KR20220043692A - Supported metallocene catalyst and preparing mehtod a polyolefin using the same - Google Patents

Abstract

The present invention relates to a supported metallocene catalyst and a preparation method of a polyolefin using the same, and more specifically, to a supported metallocene catalyst which can prepare a polyolefin that exhibits excellent slip properties even when a slip agent is not added or a small amount of the slip agent is added and a preparation method of a polyolefin using the same.

Description

Supported metallocene catalyst and method for producing polyolefin using the same

The present invention relates to a supported metallocene catalyst and a method for preparing polyolefin using the same. More specifically, it relates to a supported metallocene catalyst capable of producing a polyolefin exhibiting excellent slip properties even when a slip agent is not added or a small amount is added, and a polyolefin production method using the same.

Transition metal-based olefin polymerization catalysts applied in commercial processes can be classified into Ziegler-Natta catalysts, chromium catalysts and metallocene catalysts. The Ziegler-Natta catalyst is a multisite catalyst, and there is a limit to securing desired physical properties because the composition distribution of the comonomer is not uniform. A metallocene catalyst is a single site catalyst, and a polyolefin with a narrow molecular weight distribution and a uniform comonomer composition distribution is obtained. There are characteristics that can change the back. As such, the metallocene catalyst is easier to control the molecular weight distribution of polyolefin compared to the existing Ziegler-Natta catalyst and can control the comonomer distribution of the polyolefin, so it is advantageous for simultaneously improving the mechanical properties and processability of the polyolefin. However, polyolefins prepared using a metallocene catalyst have a problem in that processability is poor due to a narrow molecular weight distribution.

On the other hand, in the case of a polyolefin resin used as a food container, such as a bottle cap, excellent processability, mechanical properties, and environmental stress cracking resistance are required. Accordingly, there is a continuous demand for a technology for producing polyolefins usable as food containers such as bottle caps by precisely controlling molecular weight, molecular weight distribution, and comonomer distribution.

In addition, when manufacturing a bottle cap using high-density polyethylene, it is important that an application torque when the cap is fastened and an opening torque when the cap is opened are maintained in an appropriate range. If the torque is too low, the bottle cap may loosen during transportation or storage of the final product. Conversely, if the torque is too high, there may be a problem that the bottle cap does not move and does not open even if the consumer applies force to rotate the bottle cap to use the final product.

A physical property of polyethylene related to the torque of the bottle cap is a slip property. In order to provide an appropriate slip property, a slip agent is generally added during extrusion of polyethylene or molding of a bottle cap. However, if a slip agent is added after polyethylene is manufactured, the slip agent is added over a certain amount, which may cause problems such as cost increase, odor, etc. There is a problem that the slip agent may leak into the beverage. Therefore, there is a need for a technology capable of realizing appropriate slip characteristics and torque even if a slip agent is not used or a small amount is used.

An object of the present invention is to provide a supported metallocene catalyst capable of producing a polyolefin exhibiting excellent slip properties even when a slip agent is not added or a small amount is added, and a method for producing a polyolefin using the same.

According to an embodiment of the present invention, a metallocene compound; cocatalyst compounds; and a supported metallocene catalyst in which a slip agent is supported on a carrier.

In addition, the present invention provides a method for producing a polyolefin by polymerizing an olefin-based monomer in the presence of the supported metallocene catalyst.

The supported metallocene catalyst according to the present invention can produce polyolefins exhibiting excellent slip properties even when a slip agent is not added or only a small amount is added. Accordingly, it can be usefully applied to the production of polyolefins used for the manufacture of beverage containers or bottle caps requiring these properties.

In the present invention, terms such as first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.

In addition, the terminology used herein is used only to describe exemplary embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as "comprise", "comprising" or "have" are intended to designate the existence of an embodied feature, number, step, element, or a combination thereof, but one or more other features or It should be understood that the existence or addition of numbers, steps, elements, or combinations thereof, is not precluded in advance.

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

Hereinafter, the present invention will be described in more detail.

According to one embodiment of the invention, a metallocene compound; cocatalyst compounds; and a supported metallocene catalyst in which a slip agent is supported on a carrier.

When manufacturing a bottle cap using high-density polyethylene, it is important that an application torque when the cap is fastened and an opening torque when the cap is opened are maintained in an appropriate range. If the torque is too low, the bottle cap may loosen during transportation or storage of the final product. Conversely, if the torque is too high, there may be a problem that the bottle cap does not move and does not open even if the consumer applies force to the bottle cap to use the final product.

The physical property of polyethylene related to the torque of the bottle cap is the slip property. In order to provide an appropriate slip property, in general, when the polyethylene is extruded or the bottle cap is molded, about 1000 to 2000 ppm of a slip agent is added compared to polyethylene. When a slip agent is added after polyethylene is manufactured, the slip agent is added over a certain amount, which may cause problems such as cost increase, odor, etc. I have a problem with spills into drinks. Therefore, there is a need for a technology capable of realizing appropriate slip characteristics and torque even if a slip agent is not used or a small amount is used.

The present invention is to solve the above problems, and according to one embodiment of the present invention, instead of injecting a slip agent during extrusion of polyethylene or molding a bottle cap, a metallocene compound, a promoter compound, etc., a slip agent A polyolefin is prepared using a supported metallocene catalyst prepared by supporting it together on a carrier. Injection-molded products manufactured using the polyolefin prepared in this way have excellent slip properties and excellent slip properties even when only a very small amount of 5% or less, 2% or less, or 1% or less is used compared to the conventional slip agent usage. It was completed based on the fact that it can represent an appropriate torque.

Manufactured due to the effect of dispersing the slip agent at a micro level during polymerization of olefinic monomers by supporting the slip agent on a supported metallocene catalyst instead of mixing it in the extrusion of polyethylene or the molding step of the bottle cap as in the prior art. The polyolefin will have improved slip properties. Therefore, when a molded article such as a bottle cap is manufactured using the polymerized polyolefin, a molded article exhibiting excellent slip characteristics and appropriate torque can be manufactured without inhibiting other mechanical properties.

According to one embodiment of the invention, the slip agent is cis-13-docosenamide (cis-13-Docosenamide), stearamide (stearamide) and oleamide (oleamide) It may include one or more selected from the group consisting of. Preferably, cis-13-docosenamide may be used as a slip agent.

According to one embodiment of the present invention, 1 to 15 parts by weight of the slip agent may be included based on 100 parts by weight of the carrier.

More specifically, the slip agent may be 1 part by weight or more, or 5 parts by weight or more, and 15 parts by weight or less, or 12 parts by weight or less, or 10 parts by weight or less based on 100 parts by weight of the carrier. If the content of the slip agent is too low, the effect of improving the slip properties is insignificant, and if it is too high, the activity of the supported metallocene catalyst may be reduced.

According to one embodiment of the present invention, the type of the metallocene compound supported on the supported metallocene catalyst is not particularly limited, and any metallocene compound known to be usable in polymerization of polyolefin, particularly high-density polyethylene, may be used without limitation. can

In addition, the supported metallocene catalyst of the present invention may be a single supported metallocene catalyst on which one type of metallocene compound is supported, or a hybrid supported metallocene catalyst on which two or more different metallocene compounds are supported. there is.

In addition, according to one embodiment of the present invention, the order in which the slip agent is supported is not particularly limited, and may be appropriately supported before or after each of the metallocene compound and the cocatalyst compound. Preferably, the slip agent may be supported in the last step after the metallocene compound and the promoter compound are supported on the carrier.

According to one embodiment of the present invention, the supported metallocene catalyst may be a hybrid supported metallocene catalyst in which different first metallocene compounds and second metallocene compounds are supported.

According to one embodiment of the present invention, the first metallocene compound may be represented by Formula 1 below, and the second metallocene compound may be represented by Formula 2 below:

[Formula 1]

[Formula 2]

[Cp ₁ (R ₁₁ ) _u ][Cp ₂ (R ₁₂ ) _v ]M ₂ X ₃ X ₄

In Formulas 1 and 2,

C ₁ is any one of the ligands represented by the following formulas 3 to 6,

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

R ₁ to R ₆ are the same as or different from each other, and each independently represent any one of hydrogen, a C 1 to C 30 hydrocarbyl group, and a C 1 to C 30 hydrocarbyloxy group;

Z is -O-, -S-, -NR ₇ - or -PR ₇ -;

R ₇ is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, and a silylhydrocarbyl group having 1 to 20 carbon atoms,

M ₁ and M ₂ are the same as or different from each other, and are each independently Ti, Zr or Hf,

X ₁ to X ₄ are the same as or different from each other, and each independently a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms,

또는

이며, T is an alkylene group having 1 to 5 carbon atoms,

or

is,

T ₁ is C, Si, Ge, Sn or Pb,

Y ₁ and Y ₂ are the same as or different from each other, and are each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a hydrocarbyl group having 1 to 30 carbon atoms substituted with a halogen, and -NR ₉ R ₁₀ any one of,

R ₉ and R ₁₀ are each independently any one of hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms, or are connected to each other to form an aliphatic or aromatic ring,

Cp ₁ and Cp ₂ are the same as or different from each other, and each independently represents any one of a cyclopentadienyl group, an indenyl group, 4,5,6,7-tetrahydro-1-indenyl and a fluorenyl group,

R ₁₁ and R ₁₂ are the same as or different from each other, and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms and a hydrocarbyl group having 1 to 30 carbon atoms substituted with halogen,

u and v are each independently an integer between 0 and 5;

Specifically, in the hybrid supported metallocene catalyst, R ₁ to R ₄ of Formulas 3 to 6 are the same or different from each other and each independently represent any one of hydrogen and a hydrocarbyl group having 1 to 10 carbon atoms, R ₅ and R ₆ The first metallocene compound may be the same or different from each other and each independently include any one of a C 1 to C 10 hydrocarbyl group.

The hybrid supported metallocene catalyst may include a first metallocene compound in which Z is -NR ₇ - and R ₇ is any one of a C 1 to C 10 hydrocarbyl group.

이고, 상기 T₁이 C 또는 Si이며, Y₁ 및 Y₂가 서로 동일하거나 상이하고 각각 독립적으로 탄소수 1 내지 30의 하이드로카빌기, 탄소수 1 내지 30의 하이드로카빌옥시기 및 탄소수 2 내지 30의 하이드로카빌옥시하이드로카빌기 중 어느 하나인 제 1 메탈로센 화합물을 포함할 수 있다. The hybrid supported metallocene catalyst is T

, wherein T ₁ is C or Si, and Y ₁ and Y ₂ are the same as or different from each other and each independently a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, and a hydrocarbyl group having 2 to 30 carbon atoms. The first metallocene compound which is any one of carbyloxyhydrocarbyl groups may be included.

The hybrid supported metallocene catalyst may include a first metallocene compound in which X ₁ and X ₂ are the same as or different from each other and each independently any one of halogen.

Unless otherwise limited herein, the following terms may be defined as follows.

The hydrocarbyl group is a monovalent functional group in which a hydrogen atom is removed from hydrocarbon, and is 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 alkyl group. It may include a nylaryl group and the like. The hydrocarbyl group having 1 to 30 carbon atoms may be a hydrocarbyl group having 1 to 20 carbon atoms or 1 to 10 carbon atoms. Specifically, the hydrocarbyl group having 1 to 30 carbon atoms is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, and a n-hexyl group. , a straight-chain, branched-chain or cyclic alkyl group such as n-heptyl group and cyclohexyl group; Or it may be an aryl group such as a phenyl group, a naphthyl group, or an anthracenyl group.

The hydrocarbyloxy group is a functional group in which a hydrocarbyl group is bonded to oxygen. Specifically, the hydrocarbyloxy group having 1 to 30 carbon atoms may be a hydrocarbyloxy group having 1 to 20 carbon atoms or 1 to 10 carbon atoms. More specifically, the hydrocarbyloxy group having 1 to 30 carbon atoms is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentoxy group , a straight-chain, branched-chain or cyclic alkoxy group such as n-hexoxy group, n-heptoxy group, cyclohexoxy group; Alternatively, it may be 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 a hydrocarbyl group are substituted with one or more hydrocarbyloxy groups. Specifically, the hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms may be a hydrocarbyloxyhydrocarbyl group having 2 to 20 carbon atoms or 2 to 15 carbon atoms. More specifically, the hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms 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 It may be a oxymethyl group, a tert-butoxyethyl group, a tert-butoxyhexyl group, or a phenoxyhexyl group.

The 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 hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms may be a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms. More specifically, the hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms is an alkyl group such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group, and a dimethylpropylsilyl group. silyl group; alkoxysilyl groups such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group and a dimethoxyethoxysilyl group; It may be an alkoxyalkylsilyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, and a dimethoxypropylsilyl group.

The silylhydrocarbyl group having 1 to 20 carbon atoms is a functional group in which at least one hydrogen of the hydrocarbyl group is substituted with a silyl group. The silyl group may be -SiH ₃ or a hydrocarbyl (oxy)silyl group. Specifically, the silylhydrocarbyl group having 1 to 20 carbon atoms may be a silylhydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. More specifically, the silylhydrocarbyl group having 1 to 20 carbon atoms may be -CH ₂ -SiH ₃ , a methylsilylmethyl group, or a dimethylethoxysilylpropyl group.

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

The sulfonate group has a structure of -O-SO ₂ -R ^a , and R ^a may be a hydrocarbyl group having 1 to 30 carbon atoms. Specifically, the sulfonate group having 1 to 30 carbon atoms may be a methanesulfonate group or a phenylsulfonate group.

A sulfone group having 1 to 30 carbon atoms has a structure of -R ^b' -SO ₂ -R ^b" , wherein R ^b' and R ^b" are the same as or different from each other and each independently any one of a C 1 to C 30 hydrocarbyl group can Specifically, the sulfone group having 1 to 30 carbon atoms may be a methylsulfonylmethyl group, a methylsulfonylpropyl group, a methylsulfonylbutyl group, or a phenylsulfonylpropyl group.

The alkylene group is a divalent functional group in which two hydrogen atoms are removed from an alkane. Specifically, the alkylene group having 1 to 5 carbon atoms may be a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group.

In the present specification, that two substituents adjacent to each other are connected to each other to form an aliphatic or aromatic ring means that the atom(s) of the two substituents and the valence (atoms) to which the two substituents are bonded are connected to each other to form a ring do. Specifically, examples in which R ₉ and R ₁₀ of -NR ₉ R ₁₀ are connected to each other to form an aliphatic ring include a piperidinyl group, and R ₉ and R ₁₀ of -NR ₉ R ₁₀ are Examples of the aromatic ring connected to each other may be exemplified by a pyrrolyl group.

The above-mentioned substituents are optionally a hydroxyl group within the range of exhibiting the same or similar effect as the desired effect; halogen; hydrocarbyl group; hydrocarbyloxy group; a hydrocarbyl group or a hydrocarbyloxy group containing at least one hetero atom among the heteroatoms of Groups 14 to 16; -SiH ₃ ; hydrocarbyl (oxy) silyl group; phosphine group; phosphide group; sulfonate group; And it may be substituted with one or more substituents selected from the group consisting of a sulfone group.

The first metallocene compound represented by Formula 1 includes an aromatic ring compound including thiophene as different ligands and a base compound including Group 14 or 15 atoms, and the different ligands are -T It is crosslinked by - and has a structure in which M ₁ (X ₁ )(X ₂ ) exists between different ligands. The first metallocene compound having such a specific structure has excellent loading stability, exhibits high activity during olefin polymerization, and can provide a high molecular weight polyolefin.

Specifically, the ligand of C ₁ in the structure of the first metallocene compound represented by Chemical Formula 1 may affect, for example, olefin polymerization activity and olefin copolymerization properties.

In particular, as a C ₁ ligand, in Formulas 3 to 6, R ₁ to R ₄ is any one of hydrogen and a C 1 to C 10 hydrocarbyl group, and R ₅ and R ₆ are any of a C 1 to C 10 hydrocarbyl group The first metallocene compound of Formula 1 including one ligand may provide a catalyst exhibiting very high activity and high comonomer conversion in an olefin polymerization process.

In addition, the Z ligand in the structure of the first metallocene compound represented by Formula 1 may affect, for example, olefin polymerization activity.

In particular, when Z in Formula 1 is -NR ₇ - and R ₇ is any one of a C 1 to C 10 hydrocarbyl group, a catalyst exhibiting very high activity in olefin polymerization can be provided.

의 구조를 가질 수 있으며, 여기서 T₁은 C 또는 Si이고, Y₁ 및 Y₂는 서로 동일하거나 상이하며 각각 독립적으로 탄소수 1 내지 30의 하이드로카빌기, 탄소수 1 내지 30의 하이드로카빌옥시기 및 탄소수 2 내지 30의 하이드로카빌옥시하이드로카빌기 중 어느 하나일 수 있다. The C ₁ ligand and the Z ligand may be cross-linked by -T- to exhibit excellent loading stability. For this effect, the -T- is

where T ₁ is C or Si, Y ₁ and Y ₂ are the same as or different from each other and each independently a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, and a carbon number It may be any one of 2 to 30 hydrocarbyloxyhydrocarbyl groups.

On the other hand, M ₁ (X ₁ )(X ₂ ) exists between the cross-linked cyclopentadienyl ligand and the tetrahydroindenyl ligand, and M ₁ (X ₁ )(X ₂ ) affects the storage stability of the metal complex. can affect

In order to ensure this effect more effectively, a metallocene compound in which X ₁ and X ₂ are each independently any one of halogen may be used.

As an example, as the first metallocene compound for providing a polyolefin having a higher molecular weight and exhibiting superior activity during olefin polymerization, compounds represented by the following Chemical Formulas 7 to 10 may be exemplified.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 7 to 10, R ₁ To R ₄ Are the same as or different from each other, and each independently represent any one of hydrogen and a C 1 to C 10 hydrocarbyl group,

R ₅ To R ₇ Are the same as or different from each other, and each independently represent any one of a C 1 to C 10 hydrocarbyl group,

M ₁ is Ti, Zr or Hf,

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

T ₁ is C or Si,

Y ₁ and Y ₂ are the same as or different from each other and each independently any one of a C 1 to C 30 hydrocarbyl group, a C 1 to C 30 hydrocarbyloxy group, and a C 2 to C 30 hydrocarbyloxy hydrocarbyl group.

The first metallocene compound represented by Formula 1 may be synthesized by applying known reactions, and more detailed synthesis methods may refer to Examples.

Unlike the first metallocene compound, when the second metallocene compound represented by Chemical Formula 2 is activated by an appropriate method and used as a catalyst for olefin polymerization, a low molecular weight polyolefin can be provided. Accordingly, the hybrid supported metallocene catalyst including the first and second metallocene compounds may provide a polyolefin having a broad molecular weight distribution.

Specifically, Cp ₁ and Cp ₂ of Formula 2 may be a cyclopentadienyl group. Cp ₁ and Cp ₂ are cyclopentadienyl groups, and the second metallocene compound in which the cyclopentadiethyl group is not bridged shows low copolymerizability with respect to alpha-olefin during olefin polymerization, and has a low molecular weight. It produces predominantly polyolefins. Therefore, when this second metallocene compound is mixed and supported on the same carrier as the first metallocene compound of Formula 1, the molecular weight distribution of the polyolefin, the distribution of the copolymerized monomer in the polyolefin chain, and the copolymerization characteristics of the olefin are easily improved. By adjusting the desired physical properties of the polyolefin can be more easily realized.

The Cp ₁ may be substituted with 1 to 5 R ₁₁ , and Cp ₂ may be substituted with 1 to 5 R ₁₂ . When u is an integer of 2 or more in Formula 2, a plurality of R ₁₁ may be the same as or different from each other. In addition, when v in Formula 2 is an integer of 2 or more, a plurality of R ₁₂ may also be the same as or different from each other.

R ₁₁ and R ₁₂ may each independently be any one of hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, a hydrocarbyloxy group having 1 to 10 carbon atoms, and a hydrocarbyloxyhydrocarbyl group having 2 to 20 carbon atoms. The second metallocene compound in which R ₁₁ and R ₁₂ has the substituents as described above may have excellent loading stability.

In addition, X ₃ and X ₄ of Formula 2 may be the same as or different from each other and may each independently be any one of halogen. In the second metallocene compound in which X ₃ and X ₄ have the above substituents, a halogen group may be easily substituted with an alkyl group by reaction with an alkyl metal or methylaluminoxane as a promoter. In addition, the second metallocene compound forms an ionic intermediate with the cocatalyst by subsequent alkyl abstraction to more easily provide a cationic form, which is an active species of an olefin polymerization reaction. can

As an example, as a second metallocene compound for providing a polyolefin having a broad molecular weight distribution by combining with the first metallocene compound, the following compounds may be exemplified.

The first and second metallocene compounds may be combined in an appropriate amount according to the physical properties of the polyolefin to be prepared. For example, in order to provide a polyolefin having a broad molecular weight distribution and a high molecular weight, the first and second metallocene compounds may be used in a molar ratio of 1:0.5 to 1:5. Accordingly, desired physical properties can be more easily realized by easily controlling the molecular weight distribution of the polyolefin, the distribution of the copolymerized monomer in the polymer chain, and the copolymerization characteristics of the olefin.

The hybrid supported metallocene catalyst may include a second metallocene compound in which Cp ₁ and Cp ₂ are cyclopentadienyl groups.

In the hybrid supported metallocene catalyst, R ₁₁ and R ₁₂ are the same as or different from each other, and each independently hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, a hydrocarbyloxy group having 1 to 10 carbon atoms, and a hydrocarbyl group having 2 to 20 carbon atoms. It may include a second metallocene compound that is any one of the carbyloxyhydrocarbyl groups.

The hybrid supported metallocene catalyst may include a second metallocene compound in which X ₃ and X ₄ are the same as or different from each other and each independently any one of halogen.

The hybrid supported metallocene catalyst may further include a co-catalyst compound to activate the metallocene compounds serving as catalyst precursors. As the co-catalyst compound, those commonly used in the art to which the present invention pertains may be applied without particular limitation. As a non-limiting example, the promoter compound may be at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 11 to 13.

[Formula 11]

R ₂₀ -[Al(R ₁₉ )-O] _n -R ₂₁

In the above formula (11),

R ₁₉ , R ₂₀ and R ₂₁ are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen;

n is an integer greater than or equal to 2,

[Formula 12]

D(R ₂₂ ) ₃

In the above formula (12),

D is aluminum or boron,

R ₂₂ is each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen;

[Formula 13]

[LH] ⁺ [W(A) ₄ ] ^- or [L] ⁺ [W(A) ₄ ] ^-

In Formula 13,

L is a neutral or cationic Lewis base, H is a hydrogen atom,

W is a group 13 element, A is each independently a hydrocarbyl group having 1 to 20 carbon atoms; a hydrocarbyloxy group having 1 to 20 carbon atoms; and one or more of the substituents in which one or more hydrogen atoms of these substituents are substituted with one or more substituents among halogen, a C1-20 hydrocarbyloxy group, and a C1-C20 hydrocarbyl(oxy)silyl group.

Non-limiting examples of the compound represented by Formula 11 include methylaluminoxane, ethylaluminoxane, iso-butylaluminoxane, or tert-butylaluminoxane. And, non-limiting examples of the compound represented by Formula 12 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-sec-butylaluminum , tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaaluminum, dimethylaluminum methoxide or dimethylaluminum Ethoxide etc. are mentioned. Finally, non-limiting examples of the compound represented by Formula 13 include trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate, N,N-dimethylanyl Linium tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2, 3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)borate, N,N-dimethyl-2,4,6-trimethylanilinium Tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(2,3,4,6-tetra Fluorophenyl)borate, hexadecyldimethylammonium tetrakis(pentafluorophenyl)borate, N-methyl-N-dodecylanilinium tetrakis(pentafluorophenyl)borate or methyldi(dodecyl)ammonium tetrakis( pentafluorophenyl) borate and the like.

Such a supported metallocene catalyst may be prepared by, for example, supporting a promoter on a support, loading a metallocene compound, which is a catalyst precursor, on a support supported on a promoter, and loading a slip agent. .

The content of the carrier, the promoter, and the metallocene compound used to use the supported metallocene catalyst may be appropriately adjusted according to the desired physical properties or effects of the supported metallocene catalyst.

Specifically, in the step of supporting the cocatalyst on the carrier, the carrier and the cocatalyst dried at a high temperature are mixed and stirred at a temperature of about 20 to about 120° C. to prepare a support for the cocatalyst.

In addition, in the step of supporting the catalyst precursor on the promoter supported carrier, the metallocene compound is added to the promoter supported carrier and stirred at a temperature of about 20 to about 120° C. to prepare a supported metallocene catalyst.

If the catalyst precursor includes two different metallocene compounds, the first metallocene compound is added, stirred at a temperature of about 20 to about 120° C., and then the second metallocene compound is added. and stirring it again at a temperature of about 20 to about 120° C. to prepare a hybrid supported metallocene catalyst.

Next, the slip agent is supported on the support on which the promoter and the metallocene catalyst are supported. In this case, the slip agent may be supported in a solution state using a solvent such as toluene (toluene), and may be supported by stirring with the carrier at a temperature of about 40 to about 100 °C.

In preparing the supported metallocene catalyst, a hydrocarbon solvent such as pentane, hexane, or heptane, or an aromatic solvent such as benzene or toluene may be used as the reaction solvent.

For a specific method of preparing the supported metallocene catalyst, reference may be made to Examples to be described later. However, the preparation method of the supported metallocene catalyst is not limited to the content described herein, and the preparation method may additionally employ a step commonly employed in the technical field to which the present invention belongs, and the preparation method The step(s) of can be changed by the step(s) which are usually changeable.

According to one embodiment of the present invention, there may be provided a method for producing a polyolefin comprising polymerizing an olefin-based monomer in the presence of the supported metallocene catalyst.

As described above, when polyolefin obtained by polymerization of an olefin-based monomer in the presence of the supported metallocene catalyst is used, slip properties are excellent, and excellent slip properties are achieved even when no or little additional slip agent is added during injection molding. It is possible to manufacture a molded article that shows sex.

Examples of the olefinic monomer polymerizable with the supported metallocene catalyst include ethylene, alpha-olefin, and cyclic olefin, and a diene olefinic monomer or triene olefinic monomer having two or more double bonds can also be polymerized. Do. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode cene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc. are available, and two or more of these monomers may be mixed and copolymerized. When the polyolefin is a copolymer of ethylene and other comonomers, the comonomer is at least one comonomer selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. desirable.

For the polymerization reaction of the olefinic monomer, various polymerization processes known as polymerization of the olefinic monomer, such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process, or an emulsion polymerization process, may be employed.

Specifically, the polymerization reaction may be performed at a temperature of about 50 to about 110° C. or about 60 to about 100° C. and a pressure of about 1 to about 100 kgf/cm ² or about 1 to about 50 kgf/cm ² .

In addition, in the polymerization reaction, the supported metallocene catalyst may be used in a dissolved or diluted state in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like. In this case, by treating the solvent with a small amount of alkylaluminum or the like, a small amount of water or air that may adversely affect the catalyst may be removed in advance.

For a specific method of preparing the polyolefin, reference may be made to Examples to be described later. However, the production method of the polyolefin is not limited to the content described herein, and the production method may additionally employ a step commonly employed in the technical field to which the present invention belongs, and the step(s) of the production method ) can be changed by means of a usually changeable step(s).

By using the polyolefin prepared as described above, the present invention can manufacture a molded article according to various methods known to those skilled in the art, and in particular, it can be used in the manufacture of a bottle cap of a beverage container. The bottle cap can be molded by a molding method such as injection molding or continuous compression molding.

Hereinafter, the present invention will be described in detail through examples of the invention. However, these embodiments may be modified in various forms, and the scope of the invention should not be construed as being limited by the embodiments described below.

<Example>

Synthesis example of metallocene catalyst

Synthesis Example 1

(1) Preparation of Ligand A

1-benzothiophene 4.0 g (30 mmol) was dissolved in THF to prepare a 1-benzothiophene solution. Then, 14 mL (36 mmol, 2.5 M in hexane) of an n-BuLi solution and 1.3 g (15 mmol) of CuCN were added to the 1-benzothiophene solution.

Then, 3.6 g (30 mmol) of tigloyl chloride was slowly added to the solution at -80°C, and the resulting solution was stirred at room temperature for about 10 hours.

Thereafter, 10% HCl was poured into the solution to quench the reaction, and the organic layer was separated with dichloromethane to form a beige solid (2E)-1-(1-benzothien-2-yl)-2- Methyl-2-buten-1-one was obtained.

¹ H NMR (CDCl ₃ ): 7.85-7.82 (m, 2H), 7.75 (m, 1H), 7.44-7.34 (m, 2H), 6.68 (m, 1H), 1.99 (m, 3H), 1.92 (m , 3H)

A solution of 5.0 g (22 mmol) of (2E)-1-(1-benzothien-2-yl)-2-methyl-2-buten-1-one prepared above in 5 mL of chlorobenzene was stirred vigorously. 34 mL of sulfuric acid was slowly added to the solution. Then, the solution was stirred at room temperature for about 1 hour. Then, ice water was poured into the solution, the organic layer was separated with an ether solvent, and 1,2-dimethyl-1,2-dihydro-3H-benzo[b]cyclopenta[d]thiophen-3-one as a yellow solid 4.5 g (91% yield) was obtained.

¹ H NMR (CDCl ₃ ): 7.95-7.91 (m, 2H), 7.51-7.45 (m, 2H), 3.20 (m, 1H), 2.63 (m, 1H), 1.59 (d, 3H), 1.39 (d , 3H)

A solution of 2.0 g (9.2 mmol) of 1,2-dimethyl-1,2-dihydro-3H-benzo [b] cyclopenta [d] thiophen-3-one in a mixed solvent of 20 mL of THF and 10 mL of methanol 570 mg (15 mmol) of NaBH ₄ was added at 0°C. Then, the solution was stirred at room temperature for about 2 hours. Then, HCl was added to the solution to adjust the pH to 1, and the organic layer was separated with an ether solvent to obtain an alcohol intermediate.

A solution was prepared by dissolving the alcohol intermediate in toluene. Then, 190 mg (1.0 mmol) of p-toluenesulfonic acid was added to the solution, and the mixture was refluxed for about 10 minutes. The obtained reaction mixture was separated by column chromatography to give an orange-brown color, and 1.8 g (9.0 mmol, 98) of liquid 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (ligand A). % yield) was obtained.

¹ H NMR (CDCl ₃ ): 7.81 (d, 1H), 7.70 (d, 1H), 7.33 (t, 1H), 7.19 (t, 1H), 6.46 (s, 1H), 3.35 (q, 1H), 2.14 (s, 3H), 1.14 (d, 3H)

(2) Preparation of Ligand B

In a 250 mL schlenk flask, add 13 mL (120 mmol) of t-butylamine and 20 mL of an ether solvent, and in another 250 mL schlenk flask from the flask, 16 g (60 mmol) of (6-tert-butoxyhexyl) dichloro (methyl) silane and 40 mL of an ether solvent was added to prepare a t-butylamine solution and a (6-tert-butoxyhexyl)dichloro(methyl)silane solution, respectively. Then, the t-butylamine solution was cooled to -78°C, and a (6-tert-butoxyhexyl)dichloro(methyl)silane solution was slowly injected into the cooled solution, and the solution was stirred at room temperature for about 2 hours. did The resulting white suspension was filtered to give an ivory color, and liquid 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-chloro-1-methylsilaneamine (ligand B) was obtained.

¹ H NMR (CDCl ₃ ): 3.29 (t, 2H), 1.52-1.29 (m, 10H), 1.20 (s, 9H), 1.16 (s, 9H), 0.40 (s, 3H)

(3) crosslinking of ligands A and B

1.7 g (8.6 mmol) of 1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene (ligand A) was added to a 250 mL schlenk flask, and 30 mL of THF was added to prepare a ligand A solution. After the ligand A solution was cooled to -78°C, 3.6 mL of n-BuLi solution (9.1 mmol, 2.5M in hexane) was added to the ligand A solution, and the solution was stirred at room temperature overnight to obtain a purple-brown solution. got it Solution A was prepared by replacing the solvent of the purple-brown solution with toluene, and injecting a solution in which 39 mg (0.43 mmol) of CuCN was dispersed in 2 mL of THF.

On the other hand, solution B prepared by injecting 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-chloro-1-methylsilaneamine (ligand B) and toluene into a 250 mL schlenk flask was Cooled to -78°C. Solution A prepared above was slowly injected into the cooled solution B. And the mixture of solutions A and B was stirred at room temperature overnight. Then, by filtration and removing the resulting solid, 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(1,2-dimethyl) brown color and viscous liquid 4.2 g (>99% yield) of -3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1-methylsilaneamine (cross-linked product of ligands A and B) was obtained.

After lithiation of the cross-linked product at room temperature to confirm the structure of the cross-linked product of ligands A and B, H-NMR spectra were obtained using a sample dissolved in a small amount of pyridine-D5 and CDCl ₃ .

¹ H NMR (pyridine-D5 and CDCl ₃ ): 7.81 (d, 1H), 7.67 (d, 1H), 7.82-7.08 (m, 2H), 3.59 (t, 2H), 3.15 (s, 6H), 2.23 -1.73 (m, 10H), 2.15 (s, 9H), 1.91 (s, 9H), 1.68 (s, 3H)

(4) Preparation of transition metal compounds

1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene- in a 250mL schlenk flask 4.2 g (8.6 mmol) of 3-yl)-1-methylsilaneamine (crosslinked product of ligands A and B) was added, and 14 mL of toluene and 1.7 mL of n-hexane were added to the flask to dissolve the cross-linked product. After the solution was cooled to -78°C, 7.3 mL of an n-BuLi solution (18 mmol, 2.5M in hexane) was injected into the cooled solution. Then, the solution was stirred at room temperature for about 12 hours. Then, 5.3 mL (38 mmol) of trimethylamine was added to the solution, and the solution was stirred at about 40° C. for about 3 hours to prepare a solution C.

Meanwhile, 2.3 g (8.6 mmol) of TiCl ₄ (THF) ₂ and 10 mL of toluene were added to a 250 mL schlenk flask prepared separately to prepare a solution D in which TiCl ₄ (THF) ₂ was dispersed in toluene. Solution C prepared before solution D was slowly injected at -78°C, and the mixture of solutions C and D was stirred at room temperature for about 12 hours. Thereafter, the solution was depressurized to remove the solvent, and the resulting solute was dissolved in toluene. Then, the solid not dissolved in toluene was removed by filtration, and the solvent was removed from the filtered solution to obtain 4.2 g (83% yield) of a transition metal compound in the form of a brown solid.

¹ H NMR (CDCl ₃ ): 8.01 (d, 1H), 7.73 (d, 1H), 7.45-7.40 (m, 2H), 3.33 (t, 2H), 2.71 (s, 3H), 2.33 (d, 3H) ), 1.38 (s, 9H), 1.18 (s, 9H), 1.80-0.79 (m, 10H), 0.79 (d, 3H)

Synthesis Example 2

[tBu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ manufacture of

t-Butyl-O-(CH ₂ ) ₆ -Cl was prepared by the method presented in the literature (Tetrahedron Lett. 2951 (1988)) using 6-chlorohexanol, and NaCp was reacted with it t-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80° C. / 0.1 mmHg).

In addition, t-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78°C, n-butyllithium (n-BuLi) was slowly added thereto, and then heated to room temperature, followed by reaction for 8 hours. . The solution was again added to a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol)/THF (30 mL) at -78 ° C., and a lithium salt solution synthesized in advance was slowly added to the solution at room temperature. was further reacted for 6 hours.

All volatile substances were vacuum-dried, and a hexane solvent was added to the obtained oily liquid substance and filtered. After vacuum drying the filtered solution, hexane was added to induce a precipitate at low temperature (-20 °C). The obtained precipitate was filtered at low temperature to obtain a white solid [tBu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound (yield 92%).

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

¹³ C NMR (CDCl ₃ ): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

Preparation Example of Supported Metallocene Catalyst

Example 1

After adding 4.0 kg of toluene to the autoclave reactor and 1 kg of prepared silica, the reactor was stirred while raising the temperature of the reactor to 95°C. After the silica was sufficiently dispersed, 5.7 kg of a 10wt% methylaluminoxane (MAO)/toluene solution was added, and the mixture was stirred at 95° C. at 200 rpm for 16 hours. After the temperature was lowered to 40° C., the unreacted aluminum compound was removed by washing with a sufficient amount of toluene.

Thereafter, after raising the temperature of the reactor to 80° C., 70 g of the metallocene compound of Synthesis Example 1 was dissolved in 100 mL of toluene to make a solution, and then added to the reactor and stirred for 2 hours. Then, 35 g of the metallocene compound of Synthesis Example 2 was dissolved in 100 mL of toluene to make a solution, and then added to a reactor and stirred for 2 hours.

After dissolving 50 g of cis-13-docosenamide (cis-13-Docosenamide) in toluene, it was added to the reactor and stirred for 2 hours. Thereafter, the catalyst was cooled, the reactor temperature was lowered to room temperature, and the toluene layer was separated and removed, followed by replacement with hexane. After that, the catalyst was cooled, the hexane layer was separated and removed, and the remaining hexane was removed under reduced pressure to prepare a hybrid supported catalyst.

Example 2

After adding 4.0 kg of toluene to the autoclave reactor and 1 kg of prepared silica, the reactor was stirred while raising the temperature of the reactor to 95°C. After the silica was sufficiently dispersed, 5.7 kg of a 10wt% methylaluminoxane (MAO)/toluene solution was added, and the mixture was stirred at 95° C. at 200 rpm for 16 hours. After the temperature was lowered to 40° C., the unreacted aluminum compound was removed by washing with a sufficient amount of toluene.

Thereafter, after raising the temperature of the reactor to 80° C., 70 g of the metallocene compound of Synthesis Example 1 was dissolved in 100 mL of toluene to make a solution, and it was added to the reactor and stirred for 2 hours. Then, 35 g of the metallocene compound of Synthesis Example 2 was dissolved in 100 mL of toluene to make a solution, and then added to a reactor and stirred for 2 hours.

Thereafter, 100 g of cis-13-docosenamide was dissolved in toluene and then added to the reactor and stirred for 2 hours. Thereafter, the catalyst was cooled, the reactor temperature was lowered to room temperature, and the toluene layer was separated and removed, followed by replacement with hexane. After that, the catalyst was cooled, the hexane layer was separated and removed, and the remaining hexane was removed under reduced pressure to prepare a hybrid supported catalyst.

Comparative Example 1

After adding 4.0 kg of toluene to the autoclave reactor and 1 kg of prepared silica, the reactor was stirred while raising the temperature of the reactor to 95°C. After the silica was sufficiently dispersed, 5.7 kg of a 10wt% methylaluminoxane (MAO)/toluene solution was added, and the mixture was stirred at 95° C. at 200 rpm for 16 hours. After the temperature was lowered to 40° C., the unreacted aluminum compound was removed by washing with a sufficient amount of toluene.

Thereafter, after raising the temperature of the reactor to 80° C., 70 g of the metallocene compound of Synthesis Example 1 was dissolved in 100 mL of toluene to make a solution, and it was added to the reactor and stirred for 2 hours. Then, 35 g of the metallocene compound of Synthesis Example 2 was dissolved in 100 mL of toluene to make a solution, and then added to a reactor and stirred for 2 hours.

Thereafter, the catalyst was cooled, the reactor temperature was lowered to room temperature, and the toluene layer was separated and removed, followed by replacement with hexane. After that, the catalyst was cooled, the hexane layer was separated and removed, and the remaining hexane was removed under reduced pressure to prepare a hybrid supported catalyst.

Comparative Example 2

After adding 4.0 kg of toluene to the autoclave reactor and 1 kg of prepared silica, the reactor was stirred while raising the temperature of the reactor to 95°C. After the silica was sufficiently dispersed, 5.7 kg of a 10wt% methylaluminoxane (MAO)/toluene solution was added, and the mixture was stirred at 95° C. at 200 rpm for 16 hours. After the temperature was lowered to 40° C., the unreacted aluminum compound was removed by washing with a sufficient amount of toluene. Thereafter, after raising the temperature of the reactor to 80° C., 70 g of the metallocene compound of Synthesis Example 1 was dissolved in 100 mL of toluene to make a solution, and it was added to the reactor and stirred for 2 hours. Then, 35 g of the metallocene compound of Synthesis Example 2 was dissolved in 100 mL of toluene to make a solution, and then added to a reactor and stirred for 2 hours.

After that, 50 g of Atmer 163 (Ciba Specialty Chemicals) was dissolved in toluroene and then put into a reactor and stirred for 2 hours. Thereafter, the catalyst was cooled, the reactor temperature was lowered to room temperature, and the toluene layer was separated and removed, followed by replacement with hexane. After that, the catalyst was cooled, the hexane layer was separated and removed, and the remaining hexane was removed under reduced pressure to prepare a hybrid supported catalyst.

Polymerization of Polyethylene and Injection Manufacturing Example

Example 3

Polymerization was performed using a 180 L CSTR slurry polymerization reactor filled with hexane. Polyolefin was polymerized by continuously injecting 20 atm of ethylene, hydrogen, and the supported catalyst slurry (5 wt% hexane slurry) prepared in Example 1 into the reactor. The catalyst was injected by controlling the pressure of the reactor to be maintained at 8 bar. The amount of hexane continuously input to the reactor was fixed at 30 kg/hr while maintaining the temperature of the reactor at 80°C, and the amount of ethylene gas was fixed at 10 kg/hr. The amount of hydrogen was adjusted so that MI _2.16 of the polyolefin powder was 1.8 g/10min, and the amount of 1-butene continuously input was adjusted so that the density was 0.951 g/cm ³ . After the obtained polyethylene was extruded into pellets using an extruder, a bottle cap (weight 2.4 g, inner diameter 28 mm) was manufactured by injection molding using Engel Victory 120 equipment.

Example 4

Polymerization was performed using a 180 L CSTR slurry polymerization reactor filled with hexane. Polyolefin was polymerized by continuously injecting 20 atm of ethylene, hydrogen, and the supported catalyst slurry (5 wt% hexane slurry) prepared in Example 1 into the reactor. The catalyst was injected by controlling the pressure of the reactor to be maintained at 8 bar. The amount of hexane continuously input to the reactor was fixed at 30 kg/hr while maintaining the temperature of the reactor at 80°C, and the amount of ethylene gas was fixed at 10 kg/hr. The amount of hydrogen was adjusted so that MI _2.16 of the polyolefin powder was 1.8 g/10min, and the amount of 1-butene continuously input was adjusted so that the density was 0.951 g/cm ³ . Compared to the obtained polyethylene, cis-13-docosenamide was added in the form of 500 ppm solid and mixed, and then extruded in the form of pellets using an extruder and injection molding method using Engel Victory 120 equipment. A bottle cap (weight 2.4 g, inner diameter 28 mm) was manufactured.

Example 5

Polymerization was performed using a 180 L CSTR slurry polymerization reactor filled with hexane. Polyolefin was polymerized by continuously injecting 20 atm of ethylene, hydrogen, and the supported catalyst slurry (5 wt% hexane slurry) prepared in Example 2 into the reactor. The catalyst was injected by controlling the pressure of the reactor to be maintained at 8 bar. The amount of hexane continuously input to the reactor was fixed at 30 kg/hr while maintaining the temperature of the reactor at 80°C, and the amount of ethylene gas was fixed at 10 kg/hr. The amount of hydrogen was adjusted so that MI _2.16 of the polyolefin powder was 1.8 g/10min, and the amount of 1-butene continuously input was adjusted so that the density was 0.951 g/cm ³ . After the obtained polyethylene was extruded into pellets using an extruder, a bottle cap (weight 2.4 g, inner diameter 28 mm) was manufactured by injection molding using Engel Victory 120 equipment.

Example 6

Polymerization was performed using a 180 L CSTR slurry polymerization reactor filled with hexane. Polyolefin was polymerized by continuously injecting 20 atm of ethylene, hydrogen, and the supported catalyst slurry (5 wt% hexane slurry) prepared in Example 2 into the reactor. The catalyst was injected by controlling the pressure of the reactor to be maintained at 8 bar. The amount of hexane continuously input to the reactor was fixed at 30 kg/hr while maintaining the temperature of the reactor at 80°C, and the amount of ethylene gas was fixed at 10 kg/hr. The amount of hydrogen was adjusted so that MI _2.16 of the polyolefin powder was 1.8 g/10min, and the amount of 1-butene continuously input was adjusted so that the density was 0.951 g/cm ³ . Compared to the obtained polyethylene, cis-13-docosenamide was added in 250ppm solid form and mixed, and then extruded in the form of pellets using an extruder and injection molding method using Engel Victory 120 equipment. A bottle cap (weight 2.4 g, inner diameter 28 mm) was manufactured.

Comparative Example 3

Polymerization was performed using a 180 L CSTR slurry polymerization reactor filled with hexane. Polyolefin was polymerized by continuously injecting 20 atm of ethylene, hydrogen, and the supported catalyst slurry (5 wt% hexane slurry) prepared in Comparative Example 1 into the reactor. The catalyst was injected by controlling the pressure of the reactor to be maintained at 8 bar. The amount of hexane continuously input to the reactor was fixed at 30 kg/hr while maintaining the temperature of the reactor at 80°C, and the amount of ethylene gas was fixed at 10 kg/hr. In this case, it was not possible to secure the target polyethylene due to a fouling phenomenon in which the pump amplifier deteriorated.

Comparative Example 4

Polymerization was performed using a 180 L CSTR slurry polymerization reactor filled with hexane. Polyolefin was polymerized by continuously injecting 20 atm of ethylene, hydrogen, and the supported catalyst slurry (5 wt% hexane slurry) prepared in Comparative Example 2 into the reactor. The catalyst was injected by controlling the pressure of the reactor to be maintained at 8 bar. The amount of hexane continuously input to the reactor was fixed at 30 kg/hr while maintaining the temperature of the reactor at 80°C, and the amount of ethylene gas was fixed at 10 kg/hr. The amount of hydrogen was adjusted so that MI _2.16 of the polyolefin powder was 1.8 g/10min, and the amount of 1-butene continuously input was adjusted so that the density was 0.951 g/cm ³ . After the obtained polyethylene was extruded into pellets using an extruder, a bottle cap (weight 2.4 g, inner diameter 28 mm) was manufactured by injection molding using Engel Victory 120 equipment.

Comparative Example 5

Polymerization was performed using a 180 L CSTR slurry polymerization reactor filled with hexane. Polyolefin was polymerized by continuously injecting 20 atm of ethylene, hydrogen, and the supported catalyst slurry (5 wt% hexane slurry) prepared in Comparative Example 2 into the reactor. The catalyst was injected by controlling the pressure of the reactor to be maintained at 8 bar. The amount of hexane continuously input to the reactor was fixed at 30 kg/hr while maintaining the temperature of the reactor at 80°C, and the amount of ethylene gas was fixed at 10 kg/hr. The amount of hydrogen was adjusted so that MI _2.16 of the polyolefin powder was 1.8 g/10min, and the amount of 1-butene continuously input was adjusted so that the density was 0.951 g/cm ³ . Compared to polyethylene, 1,000 ppm of cis-13-Docosenamide was added in a solid form and mixed, and then extruded in pellet form using an extruder, and injection molded bottle cap (weight) using Engel Victory 120 equipment. 2.4 g, inner diameter 28 mm) was prepared.

<Experimental example>

The physical properties of the polyethylene prepared in Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 1 below.

1) Catalyst activity (unit: kg/g): Catalyst activity was measured by the amount of polyethylene produced per hour (kg)/input catalyst amount (g).

2) Torque (unit: in.lbs): The opening torque was measured with a torque tester (device name: _STEINFURTH TMS 5010).

Example 3 Example 4 Example 5 Example 6 Comparative Example 3 Comparative Example 4 Comparative Example 5 supported metallocene catalyst Example 1 Example 1 Example 2 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 2 catalytic activity
(Unit: kg/g) 11 11 9 9 no driving 10 10 Slip agent included in catalyst* 1ppm 1ppm 3ppm 3ppm 0 0 0 Slip agent included in injection* 0 500ppm 0 250ppm 0 0 1000ppm talk
(Unit: in.lbs) 27 25 26 25 - 30 25

(* The slip agent included in the catalyst is derived from the slip agent supported on the supported catalyst, and was calculated as the content (ppm) relative to the weight of polyethylene, and the slip agent included during injection is a slip agent that is additionally added in the injection molding process, It was calculated as the content (ppm) by weight of polyethylene.)

Referring to Table 1, when a bottle cap was prepared with polyethylene prepared using a supported metallocene catalyst on which a slip agent was supported according to an embodiment of the present invention, the catalytic activity was maintained even though the slip agent was included in a very small amount compared to polyethylene. , an appropriate opening torque was maintained in a range similar to Comparative Example 5 in which 1,000 ppm was added during injection molding without supporting the slip agent on the supported catalyst.

However, in the case of polyethylene prepared using the supported metallocene catalyst of Comparative Example 1, a fouling phenomenon in which the pump ampere decreased during polymerization occurred, and thus the target polyethylene could not be obtained. In the case of Comparative Example 4 using a catalyst supporting Atmer 163, an antistatic agent, the catalyst activity was maintained, but the opening torque was too high because there was no effect of improving the slip characteristics.

Claims (7)

metallocene compounds;
cocatalyst compounds; and
A supported metallocene catalyst comprising a slip agent supported on a carrier.
The method of claim 1,
The slip agent comprises at least one selected from the group consisting of cis-13-docosenamide, stearamide and oleamide,
supported metallocene catalyst.
The method of claim 1,
The slip agent is included in an amount of 1 to 15 parts by weight based on 100 parts by weight of the carrier,
supported metallocene catalyst.
The method of claim 1,
The supported metallocene catalyst is a single supported metallocene catalyst on which one type of metallocene compound is supported, or a hybrid supported metallocene catalyst on which different first and second metallocene compounds are supported. sign,
supported metallocene catalyst.
5. The method of claim 4,
The supported metallocene catalyst is a hybrid supported metallocene catalyst on which a first metallocene compound represented by the following Chemical Formula 1 and a second metallocene compound represented by the following Chemical Formula 2 are supported,
Supported Metallocene Catalysts:
[Formula 1]

[Formula 2]
[Cp ₁ (R ₁₁ ) _u ][Cp ₂ (R ₁₂ ) _v ]M ₂ X ₃ X ₄
In Formulas 1 and 2,
C ₁ is any one of the ligands represented by the following formulas 3 to 6,
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

R ₁ to R ₆ are the same as or different from each other, and each independently represent any one of hydrogen, a C 1 to C 30 hydrocarbyl group, and a C 1 to C 30 hydrocarbyloxy group;
Z is -O-, -S-, -NR ₇ - or -PR ₇ -;
R ₇ is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, and a silylhydrocarbyl group having 1 to 20 carbon atoms,
M ₁ and M ₂ are the same as or different from each other, and are each independently Ti, Zr or Hf,
X ₁ to X ₄ are the same as or different from each other, and each independently a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, A hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms,
T is an alkylene group having 1 to 5 carbon atoms,

or

is,
T ₁ is C, Si, Ge, Sn or Pb,
Y ₁ and Y ₂ are the same as or different from each other, and each independently hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a hydrocarbyl group having 1 to 30 carbon atoms substituted with a halogen, and -NR ₉ R ₁₀ any one of,
R ₉ and R ₁₀ are each independently any one of hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms, or are connected to each other to form an aliphatic or aromatic ring,
Cp ₁ and Cp ₂ are the same as or different from each other, and each independently represents any one of a cyclopentadienyl group, an indenyl group, 4,5,6,7-tetrahydro-1-indenyl and a fluorenyl group,
R ₁₁ and R ₁₂ are the same as or different from each other, and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms and a hydrocarbyl group having 1 to 30 carbon atoms substituted with halogen,
u and v are each independently an integer between 0 and 5;
The method of claim 1,
The promoter compound is at least one compound selected from the group consisting of compounds represented by the following formulas 11 to 13,
Supported Metallocene Catalysts:
[Formula 11]
R ₂₀ -[Al(R ₁₉ )-O] _n -R ₂₁
In the above formula (11),
R ₁₉ , R ₂₀ and R ₂₁ are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
n is an integer greater than or equal to 2,
[Formula 12]
D(R ₂₂ ) ₃
In the above formula (12),
D is aluminum or boron,
R ₂₂ is each independently any one of halogen, a C 1 to C 20 hydrocarbyl group, a C 1 to C 20 hydrocarbyloxy group, and a halogen-substituted C 1 to C 20 hydrocarbyl group,
[Formula 13]
[LH] ⁺ [W(A) ₄ ] ^- or [L] ⁺ [W(A) ₄ ] ^-
In the above formula (13),
L is a neutral or cationic Lewis base, H is a hydrogen atom,
W is a group 13 element, A is each independently a hydrocarbyl group having 1 to 20 carbon atoms; a hydrocarbyloxy group having 1 to 20 carbon atoms; and one or more of the substituents in which one or more hydrogen atoms of these substituents are substituted with one or more substituents of halogen, a C1-C20 hydrocarbyloxy group, and a C1-C20 hydrocarbyl(oxy)silyl group.
A method for producing a polyolefin, wherein the olefinic monomer is polymerized in the presence of the supported metallocene catalyst of claim 1.