KR20220043693A - Hybrid supported metallocene catalyst and preparing mehtod a polyolefin using the same - Google Patents

Abstract

The present invention relates to a hybrid-supported metallocene catalyst and a preparation method of a polyolefin using the same, and more specifically, to a hybrid-supported metallocene catalyst which can prepare a polyolefin without a sharp decrease in catalyst activity even during a polymerization process using a multi-stage reactor by increasing the stability of the catalyst and a preparation method of a polyolefin using the same.

Description

Hybrid supported metallocene catalyst and method for producing polyolefin using the same

The present invention relates to a hybrid supported metallocene catalyst and a method for preparing polyolefin using the same. More specifically, it relates to a hybrid supported metallocene catalyst capable of producing polyolefin without a sharp decrease in catalytic activity in a polymerization process using a multi-stage reactor by increasing the stability of the catalyst, and a method for preparing polyolefin 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 dual Ziegler-Natta catalyst is a multisite catalyst, and there is a limit in securing desired 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 and can control the comonomer distribution compared to the existing Ziegler-Natta catalyst, which 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.

A multi-stage reactor including two or more reactors has been used to obtain a polyolefin having a broad molecular weight distribution with improved processability with a metallocene catalyst, and through each polymerization step in such a plurality of reactors, a wider multimodal molecular weight distribution Attempts have been made to obtain polyolefins that are satisfactory. However, when a metallocene catalyst is applied, there was a problem that polymerization did not continue due to a decrease in catalytic activity in the latter reactor according to the duration of the olefin polymerization time in the reactor in the front stage, and polyolefin having a wide multimodal molecular weight distribution was stably produced. There were limits to

Therefore, there is a need for a technology capable of more effectively producing polyolefins that have multimodal molecular weight distribution and can satisfy mechanical properties and processability at the same time.

An object of the present invention is to provide a hybrid supported metallocene catalyst capable of producing polyolefin without deterioration of catalytic activity even during a polymerization process using a multi-stage reactor, and a method for producing polyolefin using the same.

According to one embodiment of the present invention, the first metallocene compound; a second metallocene compound; cocatalyst compounds; ethylene; and a diene compound supported on a carrier, to provide a hybrid supported metallocene catalyst.

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

The hybrid supported metallocene catalyst according to the present invention can produce polyolefin with little decrease in catalytic activity even during a polymerization process using a multi-stage reactor. Accordingly, it can be usefully applied to the preparation of polyolefins having excellent physical properties and processability applied to various uses.

In the present invention, terms such as first and second 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, the first metallocene compound; a second metallocene compound; cocatalyst compounds; ethylene; and a diene compound supported on a carrier, a hybrid supported metallocene catalyst is provided.

High-density polyethylene has excellent mechanical strength and can be applied to various uses such as blown molded articles, films, pipes, and injection molded articles. A single CSTR/slurry loop/solution polymerization reactor and a multi-stage CSTR/slurry loop/solution polymerization reactor can be used to produce such high density polyethylene. Among them, when polymerization is performed using a multi-stage CSTR reactor, the catalyst is generally introduced into only the first reactor. However, in the reactor after the second stage, the activity of the catalyst injected into the first reactor is rapidly reduced, and the reactor pressure rises, making it difficult to operate the process and there is a problem in that polyethylene having a desired structure cannot be obtained. In order to prevent the deterioration of the catalyst activity, a method such as introducing a catalyst to the second reactor may be applied, but in the case of the above methods, product uniformity is deteriorated and catalyst cost is increased.

The present invention is to solve the above problems, and according to one embodiment of the present invention, an olefinic supported metallocene catalyst in which ethylene and a diene compound are supported together with a metallocene compound and a cocatalyst compound Polymerize the polymer.

In this way, when prepolymerization is first performed by introducing low-pressure ethylene and diene compounds to the hybrid supported metallocene catalyst, an appropriate gap is maintained between the metallocene compounds supported on the support, so that the supported state can be stably maintained. there is. Therefore, even when the polymerization process is performed using a multi-stage CSTR reactor of two or more stages, polyolefin can be produced with little decrease in catalytic activity.

According to one embodiment of the present invention, the ethylene may be included in an amount of 0.5 to 500 parts by weight based on 100 parts by weight of the carrier. More specifically, the ethylene is included in an amount of 0.5 parts by weight or more, or 1 part by weight or more, or 2 parts by weight or more, and 500 parts by weight or less, or 250 parts by weight or less, or 100 parts by weight or less with respect to 100 parts by weight of the carrier. can

If the content of ethylene is too low, the effect of improving the catalyst activity according to the ethylene support is insufficient, and if it is too high, the catalyst particle shape control may not be possible.

According to one embodiment of the present invention, the diene compound may be a linear diene compound having 5 to 10 carbon atoms. For example, from the group consisting of 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, and 1,9-decadiene It may be one or more selected. When the number of carbon atoms of the diene compound is less than 5 or more than 10, a stable supported state may not be maintained because an appropriate gap between the metallocene compounds may not be formed because the length of the carbon chain is too short or too long. In terms of maintaining stable catalytic activity and cost, 1,5-hexadiene may be preferably used.

In addition, even when the prepolymerization is performed only with ethylene or only with the diene compound, the catalyst activity can be maintained at the beginning of the reaction, but as the polymerization time continues, the catalyst activity decreases, There is a problem that polymerization is not performed properly.

According to one embodiment of the present invention, the diene compound may be included in an amount of 0.5 to 500 parts by weight based on 100 parts by weight of the carrier. More specifically, the diene compound is included in an amount of 0.5 parts by weight or more, or 1 part by weight or more, or 2 parts by weight or more, and 500 parts by weight or less, or 250 parts by weight or less, or 100 parts by weight or less based on 100 parts by weight of the carrier. can

If the content of the diene compound is too low, the effect of improving the catalytic activity according to the support of the diene compound is insufficient. It is preferable to be included in the range.

According to one embodiment of the present invention, the ethylene and diene compound may be included in a weight ratio of 1:10 to 10:1, preferably 1:5 to 5:1 by weight. When the content of the diene compound is too low relative to ethylene, the effect of improving catalyst stability is insignificant. It is preferable to be included in the above range.

According to one embodiment of the present invention, the types of the first and second metallocene compounds supported on the hybrid supported metallocene catalyst are not particularly limited, and are known to be usable in polymerization of polyolefin, particularly high-density polyethylene. As long as it is a strong compound, it can be used without limitation. According to one embodiment, the first metallocene compound may be a compound suitable for polymerizing a polyolefin having a high molecular weight, and the second metallocene compound may be a compound suitable for polymerizing a polyolefin having a relatively low molecular weight.

In addition, according to one embodiment of the present invention, the ethylene and diene compound may be supported in the last step after the metallocene compound and the cocatalyst compound are supported on the carrier.

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, and 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 valences (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 the 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 hybrid supported metallocene catalyst may be prepared by, for example, a step of supporting a promoter on a support, a step of supporting the first and second metallocene compounds that are catalyst precursors on a support supported on a promoter, followed by ethylene, and diene It can be prepared in a step of supporting the compound is supported.

The content of the carrier, the cocatalyst, the carrier, and the first and second metallocene compounds used to use the hybrid supported catalyst may be appropriately adjusted according to the desired physical properties or effects of the hybrid supported 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.

And, in the step of supporting the catalyst precursor on the promoter supported carrier, the first metallocene compound is added to the promoter supported carrier, stirred at a temperature of about 20 to about 120° C., and then the second metallocene compound is prepared added, and stirred again at a temperature of about 20 to about 120° C. to prepare a hybrid supported catalyst.

Next, ethylene and a diene compound are supported on the support on which the promoter and the first and second metallocene catalysts are supported. At this time, the ethylene and the diene compound may be supported in a slurry state, and may be supported by stirring with the carrier at a temperature of about 25 to about 100 °C.

In preparing the hybrid 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 for preparing the supported metallocene catalyst, reference may be made to Examples to be described later. However, the preparation method of the hybrid 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 The step(s) of the method can be varied by means of a step(s) that are typically variable.

According to another aspect of the present invention, in the presence of the hybrid supported metallocene catalyst, there may be provided a method for producing a polyolefin comprising the step of polymerizing an olefinic monomer.

Examples of the olefinic monomer that can be polymerized with the hybrid 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 is also polymerized. It is possible. 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, 1,3-butadiene, 1, There are 4-pentadiene, 1,5-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like, 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 hybrid 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).

According to an embodiment of the present invention, the step of polymerizing the olefinic monomer in the presence of the hybrid supported metallocene catalyst may be performed in a multi-stage-CSTR reactor.

An example of a polyolefin polymerization method using a multi-stage-CSTR reactor will be described in more detail for each step as follows.

The metallocene catalyst supplied to the first reactor is the above-described hybrid supported metallocene catalyst, and polymerization may proceed by supplying a first olefin-based monomer such as ethylene. An organoaluminum compound for removing moisture in the reactor may be further added to the first and second reactors, and each polymerization reaction may proceed in the presence of the organic aluminum compound. Specific examples of the organoaluminum compound include trialkylaluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride or alkyl aluminum sesqui halide, and more specific examples thereof include Al (C ₂ H ₅ ) ₃ , Al(C ₂ H ₅ ) ₂ H, Al(C ₃ H ₇ ) ₃ , Al(C ₃ H ₇ ) ₂ H, Al(iC ₄ H ₉ ) ₂ H, Al(C ₈ H ₁₇ ) ) ₃ , Al(C ₁₂ H ₂₅ ) ₃ , Al(C ₂ H ₅ )(C ₁₂ H ₂₅ ) ₂ , Al(iC ₄ H ₉ )(C ₁₂ H ₂₅ ) ₂ , Al(iC ₄ H ₉ ) ₂ H, Al(iC ₄ H ₉ ) ₃ , (C ₂ H ₅ ) ₂ AlCl, (iC ₃ H ₉ ) ₂ AlCl, or (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ , and the like. Such an organoaluminum compound may be continuously added to each reactor, and may be added in a ratio of about 0.1 to 10 moles per 1 kg of the reaction medium fed into each reactor for proper moisture removal.

In addition, in the first reactor, the residence time of each raw material may be selected without particular limitation as long as it is within a range capable of forming a polyolefin having an appropriate molecular weight distribution and density distribution, but may be about 1 to about 3 hours. If the residence time in the first reactor is smaller than this, the low molecular weight polyolefin may not be properly formed and the molecular weight distribution may be narrowed, thereby reducing the processability of the final polyolefin. Conversely, if the residence time in the first reactor is too long, it is not preferable in terms of productivity.

In addition, the polymerization reaction temperature in the first reactor may be about 70 to about 90 ℃. If the polymerization reaction temperature is too low, it is not appropriate in terms of polymerization rate and productivity, and if the polymerization reaction temperature is excessively high, fouling may occur in the reactor. The polymerization reaction pressure in the first reactor may be from about 5 to about 10 bar to maintain a stable continuous process condition.

The reaction mixture in the first reactor including the above-described first olefinic monomer and the hybrid supported metallocene catalyst may further include an organic solvent serving as a reaction medium or a diluent. As the organic solvent, the above-described aliphatic hydrocarbon-based solvent may be used, and the reaction medium may be used in an amount suitable for slurry-phase polymerization, etc. in consideration of the content of the first olefin-based monomer.

The production ratio of the polyolefin produced in the first reactor described above may be about 30 to about 70 weight % with respect to the total content of the finally obtained polyolefin. After the polymerization reaction in the first reactor is performed, the slurry reaction mixture in the first reactor may be transferred to the second reactor to perform the second step. By installing a flash vessel between the first and second reactors, hydrogen and unreacted ethylene can be removed by venting.

At this time, in the second reactor, in addition to the slurry reaction mixture transferred from the first reactor, a second olefinic monomer may be additionally added to proceed with the polymerization process. At this time, in the second reactor, ethylene as the second olefinic monomer; and propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, novo At least one comonomer selected from the group consisting of nene, ethylidenenorbornene, styrene, alpha-methylstyrene and 3-chloromethylstyrene may be added together.

In addition, in the second reactor, there is little decrease in the activity of the metallocene catalyst included in the slurry reaction mixture transferred from the first reactor, so that polyolefin having a wide molecular weight distribution can be finally produced.

In the second reactor, the residence time of each raw material may be selected without particular limitation as long as it is within a range capable of forming a polyolefin having an appropriate molecular weight distribution and density distribution, but may be about 1 to about 3 hours. If the residence time in the second reactor is smaller than this, the high molecular weight polyolefin may not be properly formed, and the environmental stress cracking resistance or mechanical properties of the finally manufactured polyolefin may be reduced. Conversely, if the residence time in the second reactor is excessively If it is long, it is undesirable in terms of productivity.

In addition, the polymerization reaction temperature in the second reactor may be about 70 to about 90 ℃. If the polymerization reaction temperature is too low, it is not appropriate in terms of polymerization rate and productivity, and if the polymerization reaction temperature is excessively high, fouling may be caused in the reactor.

In addition, the polymerization reaction pressure in the first reactor may be about 5 to about 10 bar in order to maintain a stable continuous process state. The polymerization reaction pressure in the second reactor may be adjusted to be lower than about 0 to about 3 bar compared to the pressure in the first reactor. This may facilitate transfer of the slurry mixture from the first reactor to the second reactor.

In the second reactor, as in the first reactor, an aliphatic hydrocarbon-based solvent or the like may be used as a reaction medium or a diluent, and slurry-phase polymerization may be appropriately performed.

The proportion of the polyolefin formed in the second reactor described above may be about 30 to about 70 wt %, based on the total content of the finally obtained polyolefin.

Meanwhile, the above-described multi-stage-CSTR reactor may further include a post reactor for further polymerizing unreacted monomers in the slurry reaction mixture transferred from the second reactor, through which the polyolefin may be finally produced.

The polyolefin prepared according to the manufacturing method of the above-described embodiment may have a broad bimodal or multimodal molecular weight distribution due to the action of the above-described first and second stage polymerization.

Due to such a large molecular weight and a wide multimodal molecular weight distribution, the polyolefin prepared according to the production method of one embodiment of the present invention may exhibit excellent mechanical properties and processability at the same time. Therefore, it has a melt flow rate ratio (MFRR) value suitable for processing, has excellent formability, impact strength, tensile strength, especially, environmental stress cracking resistance (ESCR), and simultaneously meets mechanical properties and processability Therefore, it can be preferably used in various products.

Using the polyolefin prepared as described above, the present invention can be manufactured according to various methods known to those skilled in the art, molded articles.

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 (crosslinked 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

Preparation 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 10 wt% 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 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 adding 0.25 kg of 1,5-hexadiene to the reactor, ethylene at 2 bar was added for 1 hour to perform pre-polymerization. After venting to remove ethylene, the catalyst was settled, the hexane layer was separated and removed, and the remaining hexane was removed under reduced pressure to prepare a hybrid supported catalyst.

Comparative Preparation 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 Preparation 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, 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. Pre-polymerization was performed by introducing 2 bar of ethylene into the reactor for 1 hour. After venting to remove ethylene, the catalyst was settled, the hexane layer was separated and removed, and the remaining hexane was removed under reduced pressure to prepare a hybrid supported catalyst.

Comparative Preparation Example 3

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 adding 0.25 kg of 1,5-hexadiene to the reactor, it was stirred for 1 hour to perform pre-polymerization. After venting to remove ethylene, the catalyst was settled, the hexane layer was separated and removed, and the remaining hexane was removed under reduced pressure to prepare a hybrid supported catalyst.

Comparative Preparation Example 4

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 adding 0.25 kg of 1-hexene to the reactor, it was stirred for 1 hour to perform pre-polymerization. After venting to remove ethylene, the catalyst was settled, the hexane layer was separated and removed, and the remaining hexane was removed under reduced pressure to prepare a hybrid supported catalyst.

Polymerization Example in Single Polymerization Reactor

Example 1

20 mg of each supported catalyst prepared in Preparation Examples and Comparative Preparation Examples 1 to 4 was quantified in a dry box, placed in a 50 mL glass bottle, and sealed with a rubber diaphragm to prepare a catalyst to be taken out of the dry box and injected. Polymerization was carried out in a 2L metal alloy reactor equipped with a mechanical stirrer, temperature-controlled and used at high pressure.

0.8 kg of hexane and 1.5 g of Triisobutylaluminum (1 mol/L) solution were injected into this reactor, and the supported catalyst of Preparation Example 1 was introduced into the reactor without air contact, and then gaseous ethylene monomer was added to 10 gf/cm ² of Polymerization was carried out for 6 hours while continuously applying pressure. The polymerization was completed by first stopping the stirring and then evacuating the ethylene to remove it. The resulting polymer was dried in a vacuum oven at 70° C. for 4 hours after most of the polymerization solvent was removed by filtration.

Comparative Example 1

Ethylene polymerization was carried out in the same manner as in Example 1, except that the hybrid supported metallocene catalyst of Comparative Preparation Example 1 was used instead of the catalyst of Preparation Example 1 in Example 1.

Comparative Example 2

Ethylene polymerization was carried out in the same manner as in Example 1, except that the hybrid supported metallocene catalyst of Comparative Preparation Example 2 was used instead of the catalyst of Preparation Example 1 in Example 1.

Comparative Example 3

Ethylene polymerization was carried out in the same manner as in Example 1, except that the hybrid supported metallocene catalyst of Comparative Preparation 3 was used instead of the catalyst of Preparation Example 1 in Example 1.

Comparative Example 4

In Example 1, ethylene polymerization was carried out in the same manner as in Example 1, except that the hybrid supported metallocene catalyst of Comparative Preparation Example 4 was used instead of the catalyst of Preparation Example 1.

In Example 1 and Comparative Examples 1 to 4, catalyst activity and melt index MI ₅ of polyethylene after polymerization for 1 hour, and catalyst activity and melt index MI ₅ of polyethylene after polymerization for 6 hours are shown in Table 1 below. .

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 1 hour after polymerization catalytic activity
(KgPE/g.Cat/h) 13 15 11 13 12 MI ₅
(g/10min) 1.2 1.0 1.3 1.1 1.1 6 hours after polymerization catalytic activity
(KgPE/g.Cat/h) 11 3 2 3 2 MI ₅
(g/10min) 1.5 1.3 1.4 1.2 1.1

(In Table 1, the catalytic activity was calculated as the ratio of the weight (kg PE) of the polymer produced per mass (g) of the supported metallocene catalyst used based on the unit time (h),

Melt index (MI ₅ ) was measured at 190° C. and a load of 5 kg according to ASTM D1238.)

Referring to Table 1, when polymerization was performed using a hybrid supported metallocene catalyst on which ethylene and a diene compound were supported according to an embodiment of the present invention, there was little decrease in catalyst activity even after polymerization for 6 hours. On the other hand, Comparative Examples 1 to 4 had similar catalytic activity in the initial 1 hour, but markedly lowered the catalytic activity after polymerization for 6 hours.

Polymerization Examples in a Continuous Polymerization Reactor

Example 2

Polymerization was performed using two 180 L CSTR slurry polymerization reactors filled with hexane. Polyolefin was polymerized by continuously injecting 20 atm of ethylene, hydrogen, and the supported catalyst solution (5 wt% hexane slurry) prepared in Preparation Example 1 into the first 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 first reactor at 80° C., and the amount of ethylene gas was fixed at 10 kg/hr.

The amount of hydrogen was adjusted so that the MI _2.16 of the polyolefin powder in the first reactor was 10 g/10min. The reactant in the first reactor was vented through a flash vessel to remove ethylene and unreacted ethylene, and then transferred to the second reactor.

While maintaining the temperature of the second reactor at 80 °C, the amount of hexane continuously input to the reactor was fixed at 30 kg/hr, the amount of ethylene gas was fixed at 10 kg/hr, and the density of polyolefin powder was 0.951 g/cm ³ The amount of 1-butene continuously input was adjusted so that MI _2.16 of the polyolefin powder was adjusted to 1.0 g/10min.

Example 3

Ethylene polymerization was carried out in the same manner as in Example 2, except that the amount of hydrogen was adjusted so that MI _2.16 of the polyolefin powder in the second reactor in Example 2 was 2.0 g/10min.

Comparative Example 5

In Example 2, ethylene polymerization was carried out in the same manner as in Example 1, except that the hybrid supported metallocene catalyst of Comparative Preparation Example 1 was used instead of the catalyst of Preparation Example 1.

Comparative Example 6

In Example 2, ethylene polymerization was carried out in the same manner as in Example 1, except that the hybrid supported metallocene catalyst of Comparative Preparation 2 was used instead of the catalyst of Preparation Example 1.

Comparative Example 7

Ethylene polymerization was carried out in the same manner as in Example 1, except that in Example 2, the hybrid supported metallocene catalyst of Comparative Preparation 3 was used instead of the catalyst of Preparation Example 1.

Comparative Example 8

In Example 2, ethylene polymerization was carried out in the same manner as in Example 1, except that the hybrid supported metallocene catalyst of Comparative Preparation Example 4 was used instead of the catalyst of Preparation Example 1.

The physical properties of the polyethylene obtained in Examples 2 to 3 and Comparative Examples 5 to 8 were measured in the following manner and shown in Table 2 below.

1) Density (g/cm ³ )

The density of polyethylene was measured according to ISO 1183-2 at 23°C.

2) Melt index (MI _2.16 , g/10min)

It was measured at 190°C and a load of 2.16 kg according to ASTM D1238, and it was expressed as the weight (g) of polyethylene melted for 10 minutes.

3) molecular weight distribution (Mw/Mn)

The weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene are measured using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Agilent), and the molecular weight distribution (MWD) by dividing the weight average molecular weight by the number average molecular weight ) was calculated.

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

catalyst Reactor type number of reactors melt index
(MI _2.16 ) (g/10min)
density
(g/cm ³ ) MWD Example 2 Preparation Example 1 Multi-stage CSTR 2 1.0 0.952 14.8 Example 3 Preparation Example 1 Multi-stage CSTR 2 2.0 0.952 12.3 Comparative Example 5 Comparative Preparation Example 1 Multi-stage CSTR 2 In the second reactor, the reactor pressure rises and polymerization reaction is impossible Comparative Example 6 Comparative Preparation Example 2 Multi-stage CSTR 2 The copolymerization of the comonomer is lowered, so the polymerization reaction is impossible to the desired density. Comparative Example 7 Comparative Preparation Example 3 Multi-stage CSTR 2 In the second reactor, the reactor pressure rises and polymerization reaction is impossible Comparative Example 8 Comparative Preparation Example 4 Multi-stage CSTR 2 In the second reactor, the reactor pressure rises and polymerization reaction is impossible

Referring to Table 2, in the case of Examples 2 and 3 in which polymerization was performed in a CSTR reactor using a hybrid supported metallocene catalyst on which ethylene and a diene compound were supported according to an embodiment of the present invention, in the second reactor Polyolefin having a desired level of physical properties could be polymerized without increasing the reaction pressure.

On the other hand, in Comparative Examples 5, 7, and 8, the polymerization reaction was impossible because the reactor pressure was abnormally increased in the second reactor. The copolymerizability of butene was lowered, and the polymerization reaction was impossible until the desired density was reached.

Claims (10)

a first metallocene compound;
a second metallocene compound;
cocatalyst compounds;
ethylene; and
A hybrid supported metallocene catalyst in which a diene compound is supported on a carrier.
The method of claim 1,
The diene compound is a linear diene compound having 5 to 10 carbon atoms,
Hybrid supported metallocene catalysts.
3. The method of claim 2,
The diene compound is 1,5-hexadiene,
Hybrid supported metallocene catalysts.
The method of claim 1,
The ethylene is included in an amount of 0.5 to 500 parts by weight based on 100 parts by weight of the carrier,
Hybrid supported metallocene catalysts.
The method of claim 1,
The diene compound is included in an amount of 0.5 to 500 parts by weight based on 100 parts by weight of the carrier,
Hybrid supported metallocene catalysts.
The method of claim 1,
The ethylene and diene compounds are included in a weight ratio of 10: 1 to 1:10,
Hybrid supported metallocene catalysts.
The method of claim 1,
The first metallocene compound is represented by the following formula (1), the second metallocene compound is a compound represented by the following formula (2),
Hybrid 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 represents 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 halogen, and -NR ₉ R ₁₀ ,
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,
Hybrid 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 hybrid supported metallocene catalyst of claim 1.
The method of claim 9, wherein the olefinic monomer is polymerized in a multi-stage-CSTR reactor.