KR20240164471A - Method for preparing catalyst composition for polyolefin and method for preparing polyolefin using the same - Google Patents

Abstract

The present invention provides a method for producing a catalyst composition for polyolefin, which exhibits excellent catalytic activity and improves process stability during polyolefin production by increasing the loading ratio of a cocatalyst and a metallocene compound, and a method for producing polyolefin using the same.

Description

Method for preparing a catalyst composition for polyolefin and method for preparing polyolefin using the same {METHOD FOR PREPARING CATALYST COMPOSITION FOR POLYOLEFIN AND METHOD FOR PREPARING POLYOLEFIN USING THE SAME}

The present invention relates to a method for producing a catalyst composition for polyolefin, which exhibits excellent catalytic activity and improves process stability during the production of polyolefin by increasing the loading ratio of a cocatalyst and a metallocene compound, and a method for producing polyolefin using the same.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler-Natta catalysts have been widely applied to existing commercial processes since their invention in the 1950s, but since they are multisite catalysts with multiple active sites, they are characterized by a wide molecular weight distribution of the polymer, and there is a problem that the composition distribution of the comonomer is not uniform, which limits securing the desired properties.

Meanwhile, the metallocene catalyst is composed of a combination of a main catalyst, which is a metallocene compound as a main component, and a cocatalyst, which is an organometallic compound as a main component, aluminum. Such a metallocene catalyst is a homogeneous complex catalyst and a single site catalyst. Accordingly, a polymer manufactured using a metallocene catalyst is characterized by a narrow molecular weight distribution and a uniform comonomer composition distribution.

However, metallocene catalysts also require further improvement in terms of polymerization activity, high molecular weight, comonomer introduction, and stereoregularity.

A cocatalyst activates a metallocene catalyst to aid in the polymerization of olefins. Partially hydrolyzed aluminum alkyl compounds known as aluminoxanes have been used as cocatalysts in the production of polyolefin polymers.

The cocatalyst is mainly used in the form of a supported catalyst supported on a carrier together with the metallocene catalyst. Not only the amount of the metallocene catalyst supported, but also the amount of the cocatalyst supported affects the catalytic activity. Specifically, the higher the amount of the cocatalyst supported, the higher the catalytic activity. In addition, since the amount of the metallocene catalyst used can be reduced when the content of the cocatalyst increases, the cost of manufacturing the catalyst can be reduced.

Accordingly, various methods are being studied to increase the loading amount of aluminoxane, such as a method of controlling or pretreating the properties of the carrier, or a method of using an additive that can increase the loading amount of the cocatalyst. However, the effect of increasing the loading amount is not significant yet.

The present invention aims to solve the problems of the above-mentioned prior art and provide a method for producing a catalyst composition for polyolefin, which exhibits excellent catalytic activity and improves process stability during the production of polyolefin by increasing the loading ratio of a cocatalyst and a metallocene compound.

In addition, the present invention aims to provide a method for producing polyolefin using a catalyst composition produced by the above-mentioned production method.

According to the present invention, a method for producing a catalyst composition for polyolefin is provided, comprising: a first step of introducing an alkylaluminoxane promoter into a carrier and reacting it; a second step of introducing a phenol compound represented by the following chemical formula 1 into the product of the first step and reacting it; and a third step of introducing a metallocene compound into the product of the second step and reacting it, wherein the phenol compound is introduced in an amount of 0.001 mol or more and 0.1 mol or less per 1 mol of the promoter, and the metallocene compound is a compound represented by the following chemical formula 2 or 3.

[Chemical Formula 1]

In the above chemical formula 1,

One or both of R ¹ to R ⁶ are hydroxy groups, and the others are each independently hydrogen or a hydrocarbyl group having 1 to 30 carbon atoms, or two adjacent groups are connected to each other to form an aromatic ring which is unsubstituted or substituted with a hydrocarbyl group having 1 to 30 carbon atoms,

[Chemical formula 2]

[Cp ¹ (R ^a ) _x (R ^b ) _y ] _n [Cp ² (R ^a ') _z (R ^b ') _w ] M ¹ Z ¹ _3-n

In the above chemical formula 2,

M ¹ is a group 4 transition metal,

Cp ¹ and Cp ² are the same or different from each other, and each independently is one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals,

R ^a and R ^b are substituents of Cp ¹ , and R ^a ' and R ^b ' are substituents of Cp ² ,

R ^a and R ^a ' are the same as or different from each other, and are each independently a hydrocarbyloxy group having 1 to 30 carbon atoms or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms,

R ^b and R ^b ' are the same or different and each independently a hydrocarbyl group having 1 to 30 carbon atoms,

Z ¹ is each independently a halogen group or a hydrocarbyl group having 1 to 30 carbon atoms,

n is an integer of 0 or 1,

x and z are each independently integers 0 or 1, but x and z cannot both be integers 0,

y and w are each independently an integer from 0 to 4, such that x+y≤4, z+w≤4, and x+y+z+w≥1,

[Chemical Formula 3]

In the above chemical formula 3

C ₁ is any one of the ligands represented by the following chemical formulas 4a to 4d,

[Chemical formula 4a]

[Chemical formula 4b]

[Chemical formula 4c]

[chemical formula 4d]

In the above chemical formulas 4a to 4d,

R ₁ to R ₉ are the same or different, and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, and a hydrocarbyloxy group having 1 to 30 carbon atoms.

Z is -O-, -S-, -NR ₁₀ -, or -PR ₁₁ ,

R ₁₀ and R ₁₁ are any one of 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 ² is a group 4 transition metal,

X ₁ and X ₂ are the same or different, and each independently represents a halogen group or a hydrocarbyl group having 1 to 30 carbon atoms,

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

T ₁ is C, Si, Ge, Sn or Pb,

Y ₁ to Y ₄ are the same 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, a silyl group, 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 ₁₂ R ₁₃ ,

R ₁₂ and R ₁₃ are each independently hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms, or are connected to each other to form an aliphatic ring or an aromatic ring,

Also, in the chemical formula above, “·” indicates the bonding position with T.

In addition, according to the present invention, a method for producing a polyolefin is provided, including a step of polymerizing an olefin monomer in the presence of a polyolefin catalyst composition produced by the method for producing the polyolefin catalyst composition.

According to the manufacturing method of the present invention, a catalyst composition for polyolefin can be provided which exhibits excellent catalytic activity and improves process stability during polyolefin manufacturing by increasing the loading ratio of a cocatalyst and a metallocene compound.

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

In addition, the terminology used herein is only used to describe exemplary embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. It should be understood that the terms "comprises," "includes," or "has" in this specification are intended to specify the presence of implemented features, numbers, steps, components, or combinations thereof, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

Also, in this specification, unless specifically defined, ‘room temperature’ means 20±5℃.

The present invention may have various modifications and may take various forms, and thus specific embodiments are illustrated and described in detail below. However, this is not intended to limit the present invention to specific disclosed forms, but should be understood to include all modifications, equivalents, or substitutes included in the spirit and technical scope of the present invention.

Hereinafter, a method for producing a catalyst composition for polyolefin of the present invention and a method for producing polyolefin using the same will be described in detail.

When an alkylaluminoxane promoter is used in the production of a metallocene catalyst, alkylaluminum such as trimethylaluminum is inevitably generated. Alkylaluminum has the problem of reducing the molecular weight of polyolefins produced through aluminum chain transfer and lowering activity by forming a methylene-bridged dimer with the central metal used for polymerization.

Accordingly, the inventors of the present invention have confirmed that, when producing a catalyst composition for polyolefin, a phenolic compound having a specific structure is introduced after supporting a cocatalyst on a carrier and before supporting a metallocene compound, and is removed by reacting with alkyl aluminum derived from the cocatalyst, thereby greatly increasing the amount of cocatalyst and metallocene compound supported on the carrier during production, and as a result, polyolefin can be produced with high catalytic activity, thereby completing the present invention.

Specifically, the method for producing a catalyst composition for polyolefin according to the present invention comprises:

Step 1: adding an alkylaluminoxane promoter to the carrier and reacting it;

A second step of adding a phenol compound represented by the following chemical formula 1 to the product of the first step and causing a reaction;

A third step of adding a metallocene compound to the product of the second step and causing a reaction;

The above phenol compound is added in an amount of 0.001 mol or more and 0.1 mol or less per 1 mol of the cocatalyst,

The above metallocene compound is a compound represented by the following chemical formula 2 or chemical formula 3.

[Chemical Formula 1]

In the above chemical formula 1,

One or both of R ¹ to R ⁶ are hydroxy groups, and the others are each independently hydrogen or a hydrocarbyl group having 1 to 30 carbon atoms, or two adjacent groups are connected to each other to form an aromatic ring which is unsubstituted or substituted with a hydrocarbyl group having 1 to 30 carbon atoms,

[Chemical formula 2]

[Cp ¹ (R ^a ) _x (R ^b ) _y ] _n [Cp ² (R ^a ') _z (R ^b ') _w ] M ¹ Z ¹ _3-n

In the above chemical formula 2,

M ¹ is a group 4 transition metal,

Cp ¹ and Cp ² are the same or different from each other, and each independently is one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals,

R ^a and R ^b are substituents of Cp ¹ , and R ^a ' and R ^b ' are substituents of Cp ² ,

R ^a and R ^a ' are the same as or different from each other, and are each independently a hydrocarbyloxy group having 1 to 30 carbon atoms or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms,

R ^b and R ^b ' are the same or different and each independently a hydrocarbyl group having 1 to 30 carbon atoms,

Z ¹ is each independently a halogen group or a hydrocarbyl group having 1 to 30 carbon atoms,

n is an integer of 0 or 1,

x and z are each independently integers 0 or 1, but x and z cannot both be integers 0,

y and w are each independently an integer from 0 to 4, such that x+y≤4, z+w≤4, and x+y+z+w≥1,

[Chemical Formula 3]

In the above chemical formula 3

C ₁ is any one of the ligands represented by the following chemical formulas 4a to 4d,

[Chemical formula 4a]

[Chemical formula 4b]

[Chemical formula 4c]

[chemical formula 4d]

In the above chemical formulas 4a to 4d,

R ₁ to R ₉ are the same or different, and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, and a hydrocarbyloxy group having 1 to 30 carbon atoms.

Z is -O-, -S-, -NR ₁₀ -, or -PR ₁₁ ,

R ₁₀ and R ₁₁ are any one of 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 ² is a group 4 transition metal,

X ₁ and X ₂ are the same or different, and each independently represents a halogen group or a hydrocarbyl group having 1 to 30 carbon atoms,

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

T ₁ is C, Si, Ge, Sn or Pb,

Y ₁ to Y ₄ are the same 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, a silyl group, 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 ₁₂ R ₁₃ ,

R ₁₂ and R ₁₃ are each independently hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms, or are connected to each other to form an aliphatic ring or an aromatic ring,

Also, in the chemical formula above, “·” indicates the bonding position with T.

Each step is explained in detail below.

The first step for producing a catalyst composition for polyolefin according to the present invention is a step of introducing a cocatalyst into a carrier and causing a reaction. As a result of the first step, the cocatalyst is supported on the carrier.

Silica, alumina, magnesia or mixtures thereof may be used as the carrier. In addition, they may typically include oxides, carbonates, sulfates or nitrates such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ and Mg(NO ₃ ) ₂ .

In addition, the carrier may include a hydroxyl group or a siloxane group on the surface. When a hydroxyl group and a siloxane group are present on the surface of the carrier, the support efficiency of the carrier increases due to the reaction with the cocatalyst or metallocene compound, and as a result, the carrier can support a larger amount of the cocatalyst and the metallocene compound.

Accordingly, the manufacturing method according to the present invention may further include a pretreatment step for the carrier, in which the carrier is dried at a high temperature, specifically 200 to 800° C., more specifically 300 to 600° C., and under vacuum conditions before using the carrier for manufacturing a catalyst. Through the pretreatment as described above, moisture on the surface of the carrier can be removed, thereby suppressing the reaction between the moisture on the surface and the cocatalyst, and also increasing the content of highly reactive hydroxyl groups or siloxane groups on the surface of the carrier.

Additionally, pretreatment of the above carrier can be performed under vacuum conditions.

In addition, the pretreatment for the carrier can be performed for 6 to 18 hours, or 10 to 15 hours, and more specifically, can be performed so that the content of hydroxyl groups on the surface of the carrier becomes 0.1 to 10 mmol/g, more specifically 0.5 to 5 mmol/g.

More specifically, the carrier may be silica, and even more specifically, silica manufactured through the above-described pretreatment.

Meanwhile, specific examples of the alkylaluminoxane cocatalyst include alkylaluminoxanes having 1 to 10 carbon atoms, such as methylaluminoxane (MAO), ethylaluminoxane, iso-butylaluminoxane, or tert-butylaluminoxane, and one or a mixture of two or more of these may be used.

More specifically, the cocatalyst may be methylaluminoxane (MAO).

The support of the cocatalyst on the above-mentioned carrier can be performed by mixing the carrier and the cocatalyst in a solvent and then reacting them while stirring at a temperature of 20 to 120°C, more specifically, 80 to 100°C.

The above carrier and cocatalyst can be introduced in a weight ratio of 2:1 to 1:2.

In addition, as the solvent, an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, etc., or an aromatic hydrocarbon solvent such as benzene, toluene, etc. can be used.

Additionally, the stirring can be performed at a speed of 150 to 300 rpm, more specifically, 200 to 250 rpm.

In this way, when the promoter is supported on the carrier before the catalyst components such as the metallocene compound during the manufacture of the catalyst composition, the promoter reacts with the hydroxyl group on the surface of the carrier and can act as a scavenger for impurities such as moisture and catalyst foreign substances. As a result, a uniform catalyst can be manufactured, and the deactivation of the metallocene compounds supported after the promoter is supported can be prevented and reduced, thereby making it possible to manufacture a highly active catalyst composition.

As a result of the reaction in the first step, the cocatalyst is supported on the carrier.

Accordingly, the product (or reaction product) obtained as a result of the reaction in the first step further includes alkyl aluminum contained in and derived from the promoter, together with the carrier on which the promoter is supported.

Next, the second step is a step of adding and reacting a phenol compound represented by the chemical formula 1 to the product obtained as a result of the first step.

Among the products obtained as a result of the above first step, there are a carrier loaded with a cocatalyst and alkyl aluminum derived from the cocatalyst. In this case, when a phenol compound is added, the phenol compound having a large steric hindrance around the phenol group preferentially reacts with the alkyl aluminum having a small steric hindrance. The reaction product of the phenol compound and the alkyl aluminum does not react with the carrier and the metallocene compound, and can be separated and removed through a process such as filtration after the subsequent metallocene compound loading step.

Specifically, the phenol compound may be a compound represented by the following chemical formula 1-1 or 1-2:

[Chemical Formula 1-1]

In the above chemical formula 1-1,

R ¹¹ is a hydroxy group,

R ¹² to R ¹⁶ are each independently hydrogen or a hydrocarbyl group having 1 to 30 carbon atoms, and at least one of R ¹² and R ¹⁶ adjacent to R ¹¹ is a hydrocarbyl group having 1 to 30 carbon atoms,

[Chemical Formula 1-2]

In the above chemical formula 1-2,

One or both of R ²¹ to R ²⁴ are hydroxy groups, and the others are each independently hydrogen or a hydrocarbyl group having 1 to 30 carbon atoms,

R is a hydrocarbyl group having 1 to 30 carbon atoms,

a is an integer from 0 to 4.

More specifically, in the chemical formula 1-1, R ¹¹ is a hydroxy group, and R ¹² to R ¹⁶ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, wherein at least one of R ¹² and R ¹⁶ adjacent to R ¹¹ may be an alkyl group having 1 to 30 carbon atoms.

More specifically, in the chemical formula 1-1, R ¹¹ is a hydroxy group, and R ¹² to R ¹⁶ are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 18 carbon atoms, or an alkylaryl group having 7 to 18 carbon atoms, wherein at least one of R ¹² and R ¹⁶ adjacent to R ¹¹ may be a straight-chain or branched alkyl group having 1 to 12 carbon atoms.

More specifically, in the chemical formula 1-1, R ¹¹ is a hydroxy group, R ¹² and R ¹⁶ are each independently a branched alkyl group having 3 to 6 carbon atoms, such as a t-butyl group, R ¹³ and R ¹⁵ are each hydrogen, and R ₁₄ may be a straight-chain or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group.

In addition, in the chemical formula 1-2, one or both of R ²¹ to R ²⁴ are hydroxy groups, and the others can each independently be hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkylnyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms.

More specifically, one or both of R ²¹ to R ²⁴ are hydroxy groups, and the others can each independently be hydrogen, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 18 carbon atoms, or an alkylaryl group having 7 to 18 carbon atoms.

More specifically, any two of R ²¹ to R ²⁴ may be hydroxy groups, and the others may each be hydrogen.

In addition, in the chemical formula 1-2, R is specifically an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkylnyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, and more specifically, may be a straight-chain or branched alkyl group having 1 to 12 carbon atoms.

Also, in the chemical formula 1-2, a is an integer from 0 to 4.

If the above a is 0, it means that the compound of chemical formula 1-2 is unsubstituted by R.

In addition, if the above a is an integer from 2 to 4, plural R are each independently as defined above.

Specific examples of the above phenol compounds include 2,6-di-tert-butyl-4-methylphenol or 1,4-dihydroxynaphthalene, and one or a mixture of two or more of these may be used.

The reaction between the above phenol compound and alkyl aluminum can be carried out by adding the phenol compound to the carrier obtained as a result of the first step, specifically, the carrier carrying the cocatalyst, and stirring.

At this time, the phenol compound may be introduced in an amount of 0.001 mol or more and 0.1 mol or less per 1 mol of the cocatalyst. When used in the above content range, the alkyl aluminum removal effect caused by the use of the cocatalyst is excellent, and as a result, the catalytic activity may be further enhanced. More specifically, the phenol compound may be introduced in an amount of 0.001 mol or more, or 0.01 mol or more, or 0.02 mol or more, or 0.025 mol or more, and 0.1 mol or less, or 0.05 mol or less, or 0.040 mol or less, or 0.035 mol or less, or 0.03 mol or less per 1 mol of the cocatalyst.

In addition, the reaction of the phenol compound with the alkyl aluminum can be performed at a temperature of 20 to 60°C, more specifically, 30 to 50°C, or 30 to 40°C.

In addition, when reacting the above phenol compound with alkyl aluminum, stirring can be performed at a speed of 150 to 300 rpm, more specifically, 200 to 250 rpm.

In addition, the reaction between the above phenol compound and alkyl aluminum can be carried out in a solvent. At this time, the solvent may be a hydrocarbon solvent such as pentane, hexane, heptane, etc.; or an aromatic solvent such as benzene, toluene, etc.

As a result of the above second step, a reaction product of a phenol compound and alkyl aluminum is generated.

In addition, the phenol compound introduced in the second step reacts with the alkyl aluminum, but some of the phenol compound may be supported on the carrier. Accordingly, the product obtained as a result of the second step may include a reaction product of the phenol compound and the alkyl aluminum, along with a cocatalyst and a carrier on which the phenol compound is supported.

Next, the third step is a step of adding a metallocene compound to the product obtained as a result of the second step and causing a reaction. As a result of the third step, the metallocene compound is supported on the carrier.

The above metallocene compound may be a compound represented by the following chemical formula 2 or chemical formula 3:

[Chemical formula 2]

[Cp ¹ (R ^a ) _x (R ^b ) _y ] _n [Cp ² (R ^a ') _z (R ^b ') _w ] M ¹ Z ¹ _3-n

In the above chemical formula 2,

M ¹ is a group 4 transition metal,

Cp ¹ and Cp ² are the same or different from each other, and each independently is one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals,

R ^a and R ^b are substituents of Cp ¹ , and R ^a ' and R ^b ' are substituents of Cp ² ,

R ^a and R ^a ' are the same as or different from each other, and are each independently a hydrocarbyloxy group having 1 to 30 carbon atoms or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms,

R ^b and R ^b ' are the same or different and each independently a hydrocarbyl group having 1 to 30 carbon atoms,

Z ¹ is each independently a halogen group or a hydrocarbyl group having 1 to 30 carbon atoms,

n is an integer of 0 or 1,

x and z are each independently integers 0 or 1, but x and z cannot both be integers 0,

y and w are each independently an integer from 0 to 4, such that x+y≤4, z+w≤4, and x+y+z+w≥1,

[Chemical Formula 3]

In the above chemical formula 3

C ₁ is any one of the ligands represented by the following chemical formulas 4a to 4d,

[Chemical formula 4a]

[Chemical formula 4b]

[Chemical formula 4c]

[chemical formula 4d]

In the above chemical formulas 4a to 4d,

R ₁ to R ₉ are the same or different, and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, and a hydrocarbyloxy group having 1 to 30 carbon atoms.

Z is -O-, -S-, -NR ₁₀ -, or -PR ₁₁ ,

R ₁₀ and R ₁₁ are any one of 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 ² is a group 4 transition metal,

X ₁ and X ₂ are the same or different, and each independently represents a halogen group or a hydrocarbyl group having 1 to 30 carbon atoms,

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

T ₁ is C, Si, Ge, Sn or Pb,

Y ₁ to Y ₄ are the same 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, a silyl group, 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 ₁₂ R ₁₃ ,

R ₁₂ and R ₁₃ are each independently hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms, or are connected to each other to form an aliphatic ring or an aromatic ring,

Also, in the chemical formula above, “·” indicates the bonding position with T.

Unless otherwise specified in this specification, the following terms may be defined as follows:

A hydrocarbyl group is a monovalent functional group in which a hydrogen atom is removed from a hydrocarbon, and includes an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, an arylalkynyl group, an alkylaryl group, an alkenylaryl group, and an alkynylaryl group. In addition, 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 straight-chain or branched alkyl group such as 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, an n-hexyl group, or an n-heptyl group; a cycloalkyl group such as a cyclohexyl group; Or it may be an aryl group such as a phenyl group, a naphthyl group, or 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 may be a straight-chain, branched-chain or cyclic alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a tert-butoxy group, an n-pentoxy group, an n-hectoxy group, an n-heptoxy group, a cyclohectoxy group, or the like; or an aryloxy group such as a phenoxy group or a naphthalenoxy group.

A hydrocarbyloxyhydrocarbyl group is a functional group in which at least one hydrogen atom of a hydrocarbyl group is replaced by at least one hydrocarbyloxy group. 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 may be a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, a tert-butoxyhexyl group, a phenoxyhexyl group, or the like.

A hydrocarbyl(oxy)silyl group is a functional group in which 1 to 3 hydrogens of -SiH ₃ are replaced by 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 selected from the group consisting of alkylsilyl groups such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group, and a dimethylpropylsilyl group; an alkoxysilyl group 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.

A silylhydrocarbyl group having 1 to 20 carbon atoms is a functional group in which at least one hydrogen of the hydrocarbyl group is replaced by 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, a dimethylethoxysilylpropyl group, or the like.

The halogen group can be a fluorine group (-F), a chlorine group (-Cl), a bromine group (-Br), or an iodine group (-I).

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

In the present specification, when two adjacent substituents are connected to each other to form an aliphatic or aromatic ring, it means that the atom(s) of the two substituents and the atom(s) to which the two substituents are bonded are connected to each other to form a ring. Specifically, an example in which R ₉ and R ₁₀ of -NR ₉ R ₁₀ are connected to each other to form an aliphatic ring may include a piperidinyl group, and an example in which R ₉ and R ₁₀ of -NR ₉ R ₁₀ are connected to each other to form an aromatic ring may include a pyrrolyl group, etc.

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

The above-described substituents may be arbitrarily substituted with one or more substituents selected from the group consisting of a hydroxy group; a halogen; a hydrocarbyl group; a hydrocarbyloxy group; a hydrocarbyl group or a hydrocarbyloxy group containing at least one heteroatom from groups 14 to 16; -SiH ₃ ; a hydrocarbyl(oxy)silyl group; a phosphine group; a phosphide group; a sulfonate group; and a sulfone group, within a range that exhibits the same or similar effect as the desired effect.

Specifically, in the chemical formula 2, Cp ¹ is any one selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl radicals, and Cp ² may be a cyclopentadienyl radical. More specifically, Cp ¹ and Cp ² may each be a cyclopentadienyl group.

In addition, in the chemical formula 2, R ^a and R ^b are substituents of Cp ¹ , and R ^a ' and R ^b ' are substituents of Cp ^2. However, in the chemical formula 2, x and z are each independently an integer of 0 or 1, but x and z are not both integers of 0, and y and w are each independently an integer from 0 to 4, such that x+y≤4, z+w≤4, and x+y+z+w≥1. In addition, as an example, when y in the chemical formula 2 is an integer greater than or equal to 2, a plurality of R ^{b '} may also be the same as or different from each other. Meanwhile, when x, y, z, or w is an integer of 0, it means that it is unsubstituted.

These R ^a and R ^a ' are the same as or different from each other, and are each independently a hydrocarbyloxy group having 1 to 30 carbon atoms, or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms. More specifically, R ^a and R ^a ' may each independently be an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms. For example, R ^a and R ^a ' may each independently be a tert-butoxy(t-Bu-O)hexyl group or a tert-butoxyoctyl group. When R ^a and R ^a ' are the above-mentioned substituents, the metallocene compound can exhibit excellent catalytic activity and supported stability.

In addition, R ^b and R ^b ' are the same as or different from each other, and are each independently a hydrocarbyl group having 1 to 30 carbon atoms. More specifically, R ^b and R ^b ' can each independently be an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms. For example, R ^b and R ^b ' can each independently be a methyl group or a phenyl group.

In addition, in the chemical formula 2, M ¹ may be Ti, Zr or Hf, and more specifically, Ti or Zr.

In addition, Z ¹ in chemical formula 2 can each independently be a halogen group or an alkyl group having 1 to 12 carbon atoms, and more specifically, a chloro group or a methyl group. The metallocene compound in which Z ¹ has the above substituent can easily have the halogen group replaced with an alkyl group by a reaction with a cocatalyst. In addition, by the subsequent alkyl abstraction, the metallocene compound forms an ionic intermediate with the cocatalyst, thereby more easily providing a cationic form, which is an active species of an olefin polymerization reaction.

Specific examples of the compound represented by the above chemical formula 2 include, but are not limited to, the following compounds.

Metallocene compounds represented by the above structural formulas can be synthesized by applying known reactions.

Meanwhile, the metallocene compound represented by the chemical formula 3 includes ligands of different structures each derived from an aromatic ring compound including thiophene and a base compound including a group 15 or 16 atom, and the ligands are bridged by -T- and have a structure in which M ₁ (X ₁ )(X ₂ ) exists between the ligands. Due to these structural features, the compound exhibits excellent support stability and high activity during olefin polymerization, and as a result, an olefin polymer having a high molecular weight can be produced.

Specifically, the ligand of C ₁ in the structure of the metallocene compound represented by the above chemical formula 3 can affect, for example, olefin polymerization activity and copolymerization characteristics. In particular, a metallocene compound including a ligand of C ₁ in which R ₁ to R ₄ , R ₈ and R ₉ of chemical formulas 4a to 4d are each independently hydrogen or a hydrocarbyl group having 1 to 10 carbon atoms, and R ₅ to R ₇ are each independently any one of a hydrocarbyl group having 1 to 10 carbon atoms, exhibits very high activity and high comonomer conversion in an olefin polymerization process. More specifically, the ligand of C ₁ may be a ligand in which R ₁ to R ₄ , R ₈ and R ₉ of chemical formulae 4a to 4d are each independently hydrogen or alkyl having 1 to 10 carbon atoms, and R ₅ to R ₇ are each independently alkyl having 1 to 10 carbon atoms, and more specifically, a ligand in which R ₁ to R ₄ , R ₈ and R ₉ are each independently hydrogen or methyl, and R ₅ to R ₇ are each methyl.

In addition, the Z ligand within the structure of the metallocene compound represented by the chemical formula 3 may affect, for example, olefin polymerization activity.

In particular, when Z in chemical formula 3 is -NR ₁₀ - and R ₁₀ is any one of hydrocarbyl groups having 1 to 10 carbon atoms, more specifically, when it is alkyl having 1 to 10 carbon atoms, and even more specifically, when it is C _3-6 branched alkyl such as t-butyl, a catalyst exhibiting very high activity in an olefin polymerization process can be provided.

In addition, the ligand of C ₁ and the ligand of Z can be cross-linked by -T- to exhibit excellent support stability. In addition, to enhance this effect, the -T- has the structure of, where T ₁ is C or Si, and Y ₁ has 1 to 30 carbon atoms. Hydrocarbyl group and carbon number 1 to 30 Any one of the hydrocarbyloxy groups, and Y ₂ has 2 to 30 carbon atoms. It can be any one of hydrocarbyloxyhydrocarbyl groups. Specifically, T ₁ is Si, Y ₁ is alkyl having 1 to 20 carbon atoms, or 1 to 10 carbon atoms, and Y ₂ is alkoxyalkyl having 2 to 20 carbon atoms, or 2 to 10 carbon atoms, or an aryloxyalkyl group having 7 to 20 carbon atoms, or 7 to 14 carbon atoms. More specifically, T ₁ is Si, Y ₁ is any one of a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and Y ₂ can be any one of a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, a tert-butoxyhexyl group, and a phenoxyhexyl group.

Meanwhile, M ² (X ₁ )(X ₂ ) exists between the ligand of the bridged C ₁ and the ligand of Z, and M ² (X ₁ )(X ₂ ) can affect the storage stability of the metal complex.

To more effectively secure this effect, X ₁ and X ₂ may each independently be a halogen group or an alkyl group having 1 to 6 carbon atoms, and more specifically, a chloro group or a methyl group.

More specifically, the metallocene compound represented by the chemical formula 3 may be any one of the compounds represented by the following chemical formulas 5 to 8:

[Chemical Formula 5]

[Chemical formula 6]

[Chemical formula 7]

[Chemical formula 8]

In the above chemical formulas 5 to 8, R ₁ to R ₁₀ , M ² , X ₁ , X ₂ , T ₁ , Y ₁ and Y ₂ are as defined above.

Specifically, in the chemical formulas 5 to 8, R ₁ to R ₄ , R ₈ and R ₉ are the same as or different from each other, and are each independently hydrogen or a hydrocarbyl group having 1 to 10 carbon atoms, more specifically, each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and even more specifically, each independently hydrogen or methyl,

R ₅ to R ₇ are the same or different, and are each independently any one of hydrocarbyl groups having 1 to 10 carbon atoms, more specifically any one of alkyl groups having 1 to 10 carbon atoms, and even more specifically, R ₅ to R ₇ are each methyl,

M ² is Ti, Zr or Hf, more specifically Ti or Zr,

X ₁ and X ₂ are the same or different from each other, and each independently represents a halogen group and an alkyl group having 1 to 6 carbon atoms, more specifically, each independently represents a chloro group or a methyl group,

T ₁ is C or Si, more specifically Si,

Y ₁ is a group having 1 to 30 carbon atoms. Hydrocarbyl group and carbon number 1 to 30 Any one of the hydrocarbyloxy groups, and Y ₂ has 2 to 30 carbon atoms. Any one of hydrocarbyloxyhydrocarbyl groups, more specifically, Y ₁ is an alkyl having 1 to 20 carbon atoms, or 1 to 10 carbon atoms, Y ₂ is an alkoxyalkyl having 2 to 20 carbon atoms, or 2 to 10 carbon atoms, or an aryloxyalkyl group having 7 to 20 carbon atoms, or 7 to 14 carbon atoms, and more specifically, Y ₁ is any one of a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and Y ₂ is any one of a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, a tert-butoxyhexyl group, and a phenoxyhexyl group.

More specifically, the compound represented by the chemical formula 3 may be any one of the following compounds:

The support of the above metallocene compound can be performed by adding the metallocene compound to the support obtained in the second step, stirring, and reacting.

The supporting process of the above metallocene compound can be performed in a solvent, and at this time, a hydrocarbon solvent such as pentane, hexane, heptane, etc., or an aromatic solvent such as benzene, toluene, etc. can be used as the solvent.

In addition, the support of the metallocene compound can be performed at a temperature of 20 to 60°C, more specifically, 30 to 50°C, or 30 to 40°C.

In addition, when supporting the metallocene compound, stirring can be performed at a speed of 150 to 300 rpm, more specifically, 200 to 250 rpm.

In addition, the metallocene compound may be introduced in an amount where the molar ratio of the phenol-based compound to 1 mole of the metallocene compound is greater than 0 and less than or equal to 10. When used in the above content range, the effect of removing alkyl aluminum generated by the use of a promoter is excellent, and as a result, the catalytic activity can be further enhanced. More specifically, the molar ratio of the phenol-based compound to 1 mole of the metallocene compound may be introduced in an amount of 0.1 or more, or 0.5 or more, or 1 or more, or 1.5 or more, or 2 or more, and 10 or less, or 8 or less, or 5 or less.

In addition, the metallocene compound may be introduced in the form of a solution dissolved in a solvent, and at this time, an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, etc., or an aromatic hydrocarbon solvent such as benzene, toluene, etc. may be used as the solvent.

As a result of the reaction in the third step, the metallocene compound is supported on the carrier.

Accordingly, the product obtained as a result of the third step includes a carrier loaded with a cocatalyst and a metallocene compound, and a reaction product of a phenolic compound and an alkyl aluminum in the second step, and the carrier may further include a phenolic compound loaded thereon. In addition, the reaction product of the phenolic compound and the alkyl aluminum does not react with the carrier and the metallocene compound, and can be removed through a separation and removal process.

Accordingly, the method for manufacturing a catalyst composition according to the present invention may further include, after the third step, a step (fourth step) of separating and removing impurities including reaction products of a phenol compound and alkyl aluminum, unreacted compounds, etc. from the resulting product.

Since the supported catalyst obtained as a result of the reaction in the third step is in a solid state and the reaction product of the phenol compound and the alkyl aluminum exists in a dissolved state in a solvent, the separation and removal step can be performed through a conventional impurity removal method such as filtration.

For example, the product of the third step may be filtered to first separate and remove the reaction product of the phenol compound and the alkyl aluminum, and the resulting product may be washed by adding a washing solvent for the reaction product of the phenol compound and the alkyl aluminum, and then filtered to secondarily separate and remove the reaction product of the phenol compound and the alkyl aluminum. In this case, the second separation and removal process may be repeated one or more times.

Additionally, the above filtration process can be performed using a device such as a filter dryer.

In addition, as a washing solvent for the reaction product of the phenol compound and the alkyl aluminum, any solvent that can dissolve only the reaction product of the phenol compound and the alkyl aluminum without leaching or decomposing the cocatalyst and metallocene compound supported on the supported catalyst can be used. Specifically, an aliphatic hydrocarbon solvent such as pentane, hexane, or heptane; or an aromatic hydrocarbon solvent such as benzene or toluene can be used.

The catalyst composition manufactured by the above-described manufacturing method can exhibit excellent catalytic activity during the manufacture of polyolefin and can also improve process stability due to the increased loading rate for the cocatalyst and metallocene compound due to the reduction and removal of alkyl aluminum during the manufacture of the catalyst composition.

Accordingly, according to the present invention, a catalyst composition manufactured by the above-described manufacturing method is provided.

The catalyst composition specifically comprises a carrier, a cocatalyst supported on the carrier, and a metallocene compound. In addition, the catalyst composition may further comprise a phenolic compound. In this case, the phenolic compound may be supported on the carrier.

The above carrier, cocatalyst, metallocene compound, and phenol compound are the same as those described in the manufacturing method above.

More specifically, in the catalyst composition, the carrier may be silica, more specifically silica that has been dried and pretreated at a high temperature of 200 to 800°C to have a hydroxyl group or a siloxane group on the surface. In addition, in the catalyst composition, the cocatalyst may be specifically alkylaluminoxane having 1 to 20 carbon atoms, more specifically methylaluminoxane. In addition, in the catalyst composition, the phenol compound may be a compound that contains one phenol group or naphthalene group as an aromatic group and one or two hydroxyl groups, and more specifically may be 2,6-Di-tert-butyl-4-methylphenol or 1,4-Dihydroxynaphthalene. In addition, in the catalyst composition, the metallocene compound may be a compound represented by the chemical formula 2 or 3.

In addition, in the catalyst composition, the support ratio of the cocatalyst calculated according to the following mathematical formula 1, specifically, the support ratio of the alkylaluminoxane may be 80% or more, more specifically, 85% or more, and the support ratio of the metallocene compound calculated according to the following mathematical formula 2, specifically, the support ratio of the metallocene compound represented by the chemical formula 2 or 3 may be 80% or more, or 83% or more.

[Mathematical formula 1]

Promoter loading rate (%) = [Al detection amount / Al amount of added promoter] X 100

[Mathematical formula 2]

Metallocene compound loading rate (%) = [Amount of metal component detected in metallocene compound / Amount of metal component in input metallocene compound] X 100

More specifically, the catalyst composition comprises a carrier, and an alkylaluminoxane promoter, a metallocene compound, and a phenolic compound supported on the carrier, wherein the carrier is silica, and the promoter support ratio calculated by the mathematical formula 1 may be 80% or more, and the metallocene compound support ratio calculated by the mathematical formula 2 may be 80% or more. In addition, the metallocene compound may be a compound represented by the chemical formula 2 or 3.

The above-described catalyst composition exhibits excellent catalytic activity in the production of an olefin polymer, and enables the production of a polyolefin having improved properties, particularly a high molecular weight and a narrow molecular weight distribution.

Accordingly, according to the present invention, a method for producing polyolefin is provided, comprising a step of polymerizing an olefin monomer in the presence of the above-described catalyst composition.

The method for producing polyolefin according to the present invention can be performed according to a conventional olefin polymerization process, except for using the above-described catalyst composition.

Specifically, examples of the olefin monomer include ethylene, alpha-olefin, cyclic olefin, etc., and diene olefin monomers or triene olefin monomers having two or more double bonds can also be polymerized. Specific examples of the above monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc., and two or more types of these monomers can be mixed and copolymerized. When the above olefin polymer is a copolymer of ethylene and another comonomer, it is preferable that 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.

For the polymerization reaction of the above olefin monomer, various polymerization processes known as polymerization reactions of olefin monomers, such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process, or an emulsion polymerization process, can be employed.

In addition, the polymerization reaction of the above olefin monomer can be performed at a temperature of 50 to 110°C, more specifically 60 to 100°C, and under a pressure of 1 to 100 kgf/cm ² , more specifically 1 to 50 kgf/cm ² .

The polyolefin manufactured by the above method has a high molecular weight and a narrow molecular weight distribution because it is manufactured using the above catalyst composition.

Specifically, the polyolefin may have a weight average molecular weight (Mw) of 115,000 g/mol or more, more specifically 115,000 to 2,000,000 g/mol, and a molecular weight distribution (MWD) of 2.2 or less, more specifically 2.0 to 2.2. Accordingly, the polyolefin may exhibit excellent mechanical strength properties.

Meanwhile, the weight average molecular weight and molecular weight distribution of the polyolefin can be measured through gel permeation chromatography analysis, and the specific method and conditions thereof are as described in the experimental examples below.

Hereinafter, preferred examples are presented to help understand the present invention. However, the following examples are provided only to help understand the present invention more easily, and the content of the present invention is not limited thereby.

<Preparation of catalyst composition>

Manufacturing example 1

6.0 kg of toluene solution was placed in a 20 L stainless steel (SUS) high-pressure reactor, and the reactor temperature was maintained at 40°C. 1,000 g of silica (SYLOPOL 948, manufactured by Grace Davison) dehydrated by applying vacuum at a temperature of 600°C for 12 hours was placed in the reactor, and the silica was sufficiently dispersed.

In the above reactor, 9.4 kg of a 10 wt% methylaluminoxane (MAO) toluene solution was added and reacted while stirring at 200 rpm at 95°C for 12 hours.

After the reaction was completed, the reactor temperature was lowered to 40°C, 2.0 kg of toluene was added, and a solution prepared by dissolving 92 g of 2,6-Di-tert-butyl-4-methylphenol as a phenol compound in 500 mL of toluene was additionally added to the reactor, and the reaction was performed while stirring at 200 rpm at 40°C for 2 hours.

After the reaction was completed, a solution prepared by dissolving 127 g of a metallocene compound (1a) having the following structure in 1 L of toluene was introduced into the reactor and stirred at 200 rpm for 2 hours at 40° C. At this time, the molar ratio of the phenol compound to 1 mol of the cocatalyst MAO was 0.03, and the molar ratio of the phenol compound to 1 mol of the metallocene compound (1a) was 2.

After the reaction was completed, the resulting toluene slurry was transferred to a filter dryer and subjected to the first filtration to first separate and remove impurities. In addition, 3.0 kg of hexane was additionally added to the reactor to dissolve the remaining obtained material adhered to the wall of the reactor, the resulting hexane slurry was transferred to the filter dryer and mixed with the first filtrate existing in the filter dryer, and the resulting mixture was subjected to the second filtration to second separate and remove impurities. The resulting filtrate was dried under reduced pressure at 40° C. for 4 hours, and a catalyst composition including a 1 kg-SiO ₂ supported catalyst was obtained.

(1a)

Manufacturing example 2

A catalyst composition was prepared by the same method as in Preparation Example 1, except that 1,4-Dihydroxynaphthalene as a phenol compound was used in an amount of 0.025 mol per 1 mol of MAO.

Manufacturing example 3

A catalyst composition was prepared by the same method as in Manufacturing Example 1, except that 107 g of a metallocene compound (1b) having the following structure was used as the metallocene compound.

(1b)

Comparative manufacturing example 1

A catalyst composition was prepared by the same method as in Manufacturing Example 1, except that the phenol compound was not used.

Comparative manufacturing example 2

A catalyst composition was prepared in the same manner as in Manufacturing Example 1, except that 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (ETHANOX330, Sigma-Aldrich) as a phenol compound was used in an amount of 0.007 molar ratio per 1 mol of MAO.

Comparative manufacturing example 3

6.0 kg of toluene solution was placed in a 20 L stainless steel (SUS) high-pressure reactor, and the reactor temperature was maintained at 40°C. 1,000 g of silica (SYLOPOL 948, manufactured by Grace Davison) dehydrated by applying vacuum at 600°C for 12 hours was placed in the reactor, and the silica was sufficiently dispersed.

In a separate reactor from the above, a solution prepared by dissolving 92 g of 2,6-Di-tert-butyl-4-methylphenol as a phenol compound in 500 mL of toluene was added to 9.4 kg of a 10 wt% methylaluminoxane (MAO) toluene solution, and the mixture was stirred at 40° C. and 200 rpm for 2 hours to allow the reaction to proceed. At this time, the molar ratio of the phenol compound to 1 mol of the MAO as a cocatalyst was 0.03. The resulting reaction product was added to the reactor where the silica was dispersed, and the mixture was stirred at 95° C. and 200 rpm for 12 hours to allow the reaction to proceed.

After the reaction was completed, a solution prepared by dissolving 127 g of a metallocene compound (1a) of the following structure in 1 L of toluene was added to the resulting reaction product, and the reaction was carried out while stirring at 200 rpm at 40° C. for 2 hours.

After the reaction was completed, the resulting toluene slurry was transferred to a filter dryer and subjected to the first filtration to first separate and remove impurities. In addition, 3.0 kg of hexane was additionally added to the reactor to dissolve the remaining obtained material adhering to the wall of the reactor, the resulting hexane slurry was transferred to the filter dryer and mixed with the first filtrate existing in the filter dryer, and the resulting mixture was subjected to the second filtration to second separate and remove impurities. The resulting filtrate was dried under reduced pressure at 40° C. for 4 hours to prepare a catalyst composition including a 1 kg-SiO ₂ supported catalyst.

(1a)

Comparative manufacturing example 4

A catalyst composition was prepared by the same method as in Manufacturing Example 3, except that the phenol compound was not used in Manufacturing Example 3.

Comparative manufacturing example 5

A catalyst composition was prepared by the same method as in Manufacturing Example 1, except that pentafluorophenol, as a phenol compound, was added in an amount of 0.03 mol per 1 mol of MAO.

Comparative manufacturing example 6

6.0 kg of toluene solution was placed in a 20 L stainless steel (SUS) high-pressure reactor, and the reactor temperature was maintained at 40°C.

In the above reactor, a solution prepared by dissolving 9.4 kg of a 10 wt% methylaluminoxane (MAO) toluene solution and 127 g of a metallocene compound (1a) in 1 L of toluene was introduced, and the reaction was performed while stirring at 200 rpm at 40° C. for 2 hours.

In a separate reactor from the above, 2.0 kg of toluene was charged, and 1,000 g of silica (SYLOPOL 948, manufactured by Grace Davison) dehydrated at 600°C for 12 hours under vacuum was charged into the reactor, and the silica was sufficiently dispersed. Then, a solution prepared by dissolving 92 g of 2,6-Di-tert-butyl-4-methylphenol as a phenol compound in 500 mL of toluene was charged, and the mixture was stirred at 40°C for 2 hours and reacted at 200 rpm. The resulting reactant was charged into the reactor, and the mixture was stirred at 95°C for 12 hours and reacted at 200 rpm. At this time, the molar ratio of the phenol compound to 1 mol of the cocatalyst MAO was 0.03, and the molar ratio of the phenol compound to 1 mol of the metallocene compound (1a) was 2.

After the reaction was completed, the resulting toluene slurry was transferred to a filter dryer and subjected to the first filtration to first separate and remove impurities. In addition, 3.0 kg of hexane was additionally added to the reactor to dissolve the remaining obtained material adhering to the wall of the reactor, the resulting hexane slurry was transferred to the filter dryer and mixed with the first filtrate existing in the filter dryer, and the resulting mixture was subjected to the second filtration to second separate and remove impurities. The resulting filtrate was dried under reduced pressure at 40° C. for 4 hours, and a catalyst composition including a 1 kg-SiO ₂ supported catalyst was obtained.

Comparative manufacturing example 7

6.0 kg of toluene solution was placed in a 20 L stainless steel (SUS) high-pressure reactor, and the reactor temperature was maintained at 40°C.

In the above reactor, a solution prepared by dissolving 9.4 kg of a 10 wt% methylaluminoxane (MAO) toluene solution and 127 g of a metallocene compound (1a) in 1 L of toluene was introduced, and the reaction was performed while stirring at 200 rpm at 40° C. for 2 hours.

After the reaction was completed, 1,000 g of silica (SYLOPOL 948, manufactured by Grace Davison) dehydrated under vacuum at 600°C for 12 hours was added to the reactor, and after sufficiently dispersing the silica, the reaction was carried out while stirring at 200 rpm at 95°C for 12 hours.

After the reaction was completed, 2.0 kg of toluene was added to the reactor, and a solution prepared by dissolving 92 g of 2,6-Di-tert-butyl-4-methylphenol as a phenol compound in 500 mL of toluene was additionally added to the reactor, and the reaction was performed while stirring at 200 rpm at 40° C. for 2 hours. At this time, the molar ratio of the phenol compound to 1 mol of the cocatalyst MAO was 0.03, and the molar ratio of the phenol compound to 1 mol of the metallocene compound (1a) was 2.

After the reaction was completed, the resulting toluene slurry was transferred to a filter dryer and subjected to the first filtration to first separate and remove impurities. In addition, 3.0 kg of hexane was additionally added to the reactor to dissolve the remaining obtained material adhering to the wall of the reactor, the resulting hexane slurry was transferred to the filter dryer and mixed with the first filtrate existing in the filter dryer, and the resulting mixture was subjected to the second filtration to second separate and remove impurities. The resulting filtrate was dried under reduced pressure at 40° C. for 4 hours, and a catalyst composition including a 1 kg-SiO ₂ supported catalyst was obtained.

Comparative manufacturing example 8

A catalyst composition was prepared in the same manner as in Manufacturing Example 1, except that 115 g of a metallocene compound (2a) having the following structure was used as the metallocene compound. At this time, the molar ratio of the phenol compound to 1 mol of MAO as a cocatalyst was 0.03, and the molar ratio of the phenol compound to 1 mol of the metallocene compound (2a) was 2.

(2a)

Comparative manufacturing example 9

A catalyst composition was manufactured using the same method as in Comparative Manufacturing Example 8, except that the phenol compound was not used.

Comparative manufacturing example 10

A catalyst composition was prepared by the same method as in Manufacturing Example 1, except that 2,6-Di-tert-butyl-4-methylphenol, a phenol compound, was used in an amount of 0.3 molar ratio per 1 mol of MAO.

<Polyethylene manufacturing>

Example 1

Polyethylene was manufactured by polymerizing ethylene in the presence of the catalyst composition manufactured in Manufacturing Example 1.

Specifically, 20 mg of the catalyst composition manufactured in the above Manufacturing Example 1 was quantified in a dry box, placed in a 30 ml glass bottle, sealed with a rubber septum, taken out of the dry box, and prepared for injection.

The polymerization was carried out in a 2 L metal alloy reactor equipped with a mechanical stirrer, which is temperature-controlled and can be used at high pressure. 1 L of hexane containing 0.5 mmol of triethylaluminum was introduced into the reactor, and the catalyst composition prepared above was introduced into the reactor without contact with air. Then, the polymerization was performed for 1 hour while continuously adding gaseous ethylene monomer at a pressure of 50 psig at 80° C. The polymerization was completed by first stopping the stirring and then exhausting and removing the ethylene. The resulting reaction product was filtered to remove the polymerization solvent, and then dried in an oven at 70° C. for 4 hours to obtain polyethylene.

Examples 2 to 3

Polyethylene was manufactured using the same method as in Example 1, except that the catalyst compositions manufactured in Manufacturing Examples 2 and 3 were used.

Comparative examples 1 to 10

Polyethylene was manufactured using the same method as in Example 1, except that the catalyst compositions manufactured in Comparative Manufacturing Examples 1 to 10 were used.

Experimental Example 1

For the catalyst compositions manufactured in the above Manufacturing Examples and Comparative Manufacturing Examples, the Al content and Zr content in the catalyst compositions were measured using the following methods, and the cocatalyst loading rate and the metallocene loading rate were calculated, respectively. In addition, the catalytic activity during the polymerization manufacturing of polyethylene according to the Examples and Comparative Examples, and the weight average molecular weight (Mw) and molecular weight distribution (MWD) of the manufactured polyethylene were measured using the following methods, respectively.

(1) Al content (weight%) and Zr content (weight%)

The Al content and Zr content in the catalyst composition were respectively measured using ICP analysis.

Specifically, the catalyst compositions manufactured in the above Manufacturing Examples and Comparative Manufacturing Examples were analyzed using an ICP-OES (PerkinElmer) analyzer, and the Al content and Zr content in the catalyst compositions were calculated from the analysis results using ICP software Syngistix. Using the calculated values, the relative ratio of the Al content based on the total weight of the catalyst composition was expressed as a percentage. The Zr content in the catalyst composition was also calculated using the same method.

(2) Promoter loading rate (%) and metallocene loading rate (%)

The Al content and Zr content in the catalyst composition calculated in (1) above were used as the Al detection amount and the metal component detection amount of the metallocene compound, respectively, and the promoter support rate (%) and the metallocene support rate (%) were calculated according to the following mathematical equations 1 and 2, respectively.

[Mathematical formula 1]

Promoter loading rate (%) = [Al detected amount / Al amount in the introduced promoter] X 100

[Mathematical formula 2]

Metallocene compound loading rate (%) = [Amount of metal component detected in metallocene compound / Amount of metal component in the introduced metallocene compound] X 100

(3) Catalytic activity

Catalytic activity (Activity, kg PE/gㆍcatㆍhr) is a value calculated as the ratio of the weight of polyethylene (kg PE) produced per the weight of catalyst composition (gㆍCat) used per unit time (h).

(4) Weight average molecular weight (Mw) and molecular weight distribution (MWD)

For the polyethylene manufactured in the above examples and comparative examples, the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through gel permeation chromatography (GPC) analysis, and the measured weight average molecular weight was divided by the number average molecular weight to obtain the molecular weight distribution (MWD = Mw/Mn).

Specifically, the measurement sample was measured using a Waters PL-GPC220 instrument with a Polymer Laboratories PLgel MIX-B 300 mm length column. The measurement temperature was 160°C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was measured at a rate of 1 mL/min. The polyethylene sample was pretreated by dissolving it in 1,2,4-trichlorobenzene containing 0.025% BHT at 160°C for 4 hours using a GPC analysis instrument PL-GP220, preparing it at a concentration of 20 mg/10 mL, and then supplying it in an amount of 200 μL. The values of Mw and Mn were measured using a calibration curve formed using a polystyrene standard. The molecular weights (g/mol) of polystyrene standards were 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000, nine types.

Types of catalyst compositions Metallocene type Types of phenol derivatives Al content
(weight%) Zr content
(weight%) Co-catalyst
Carrying rate
(%) Metallocene compounds
Carrying rate
(%) Active
(kgPE/gCat·h)
Mw (g/mol) MWD Example 1 Manufacturing example 1 1a 2,6-Di-tert-butyl-4-methylphenol 16.9 0.46 88.9 83.2 16.7 119,000 2.2 Example 2 Manufacturing example 2 1a 1,4-Dihydroxynaphthalene 16.8 0.45 88.0 81.0 14.2 118,000 2.1 Example 3 Manufacturing example 3 1b 2,6-Di-tert-butyl-4-methylphenol 16.6 0.26 85.9 86.5 8.8 1,420,000 2.1 Comparative Example 1 Comparative manufacturing example 1 1a - 14.1 0.47 67.5 77.4 10.6 119,000 2.3 Comparative Example 2 Comparative manufacturing example 2 1a 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene 12.3 0.38 55.2 58.6 8.6 132,000 2.2 Comparative Example 3 Comparative manufacturing example 3 1a 2,6-Di-tert-butyl-4-methylphenol 17.3 0.41 91.8 74.8 9.1 98,000 2.5 Comparative Example 4 Comparative manufacturing example 4 1b - 15.3 0.25 75.7 81.1 6.1 1,420,000 2.0 Comparative Example 5 Comparative manufacturing example 5 1a Pentafluorophenol 15.1 0.50 75.4 85.8 11.6 120,000 2.3 Comparative Example 6 Comparative manufacturing example 6 1a 2,6-Di-tert-butyl-4-methylphenol 16.4 0.39 84.1 68.8 5.1 100,000 4.8 Comparative Example 7 Comparative manufacturing example 7 1a 2,6-Di-tert-butyl-4-methylphenol 14.6 0.40 70.6 66.5 6.9 110,000 2.7 Comparative Example 8 Comparative manufacturing example 8 2a 2,6-Di-tert-butyl-4-methylphenol 11.4 0.24 48.8 35.7 8.0 102,000 2.3 Comparative Example 9 Comparative manufacturing example 9 2a - 11.2 0.25 47.7 35.9 7.9 101,000 2.3 Comparative Example 10 Comparative manufacturing example 10 1a 2,6-Di-tert-butyl-4-methylphenol 13.3 0.39 61.6 62.1 7.2 124,000 2.9

As a result of the experiment, the catalyst compositions of Manufacturing Examples 1 and 2 showed an MAO loading rate increased by about 10% or more compared to Comparative Manufacturing Examples 1 and 2 containing the same metallocene compound (1a), and the catalyst composition of Manufacturing Example 3 showed an MAO loading rate increased by 5% or more compared to Comparative Manufacturing Example 4 containing the same metallocene compound (1b). As a result, as shown in Examples 1 to 3, when polyethylene was produced using the catalyst compositions of Manufacturing Examples 1 to 3, high catalytic activity was exhibited.

Meanwhile, the catalyst composition of Comparative Manufacturing Example 3 had a high MAO loading ratio but a low metallocene compound loading ratio compared to Manufacturing Examples 1 and 2 due to the difference in the loading order, and as a result, the catalytic activity was also significantly reduced. In general, if the MAO loading ratio is high, the catalytic activity can be significantly improved even if the metallocene loading ratio is low. However, since the catalyst composition of Comparative Manufacturing Example 3 is manufactured by a method in which MAO and a phenolic compound are first reacted, and then the loading process for the carrier and the loading process for the metallocene compound are sequentially performed, the MAO and the phenolic compound are clumped together to form one large unit, and since this unit is supported on the carrier, the MAO loading ratio is high, but the reaction site of MAO is covered, so it cannot act on the metallocene compound to increase the activity, and thus it is expected that the catalytic activity was reduced.

In addition, from the results of Comparative Examples 2, 5, 8 and 9, it can be seen that when the structural requirements of the phenol compound and the structural requirements of the metallocene compound in the present invention are simultaneously satisfied, the effects of increasing the loading amount and improving the catalytic activity accordingly can be sufficiently realized.

In addition, in the case of the catalyst compositions of Comparative Manufacturing Examples 6 and 7, which were manufactured by a method that did not satisfy the conditions of the manufacturing step of the catalyst composition according to the present invention, the loading rate of the metallocene compound was greatly reduced compared to Manufacturing Examples 1 to 3, and as a result, the catalytic activity during the polymerization of polyethylene was also greatly reduced. From these results, it was confirmed that when the manufacturing step of the catalyst composition according to the present invention is satisfied, the effects of improving the loading rate and thus increasing the catalytic activity can be implemented.

In addition, in the case of Comparative Manufacturing Example 10 where the amount of phenol compound loaded during the manufacture of the catalyst composition exceeded 0.1 mol based on 1 mol of MAO, the amount of metallocene compound loaded decreased, and as a result, the catalytic activity also decreased. From these results, it was confirmed that the amount of phenol compound loaded should be controlled within an optimal range in order to increase the amount of metallocene compound loaded and thereby improve the catalytic activity.

Claims (15)

Step 1: adding an alkylaluminoxane promoter to the carrier and reacting it;
A second step of adding a phenol compound represented by the following chemical formula 1 to the product of the first step and causing a reaction;
A third step of adding a metallocene compound to the product of the second step and causing a reaction;
The above phenol compound is added in an amount of 0.001 mol or more and 0.1 mol or less per 1 mol of the cocatalyst,
The above metallocene compound is a compound represented by the following chemical formula 2 or chemical formula 3.
Method for producing a catalyst composition for polyolefin:
[Chemical Formula 1]

In the above chemical formula 1,
One or both of R ¹ to R ⁶ are hydroxy groups, and the others are each independently hydrogen or a hydrocarbyl group having 1 to 30 carbon atoms, or two adjacent groups are connected to each other to form an aromatic ring which is unsubstituted or substituted with a hydrocarbyl group having 1 to 30 carbon atoms,
[Chemical formula 2]
[Cp ¹ (R ^a ) _x (R ^b ) _y ] _n [Cp ² (R ^a ') _z (R ^b ') _w ] M ¹ Z ¹ _3-n
In the above chemical formula 2,
M ¹ is a group 4 transition metal,
Cp ¹ and Cp ² are the same or different from each other, and each independently is one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals,
R ^a and R ^b are substituents of Cp ¹ , and R ^a ' and R ^b ' are substituents of Cp ² ,
R ^a and R ^a ' are the same as or different from each other, and are each independently a hydrocarbyloxy group having 1 to 30 carbon atoms or a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms,
R ^b and R ^b ' are the same or different and each independently a hydrocarbyl group having 1 to 30 carbon atoms,
Z ¹ is each independently a halogen group or a hydrocarbyl group having 1 to 30 carbon atoms,
n is an integer of 0 or 1,
x and z are each independently integers 0 or 1, but x and z cannot both be integers 0,
y and w are each independently an integer from 0 to 4, such that x+y≤4, z+w≤4, and x+y+z+w≥1,
[Chemical Formula 3]

In the above chemical formula 3
C ₁ is any one of the ligands represented by the following chemical formulas 4a to 4d,
[Chemical formula 4a]

[Chemical formula 4b]

[Chemical formula 4c]

[chemical formula 4d]

In the above chemical formulas 4a to 4d,
R ₁ to R ₉ are the same or different, and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, and a hydrocarbyloxy group having 1 to 30 carbon atoms.
Z is -O-, -S-, -NR ₁₀ -, or -PR ₁₁ ,
R ₁₀ and R ₁₁ are any one of 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 ² is a group 4 transition metal,
X ₁ and X ₂ are the same or different, and each independently represents a halogen group or a hydrocarbyl group having 1 to 30 carbon atoms,
T is an alkylene group having 1 to 5 carbon atoms, or And,
T ₁ is C, Si, Ge, Sn or Pb,
Y ₁ to Y ₄ are the same 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, a silyl group, 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 ₁₂ R ₁₃ ,
R ₁₂ and R ₁₃ are each independently hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms, or are connected to each other to form an aliphatic ring or an aromatic ring,
Also, in the chemical formula above, “·” indicates the bonding position with T.
In the first paragraph,
The above phenol compound is a compound represented by the following chemical formula 1-1 or 1-2.
A method for producing a catalyst composition for polyolefin.
[Chemical Formula 1-1]

In the above chemical formula 1-1,
R ¹¹ is a hydroxy group,
R ¹² to R ¹⁶ are each independently hydrogen or a hydrocarbyl group having 1 to 30 carbon atoms, and at least one of R ¹² and R ¹⁶ adjacent to R ¹¹ is a hydrocarbyl group having 1 to 30 carbon atoms,
[Chemical Formula 1-2]

In the above chemical formula 1-2,
One or both of R ²¹ to R ²⁴ are hydroxy groups, and the others are each independently hydrogen or a hydrocarbyl group having 1 to 30 carbon atoms,
R is a hydrocarbyl group having 1 to 30 carbon atoms,
a is an integer from 0 to 4.
In the first paragraph,
The above phenol compound is 2,6-di-tert-butyl-4-methylphenol or 1,4-dihydroxynaphthalene.
A method for producing a catalyst composition for polyolefin.
In the first paragraph,
The above phenol compound is added in an amount of 0.01 mol or more and 0.05 mol or less per 1 mol of the cocatalyst.
A method for producing a catalyst composition for polyolefin.
In the first paragraph,
The above-mentioned cocatalyst is an alkylaluminoxane having 1 to 20 carbon atoms.
A method for producing a catalyst composition for polyolefin.
In the first paragraph,
The above cocatalyst is methylaluminoxane,
A method for producing a catalyst composition for polyolefin.
In the first paragraph,
The carrier comprises silica, alumina, magnesia or a mixture thereof.
A method for producing a catalyst composition for polyolefin.
In the first paragraph,
Before the first step, a step of drying the carrier under vacuum conditions at a temperature of 200 to 800°C is further included.
A method for producing a catalyst composition for polyolefin.
In the first paragraph,
M ¹ and M ² are each independently titanium or zirconium,
A method for producing a catalyst composition for polyolefin.
In the first paragraph,
The compound represented by the above chemical formula 2 is selected from the group consisting of:
A method for producing a catalyst composition for polyolefin.

In the first paragraph,
The compound represented by the above chemical formula 3 is selected from the group consisting of:
A method for producing a catalyst composition for polyolefin.

In the first paragraph,
The molar ratio of the phenol compound to 1 mole of the above metallocene compound is greater than 0 and less than or equal to 10.
A method for producing a catalyst composition for polyolefin.
In the first paragraph,
In the second step, the phenol compound reacts with the alkyl aluminum present in the product of the first step.
A method for producing a catalyst composition for polyolefin.
In the first paragraph,
The above manufacturing method further includes, after the third step, a fourth step of separating and removing the reaction product of the phenol compound and alkyl aluminum present in the product of the third step.
A method for producing a catalyst composition for polyolefin.
A method for producing a polyolefin comprising the steps of polymerizing an olefin monomer in the presence of a catalyst composition for polyolefin produced by the manufacturing method according to claim 1.
Method for producing polyolefin.