a plane containing a transition metal such as zirconium (Zr) or hafnium (Hf) represented by .

In addition, in the present specification, the term "meso isomer" or "meso isomer" is a stereoisomer of the above-described racemic isomer, wherein the same substituent on two cyclopentadienyl moieties is represented by Formula 1 or Formula 2 above. A transition metal represented by M ₁ or M ₂ , for example, a plane containing a transition metal such as zirconium (Zr) or hafnium (Hf) and the center of the cyclopentadienyl moiety are on the same side.

In the hybrid supported metallocene catalyst of the present invention, the first metallocene compound and the second metallocene compound may be supported at a molar ratio of about 0.3:1 to about 4:1. By including the first and second metallocene compounds in the above mixing molar ratio, excellent supporting performance, catalytic activity, and high copolymerizability may be exhibited. In particular, when low-density polyethylene is produced in a slurry process using such a mixed supported catalyst, process stability is improved and the fouling problem that has occurred in the past can be prevented. In particular, when the loading ratio of the first metallocene compound and the second metallocene compound exceeds about 4:1, only the first metallocene compound plays a dominant role and copolymerizability decreases, resulting in low-density polyethylene production. It can get difficult. In addition, when the loading ratio is less than about 0.3:1, only the second metallocene compound plays a dominant role, making it difficult to reproduce the molecular structure of the desired polymer.

Specifically, the first metallocene compound and the second metallocene compound have a molar ratio of about 0.5:1 to about 4:1, or a molar ratio of about 1:1 to about 4:1, or A mixed supported metallocene catalyst supported in a molar ratio of about 1:1 to about 2:1 is preferred for producing polyethylene having high activity in ethylene polymerization, excellent copolymerizability, and improved mechanical properties.

That is, in the case of the hybrid supported metallocene catalyst of the present invention in which the first metallocene compound and the second metallocene compound are supported in the molar ratio, the film properties of polyethylene are reduced due to the interaction of two or more catalysts. can be further improved.

In the hybrid supported metallocene catalyst of the present invention, a carrier containing a hydroxyl group on the surface may be used as a carrier for supporting the first metallocene compound and the second metallocene compound, and is preferably dried. It may be one containing highly reactive hydroxyl groups and siloxane groups on the surface from which moisture has been removed.

For example, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are typically oxides, carbonates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) ₂ , It may contain sulfate and nitrate components.

The drying temperature of the carrier is preferably from about 200 ^° C to about 800 ^° C, more preferably from about 300 ^° C to about 600 ^° C, and most preferably from about 300 ^° C to about 400 ^° C. When the drying temperature of the carrier is less than 200 ^° C, the moisture on the surface is too high, and the moisture on the surface reacts with the cocatalyst described below ^. This is not preferable because a lot of hydroxyl groups are lost and only siloxane groups remain, reducing the reaction site with the cocatalyst.

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

If the amount of the hydroxy group is less than about 0.1 mmol / g, there are few reaction sites with the cocatalyst, and if it exceeds about 10 mmol / g, it may be due to moisture in addition to the hydroxy group present on the surface of the carrier particle. Not desirable.

For example, the total amount of the first and second metallocene compounds loaded on the carrier such as silica, that is, the amount of the metallocene compound loaded may be 0.01 mmol/g to 1 mmol/g based on 1 g of the carrier. That is, it is preferable to control the loading amount to fall within the aforementioned range in consideration of the contribution effect of the catalyst by the metallocene compound.

Meanwhile, the hybrid supported metallocene catalyst may be one in which one or more of the first metallocene compound and one or more of the second metallocene compound are supported on a carrier together with a cocatalyst compound. The cocatalyst may be any cocatalyst used when polymerizing olefins in the presence of a general metallocene catalyst. This cocatalyst causes a bond to be formed between the hydroxyl group in the carrier and the Group 13 transition metal. In addition, since the cocatalyst is present only on the surface of the carrier, it can contribute to securing the unique characteristics of the specific hybrid catalyst configuration herein without fouling phenomenon in which polymer particles are entangled with each other or on the wall of the reactor.

In addition, the supported hybrid metallocene catalyst of the present invention may further include one or more cocatalysts selected from the group consisting of compounds represented by Formulas 3 to 5 below.

[Formula 3]

-[Al(R ³¹ )-O] _c -

In Formula 3,

each R ³¹ is independently halogen, C _1-20 alkyl or C _1-20 haloalkyl;

c is an integer greater than or equal to 2;

[Formula 4]

D(R ⁴¹ ) ₃

In Formula 4,

D is aluminum or boron;

each R ⁴¹ is independently hydrogen, halogen, C _1-20 hydrocarbyl or halogen-substituted C _1-20 hydrocarbyl;

[Formula 5]

[LH] ⁺ [Q(E) ₄ ] ^- or [L] ⁺ [Q(E) ₄ ] ^-

In Formula 5,

L is a neutral or cationic Lewis base;

[LH] ⁺ is a Bronsted acid,

Q is Br ³⁺ or Al ³⁺ ;

E is each independently C _6-40 aryl or C _1-20 alkyl, wherein the C _6-40 aryl or C _1-20 alkyl is unsubstituted or halogen, C _1-20 alkyl, C _1-20 alkoxy, And C _6-40 It is substituted with one or more substituents selected from the group consisting of aryloxy.

The compound represented by Chemical Formula 3 may be, for example, an alkylaluminoxane such as modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane.

The alkyl metal compound represented by Formula 4 is, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethylchloro Aluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminium, tripentylaluminium, triisopentylaluminium, trihexylaluminum, ethyldimethylaluminium, methyldiethylaluminum, triphenylaluminum, tri-p-tolyl aluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like.

The compound represented by Formula 5 is, for example, triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium 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 tetrapentafluorophenyl boron, N,N-dimethylanilinium tetraphenyl boron, N,N -Diethylanilinium tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethylammonium tetrapentafluorophenyl boron, triphenylphosphonium tetraphenyl boron, trimethylphosphonium tetraphenyl Boron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra(p-tolyl) aluminum, tripropylammonium tetra( p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, Tributylammonium tetrapentafluorophenyl aluminum, N,N-dimethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenyl Aluminum, diethylammonium tetrapentafluorophenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, triphenyl carbonium tetraphenyl boron, triphenyl carbonium tetraphenyl aluminum, triphenyl carbonone Umtetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, and the like may be used.

In addition, the hybrid supported metallocene catalyst may include the cocatalyst and the first metallocene compound in a molar ratio of about 1:1 to about 1:10000, preferably about 1:1 to about 1:1000. It may be included in a molar ratio of, more preferably about 1:10 to about 1:100 may be included in the molar ratio.

In addition, the hybrid supported metallocene catalyst may also include the cocatalyst and the second metallocene compound in a molar ratio of about 1:1 to about 1:10000, preferably about 1:1 to about 1:1000. It may be included in a molar ratio of, more preferably about 1:10 to about 1:100 may be included in the molar ratio.

At this time, if the molar ratio is less than about 1, the metal content of the cocatalyst is too small, so catalytically active species are not well formed, and activity may be low. there is.

The supported amount of the cocatalyst may be about 5 mmol to about 20 mmol based on 1 g of the carrier.

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

Alternatively, the hybrid supported metallocene catalyst may include supporting a cocatalyst on a carrier; supporting a second metallocene compound on the support on which the cocatalyst is supported; and supporting the first metallocene compound on the carrier on which the cocatalyst and the second metallocene compound are supported.

Alternatively, the hybrid supported metallocene catalyst may include supporting the first metallocene compound on a carrier; supporting a cocatalyst on the carrier on which the first metallocene compound is supported; and supporting a second metallocene compound on a carrier on which the cocatalyst and the first metallocene compound are supported.

In the above method, the supporting conditions are not particularly limited and may be carried out within a range well known to those skilled in the art. For example, it may be carried out by appropriately using high-temperature supporting and low-temperature supporting, for example, the supporting temperature may be in the range of about -30 ° C to about 150 ° C, preferably about 50 ° C to about 98 ° C, or It may be from about 55 °C to about 95 °C. The loading time may be appropriately adjusted according to the amount of the first metallocene compound to be loaded. The supported catalyst 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 being filtered with an aromatic hydrocarbon such as toluene.

In addition, the preparation of the supported catalyst may be performed in a solvent or without a solvent. When a solvent is used, usable solvents include aliphatic hydrocarbon solvents such as hexane or pentane, aromatic hydrocarbon solvents such as toluene or benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, diethyl ether or tetrahydrofuran (THF ), and most organic solvents such as acetone and ethyl acetate, and hexane, heptane, toluene, or dichloromethane is preferable.

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

The above-described hybrid supported catalyst can exhibit excellent supported performance, catalytic activity and high copolymerizability, and even if low density polyethylene is produced in a slurry process under such a supported hybrid catalyst, problems related to conventional productivity reduction and fouling are prevented and process stability is improved. can improve

The method for preparing the polyethylene copolymer may be carried out by a slurry polymerization method using ethylene and alpha-olefin as raw materials in the presence of the above-described mixed supported catalyst and applying conventional equipment and contact technology.

The method for preparing the polyethylene copolymer 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, the copolymerization step may be performed by reacting an alpha-olefin in an amount of about 0.45 mole or less, or about 0.1 mole to about 0.45 mole, based on 1 mole of ethylene. More specifically, the alpha-olefin is about 0.4 mole or less, or 0.38 mole or less, or 0.35 mole or less, or 0.31 mole or less, and about 0.15 mole or more, or about 0.2 mole or more, or about 0.25 mole or less based on 1 mole of ethylene. or more, or about 0.28 mole or more, the copolymerization reaction can be carried out.

The method for producing the polyethylene copolymer has the characteristics of a stable process and reproducible high drop impact strength of the product because it does not require an increase in the content of the comonomer to lower the product density.

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-eicosene, and mixtures thereof, preferably 1-hexene.

Specifically, in the manufacturing method of the polyethylene copolymer, for example, 1-hexene may be used as the alpha-olefin. Accordingly, in the slurry polymerization, a low density polyethylene copolymer may be prepared by polymerizing the ethylene and 1-hexene.

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 from about 60 ^° C to about 120 ^° C. Also, the polymerization pressure may be from about 1 bar to about 100 bar, or from about 5 bar to about 90 bar, or from about 10 bar to about 80 bar, or from about 15 bar to about 70 bar, or from about 20 bar to about 60 bar. there is.

The supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof, and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane, and chlorobenzene. It can be injected by dissolving or diluting in a hydrocarbon solvent substituted with a chlorine atom. The solvent used here is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkyl aluminum, and it is also possible to use a cocatalyst further.

For example, the polymerization step may include 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 15 ppm, based on the ethylene content. It can be done with an input of about 100 ppm.

In this ethylene polymerization process, the transition metal compound of the present invention can exhibit high catalytic activity. For example, the catalytic activity during ethylene polymerization is about 4.8 kg PE /g Cat hr or more or about 4.8 kg PE /g cat hr to about 50 kg PE /g cat hr, specifically at least 5.0 kg PE /g cat hr or about 5.0 kg PE /g cat hr hr to about 40 kg PE /g cat hr, specifically greater than or equal to 5.1 kg PE /g cat hr or about 5.1 kg PE /g cat hr to about 35 kg PE /g cat hr. there is.

As such, the polyethylene copolymer according to the present invention may be prepared by copolymerizing ethylene and alpha-olefin using the above-described supported metallocene catalyst.

At this time, the polyethylene produced may be an ethylene 1-hexene copolymer.

According to another embodiment of the invention, a polyethylene copolymer obtained by the above-described manufacturing method is provided.

As the method for preparing the polyethylene copolymer is carried out by slurry polymerization in the presence of the above-described mixed supported catalyst, it is possible to provide a polyethylene copolymer having excellent mechanical properties.

Linear low density polyethylene (LLDPE) is produced by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and is a resin having a narrow molecular weight distribution and short chain branches of a certain length. Linear low-density polyethylene film has high breaking strength, elongation, tear strength, drop impact strength, etc. along with the characteristics of general polyethylene, so it is increasingly used in stretch films and overlap films, which are difficult to apply to conventional low-density polyethylene or high-density polyethylene. are doing

On the other hand, it is known that the transparency and drop impact strength of linear low-density polyethylene generally increase as the density decreases. However, when a lot of comonomers are used to produce low-density polyethylene, the frequency of fouling increases in the slurry polymerization process, and the amount of antiblocking must be increased because of the stickiness when producing films containing them. there is a problem with In addition, there are problems such as an unstable production process or a decrease in bulk density due to deterioration of morphology characteristics of polyethylene produced.

In the present invention, the above-described hybrid supported catalyst has excellent mechanical properties with high drop impact strength during film formation, while preventing problems related to productivity reduction and fouling that conventionally occur when low-density polyethylene copolymers are prepared by slurry polymerization Polyethylene copolymers can be provided.

Accordingly, the polyethylene copolymer may be low density polyethylene having a density of about 0.930 g/cm 3 or less according to ASTM D 792 of the American Society for Testing and Materials. Specifically, the density is about 0.910 g/cm 3 or greater, or about 0.911 g/cm 3 or greater, or about 0.912 g/cm 3 or greater, or about 0.913 g/cm 3 or greater, or about 0.915 g/cm 3 or greater, and about 0.925 g/cm 3 or greater. cm 3 or less, about 0.923 g/cm 3 or less, or about 0.920 g/cm 3 or less, or about 0.918 g/cm 3 or less, or about 0.917 g/cm 3 or less, or about 0.9168 g/cm 3 or less. The density of the polyethylene copolymer should satisfy the aforementioned range in terms of ensuring excellent transparency and high impact strength during film processing.

In addition, the polyethylene copolymer may have a melt index (MI _2.16 , 190 ^° C, measured under a load of 2.16 kg) of about 0.5 g / 10 min to about 2.0 g / 10 min, measured according to ASTM D 1238 of the American Society for Testing and Materials. . Specifically, the melt index (MI _2.16 , 190 ^° C, measured under a load of 2.16 kg) is about 0.7 g / 10 min or more, about 0.8 g / 10 min or more, about 0.9 g / 10 min or more, or about 0.98 g / 10 min or more , about 1.8 g/10 min or less, or about 1.5 g/10 min or less, or about 1.5 g/10 min or less.

In addition, the polyethylene copolymer may have an apparent density (BD, Bulk Density) of about 0.2 g/mL or more, or about 0.2 g/mL to about 0.7 g/mL, measured according to ASTM D 1895 of the American Society for Testing and Materials. . Specifically, the apparent density is about 0.25 g/mL or greater, or about 0.3 g/mL or greater, or about 0.35 g/mL or greater, or about 0.4 g/mL or greater, or about 0.41 g/mL or greater, and about 0.6 g /mL or less, or about 0.5 g/mL or less, or about 0.48 g/mL or less, or about 0.47 g/mL or less, or about 0.46 g/mL or less. or about 0.45 g/mL or less. The apparent density should satisfy the aforementioned range in terms of securing excellent morphology of the polyethylene copolymer.

In particular, the polyethylene copolymer, after preparing a polyethylene copolymer film (BUR 2.3, film thickness of 48 μm to 52 μm, for example, film thickness of 50 μm) using a film forming machine, the American Society for Testing and Materials standard ASTM D 1709 The drop impact strength measured according to the standard may be about 1200 g or more or about 1200 g to about 3500 g. Specifically, the drop impact strength may be about 1350 g or more, or about 1500 g or more, or about 1550 g or more, or about 1600 g or more, or about 1650 g or more, or about 1700 g or more. The higher the drop impact strength value, the better, so the upper limit is not particularly limited, but in terms of preventing deterioration of various physical properties such as processability of the film, it is about 3200 g or less, or about 3000 g or less, or about 2800 g or less, or about 2500 g or less, or about 2200 g or less, or about 2000 g or less. The drop impact strength of the polyethylene copolymer should satisfy the above-described range in terms of securing high mechanical properties with excellent processability when forming a film such as a blown film.

In addition, the polyethylene copolymer, after manufacturing a polyethylene copolymer film (BUR 2.3, film thickness of 48 μm to 52 μm, for example, film thickness of 50 μm) using a film forming machine, according to ISO 13468 standards of the International Organization for Standardization The measured haze of the film may be about 12% or less. Specifically, the haze may be about 11% or less, or about 10% or less, or about 9% or less. The lower the haze value, the better, so the lower limit is not particularly limited, but may be, for example, about 4% or more, about 5% or more, or about 6% or more.

Meanwhile, the polyethylene copolymer may have a molecular weight distribution (PDI) of about 2.0 to about 6.0, or about 2.0 to about 5.0, or about 2.0 to about 4.0.

For example, the molecular weight distribution (Mw/Mn) of the polyethylene is determined by measuring the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water) , which can be obtained by dividing the weight average molecular weight by the number average molecular weight.

Specifically, a Waters PL-GPC220 instrument may be used as a gel permeation chromatography (GPC) apparatus, and a Polymer Laboratories PLgel MIX-B 300 mm long column may be used. At this time, the measurement temperature is 160 ^° C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) can be used as a solvent, and the flow rate can be applied at 1 mL / min. Polyethylene samples were pretreated by melting in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160 ^o C for 10 hours using a GPC analyzer (PL-GP220), respectively, and 10 mg/10mL After preparing to a concentration, it can be measured by supplying 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, 4000000 g/mol, 10000000 g 9 types of /mol can be used.

In addition, the weight average molecular weight of the polyethylene copolymer may be about 50000 g / mol to about 200000 g / mol. Specifically, the polyethylene copolymer has a weight average molecular weight of about 60000 g/mol or more, or about 65000 g/mol, or 70000 g/mol, and about 190000 g/mol or less, or about 180000 g/mol or less, or about 150000 g/mol.

Therefore, with the above manufacturing method, the polyethylene copolymer can be used for various purposes requiring such physical properties, in particular, it can be used for agricultural/industrial and packaging purposes requiring high drop impact strength, and can be applied to conventional low-density polyethylene or high-density polyethylene. It can also be used for this difficult stretch film.

The hybrid supported metallocene catalyst according to the present invention exhibits excellent process stability and high polymerization activity in ethylene polymerization, and has an excellent effect of preparing a polyethylene copolymer with excellent mechanical properties due to high comonomer incorporation.

Hereinafter, the action and effect of the invention will be described in more detail through specific examples of the invention. However, these embodiments are only presented as examples of the invention, and the scope of the invention is not determined thereby.

[Example]

<Preparation of the first metallocene compound>

Synthesis Example 1

n-butyl chloride and cyclopentadienyl sodium (NaCp) were reacted to obtain n-butyl cyclopentadiene (n-BuCp). After that, n-BuCp was dissolved in tetrahydrofuran (THF) at -78 ^o C, normal butyllithium (n-BuLi, 2.5 M in hexane) was slowly added, the temperature was raised to room temperature again, and reacted for 8 hours. . The lithium salt solution thus prepared was slowly added to a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol)/THF (30 mL) at -78 ^o C and further reacted at room temperature for 6 hours. . All volatile substances were vacuum dried, and hexane solvent was added to the obtained oily liquid substance to filter out. After vacuum drying the filtered solution, hexane was added to induce a precipitate at low temperature (-20 ^° C). The resulting precipitate was filtered at low temperature to obtain [(CH ₃ )(CH ₂ ) ₃ -C ₅ H ₄ ] ₂ ZrCl ₂ compound in the form of a white solid (yield: 50%).

Synthesis Example 2

Using 6-chlorohexanol, t-butyl-O-(CH ₂ ) ₆ -Cl was prepared by the method described in the literature (Tetrahedron Lett. 2951 (1988)), and cyclopentathienyl sodium (NaCp) was added thereto. The reaction gave t-butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ (yield 60%, bp 80 ^o C/0.1 mmHg).

Also, after dissolving t-butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ in tetrahydrofuran (THF) at -78 ^o C and slowly adding n-butyllithium (n-BuLi, 2.5 M in hexane), , After raising the temperature to room temperature, it was reacted for 8 hours. The lithium salt solution synthesized above was slowly added to the suspension solution of ZrCl ₄ (THF) ₂ (170 g, 4.50 mmol)/THF (30 mL) at -78 ^o C and further reacted at room temperature for 6 hours. made it All volatile substances were removed by vacuum drying, and hexane was added to the obtained oily liquid substance for filtering. After vacuum drying the filter solution, hexane was added to induce a precipitate at low temperature (-20 ^° C). The obtained precipitate was filtered at low temperature to obtain [tert-butyl-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ ] in the form of a white solid (yield: 92%).

¹ H-NMR (300 MHz, CDCl ₃ , ppm): δ 6.28 (t, J=2.6 Hz, 2H), 6.19 (t, J=2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J = 8 Hz), 1.7 - 1.3 (m, 8H), 1.17 (s, 9H).

¹³ C-NMR (300 MHz, CDCl ₃ , ppm): δ 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.31, 30.14, 29.18, 27.58, 26.00.

Comparative Synthesis Example 1

Preparation of (6-t-butoxyhexyl)fluorenylmethylsilane

From the reaction between t-butyl-O-(CH ₂ ) ₆ Cl compound and Mg(0) in diethyl ether (Et ₂ O) solvent, Grignard reagent tBu-O-(CH ₂ ) ₆ MgCl solution 0.14 mol was obtained. To this, a methyltrichlorosilane (MeSiCl ₃ ) compound (24.7 mL, 0.21 mol) was added at -100 ^o C, stirred at room temperature for 3 hours or more, and the filtered solution was vacuum-dried (6-t-part A compound of toxyhexyl)methylsilane dichloride [tBu-O-(CH ₂ ) ₆ SiMeCl ₂ ] was obtained (yield: 84%). _{fluorenyllithium} ( _4.82 g, _0.028 mol ⁾ / hexane (150 mL) solution was added slowly over 2 hours. Filter off the white precipitate (LiCl) and extract the desired product with hexane to vacuum dry all volatiles to obtain (6-t-butoxyhexyl)fluorenylmethylsilane [tBu-O-(CH ₂ ) as a pale yellow oil. ₆ )SiMe(9-C ₁₃ H ₁₀ )] was obtained (yield: 99%).

Preparation of (t-butoxyhexyl)(cyclopentadienyl)(fluorenyl)methylsilane

After adding THF solvent (50 mL) and reacting with C ₅ H ₅ Li (2.0 g, 0.028 mol) / THF (50 mL) solution at room temperature for more than 3 hours, all volatile substances were vacuum-dried and extracted with hexane. (t-butoxyhexyl)(cyclopentadienyl)(fluorenyl)methylsilane [(tBu-O-(CH ₂ ) ₆ )(CH ₃ )Si(C ₅ H ₅ )(9-C ₁₃ H ₁₀ )] was obtained (yield: 95%). The structure of the ligand was confirmed through ¹ H NMR.

Preparation of (t-butoxyhexyl) (methyl) silanyl (cyclopentadienyl) (fluorenyl) zirconium dichloride

Also, (t-butoxyhexyl)(cyclopentadienyl)(fluorenyl)methylsilane [(tBu-O-(CH ₂ ) ₆ )(CH ₃ )Si(C ₅ H ₅ ) at -78 ^o C (9-C ₁₃ H ₁₀ )] (12 g, 0.028 mol) / THF (100 mL) was added with 2 equivalents of n-BuLi and reacted for 4 hours or more while raising the temperature to room temperature to obtain an orange solid form (tBu-O- (CH ₂ ) ₆ )(CH ₃ )Si(C ₅ H ₅ Li)(9-C ₁₃ H ₁₀ Li) was obtained (yield: 81%). Also, at -78 ^o C, a dilithium salt (2.0 g, 4.5 mmol) / ether (30 mL) was added to a suspension solution of ZrCl ₄ (1.05 g, 4.50 mmol) / ether (30 mL). The solution was added slowly and reacted for an additional 3 hours at room temperature. All volatile substances were vacuum dried, and dichloromethane solvent was added to the obtained oily liquid substance to filter out. After vacuum drying the filtered solution, hexane was added to induce a precipitate. The obtained precipitate was washed with hexane several times to obtain racemic-(t-butoxyhexyl)(methyl)silanyl(cyclopentadienyl)(fluorenyl)zirconium dichloride [racemic-(t-Bu- A compound of O-(CH ₂ ) ₆ )(CH ₃ )Si(C ₅ H ₄ )(9-C ₁₃ H ₉ )ZrCl ₂ ] was obtained (yield: 54%).

Comparative Synthesis Example 2

After dissolving indene (5 g, 0.043 mol) in hexane (150 mL), mixing thoroughly, cooling to -30 ° C, a 2.5 M n-butyllithium (n-BuLi) hexane solution in the hexane solution in which the indene was dissolved ( 17 ml, 0.043 mol) was slowly dropped. Then, after slowly raising the temperature to room temperature, the mixture was stirred at room temperature for 12 hours. The resulting white suspension was filtered through a glass filter to obtain a white solid compound, and after sufficiently drying the white solid compound, an indene lithium salt (yield: 99%) was obtained.

Cyclopentadienyl zirconium trichloride (Cp-ZrCl ₃ , 2.24 g, 8.53 mmol) was slowly dissolved in diethyl ether (30 mL) and then cooled to -30 °C. To the diethyl ether solution in which CpZrCl ₃ was dissolved, indene lithium salt (1.05 g, 8.53 mmol) dissolved in diethyl ether (15 mL) was slowly dropped and stirred overnight to obtain indenyl (cyclopentadienyl zirconium dichloride [ Indenyl(cyclopentadienyl)]ZrCl ₂ )] was obtained (yield: 97%).

Comparative Synthesis Example 3

Preparation of (6-t-butoxyhexyl)dichloromethylsilane

100 mL of t-butoxyhexyl magnesium chloride solution (0.14 mol, ether) was slowly added dropwise to 100 mL of trichloromethylsilane solution (0.21 mol, hexane) at -100 ° C for 3 hours, and then at room temperature for 3 hours. Stir.

After separating the transparent organic layer from the mixed solution, excess trichloromethylsilane was removed from the separated transparent organic layer by vacuum drying. As a result, a transparent liquid (6-t-butoxyhexyl)dichloromethylsilane was obtained (yield: 84%).

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ 0.76 (3H, s), 1.11 (2H, t), 1.18 (9H, s), 1.32 - 1.55 (8H, m), 3.33 (2H, t) ).

(6-(t-butoxy)hexyl)(4-(4-(t-butyl)phenyl)-2-methyl-1H-inden-1-yl)(methyl)(2-isopropyl-4-(4 Preparation of (t-butyl)phenyl)-1H-inden-1-yl)silane

20 g (76.222 mmol) of 2-methyl-4-(4-(t-butyl)phenyl)indene was mixed with hexane and methyl tert-butyl ether (MTBE, methyl tertiary butyl ether) (Hex/MTBE = 15/1 After dissolving in 640mL of volume ratio), 33.5 mL of n-BuLi (2.5 M in hexane) was slowly added dropwise to the solution at -20 °C. Thereafter, the resulting reaction mixture was stirred at room temperature for one day, and then 80.5 mL of a solution of 19.7 g (72.411 mmol) of (6-t-butoxyhexyl)dichloromethylsilane prepared previously in the mixed solution was dissolved in hexane at -20 °C. was slowly added, and the resulting reaction mixture was stirred at room temperature for one day. Thereafter, the reaction mixture was distilled under reduced pressure to remove the solvent, redispersed in hexane, and filtered under reduced pressure. Then, the filtered solution was dried to obtain monosilane.

Meanwhile, in a separately prepared flask, 22.1 g (76.222 mmol) of 2-isopropyl-4-(4-(t-butyl)phenyl)indene and 136.5 mg (1.525 mmol) of CuCN were dissolved in 200 mL of diethyl ether, -20 33.5 mL of n-butyllithium solution (2.5M in hexane) was slowly added dropwise to the solution at °C. Thereafter, the obtained reaction mixture was stirred at room temperature for one day, and monosilane prepared previously was dissolved in 180 mL of diethyl ether and added to the reaction mixture. Thereafter, the obtained reaction mixture was stirred at room temperature for one day, and organic substances were extracted using water and MTBE, and distilled under reduced pressure. Subsequently, the product distilled under reduced pressure was purified through column chromatography to obtain a final ligand in a yield of 67%.

(6-(t-butoxy)hexyl)(4-(4-(t-butyl)phenyl)-2-methyl-1H-inden-1-yl)(methyl)(2-isopropyl-4-(4 Preparation of (t-butyl)phenyl)-1H-inden-1-yl)silane zirconium dichloride

The previously prepared (6-(t-butoxy)hexyl)(4-(4-(t-butyl)phenyl)-2-methyl-1H-inden-1-yl)(methyl)(2-isopropyl-4 After dissolving 1.00 g (1.331 mmol) of -(4-(t-butyl)phenyl)-1H-inden-1-yl)silane in 33 mL of diethyl ether, add n-butyllithium solution ( 2.5 M in hexane) 1.1mL was slowly added dropwise. Thereafter, the obtained reaction mixture was stirred at room temperature for about 4 hours, and then bis(N,N'-diphenyl-1,3-propanediamido)dichlorozirconium bis(tetrahydrofuran) [Zr(C After dissolving 706 mg (1.331 mmol) of ₅ H ₆ NCH ₂ CH ₂ CH ₂ NC ₅ H ₆ )Cl ₂ (C ₄ H ₅ O) ₂ ] in 33 mL of diethyl ether, the mixture was added at room temperature and stirred for one day. Thereafter, the red reaction solution was cooled to -20 °C, 4 equivalents of a 1 M HCl diethyl ether solution was slowly added dropwise to the cooled solution, and the resulting solution was stirred again at room temperature for 1 hour. Thereafter, after filtering and vacuum drying, the obtained solid was dissolved in pentane, crystals were precipitated for 48 hours, filtered under reduced pressure, and the solid was dried to obtain an orange transition metal compound, (6-(t-butoxy)hexyl)(4-( 4-(t-butyl)phenyl)-2-methyl-1H-inden-1-yl)(methyl)(2-isopropyl-4-(4-(t-butyl)phenyl)-1H-inden-1- 1) Silane zirconium dichloride was obtained in a yield of 8% (rac only).

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): δ 1.05 (3H, d), 1.09 (3H, d), 1.20 (3H, s), 1.34 (9H, s), 1.50 - 1.93 (10H, m ), 2.27 - 2.31 (1H, m), 3.37 (2H, t), 6.48 (1H, s) 6.98 (1H, s), 7.01 (1H, s), 7.09 - 7.12 (2H, m), 7.34 - 7.70 (12H, m).

<Preparation of the second metallocene compound>

Synthesis Example 3

Preparation of 1-bromo-4-(tertiary-butoxymethyl)benzene

H ₂ SO ₄ (1.47 mL) and anhydrous MgSO ₄ (12.9 g, 107 mmol) were added to CH ₂ Cl ₂ (80 mL) and stirred at room temperature for 15 minutes. After dissolving 4-bromobenzyl alcohol (5.0 g, 26.7 mmol) and t -butanol (12.8 mL, 134 mmol) in CH ₂ Cl ₂ (30 mL) in another flask, the above mixture was added. After stirring the mixture at room temperature overnight, sat. NaHCO ₃ was added. Water was removed with anhydrous MgSO ₄ , and the obtained solution was concentrated under reduced pressure and purified by column chromatography (E/H = 1/20) to obtain 1-bromo-4-(tert-butoxymethyl)benzene [ 1-bromo-4-( tert -butoxymethyl)benzene] (5.9 g, 90%) was obtained as a white solid.

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ 1.28 (9H, s), 4.39 (2H, s), 7.22 (2H, d), 7.44 (2H, d).

Preparation of 7-((4-tertiary-butoxymethyl)phenyl)-2-methyl-1H-indene

The previously prepared 1-bromo-4-(tert-butoxymethyl)benzene (4.52 g, 18.6 mmol) was dissolved in anhydrous THF (20 mL) under argon (Ar). After lowering the temperature to -78 ^o C and adding n -butyllithium solution ( n -BuLi, 2.5 M in hexane, 8.2 mL), the mixture was stirred at room temperature for 30 minutes. After lowering the temperature again to -78 ^o C and adding trimethyl borate (6.2 mL, 55.6 mmol), the mixture was stirred at room temperature overnight. A saturated aqueous ammonium chloride solution (sat. NH ₄ Cl) was added to the reaction solution, followed by extraction with methyl tertiary butyl ether (MTBE). Anhydrous MgSO ₄ was added and filtered to remove moisture. After concentrating the solution under reduced pressure, the next reaction proceeded without further purification.

The compound obtained above and 7-bromo-2-methyl-1 H -indene [7-bromo-2-methyl-1 H -indene] (3.87 g, 18.6 mmol), Na ₂ CO ₃ (5.91 g, 55.8 mmol) Toluene (40 mL), H ₂ O (20 mL), EtOH (20 mL) was put into a mixed solvent and stirred. Tetrakis triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 1.07 g. 0.93 mmol) was added to the above solution and stirred at 90 ^° C. overnight. After the reaction was completed, MTBE and water were added and the organic layer was separated. After removing moisture with anhydrous MgSO ₄ and concentrating the obtained solution under reduced pressure, it was purified by column chromatography (E/H = 1/30) to obtain 7-((4-tert-butoxymethyl)phenyl)-2 -Methyl- 1H -indene [7-(4- tert -butoxymethyl)phenyl)-2-methyl- 1H- indene] (2.9 g, 53%) was obtained.

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ 1.33 (9H, s), 2.14 (3H, s), 3.36 (2H, s), 4.50 (2H, s), 6.53 (1H, s), 7.11 - 7.45 (7H, m).

Preparation of bis(4-(4-tertiary-butoxymethyl)phenyl)-2methyl-1H-inden-1-yl)dimethylsilane

The previously prepared 7-((4-tert-butoxymethyl)phenyl)-2-methyl-1 H -indene (2.88 g, 9.85 mmol) and CuCN (44 mg, 0.49 mmol) were mixed with toluene under argon (Ar). (18 mL) and THF (2 mL). This solution was cooled to -30 ^o C and n -BuLi (2.5 M in hexane, 4.1 mL) was slowly added. After stirring at this temperature for about 20 minutes, the temperature was raised to room temperature, followed by stirring for 2.5 hours. Dichlorodimethysilane (0.59 mL, 4.89 mmol) was added to the solution and stirred overnight at room temperature. After the reaction was completed, MTBE and water were added, and the organic layer was separated. The obtained organic layer was dried with anhydrous MgSO ₄ , concentrated and purified by column chromatography (hexane) to obtain bis(4-(4-tert-butoxymethyl)phenyl)-2methyl-1 H -indene- 1-yl)dimethylsilane [bis(4-(4- tert- butoxymethyl)phenyl)-2-methyl-1 H -inden-1-yl)dimethylsilane] (2.95 g, 93%) was obtained as a white solid.

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ -0.20 (6H, s), 1.35 (18H, s), 2.19 (3H, s), 2.25 (3H, s), 3.81 (2H, s) , 4.53 (4H, s), 6.81 (2H, s), 7.18 - 7.52 (14H, m).

Dimethylsilanyl-bis(4-(4-tert-butoxymethyl)phenyl)-2-methyl-1 H -Inden-1-yl) Preparation of zirconium dichloride

Bis(4-(4-tertiary-butoxymethyl)phenyl)-2methyl-1 H -inden-1-yl)dimethylsilane (2.0 g, 3.12 mmol) previously prepared was added to 50 mL shh under argon (Ar). It was put in a Schlenk flask and dissolved by injecting diethyl ether (20 mL). After lowering the temperature to -78 ^o C and adding n -BuLi (2.5 M in hexane, 2.7 mL), the mixture was stirred at room temperature for 2 hours. The solvent was distilled under vacuum and ZrCl ₄ (THF) ₂ (1.18 g, 3.12 mmol) was added in a glove box, and the temperature was lowered to -78 ^° C. After adding diethyl ether (20 mL) to the mixture, the mixture was heated to room temperature and stirred overnight. The solvent was distilled under reduced pressure and dissolved in CH ₂ Cl ₂ to remove solids. The solid obtained by concentrating the solution under reduced pressure was washed with toluene and CH ₂ Cl ₂ to obtain racemic rich yellow solid dimethylsilanyl-bis(4-(4-tert-butoxymethyl)phenyl)-2-methyl -1 H -inden-1-yl) zirconium dichloride [dimethylsilanyl-bis(4-(4- tert -butoxymethyl)phenyl)-2-methyl-1 H -inden-1-yl)zirconium dichloride (260 mg, 10%, r/m about 16/1).

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ 1.28 (18H, s), 1.33 (6H, s), 2.24 (6H, s), 4.46 (4H, s), 6.93 (2H, s), 7.08 - 7.65 (14H, m).

Synthesis Example 4

Preparation of 1-bromo-4-(methoxymethyl)benzene

Dimethyl sulfoxide (DMSO, 117 mL)/KOH (214 mmol, 12 g) was put in a flask, 4-bromobenzyl alcohol (53.5 mmol, 10.0 g) was added, and the mixture was stirred at room temperature for 1 hour. After adding Mel (107 mmol, 6.6 mL) to the reaction mixture, the mixture was stirred for 10 minutes. After the reaction was completed, the reactant was put into H ₂ O and then extracted with CH ₂ Cl ₂ . The organic layer was dried over anhydrous MgSO ₄ and then vacuum dried to obtain 1-bromo-4-(methoxymethyl)benzene [1-bromo-4-methoxymethyl benzene] (10.6 g, 99%).

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ 3.41 (3H, s), 4.39 (2H, s), 7.11 -7.53 (4H, m).

Preparation of 7-(4-methoxymethyl)phenyl)-2-methyl-1H-indene

The previously prepared 1-bromo-4-(methoxymethyl)benzene (9.3 g, 46.3 mmol) was dissolved in anhydrous THF (40 mL) under argon (Ar). After lowering the temperature to -78 ^o C and adding n-butyllithium (n-BuLi, 2.5 M in hexane, 20.4 mL), the mixture was stirred at room temperature for 30 minutes. After lowering the temperature again to -78 ^o C and adding trimethyl borate (15.5 mL, 139 mmol), the mixture was stirred at room temperature overnight. A saturated aqueous ammonium chloride solution (sat. NH ₄ Cl) was added to the reaction solution, followed by extraction with MTBE. Anhydrous MgSO ₄ was added and filtered to remove moisture. After concentrating the solution under reduced pressure, the next reaction proceeded without further purification.

The compound obtained above, 7-bromo-2-methyl-1 H -indene (9.63 g, 46.3 mmol) and Na ₂ CO ₃ (14.7 g, 139 mmol) were mixed with toluene (80 mL) and H ₂ O (40 mL). , ethanol (EtOH, 40 mL) into a mixed solvent and stirred. Pd(PPh ₃ ) ₄ (1.07 g. 2.32 mmol) was added to the above solution and stirred overnight at 90 ^° C. After the reaction was completed, MTBE and water were added and the organic layer was separated. After removing moisture with anhydrous MgSO ₄ and concentrating the obtained solution under reduced pressure, it was purified by column chromatography (E/H = 1/30) to obtain 7-(4-methoxymethyl)phenyl)-2-methyl-1 H -indene [7-(4-(methoxymethyl)phenyl)-2-methyl-1 H -indene] (6.9 g, 60%) was obtained.

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ 2.15 (3H, s), 3.35 (2H, s), 3.38 (3H, s), 4.48 (2H, s), 6.55 (1H, s), 7.05 - 7.44 (7H, m).

Preparation of bis(4-(4-methoxymethyl)phenyl)-2-methyl-1H-inden-1-yl)dimethylsilane

The previously prepared 7-(4-methoxymethyl)phenyl)-2-methyl- 1H -indene (4.21 g, 16.8 mmol) and CuCN (75 mg, 0.84 mmol) were dissolved in toluene (36 mL) under argon (Ar). and THF (4 mL). This solution was cooled to -30 ^o C and n -BuLi (2.5 M in hexane, 7.4 mL) was slowly added. After stirring at this temperature for about 20 minutes, the temperature was raised to room temperature, followed by stirring for 2.5 hours. Dichlorodimethysilane (1.01 mL, 8.4 mmol) was added to the solution and stirred overnight at room temperature. After the reaction was completed, MTBE and water were added, and the organic layer was separated. The obtained organic layer was dried with anhydrous MgSO ₄ , concentrated and purified by column chromatography (hexane) to obtain bis(4-(4-methoxymethyl)phenyl)-2-methyl-1 H -indene-1- 1) Dimethylsilane [bis(4-(4-metoxymethyl)phenyl)-2-methyl- 1H -inden-1-yl)dimethylsilane] (4.21 g, 90%) was obtained as a white solid.

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ -0.21 (6H, s), 2.20 (3H, s), 2.23 (3H, s), 3.40 (6H, s), 3.82 (2H, s) , 4.50 (4H, s), 6.79 (2H, s), 7.15 - 7.53 (14H, m).

Preparation of dimethylsilanyl-bis(4-(4-methoxymethyl)phenyl)-2-methyl-1H-inden-1-yl)zirconium dichloride

The previously prepared bis(4-(4-methoxymethyl)phenyl)-2-methyl-1 H -inden-1-yl)dimethylsilane (3.0 g, 5.39 mmol) was placed in a 50 mL shrink flask under argon (Ar). (Schlenk flask) and dissolved by injecting diethyl ether (30 mL). After lowering the temperature to -78 ^o C and adding n -BuLi (2.5 M in hexane, 4.7 mL), the mixture was stirred at room temperature for 2 hours. The solvent was distilled under vacuum and ZrCl ₄ (THF) ₂ (2.04 g, 5.39 mmol) was added in a glove box, and the temperature was lowered to -78 ^° C. After adding diethyl ether (30 mL) to the mixture, the mixture was heated to room temperature and stirred overnight. The solvent was distilled under reduced pressure and dissolved in CH ₂ Cl ₂ to remove solids. The solid obtained by concentrating the solution under reduced pressure was washed with toluene and CH ₂ Cl ₂ to obtain a racemic rich yellow solid dimethylsilanyl-bis(4-(4-methoxymethyl)phenyl)-2-methyl-1 H -inden-1-yl) zirconium dichloride [dimethylsilanyl-bis(4-(4-metoxymethyl)phenyl)-2-methyl-1 H -inden-1-yl)-zirconium dichloride] (425 mg, 11%, r /m about 10/1).

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ 1.31 (6H, s), 2.22 (6H, s), 3.39 (6H, s), 4.43 (4H, s), 6.91 (2H, s), 7.09 - 7.64 (14H, m).

Synthesis Example 5

Preparation of 1-bromo-4-(tertiary-butoxymethyl)benzene

H ₂ SO ₄ (1.47 mL) and anhydrous MgSO ₄ (12.9 g, 107 mmol) were added to CH ₂ Cl ₂ (80 mL) and stirred at room temperature for 15 minutes. After dissolving 4-bromobenzyl alcohol (5.0 g, 26.7 mmol) and t-butanol ( t -butanol, 12.8 mL, 134 mmol) in CH ₂ Cl ₂ (30 mL) in another flask, The above mixture was added. After stirring the mixture at room temperature overnight, sat. NaHCO ₃ was added. Water was removed with anhydrous MgSO ₄ , and the resulting solution was concentrated under reduced pressure and purified by column chromatography (E/H = 1/20) to obtain 1-bromo-4-(tert-butoxymethyl)benzene [ 1-bromo-4-( tert -butoxymethyl)benzene] (5.9 g, 90%) was obtained as a white solid.

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ 1.28 (9H, s), 4.39 (2H, s), 7.22 (2H, d), 7.44 (2H, d).

7-(4-tertiary-butoxymethyl)phenyl)-2-methyl-1 H -Manufacture of indene

The previously prepared 1-bromo-4-(tert-butoxymethyl)benzene (4.52 g, 18.6 mmol) was dissolved in anhydrous THF (20 mL) under argon (Ar). After lowering the temperature to -78 ^o C and adding n -butyllithium solution ( n -BuLi, 2.5 M in hexane, 8.2 mL), the mixture was stirred at room temperature for 30 minutes. After lowering the temperature again to -78 ^o C and adding trimethyl borate (6.2 mL, 55.6 mmol), the mixture was stirred at room temperature overnight. sat. After adding NH ₄ Cl, the mixture was extracted with MTBE. Anhydrous MgSO ₄ was added and filtered to remove moisture. After concentrating the solution under reduced pressure, the next reaction proceeded without further purification.

The compound obtained above, 7-bromo-2-methyl-1 H -indene (3.87 g, 18.6 mmol) and Na ₂ CO ₃ (5.91 g, 55.8 mmol) were mixed with toluene (40 mL) and H ₂ O (20 mL). , EtOH (20 mL) was added to the mixed solvent and stirred. Pd(PPh ₃ ) ₄ (1.07 g. 0.93 mmol) was added to the above solution and stirred at 90 ^° C overnight. After the reaction was completed, MTBE and water were added and the organic layer was separated. After removing moisture with anhydrous MgSO ₄ and concentrating the obtained solution under reduced pressure, it was purified by column chromatography (E/H = 1/30) to obtain 7-(4-tert-butoxymethyl)phenyl)-2- Methyl- 1H -indene [7-(4- tert -butoxymethyl)phenyl)-2-methyl- 1H- indene] (2.9 g, 53%) was obtained.

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ 1.33 (9H, s), 2.14 (3H, s), 3.36 (2H, s), 4.50 (2H, s), 6.53 (1H, s), 7.11 - 7.45 (7H, m).

Preparation of bis(4-(4-tertiary-butoxymethyl)phenyl)-2-methyl-1H-inden-1-yl)diethylsilane

7-(4-tert-butoxymethyl)phenyl)-2-methyl- 1H -indene (2.88 g, 9.85 mmol) and CuCN (44 mg, 0.49 mmol) prepared above were mixed with toluene (Ar) under argon (Ar). 18 mL) and THF (2 mL). This solution was cooled to -30 ^o C and n -BuLi (2.5 M in hexane, 4.1 mL) was slowly added. After stirring at this temperature for about 20 minutes, the temperature was raised to room temperature, followed by stirring for 2.5 hours. Dichlorodiethylsilane (0.73 mL, 4.89 mmol) was added to the solution and stirred at room temperature overnight. After the reaction was completed, MTBE and water were added, and the organic layer was separated. The obtained organic layer was dried with anhydrous MgSO ₄ , concentrated, and purified by column chromatography (hexane) to obtain bis(4-(4-tert-butoxymethyl)phenyl)-2-methyl-1 H -indene. -1-yl)diethylsilane [bis(4-(4- tert -butoxymethyl)phenyl)-2-methyl- 1H- inden-1-yl)diethylsilane] (2.95 g, 93%) as a white solid got it

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ -0.20 (6H, s), 1.35 (18H, s), 2.19 (3H, s), 2.25 (3H, s), 3.81 (2H, s) , 4.53 (4H, s), 6.81 (2H, s), 7.18 - 7.52 (14H, m).

Diethylsilanyl-bis(4-(4-tert-butoxymethyl)phenyl)-2-methyl-1 H -Inden-1-yl) preparation of diethylsilane zirconium dichloride

Bis(4-(4-tertiary-butoxymethyl)phenyl)-2-methyl-1 H -inden-1-yl)diethylsilane (2.0 g, 3.12 mmol) prepared above was heated to 50 °C under argon (Ar). It was put in a mL Schlenk flask and dissolved by injecting diethyl ether (20 mL). After lowering the temperature to -78 ^o C and adding n -BuLi (2.5 M in hexane, 2.7 mL), the mixture was stirred at room temperature for 2 hours. The solvent was distilled under vacuum and ZrCl ₄ (THF) ₂ (1.18 g, 3.12 mmol) was added in a glove box, and the temperature was lowered to -78 ^° C. After adding diethyl ether (20 mL) to the mixture, the mixture was heated to room temperature and stirred overnight. The solvent was distilled under reduced pressure and dissolved in CH ₂ Cl ₂ to remove solids. The solid obtained by concentrating the solution under reduced pressure was washed with toluene and CH ₂ Cl ₂ to obtain racemic rich yellow solid diethylsilanyl-bis(4-(4-tert-butoxymethyl)phenyl)-2- Methyl- 1 H -inden- 1 -yl) diethylsilane zirconium dichloride (260 mg, 10%, r/m about 16/1).

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): δ 1.28 (18H, s), 1.33 (6H, s), 2.24 (6H, s), 4.46 (4H, s), 6.93 (2H, s), 7.08 - 7.65 (14H, m).

Comparative Synthesis Example 4

Preparation of methyl (6-tertiary-butoxyhexyl) dichlorosilane

After adding 50 g of Mg(s) to a 10 L reactor at room temperature, 300 mL of THF was added. After adding 0.5 g of I ₂ , the temperature of the reactor was maintained at 50 ^° C. After the reactor temperature was stabilized, 250 g of 6-tertiary-butoxyhexyl chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. As 6-t-butoxyhexyl chloride was added, it was observed that the temperature of the reactor increased by 4 to 5 ^° C. The mixture was stirred for 12 hours while continuously adding 6-tertiary-butoxyhexyl chloride to obtain a black reaction solution. After taking 2 mL of the resulting black solution, water was added to obtain an organic layer, and it was confirmed through ¹ H-NMR that it was 6-t-butoxyhexane, from which it was confirmed that the Grignard reaction proceeded well. From this, 6- tert -butoxyhexyl magnesium chloride was synthesized.

After adding 500 g of MeSiCl ₃ and 1 L of THF to the reactor, the temperature of the reactor was cooled to -20 ^° C. 560 g of the previously synthesized 6-tertiary-butoxyhexyl magnesium chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. After the feeding of the Grignard reagent was completed, the reactor was stirred for 12 hours while slowly raising the temperature to room temperature, and it was confirmed that white MgCl ₂ salt was produced. 4 L of hexane was added and salts were removed through labdori to obtain a filtrate through a filter. After adding the obtained filtrate to a reactor, hexane was removed at 70 ^° C to obtain a pale yellow liquid. It was confirmed that the obtained liquid was methyl(6-tert-butoxyhexyl)dichlorosilane [methyl(6- tert -butoxyhexyl)dichlorosilane] through ¹ H-NMR.

¹ H-NMR (500 MHz, CDCl ₃ ): δ 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 ( s, 3H).

Preparation of methyl(6-tert-butoxyhexyl)(tetramethylcyclopentadienyl)-tert-butylaminosilane

After adding 1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF to the reactor, the reactor temperature was cooled to -20 ^° C. 480 mL of n -BuLi (2.5 M in hexane) was added to the reactor at a rate of 5 mL/min using a feeding pump. After adding n-BuLi, the reactor was stirred for 12 hours while slowly raising the temperature to room temperature. An equivalent of methyl(6-t-butoxyhexyl)dichlorosilane (326 g, 350 mL) was then rapidly added to the reactor. After stirring for 12 hours while slowly raising the temperature of the reactor to room temperature, the temperature of the reactor was cooled to 0 ^° C again, and then 2 equivalents of tert-butyl amine (t-BuNH ₂ ) was added. The reactor was stirred for 12 hours while slowly raising the temperature to room temperature. Then, THF was removed and 4 L of hexane was added to obtain a salt-free filter solution through Labdori. After the filter solution was added to the reactor again, hexane was removed at 70 ^° C to obtain a yellow solution. Through ¹ H-NMR, it was confirmed that it was methyl (6-t-butoxyhexyl) (tetramethylcyclopentadiene) t-butylaminosilane [methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane].

Preparation of (tertiary-butoxyhexyl)methylsilanyl(tetramethylcyclopentadienyl)(tert-butyl amino)titanium dichloride

THF from n-BuLi and the previously prepared ligand compound, methyl(6-t-butoxyhexyl)(tetramethylcyclopentadiene)t-butylaminosilane [methyl(6-t-butoxyhexyl)(tetramethylCpH)t-butylaminosilane] 10 mmol of TiCl ₃ (THF) ₃ was quickly added to the dilithium salt of the ligand at -78 ^° C synthesized in solution. The reaction solution was stirred for 12 hours while slowly raising the temperature from -78 ^o C to room temperature. Subsequently, an equivalent amount of PbCl ₂ (10 mmol) was added at room temperature and stirred for 12 hours to obtain a dark blue solution. After removing THF from the resulting reaction solution, hexane was added to filter the product. After removing hexane from the obtained filter solution, ( ^tertiary -butoxyhexyl)methylsilanyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride [t-Bu-O- (CH ₂ ) ₆ ] (CH ₃ )Si(C ₅ (CH ₃ ) ₄ )(tBu—N)TiCl ₂ ].

¹ H-NMR (500 MHz, CDCl ₃ ): δ 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 - 0.8 (m), 1.4 (s, 9H), 1.2 ( s, 9H), 0.7 (s, 3H).

Comparative Synthesis Example 5

Preparation of 7-phenyl-2-methyl-1H-indene

Bromobenzene (2.92 g, 18.6 mmol) was dissolved in anhydrous THF (20 mL) under argon (Ar). After lowering the temperature to -78 ^o C and adding n -butyllithium ( n -BuLi, 2.5 M in hexane, 8.2 mL), the mixture was stirred at room temperature for 30 minutes. After lowering the temperature again to -78 ^o C and adding trimethyl borate (6.2 mL, 55.6 mmol), the mixture was stirred at room temperature overnight. sat. After adding NH ₄ Cl, the mixture was extracted with MTBE. Anhydrous MgSO ₄ was added and filtered to remove moisture. After concentrating the solution under reduced pressure, the next reaction proceeded without further purification.

Toluene ( ₄₀ mL), _{H 2 O} ( 20 mL), EtOH (20 mL) was added to the mixed solvent and stirred. Pd(PPh ₃ ) ₄ (1.07 g. 0.93 mmol) was added to the above solution and stirred at 90 ^° C overnight. After the reaction was completed, MTBE and water were added and the organic layer was separated. Water was removed with anhydrous MgSO ₄ , and the resulting solution was concentrated under reduced pressure and purified by column chromatography (E/H = 1/30) to obtain 7-phenyl-2-methyl-1 H -indene (7-phenyl- 2-methyl-1 H -indene) was obtained.

Preparation of bis(4-phenyl-2-methyl-1H-inden-1-yl)dimethylsilane

The previously prepared 7-phenyl-2-methyl-1 H -indene (2.02 g, 9.85 mmol) and CuCN (44 mg, 0.49 mmol) were dissolved in toluene (18 mL) and THF (2 mL) under argon (Ar). . This solution was cooled to -30 ^o C and n -BuLi (2.5 M in hexane, 4.1 mL) was slowly added. After stirring at this temperature for about 20 minutes, the temperature was raised to room temperature, followed by stirring for 2.5 hours. Dichlorodimethysilane (0.59 mL, 4.89 mmol) was added to the solution and stirred overnight at room temperature. After the reaction was completed, MTBE and water were added, and the organic layer was separated. The obtained organic layer was dried with anhydrous MgSO ₄ , concentrated and purified by column chromatography (hexane) to obtain bis(4-phenyl-2-methyl-1 H -inden-1-yl)-dimethyl-silane (bis (4-phenyl-2-methyl-1 H -inden-1-yl)-dimethyl-silane) was obtained as a white solid.

Preparation of dimethylsilanyl-bis(4-phenyl-2-methyl-1H-inden-1-yl)zirconium dichloride

The previously prepared bis(4-phenyl-2-methyl-1 H -inden-1-yl)-dimethyl-silane (2.0 g, 3.12 mmol) was placed in a 50 mL Schlenk flask under argon (Ar). It was dissolved by injecting diethyl ether (20 mL). After lowering the temperature to -78 ^o C and adding n -BuLi (2.5 M in hexane, 2.7 mL), the mixture was stirred at room temperature for 2 hours. The solvent was distilled under vacuum and ZrCl ₄ (THF) ₂ (1.18 g, 3.12 mmol) was added in a glove box, and the temperature was lowered to -78 ^° C. After adding diethyl ether (20 mL) to the mixture, the mixture was heated to room temperature and stirred overnight. The solvent was distilled under reduced pressure and dissolved in CH ₂ Cl ₂ to remove solids. The solid obtained by concentrating the solution under reduced pressure was washed with toluene and CH ₂ Cl ₂ to obtain a racemic rich yellow solid dimethylsilanyl-bis(4-phenyl-2-methyl-1 H -inden-1-yl)zirconium. Dichloride [dimethylsilanyl-bis(4-phenyl-2-methyl-1 h -inden-1-yl)zirconium dichloride] (260 mg, 10%, r/m about 16/1) was obtained.

<Preparation of Supported Catalyst>

Example 1: Preparation of a hybrid supported metallocene catalyst

First, silica (SP952 manufactured by Grace Davison) was dehydrated and dried under vacuum at 250 ^° C. for 12 hours to prepare a carrier.

Then, 3.0 kg of toluene solution was put into a high-pressure reactor made of stainless steel (sus) with a capacity of 20 L, 1000 g of silica (Grace Davison, SP952) prepared earlier was added, and the reactor temperature was raised to 40 ^° C while stirring did After the silica was sufficiently dispersed for 60 minutes, 8 kg of a 10 wt% methylaluminoxane (MAO)/toluene solution was added and stirred at 200 rpm for 12 hours. After raising the temperature of the reactor to 60 ^° C, 0.1 mmol of the first metallocene compound prepared in Synthesis Example 1 was dissolved in toluene in a solution state, added, and reacted at 50 ^° C with stirring at 200 rpm for 2 hours.

After completion of the reaction, 0.05 mmol of the second metallocene compound prepared in Synthesis Example 3 was dissolved in toluene, and reacted at 50 ^° C. with stirring at 200 rpm for 2 hours.

After the reaction was completed, stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decanted. Thereafter, after washing with a sufficient amount of toluene, 50 mL of toluene was added again, stirring was stopped for 10 minutes, and then washed with a sufficient amount of toluene to remove compounds that did not participate in the reaction. Thereafter, 3.0 kg of hexane was added to the reactor and stirred, and then the hexane slurry was transferred to a filter and filtered.

A hybrid supported catalyst was obtained by first drying at room temperature for 5 hours under reduced pressure and secondarily drying at 50 ^° C. for 4 hours under reduced pressure.

Example 2: Preparation of a hybrid supported metallocene catalyst

Hybrid support was carried out in the same manner as in Example 1, except that 0.2 mmol of the metallocene compound prepared in Synthesis Example 1 was added and 0.05 mmol of the metallocene compound prepared in Synthesis Example 4 was added. A metallocene catalyst was prepared.

Example 3: Preparation of a hybrid supported metallocene catalyst

Hybrid support was carried out in the same manner as in Example 1, except that 0.08 mmol of the metallocene compound prepared in Synthesis Example 2 was added and 0.08 mmol of the metallocene compound prepared in Synthesis Example 3 was added. A metallocene catalyst was prepared.

Example 4: Preparation of a hybrid supported metallocene catalyst

Hybrid support was carried out in the same manner as in Example 1, except that 0.1 mmol of the metallocene compound prepared in Synthesis Example 1 was added and 0.05 mmol of the metallocene compound prepared in Synthesis Example 5 was added. A metallocene catalyst was prepared.

Comparative Example 1: Preparation of a hybrid supported metallocene catalyst

Hybridization was performed in the same manner as in Example 1, except that 0.1 mmol of the metallocene compound prepared in Comparative Synthesis Example 1 was added and 0.05 mmol of the metallocene compound prepared in Synthesis Example 3 was added. A supported metallocene catalyst was prepared.

Comparative Example 2: Preparation of a hybrid supported metallocene catalyst

Hybridization was performed in the same manner as in Example 1, except that 0.1 mmol of the metallocene compound prepared in Comparative Synthesis Example 2 was added and 0.05 mmol of the metallocene compound prepared in Synthesis Example 3 was added. A supported metallocene catalyst was prepared.

Comparative Example 3: Preparation of a hybrid supported metallocene catalyst

Hybridization was performed in the same manner as in Example 1, except that 0.1 mmol of the metallocene compound prepared in Comparative Synthesis Example 3 was added and 0.05 mmol of the metallocene compound prepared in Synthesis Example 3 was added. A supported metallocene catalyst was prepared.

Comparative Example 4: Preparation of Hybrid Supported Metallocene Catalyst

Hybridization was performed in the same manner as in Example 1, except that 0.1 mmol of the metallocene compound prepared in Synthesis Example 2 was added and 0.05 mmol of the metallocene compound prepared in Comparative Synthesis Example 4 was added. A supported metallocene catalyst was prepared.

Comparative Example 5: Preparation of a hybrid supported metallocene catalyst

The hybrid supported metal was used in the same manner as in Example 1, except that the metallocene compound (catalyst G) of Comparative Synthesis Example 5 was used as the second precursor instead of the metallocene compound prepared in Synthesis Example 3. A rosen catalyst was prepared.

<Test Example>

Test Example 1: Production of polyethylene

Under the conditions shown in Table 1 below, ethylene-1-hexene was slurry polymerized in the presence of each of the supported catalysts prepared in Examples and Comparative Examples.

At this time, the polymerization reactor was an iso-butane (i-C4) slurry loop process continuous polymerization reactor, the reactor volume was 140 L, and the reaction flow rate was about 7 m/s. Gases (ethylene, hydrogen) required for polymerization and 1-hexene, a comonomer, were constantly and continuously introduced, and individual flow rates were adjusted according to target products. Concentrations of all gases and comonomer 1-hexene were confirmed by on-line gas chromatograph. The supported catalyst was introduced into the isobutane slurry, the reactor pressure was maintained at about 40 bar, and the polymerization temperature was carried out at about 85 ^° C.

first precursor second precursor catalyst
precursor
mole ratio* ethylene
(C2, kg/h) i-butane
(i-C4, kg/h) 1-Hexene
(C6, % by weight) _H2
(ppm)** C6/C2*** Example 1 synthesis example
One synthesis example
3 2:1 25.2 28 15 34 0.3 Example 2 synthesis example
One synthesis example
3 4:1 25.1 32 15 34 0.28 Example 3 synthesis example
2 synthesis example
4 1:1 25 32 15 33 0.31 Example 4 synthesis example
One synthesis example
5 2:1 25 32 15 33 0.31 Comparative Example 1 comparison
synthesis example
One synthesis example
3 2:1 25.1 30 12 27 0.51 Comparative Example 2 comparison
synthesis example
2 synthesis example
3 2:1 25 30 12 33 0.35 Comparative Example 3 comparison
synthesis example
3 synthesis example
3 2:1 25 30 15 34 0.4 Comparative Example 4 synthesis example
2 comparison
synthesis example
4 2:1 25 30 15 30 0.35 Comparative Example 5 synthesis example
One comparison
synthesis example
5 2:1 25 30 15 30 0.4 * Catalyst precursor molar ratio is represented by the molar ratio of the first metallocene compound: the second metallocene compound
**Hydrogen input is in ppm based on ethylene content
*** C6/C2: Molar ratio of 1-hexene to ethylene in the slurry reactor

Test Example 2: Evaluation of activity, process stability and physical properties of polyethylene supported hybrid catalysts

Catalytic activity, process stability and physical properties of the polyethylene copolymer pins of the Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below.

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

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

(2) melt index (MI)

The melt index (MI _2.16 ) was measured under a load of 2.16 kg under 190 ^° C according to ASTM D 1238 of the American Society for Testing and Materials, and was expressed as the weight (g) of the polymer melted for 10 minutes.

(3) Density

Density (g/cm ³ ) was measured according to ASTM D 792 of the American Society for Testing and Materials.

(4) Bulk Density (BD)

Bulk Density was measured according to ASTM D 1895, American Society for Testing and Materials.

(5) Process stability according to fouling

In the polyethylene copolymer manufacturing process, it is checked whether a fouling phenomenon in which the solid product etc. sticks to the device inside the reactor and the wall surface occurs, and if no fouling occurs, the process stability is marked as 'good', and the fouling occurs. The case was marked as 'poor' for process stability, and the results are shown in Table 2 below.

(6) Drop impact strength

After preparing a film (BUR 2.3, film thickness 50 μm) using a film forming machine with the polyethylene copolymer prepared using the catalysts of the above Examples and Comparative Examples, according to ASTM D 1709 [Method A] of the American Society for Testing and Materials Measurements were made 20 or more times per film sample according to the method, and the drop impact strength was obtained as an average value.

activation
(kg PE/g·cat·hr) MI _2.16 (g/10min) Density (g/cm ³ ) BD (g/mL) process
stability Drop impact strength (g) Example 1 5.8 1.06 0.9159 0.42 good 1820 Example 2 5.1 1.10 0.9168 0.44 good 1700 Example 3 5.2 1.01 0.9164 0.41 good 1780 Example 4 5.6 0.98 0.9161 0.42 good 1750 Comparative Example 1 4.5 0.98 0.9169 0.37 good 900 Comparative Example 2 4.5 1.0 0.9170 0.38 good 700 Comparative Example 3 5.5 1.0 0.9170 0.40 bad 850 Comparative Example 4 4.0 0.95 0.9168 0.38 good 1100 Comparative Example 5 3.5 1.05 0.9165 0.37 bad 800

As shown in Table 2, the present invention shows excellent process stability and high polymerization activity in the ethylene polymerization reaction compared to the hybrid supported catalysts of Comparative Examples 1 to 5 by using the specific hybrid supported catalysts of Examples 1 to 4. , it can be seen that fouling does not occur in the manufacturing process due to high comonomer incorporation characteristics and process stability is excellent. In addition, according to the present invention, it was confirmed that a low-density polyethylene copolymer having high drop impact strength during film formation can be prepared.

Claims (18)

At least one first metallocene compound selected from compounds represented by Formula 1 below;
at least one second metallocene compound selected from compounds represented by Formula 2 below; and
a carrier supporting the first and second metallocene compounds;
A hybrid supported metallocene catalyst comprising:
[Formula 1]
(Cp ¹ R ^a ) _n (Cp ² R ^b )M ¹ Q ¹ _3-n
In Formula 1,
M ¹ is a Group 4 transition metal;
Cp ¹ and Cp ² are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. one, which is unsubstituted or substituted with a C _1-20 hydrocarbon;
R ^a and R ^b are the same as or different from each other, and are each independently hydrogen, C _1-20 alkyl, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-20 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl, provided that R at least one of ^a and R ^b is not hydrogen;
Q ¹ is halogen, C _1-20 alkyl, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkylene, substituted or unsubstituted amino group, C _2-20 alkoxyalkyl, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;
n is 1 or 0;
[Formula 2]

In Formula 2,
M ² is a Group 4 transition metal;
A is carbon, silicon, or germanium;
X ¹ and X ² are the same as or different from each other, and each independently represents halogen or C _1-20 alkyl;
L ¹ and L ² are the same as or different from each other, and each independently represents C _1-20 alkylene;
D ¹ and D ² are oxygen;
R ¹ and R ² are the same as or different from each other, and are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 is an arylalkyl of;
R ³ and R ⁴ are the same as or different from each other, and each independently represent C _1-20 alkyl.
According to claim 1,
M ¹ is zirconium or hafnium;
Cp ¹ and Cp ² are each cyclopentadienyl, indenyl, or fluorenyl;
R ^a and R ^b are each hydrogen, C _1-6 straight chain or branched alkyl, C _2-6 alkynyl, C _1-6 alkoxy-substituted C _1-6 alkyl, C _6-12 aryl-substituted C _1-6 alkyl or C _6-12 aryl, provided that at least one of R ^a and R ^b is not hydrogen;
Q ¹ is each halogen;
A hybrid supported metallocene catalyst.
According to claim 1,
The first metallocene compound is represented by any one of the following structural formulas,
Hybrid Supported Metallocene Catalysts:

.
According to claim 1,
M ² is zirconium or hafnium;
A is silicon;
X ¹ and X ² are each halogen,
A hybrid supported metallocene catalyst.
According to claim 1,
L ¹ and L ² are each C _1-3 alkylene;
R ¹ and R ² are each C _1-6 straight-chain or branched alkyl, or C _6-12 aryl;
A hybrid supported metallocene catalyst.
According to claim 1,
R ³ and R ⁴ are each C _1-6 alkyl;
A hybrid supported metallocene catalyst.
According to claim 1,
The second metallocene compound is represented by any one of the following structural formulas,
Hybrid Supported Metallocene Catalysts:

.
According to claim 1,
The first metallocene compound and the second metallocene compound are supported in a molar ratio of 0.3: 1 to 4: 1,
A hybrid supported metallocene catalyst.
According to claim 1,
The carrier contains a hydroxyl group and a siloxane group on the surface,
A hybrid supported metallocene catalyst.
According to claim 9,
The carrier is at least one selected from the group consisting of silica, silica-alumina and silica-magnesia,
A hybrid supported metallocene catalyst.
In the presence of the mixed supported metallocene catalyst of claim 1, comprising the step of copolymerizing ethylene and an alpha-olefin,
A method for preparing a polyethylene copolymer.
According to claim 11,
The copolymerization step consists of reacting an alpha-olefin in an amount of 0.45 mole or less based on 1 mole of ethylene.
A method for preparing a polyethylene copolymer.
According to claim 11,
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 and 1-eicosene,
A method for producing a polyethylene copolymer.
A polyethylene copolymer obtained by the production method of claim 11.
According to claim 14,
Ethylene 1-hexene copolymer,
polyethylene copolymer.
According to claim 14,
The melt index (MI _2.16 , 190 ^o C, measured under a load of 2.16 kg) measured according to ASTM D 1238 of the American Society for Testing and Materials is 0.5 g / 10 min to 2.0 g / 10 min,
polyethylene copolymer.
According to claim 14,
The apparent density measured according to the American Society for Testing and Materials standard ASTM D 1895 is 0.2 g / mL or more,
polyethylene copolymer.
According to claim 14,
After manufacturing a polyethylene copolymer film (BUR 2.3, film thickness of 48 μm to 52 μm) using a film forming machine, the drop impact strength measured according to the ASTM D 1709 standard of the American Society for Testing and Materials is 1200 g or more,
polyethylene copolymer.