KR20200139513A - Supported catalyst for olefin polymerization, method for preparing the same and method for preparing polyolefin using the same - Google Patents

Abstract

The present invention relates to a supported catalyst for olefin polymerization, a manufacturing method thereof, and a method for manufacturing a polyolefin using the same, wherein the supported catalyst includes: a main catalyst containing a metallocene compound; a cocatalyst comprising alkyl aluminum and an aluminoxane compound; an aromatic compound combined with two or more polar groups selected from among a hydroxyl group (-OH), an amine group (-NH_2), a thiol group (-SH), a carboxyl group (-COOH), and an amide group (-CONH_2) and one or more halogen groups; and a carrier supporting the main catalyst, cocatalyst, and aromatic compound, and having a functional group bonded to the surface thereof. Also, a molar ratio of the functional group to the alkyl aluminum is 0.7 or more and 3.5 or less, and a molar ratio of the aromatic compound to the alkyl aluminum is 0.5 or more and 1.9 or less.

Description

A supported catalyst for olefin polymerization, a method for manufacturing the same, and a method for manufacturing a polyolefin using the same {SUPPORTED CATALYST FOR OLEFIN POLYMERIZATION, METHOD FOR PREPARING THE SAME AND METHOD FOR PREPARING POLYOLEFIN USING THE SAME}

The present invention relates to a supported catalyst for olefin polymerization, a method for preparing the same, and a method for preparing a polyolefin using the same, and specifically, by including a functional group bonded to the surface of a support, an alkyl aluminum and an aromatic compound in an appropriate molar ratio, it is excellent in activity and catalyst aggregation is possible. It relates to a supported catalyst for olefin polymerization that does not occur, a method for producing the same, and a method for producing a polyolefin using the same.

In the process of polymerizing or copolymerizing an olefin monomer to prepare a polyolefin, various catalyst compounds are used to achieve a higher reaction efficiency and obtain a polymer having target physical properties. Catalysts used in the polymerization of such polyolefins can be classified into Ziegler-Natta-based and metallocene-based catalysts, and these two highly active catalysts have been developed according to their respective characteristics.

In general, since metallocene catalysts are homogeneous catalysts having a single type of catalytic activity point, the molecular weight distribution of the polymer is narrower than that of the Ziegler-Natta catalyst, the composition distribution of the comonomer is uniform, and the ligand structure of the catalyst is modified. It has characteristics that can change the properties of the polymer.

One of the major research interests related to these metallocene catalysts is a technology for producing high molecular weight polyolefins. However, in the case of a catalyst system that produces a large number of high molecular weight products, it is necessary to perform a complex ligand synthesis process, and has a disadvantage in that polymerization activity is inferior unless the process conditions are adjusted. Thus, as a method for increasing the activity of the metallocene catalyst, cocatalyst and support conditions, control of additives, and the like have been used.

For example, Patent Document 1 (Korean Patent Laid-Open No. 10-2011-0043464) includes the steps of first supporting a part of the cocatalyst on a carrier at a first temperature; At a second temperature lower than the first temperature, secondly supporting the remaining amount of the cocatalyst on the carrier; Supporting the first metallocene compound on the carrier; And a step of supporting a second metallocene compound on the support. The patent document 1 is intended to improve the activity of the catalyst by supporting an excessive amount of a metallocene compound and a cocatalyst, but when the olefin is polymerized using the supported catalyst prepared by the above method, the generation of fines increases and fouling (fouling). ) There was a problem that caused the phenomenon.

As another conventional method, Patent Document 2 (Korean Patent Laid-Open No. 10-2011-0053546) discloses a metallocene in which a Group 4 transition metal compound is supported on a carrier sequentially treated with a silane compound and an ionic compound having an amine group. It describes the supported catalyst composition. According to the method described above, problems in the process such as fouling have been improved, but the content of the metallocene metal component in the carrier is lowered because the support is not performed effectively, and accordingly, there is a limitation in improving the activity of the catalyst. In addition, when the supported catalyst composition further includes a cocatalyst such as an aluminoxane compound, additives such as an unreacted silane compound and an ionic compound that are not supported on the carrier may bind with the aluminoxane compound to cause catalyst aggregation. It may be, and this may cause a decrease in catalytic activity.

KR 1020110043464 A KR 1020110053546 A

The present invention is to solve the above problems, and to provide a supported catalyst for olefin polymerization that has excellent activity and does not cause agglomeration of the catalyst by including a functional group bonded to the surface of a support, an alkyl aluminum, and an aromatic compound in an appropriate molar ratio. The purpose.

Another object of the present invention is to provide a method for producing the supported catalyst and a method for producing a polyolefin using the supported catalyst.

An exemplary embodiment of the present invention, a main catalyst comprising a metallocene-based compound; A cocatalyst comprising an alkyl aluminum and an aluminoxane compound; Two or more polar groups selected from hydroxy group (-OH), amine group (-NH ₂ ), thiol group (-SH), carboxyl group (-COOH) and amide group (-CONH ₂ ) are bonded, and one or more halogen groups Bound aromatic compounds; And a carrier supporting the main catalyst, cocatalyst and an aromatic compound, and having a functional group bonded to the surface thereof, wherein the molar ratio of the functional group to the alkyl aluminum is 0.7 or more and 3.5 or less, and the aromatic compound to the alkyl aluminum It provides a supported catalyst for olefin polymerization, characterized in that the molar ratio of 0.5 to 1.9 or less.

Another exemplary embodiment of the present invention includes the steps of: (1) preparing a carrier having a functional group bonded to the surface; (2) supporting the alkyl aluminum on the carrier prepared according to the step (1); (3) A polar group selected from a hydroxy group (-OH), an amine group (-NH ₂ ), a thiol group (-SH), a carboxyl group (-COOH), and an amide group (-CONH ₂ ) on the carrier after step (2) Supporting the aromatic compound having two or more bonds and one or more halogen groups bonded thereto; (4) supporting a cocatalyst containing an aluminoxane compound on the carrier passed through the step (3); And (5) supporting a main catalyst including a metallocene-based compound on the carrier passed through the step (4), wherein the molar ratio of the functional group to the alkyl aluminum is 0.7 or more and 3.5 or less, and the alkyl aluminum It provides a method for producing a supported catalyst for olefin polymerization, characterized in that the molar ratio of the aromatic compound to is 0.5 or more and 1.9 or less.

Another exemplary embodiment of the present invention provides a method for producing a polyolefin comprising polymerizing an olefin in the presence of the supported catalyst.

According to the present invention, the main catalyst; A cocatalyst comprising an alkyl aluminum and an aluminoxane compound; Aromatic compounds; And a carrier having a functional group bonded to the surface thereof, by controlling the molar ratio of the functional group to the alkylaluminum and the molar ratio of the aromatic compound to the alkylaluminum to a specific ratio, thereby exhibiting excellent activity and preventing catalyst aggregation. No supported catalyst may be provided.

In addition, according to the method for preparing a supported catalyst of the present invention, after the alkyl aluminum is supported on a carrier, an aromatic compound, an aluminoxane compound (cocatalyst) and a main catalyst are sequentially supported thereon. Accordingly, the polar group of the aromatic compound reacts and binds to the alkyl aluminum which is firmly supported by reaction with the functional group on the surface of the carrier, and then the aluminoxane compound is bonded to the other polar group of the aromatic compound, so that each component is firmly supported on the carrier. Can be. When the olefin is polymerized using such a supported catalyst, the supported catalyst may exhibit excellent activity.

In addition, according to the above manufacturing method, catalyst aggregation caused by bonding of alkyl aluminum, aromatic compounds, and aluminoxane compounds to each other without being supported on a carrier can be suppressed, thereby reducing catalyst activity due to catalyst aggregation. Can be resolved.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, the term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent can be substituted, When two or more are substituted, two or more substituents may be the same or different from each other.

In the present specification, the "group 4 transition metal" means titanium (Ti), zirconium (Zr), or hafnium (Hf).

In the present specification, "halogen group" means fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

In addition, the term "alkyl group" described herein refers to a monovalent linear, branched or cyclic saturated hydrocarbon group composed of only carbon and hydrogen atoms, and is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl Group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group And the like, but are not limited thereto.

In addition, the term "alkenyl group" described herein refers to a straight chain, branched chain or branched hydrocarbon group containing at least one carbon-carbon double bond, and includes a methyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group , Hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, and the like, but are not limited thereto.

In addition, the term "alkynyl group" used herein refers to a hydrocarbon group containing one or more carbon-carbon triple bonds, and includes a methynyl group, an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, and Including, but not limited to, an octinyl group.

In addition, the term "aryl group" described herein refers to an organic group derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a single or fused ring system. Specific examples of the aryl group include phenyl group, naphthyl group, biphenyl group, anthryl group, fluorenyl group, phenanthryl group, triphenylenyl group, pyrenyl group, perylenyl group, chrysenyl group, naphthacenyl group, fluorane. Including, but not limited to, tenyl group and the like.

In addition, the term "alkylaryl group" described herein refers to an organic group in which at least one hydrogen of the aryl group is substituted by an alkyl group, and is methylphenyl group, ethylphenyl group, n-propylphenyl group, iso-propylphenyl group, n-butyl Phenyl group, iso-butylphenyl group, tert-butylphenyl group, and the like, but are not limited thereto.

In addition, the term "arylalkyl group" described herein refers to an organic group in which at least one hydrogen of an alkyl group is substituted by an aryl group, and includes, but is not limited to, a phenylpropyl group, a phenylhexyl group, and the like.

The alkyl group and the aryl group in the "alkylaryl group" and "arylalkyl group" may be the same as those of the aforementioned alkyl group and aryl group, but are not limited thereto.

In addition, the term “amido group” described herein refers to an amino group (-NH ₂ ) bonded to a carbonyl group (C=O), and “alkylamido group” refers to at least an amido group at -NH ₂ One hydrogen refers to an organic group substituted with an alkyl group, and "arylamido group" refers to an organic group in which at least one hydrogen in -NH ₂ of the amido group is substituted with an aryl group, and the alkyl group, the aryl group in the alkylamido group The aryl group in the amido group may be the same as the examples of the alkyl group and the aryl group described above, but is not limited thereto.

In addition, the term "alkylidene group" described herein refers to a divalent aliphatic hydrocarbon group in which two hydrogen atoms have been removed from the same carbon atom of the alkyl group, and is an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group , A pentylidene group, and the like, but are not limited thereto.

In the present specification, "alkylene group" refers to a divalent atomic group generated excluding two hydrogen atoms bonded to other two carbon atoms among saturated aliphatic hydrocarbons, and includes a methylene group, an ethylene group, a propylene group, a butylene group, etc. However, it is not limited thereto.

In the present specification, "acetal group" refers to an organic group formed by a bond between an alcohol and an aldehyde, that is, a substituent having two ether (-OR) bonds on one carbon, and a methoxymethoxy group, 1- Methoxyethoxy group, 1-methoxypropyloxy group, 1-methoxybutyloxy group, 1-ethoxyethoxy group, 1-ethoxypropyloxy group, 1-ethoxybutyloxy group, 1-(n -Butoxy)ethoxy group, 1-(iso-butoxy)ethoxy group, 1-(secondary-butoxy)ethoxy group, 1-(tertiary-butoxy)ethoxy group, 1-(cyclohexyloxy) Ethoxy group, 1-methoxy-1-methylmethoxy group, 1-methoxy-1-methylethoxy group, and the like, but are not limited thereto.

In the present specification, "ether group" is an organic group having at least one ether bond (-O-), and 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-phenoxy Ethyl group, 2-(2-methoxyethoxy)ethyl group, 3-methoxypropyl group, 3-butoxypropyl group, 3-phenoxypropyl group, 2-methoxy-1-methylethyl group, 2-methoxy- 2-methylethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-phenoxyethyl group, and the like, but are not limited thereto.

In the present specification, “silyl group” refers to a -SiH ₃ radical derived from silane, and at least one of the hydrogen atoms in the silyl group may be substituted with various organic groups such as an alkyl group and a halogen group. , Specifically, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like, but are not limited thereto.

In the present specification, "hydrocarbyl group" refers to a monovalent organic radical formed by removing a hydrogen atom from a hydrocarbon as a hydrocarbon group consisting only of carbon and hydrogen regardless of the structure such as an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, etc., It may be the same as the example of the organic groups described above, but is not limited thereto.

In the present specification, "group 13 element" means boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (TI).

In the present specification, "group 14 element" means carbon (C), silicon (Si), and germanium (Ge).

In the present specification, the meaning that two or more groups are bonded to each other to form a ring means that alkylene substituted or unsubstituted with a hydrocarbon or hetero ring, or alkenylene substituted or unsubstituted with a hydrocarbon or hetero ring, are bonded to each other to form a ring. It can mean.

Hereinafter, the present invention will be described in detail.

An exemplary embodiment of the present invention, a main catalyst comprising a metallocene-based compound; A cocatalyst comprising an alkyl aluminum and an aluminoxane compound; Two or more polar groups selected from hydroxy group (-OH), amine group (-NH ₂ ), thiol group (-SH), carboxyl group (-COOH) and amide group (-CONH ₂ ) are bonded, and one or more halogen groups Bound aromatic compounds; And a carrier supporting the main catalyst, cocatalyst and an aromatic compound, and having a functional group bonded to the surface thereof, wherein the molar ratio of the functional group to the alkyl aluminum is 0.7 or more and 3.5 or less, and the aromatic compound to the alkyl aluminum It provides a supported catalyst for olefin polymerization, characterized in that the molar ratio of 0.5 to 1.9 or less.

When the molar ratio of the functional group to the alkylaluminum is less than 0.7, the unreacted alkylaluminum, which has not been reacted on the surface of the carrier due to excessive content of the alkylaluminum relative to the functional group on the surface of the carrier, is combined with the aromatic compound and the aluminoxane compound, causing catalyst aggregation. Accordingly, there is a problem that the catalytic activity is lowered. On the other hand, when the molar ratio of the functional group to the alkylaluminum exceeds 3.5 (if the amount of alkylaluminum is insufficient relative to the functional group on the carrier surface), only a small amount of the aromatic compounds that cannot be bonded to the alkylaluminum is bonded to the carrier, and most In a state that cannot be combined, it is combined with the aluminoxane compound to cause agglomeration of the catalyst, thereby causing a problem of lowering the catalytic activity.

In addition, when the molar ratio of the aromatic compound to the alkyl aluminum is less than 0.5, the content of the aluminoxane compound supported on the carrier is small, resulting in a problem of deteriorating catalytic activity. On the other hand, when the molar ratio of the aromatic compound to the alkyl aluminum exceeds 1.9, the unreacted aromatic compound that cannot be bonded to the carrier on which the alkyl aluminum is supported reacts with the aluminoxane compound to cause a catalyst aggregation phenomenon. There is a problem that the activity decreases.

That is, the supported catalyst must satisfy both the molar ratio of the functional group to the alkylaluminum and the molar ratio of the aromatic compound to the alkylaluminum, and if any one of these conditions is not met, the catalytic activity is lowered or the catalyst is aggregated. This causes a problem to occur.

According to an exemplary embodiment of the present invention, the content of the functional group bound to the carrier is 0.3 mmol/g or more and less than 2.0 mmol/g, and the molar ratio of the functional group to the alkyl aluminum is 0.7 or more and 1.5 or less, and the alkyl aluminum to The molar ratio of the aromatic compound may be 0.7 or more and 1.7 or less. When the content of the functional group, the molar ratio of the functional group to the alkylaluminum, and the molar ratio of the aromatic compound to the alkylaluminum are included in the above ranges, a supported catalyst exhibiting more excellent activity during olefin polymerization may be provided.

According to an exemplary embodiment of the present invention, the content of the functional group bound to the carrier is 2.0 mmol/g or more and 5.0 mmol/g or less, and the molar ratio of the functional group to the alkyl aluminum is 0.9 or more and 3.5 or less, and the alkylaluminum is The molar ratio of the aromatic compound may be 0.5 or more and 1.5 or less. When the content of the functional group, the molar ratio of the functional group to the alkylaluminum, and the molar ratio of the aromatic compound to the alkylaluminum are included in the above range, a supported catalyst exhibiting more excellent activity during olefin polymerization may be provided.

As the carrier, inorganic or organic substances used in the production of catalysts in the technical field to which the present invention pertains may be used without limitation. Specifically, the carrier may be a finely ground inorganic solid carrier selected from talc, clay, silica, alumina, silica-alumina, magnesium chloride, or mixtures thereof, or spherical, particulate or finely ground polyethylene, polyvinyl chloride or polystyrene It may be an organic carrier such as.

The particle diameter of the carrier may be 0.1 μm or more and 600 μm or less, and specifically 0.3 μm or more and 100 μm or less. The surface area of the carrier may be 50 m ² /g or more and 1000 m ² /g or less, and specifically 100 m ² /g or more and 500 m ² /g or less. In addition, the pore volume of the carrier may be 0.3cc/g or more and 5.0cc/g or less, specifically 0.5cc/g or more and 3.5cc/g or less, and the pore diameter of the carrier may be 50Å or more and 500Å or less.

In order to combine with other components in the supported catalyst, a functional group is bonded to the surface of the carrier. According to an exemplary embodiment of the present invention, the functional group may include any one selected from the group consisting of a silanol group, a hydroxy group, an amine group, and a thiol group. The functional group bonded to the carrier is a group that forms a standard sigma bond in the reaction with a catalytic material or an aromatic compound (International Union of Pure and Applied Chemistry).

According to an exemplary embodiment of the present invention, the carrier may include silica having a silanol group (Si-OH) content of 0.3 mmol/g or more and 5.0 mmol/g or less. When such silica is used as a carrier, it is excellent in reactivity with alkyl aluminum or aromatic compounds, and thus a supported catalyst in which they are firmly supported on a silica carrier can be provided.

According to an exemplary embodiment of the present invention, the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tri Cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide and dimethyl aluminum ethoxide It may include at least one selected from the group consisting of seeds. In consideration of the activity of the metallocene-based compound, at least one selected from the group consisting of trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum may be used.

According to an exemplary embodiment of the present invention, the aluminoxane compound may include a compound including a unit represented by Formula 1 below.

Formula 1

In Formula 1,

b is an integer of 2 or more,

Al is aluminum,

O is oxygen,

Ra is a halogen group; Or a halogen group substituted or unsubstituted (C ₁ -C ₂₀ ) Hydrocarbyl group.

The'unit' represented by Formula 1 is a structure in which n structures in [] are connected in the compound, and when the unit represented by Formula 1 is included, other structures in the compound are not particularly limited, and the repeating unit of Formula 1 May be a cluster type, for example, a spherical compound connected to each other.

The aluminoxane compound is included in the catalyst composition together with the metallocene compound and serves to activate the metallocene compound. Specifically, in order for the metallocene-based compound to become an active catalyst component used in olefin polymerization, the ligand (Q ¹ Q ² ) in the metallocene-based compound is extracted to cationize the central metal (M) and a counterion having weak binding strength. That is, the aluminoxane compound that can act as an anion acts together as a cocatalyst.

Specifically, the aluminoxane compound may include at least one alkylaluminoxane selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and the activity of the metallocene-based compound Considering the methyl aluminoxane may be used.

The aromatic compound is a compound containing two or more polar groups and one or more halogen groups, and the two or more polar groups act as a bridge between the alkyl aluminum and the aluminoxane compound to prevent the aluminoxane compound from falling off the carrier. In addition, it plays a role of preventing dimerization of the catalyst by increasing the gap between the catalysts.

In addition, the halogen group bonded to the aromatic compound may help improve catalytic activity. Specifically, the Bronsted acid aromatic compound substituted with a halogen group formed by reaction with an alkyl aluminum and an aluminoxane compound serves to increase the activation of the catalyst. Accordingly, in the case of the supported catalyst including the aromatic compound, higher catalytic activity may be exhibited as compared with other supported catalysts in which the metal component of the metallocene supported in the support and the aluminum component of the cocatalyst are similar.

The aromatic compound may include at least one of the compounds represented by Formulas 2 to 4 below.

Formula 2

In Formula 2,

n is an integer of 2 or more, m is an integer of 1 or more,

X ¹ is the same as or different from each other, and each independently a hydroxy group (-OH); Amine group (-NH ₂ ); Thiol group (-SH); It is a carboxyl group (-COOH) or an amide group (-CONH ₂ ),

At least one selected from R ¹ is a halogen group, the rest are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ )alkyl group; (C ₂ -C ₂₀ ) alkenyl group; (C ₂ -C ₂₀ ) alkynyl group; (C ₆ -C ₂₀ ) aryl group; (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl group; (C ₁ -C ₂₀ )alkylamido group; (C ₆ -C ₂₀ ) Arylamido group; Or (C ₁ -C ₂₀ ) alkylidene group,

Formula 3

In Formula 3,

p, q, r and s are each an integer of 1 or more,

X ² and X ³ are the same as or different from each other, and each independently a hydroxy group (-OH); Amine group (-NH ₂ ); Thiol group (-SH); Carboxyl group (-COOH); Or an amide group (-CONH ₂ ),

At least one selected from R ² and R ⁴ is a halogen group, the rest are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ )alkyl group; (C ₂ -C ₂₀ ) alkenyl group; (C ₂ -C ₂₀ ) alkynyl group; (C ₆ -C ₂₀ ) aryl group; (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl group; (C ₁ -C ₂₀ )alkylamido group; (C ₆ -C ₂₀ ) Arylamido group; Or (C ₁ -C ₂₀ ) alkylidene group,

R ³ is direct linkage; Or a substituted or unsubstituted alkylene group,

Formula 4

In Formula 4,

t, u, v, w and y are each an integer of 1 or more,

X ⁴ and X ⁵ are the same as or different from each other, and each independently a hydroxy group (-OH); Amine group (-NH ₂ ); Thiol group (-SH); Carboxyl group (-COOH); Or an amide group (-CONH ₂ ),

R ⁵ and R ⁷ are the same as or different from each other, and each independently hydrogen; Halogen group; (C ₁ -C ₂₀ )alkyl group; (C ₂ -C ₂₀ ) alkenyl group; (C ₂ -C ₂₀ ) alkynyl group; (C ₆ -C ₂₀ ) aryl group; (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl group; (C ₁ -C ₂₀ )alkylamido group; (C ₆ -C ₂₀ ) Arylamido group; Or (C ₁ -C ₂₀ )alkylidene group;

At least one selected from R ⁶ and R ⁸ is a halogen group; Or a linear or branched (C ₁ -C ₂₀ )alkyl group substituted with at least one halogen group, and the remainder is hydrogen; (C ₁ -C ₂₀ )alkyl group; (C ₂ -C ₂₀ ) alkenyl group; (C ₂ -C ₂₀ ) alkynyl group; (C ₆ -C ₂₀ ) aryl group; (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl group; (C ₁ -C ₂₀ )alkylamido group; (C ₆ -C ₂₀ ) Arylamido group; Or (C ₁ -C ₂₀ ) alkylidene group.

In this case, the multifunctional aromatic compounds represented by Formulas 3 and 4 may have a left-right symmetric structure based on -R ³ -and -C-, respectively.

Specifically, at least one selected from R ¹ may be fluorine (F), at least one selected from R ² and R ⁴ may be fluorine (F), and at least one selected from R ⁶ and R ⁸ This may be fluorine (F). In the case of the aromatic compound having fluorine as a substituent as described above, the formation of Bronsted acid may be more actively progressed by reaction with the alkylaluminum and aluminoxane compound, thereby providing a highly active supported catalyst.

More specifically, the aromatic compound may include at least one of the compounds represented by Formulas 5 to 7 below. In the case of an aromatic compound having such a structure, two pairs of oxygen or nitrogen non-shared electrons contained in the compound form a coordination bond or a covalent bond between the alkyl aluminum and the aluminoxane compound, thereby helping the catalyst component to be supported firmly. have.

Formula 5

Formula 6

Formula 7

The metallocene-based compound may be represented by Formula 8 below.

Formula 8

In Formula 8,

M is a Group 4 transition metal,

Q ¹ and Q ² are the same as or different from each other, and each independently a halogen group; (C ₁ -C ₂₀ )alkyl group; (C ₂ -C ₂₀ ) alkenyl group; (C ₂ -C ₂₀ ) alkynyl group; (C ₆ -C ₂₀ ) aryl group; (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl group; (C ₁ -C ₂₀ )alkylamido group; (C ₆ -C ₂₀ ) Arylamido group; Or (C ₁ -C ₂₀ ) alkylidene group,

A is a group 14 element,

R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ )alkyl group unsubstituted or substituted with an acetal group or an ether group; (C ₂ -C ₂₀ )alkenyl group unsubstituted or substituted with an acetal group or an ether group; (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group unsubstituted or substituted with an acetal group or an ether group; (C ₆ -C ₂₀ ) Aryl (C ₁ -C ₂₀ ) alkyl group unsubstituted or substituted with an acetal group or an ether group; Or an acetal group or an ether group substituted or unsubstituted (C ₁ -C ₂₀ )silyl group,

Two or more groups of R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may be bonded to each other to form an aliphatic ring or an aromatic ring,

Two or more groups of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ may be bonded to each other to form an aliphatic ring or an aromatic ring,

R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ )alkyl group unsubstituted or substituted with an acetal group or an ether group; (C ₂ -C ₂₀ )alkenyl group unsubstituted or substituted with an acetal group or an ether group; Or an acetal group or an ether group substituted or unsubstituted (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl group.

The metallocene compound represented by Chemical Formula 8 has an ansa-metallocene structure including a cyclopentadienyl ligand and an indenyl ligand connected to each other by a bridge group containing an element of Group 14 on the periodic table. .

Specifically, A may be carbon (C) or silicon (Si), and R ¹³ and R ¹⁴ may each independently be hydrogen or a methyl group. In Formula 8, -AR ¹³ R ¹⁴ -serves as a bridge between two ligands, and the two ligands are crosslinked by -AR ¹³ R ¹⁴ -to exhibit excellent stability.

In addition, the Q ¹ and Q ² are each independently a halogen group selected from F, Cl, Br and I; Methyl group; Or it may be an ethyl group. In this case, the methyl group and the ethyl group may be substituted or unsubstituted with an acetal group or an ether group. In addition, in the metallocene compound represented by Formula 8, M positioned between the two ligands in a bonded form with Q ¹ Q ² is Ti, Zr, or Hf; Is Zr or Hf; Or may be Zr.

An exemplary embodiment of the present invention, (1) preparing a carrier having a functional group bonded to the surface; (2) supporting the alkyl aluminum on the carrier prepared according to the step (1); (3) A polar group selected from a hydroxy group (-OH), an amine group (-NH ₂ ), a thiol group (-SH), a carboxyl group (-COOH), and an amide group (-CONH ₂ ) on the carrier after step (2) Supporting the aromatic compound having two or more bonds and one or more halogen groups bonded thereto; (4) supporting a cocatalyst containing an aluminoxane compound on the carrier passed through the step (3); And (5) supporting a main catalyst including a metallocene-based compound on a carrier that has undergone the step (4) above. It provides a method for producing a supported catalyst for olefin polymerization comprising. At this time, the molar ratio of the functional group to the alkyl aluminum is 0.7 or more and 3.5 or less, and the molar ratio of the aromatic compound to the alkyl aluminum is 0.5 or more and 1.9 or less.

The step (1) may include preparing a carrier containing a functional group of 0.3 mmol/g or more and 5 mmol/g or less by firing the carrier at a temperature of 150° C. or more and 700° C. or less. The firing temperature may affect the content and form of functional groups on the surface of the carrier, and this may affect the content of alkylaluminum and aromatic compounds that can react with the carrier. In consideration of this point, when the firing temperature is controlled within the above range, the loading efficiency can be improved.

And, in the step (3), one of the polar groups of the aromatic compound may react and bond to the alkyl aluminum that is firmly supported by reaction with the functional group on the surface of the carrier according to the step (2). At this time, some of the aromatic compounds not bonded to the alkylaluminum may be bonded by reacting directly with the carrier.

In the step (4), the other polar group of the aromatic compound bonded to the alkyl aluminum supported on the carrier through the step (3) or directly bonded to the surface of the carrier may react with the aluminoxane compound.

In any one or more of the steps (2) to (5), a solvent may be used in the supporting process, and as the solvent, an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated aliphatic hydrocarbon-based solvent, or a mixture thereof may be used. have. Here, the aliphatic hydrocarbon-based solvent may include, but is not limited to, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, and the like. In addition, examples of the aromatic hydrocarbon-based solvent include, but are not limited to, benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, and the like. In addition, the halogenated aliphatic hydrocarbon-based solvent may include, but is not limited to, dichloromethane, trichloromethane, dichloroethane, trichloroethane, and the like.

In addition, the supported in steps (2) to (5) may be carried out at a temperature of -70°C or more and 200°C or less, and specifically, -50°C or more and 150°C or less, or 0°C or more and 100°C or less. What is carried out is advantageous in terms of the efficiency of the carrying process.

Another exemplary embodiment of the present invention provides a method for producing a polyolefin comprising polymerizing an olefin in the presence of the supported catalyst.

The olefin monomers are 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, nobonadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5- Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, or mixtures thereof.

The polymerization reaction of the olefin monomer may be carried out in a slurry phase, a solution phase, a gas phase, or a bulk phase. When the polymerization reaction is carried out in a liquid phase or a slurry phase, a solvent or an olefin monomer itself may be used as a medium.

Solvents usable in the polymerization reaction include aliphatic hydrocarbon solvents such as butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, methylcyclopentane, and cyclohexane; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, and chlorobenzene; Halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane and 1,2-dichloroethane; Or it may be a mixture thereof.

At this time, the amount of the supported catalyst used may be determined within a range in which the polymerization reaction of the monomer can sufficiently occur depending on the slurry, liquid, gas phase, or bulk process, and thus is not particularly limited. However, in view of the catalyst activity, the amount of the supported catalyst is based on the concentration of the central metal (M) in the metallocene compound to the metal contained in the catalyst per unit volume (L) of an olefin monomer, 10 ^{- 8} mol / L may be up to more than 1 mol / L, particularly 10 ^{- 7} or mol / L 10 ^{- 1} mol / L or less, or ¹⁰ to more than ⁷ mol / L 10 ^- can be not more than ² mol / L.

The polymerization reaction may be performed in a batch type, semi-continuous type, or continuous type reaction.

At this time, the polymerization temperature and pressure conditions are not particularly limited, and may be determined in consideration of the efficiency of the polymerization reaction according to the type of reaction to be applied and the type of reactor. The polymerization temperature may be 40°C or more and 150°C or less, and specifically 60°C or more and 100°C or less. The polymerization reaction pressure may be 1 atm or more and 100 atm or less, and specifically 5 atm or more and 50 atm or less.

Hereinafter, examples will be described in detail to illustrate the present invention in detail.

Except where otherwise noted, all ligand and catalyst synthesis experiments were performed using standard Schlenk and glovebox technology under a nitrogen atmosphere, and the organic solvent used in all reactions was refluxed under sodium metal and benzophenone to Was removed and distilled immediately before use. ¹ H-NMR analysis of the synthesized ligand and catalyst was performed at room temperature using Bruker 300 MHz.

The polymerization solvent was used after passing through a tube filled with molecular sieve 5A and activated alumina and bubbling with high-purity nitrogen to sufficiently remove moisture, oxygen and other catalyst poison substances. All polymerizations were carried out after injecting the required amount of solvent and monomers to be polymerized into a high-pressure reactor (Autoclave) completely blocked from outside air, and then adding a catalyst.

Manufacturing example 1: transition metal compound ( Tetramethylcyclopentadienyl Dimethylsilyl 2- methyl -4-(4-t-butylphenyl)indenyl zirconium Dichloride ( tetramethylcyclopentadienyl Synthesis of dimethylsilyl 2-methyl-4-(4-tert-butylphenyl)indenyl Zr dichloride))

[Step 1: Synthesis of dimethyl tetramethylcyclopentadienyl chlorosilane]

In a 2L flask, 600 ml of tetrahydrofuran and 50 g of tetramethylcyclopentadiene were added, and 170 ml of n-butyllithium (n-BuLi, 2.5M hexane solution) was slowly added dropwise under nitrogen atmosphere and -10°C conditions. Then, the reaction solution was obtained by reacting with stirring at room temperature for 12 hours. After lowering the temperature of the reaction solution to -10°C again, 170 g of dimethyl dichlorosilane was added, followed by reaction while stirring at room temperature for 12 hours, and then dried in vacuo to obtain a solid reactant. 500 ml of n-hexane was added to the solid reactant to dissolve the solid reactant, filtered through a Celite filter, and then the filtered solution was vacuum-dried to obtain 70 g of dimethyl tetramethylcyclopentadienyl chlorosilane in the form of a yellow oil. (Yield: 80%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.235 (s, 6H), 1.81 (s, 6H), 1.97 (s, 6H), 3.07 (s, 1H)

[Step 2: Synthesis of dimethyl tetramethylcyclopentadienyl 2-methyl-4-(4-tert-butylphenyl)indenyl silane). [Step 2: Synthesis of dimethyl tetramethylcyclopentadienyl 2-methyl-4-(4-t-butylphenyl) indenyl silane]

A flask in which 200 ml of toluene, 40 ml of tetrahydrofuran and 50 g of 2-methyl-4-(4-t-butylphenyl) inden were added was cooled to -10°C, and then n-BuLi (2.5M hexane solution) was added to the flask. ) 76 ml was slowly added dropwise and stirred at room temperature for 12 hours to obtain a reaction solution. After lowering the temperature of the reaction solution to -10 °C again, 38 g of dimethyl tetramethylcyclopentadienyl chlorosilane synthesized in step 1 was added thereto, and reacted with stirring at room temperature for 12 hours. When the reaction was completed, 400 ml of water was added, stirred at room temperature for 1.5 hours, extracted with toluene, dried in vacuo, and dimethyl tetramethylcyclopentadienyl 2-methyl-4-(4-t) in the form of a yellow oil. 80 g of -butylphenyl)indenyl silane was obtained (95% yield).

¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.2-0.23 (d, 6H), 1.44 (s, 9H), 1.91 (s, 6H), 2.05-2.08 (d, 6H), 2.29 (s, 3H) , 2.41(s, 1H), 3.76(s, 1H), 6.87(s, 1H)

[Step 3: Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-t-butylphenyl) indenyl zirconium dichloride (tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-tert-butylphenyl) indenyl Zr dichloride) ) Synthesis]

Dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenyl silane 50 g, 300 ml of toluene and 100 ml of diethyl ether, synthesized according to the above step 2, were added to a flask and heated to -10°C. After cooling, 90 ml of n-BuLi (2.5M hexane solution) was slowly added dropwise. When the dropwise addition was completed, the reaction temperature was raised to room temperature, stirred for 48 hours, and then filtered. The obtained filtrate was vacuum-dried to obtain 40 g (yield 80%) of tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-t-butylphenyl)indenyl dilithium salt in solid form, without purification. It was used immediately in the next reaction.

40 g of the tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-t-butylphenyl)indenyl dilithium salt, 40 ml of toluene and 10 ml of ether were added to flask #1 and stirred. In flask #2, a mixture of 30 ml of toluene and 20 g of ZrCl ₄ was prepared. The mixture solution of flask #2 was slowly added dropwise to flask #1 with a cannular, and then stirred at room temperature for 24 hours. After the stirring was completed, the mixture was vacuum-dried, extracted with 500 ml of methylene chloride, filtered through a Celite filter, and the filtrate was vacuum-dried. The solid obtained by vacuum drying was washed with 50 ml of a mixture of methylene chloride and n-hexane (volume ratio = 1:3), and then dried in vacuum to form a yellow solid tetramethylcyclopentadienyl dimethylsilyl 2-methyl. 32 g of -4-(4-t-butylphenyl)indenyl zirconium dichloride (hereinafter referred to as'transition metal compound-1') was obtained (yield 60%). The formula of the transition metal compound-1 is as follows.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.09 (s, 3H), 1.202 (s, 3H), 1.346 (s, 9H), 1.887-1.911 (d, 6H), 1.989 (s, 3H), 2.075 (s, 3H), 2.278 (s, 3H), 7.0-7.628 (m, 8H)

Preparation Example 2: Preparation of supported catalyst

In a glove box, 2.0 g of silica (manufacturer: AGC, product name: L-303-F) calcined at 600° C. was put in a Schlenk flask (100 ml), and 10 ml of anhydrous toluene solution was added thereto to obtain a silica dispersion. At this time, silanol (Si-OH) is bonded to the surface of the fired silica as a functional group, and the content of silanol per 1 g of silica is 0.6 mmol/g.

Then, 1.2 mmol of trimethylaluminum (TMA) was added dropwise to the silica dispersion and reacted at room temperature for 30 minutes, and then a solution in which 1.2 mmol of tetrafluorohydroquinone (THQ) was dissolved in 5 ml of toluene was slowly added dropwise and reacted at room temperature for 1 hour. Then, methylaluminoxane (10% by weight solution of methylaluminoxane in toluene, manufacturer: Grace) 9ml (13.5mmol based on Al) was slowly added dropwise at 0° C. and reacted with stirring for 1 hour. After completion of the reaction, the obtained reaction product was heated to 70°C, stirred for 3 hours, and cooled to 25°C. Hereinafter, the reaction product obtained by the cooling is referred to as'reactant-1'. At this time, the amount of TMA and THQ added per 1 g of silica is 0.6 mmol, respectively, and these values are described in Table 1 below.

Separately, 100 μmol of the transition metal compound-1 synthesized in a glove box was put into another 100 ml Schlenk flask, taken out of the glove box, and 10 ml of anhydrous toluene solution was added.

Subsequently, a solution containing the transition metal compound-1 was slowly added to the reactant-1 at 10° C., and then heated to 70° C. and stirred for 1 hour, cooled to 25° C., and stirred for 2 hours. Then, the resulting reaction product was washed with a sufficient amount of toluene and hexane to remove unreacted aluminum compounds. Then, it was dried in vacuum to obtain a supported catalyst-1.

Preparation Examples 3 to 7 and Preparation Examples 14 to 16: Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in Preparation Example 2, except that the amounts of TMA and THQ added per 1 g of silica were adjusted as described in Table 1 below. And, the supported catalyst obtained according to each preparation example was named as shown in Table 1 below.

Preparation Example 8: Preparation of supported catalyst

The above preparation example except that 2g of silica calcined at 200°C, 3.5mmol of TMA, 3.5mmol of THQ, and methylaluminoxane (10% by weight solution of methylaluminoxane in toluene, manufacturer: Grace) 11ml (16.5mmol based on Al) were used. Prepared in the same manner as in 2 to obtain a supported catalyst-7. At this time, the content of silanol per 1 g of the fired silica is 3.5 mmol/g, and the content of TMA and THQ added per 1 g of silica is 1.75 mmol, respectively.

Preparation Examples 9 to 13 and Preparation Examples 17 to 19: Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in Preparation Example 8, except that the contents of TMA and THQ added per 1 g of silica were adjusted as described in Table 1 below. And, the supported catalyst obtained according to each preparation example was named as shown in Table 1 below.

Si-OH (mmol/g) TMA(mmol) THQ(mmol) Si-OH/TMA ^{1 )} THQ/TMA ^{2 )} Supported catalyst Manufacturing Example 2 0.6 0.6 0.6 1.00 1.00 Supported catalyst-1 Manufacturing Example 3 0.6 0.5 0.6 1.20 1.20 Supported catalyst-2 Manufacturing Example 4 0.6 0.7 0.6 0.86 0.86 Supported catalyst-3 Manufacturing Example 5 0.6 0.6 0.3 1.00 0.50 Supported catalyst-4 Manufacturing Example 6 0.6 0.6 0.75 1.00 1.25 Supported catalyst-5 Manufacturing Example 7 0.6 0.6 One 1.00 1.67 Supported catalyst-6 Manufacturing Example 8 3.5 1.75 1.75 2.00 1.00 Supported catalyst-7 Manufacturing Example 9 3.5 One 1.75 3.50 1.75 Supported catalyst-8 Manufacturing Example 10 3.5 2 1.75 1.75 0.88 Supported catalyst-9 Manufacturing Example 11 3.5 2.5 1.75 1.40 0.70 Supported catalyst-10 Manufacturing Example 12 3.5 1.75 One 2.00 0.57 Supported Catalyst-11 Manufacturing Example 13 3.5 1.75 1.5 2.00 0.86 Supported catalyst-12 Manufacturing Example 14 0.6 0.2 0.6 3.00 3.00 Supported catalyst-13 Manufacturing Example 15 0.6 One 0.6 0.60 0.60 Supported catalyst-14 Manufacturing Example 16 0.6 0.6 1.5 1.00 2.50 Supported catalyst-15 Manufacturing Example 17 3.5 4 1.75 0.88 0.44 Supported catalyst-16 Manufacturing Example 18 3.5 1.75 3.5 2.00 2.00 Supported catalyst-17 Manufacturing Example 19 3.5 0.8 1.75 4.38 2.19 Supported Catalyst-18

1) "The ratio of the number of moles of silanol (Si-OH) to the number of moles of trimethylaluminum (TMA)" is shown per 1 g of silica.

2) "The ratio of the number of moles of tetrafluorohydroquinone (THQ) to the number of moles of trimethylaluminum (TMA)" per 1 g of silica is shown.

Example 1: Preparation of polypropylene resin

At room temperature, the inside of a stainless steel autoclave (autoclave, high pressure reactor) having an internal capacity of 2L was completely replaced with nitrogen. While maintaining nitrogen purging, 2 ml of triisobutylaluminum (1M solution in hexane) and 500 g of propylene were injected into the reactor, and then 50 mg of the supported catalyst-1 was dispersed in 5 ml of hexane using high-pressure nitrogen. And put in. Thereafter, polymerization was performed at 70° C. for 60 minutes. After completion of polymerization, the reactor was cooled to room temperature, and then unreacted propylene was removed through a discharge line to obtain a white powdery solid. The obtained white solid powder was dried for 15 hours or more while heating at 80° C. using a vacuum oven to prepare a final polypropylene resin.

Examples 2 to 12 and Comparative Examples 1 to 6: Preparation of polypropylene resin

A polypropylene resin was prepared in the same manner as in Example 1, except that the supported catalyst shown in Table 2 below was used instead of the supported catalyst-1.

<Evaluation method>

1. active

After measuring the weight (kg) of the polymer prepared for 1 hour per weight (g) of the catalyst used, the activity of the catalyst was calculated according to the following formula (1).

Activity (kg/gCat.hr) = amount of polypropylene produced (kg/hr) / amount of catalyst (g)… (One)

2. Whether catalyst is aggregated

After sieving the supported catalysts prepared according to Preparation Examples 2 to 19 with a US standard 120 mesh (125 μm) sieve, the presence or absence of a supported catalyst that did not pass through the standard sieve was evaluated to evaluate whether the catalyst was aggregated. . In Table 1 below, "x" means that the supported catalyst has passed all of the standard sieve, and "○" means that the unpassed supported catalyst remains in the standard sieve after sieving, resulting in catalyst aggregation.

Supported catalyst Active (kg/gCat.hr) Whether catalyst is aggregated Example 1 Supported catalyst-1 11.4 × Example 2 Supported catalyst-2 10.9 × Example 3 Supported catalyst-3 10.5 × Example 4 Supported catalyst-4 6.8 × Example 5 Supported catalyst-5 10.7 × Example 6 Supported catalyst-6 9.7 × Example 7 Supported catalyst-7 11.7 × Example 8 Supported catalyst-8 6.8 × Example 9 Supported catalyst-9 10 × Example 10 Supported catalyst-10 9.1 × Example 11 Supported Catalyst-11 8.3 × Example 12 Supported catalyst-12 10.3 × Comparative Example 1 Supported catalyst-13 2.2 ○ Comparative Example 2 Supported catalyst-14 2.8 ○ Comparative Example 3 Supported catalyst-15 3.1 ○ Comparative Example 4 Supported catalyst-16 3.3 ○ Comparative Example 5 Supported catalyst-17 3.7 ○ Comparative Example 6 Supported Catalyst-18 1.9 ○

Looking at Table 2, in the case of the supported catalysts prepared by adjusting the "molar ratio of Si-OH to TMA" and "molar ratio of THQ to THQ" according to the present invention (Preparation Examples 2 to 13), catalyst aggregation did not occur. In addition, in Examples 1 to 12 in which polypropylene was prepared using these, it can be seen that the supported catalyst exhibits high activity.

On the other hand, Preparation Example 15 in which the molar ratio of Si-OH to TMA is less than 0.7, Preparation Example 19 in which the molar ratio of Si-OH to TMA exceeds 3.5, Preparation Example 17 in which the molar ratio of THQ to TMA is less than 0.5, for TMA In the case of the supported catalysts prepared according to Preparation Examples 14, 16, 18 and 19 in which the molar ratio of THQ exceeded 1.9, catalyst aggregation occurred, and in Comparative Examples 1 to 6 in which polypropylene was prepared using these, the supported catalyst was remarkably It can be seen that it shows low activity.

As described above, although the present invention has been described by a limited embodiment, the present invention is not limited thereto, and the technical spirit of the present invention and the following description by those of ordinary skill in the art to which the present invention pertains. It goes without saying that various modifications and variations are possible within the equal range of the claims to be made.

Claims (9)

A main catalyst containing a metallocene compound;
A cocatalyst comprising an alkyl aluminum and an aluminoxane compound;
Two or more polar groups selected from hydroxy group (-OH), amine group (-NH ₂ ), thiol group (-SH), carboxyl group (-COOH) and amide group (-CONH ₂ ) are bonded, and one or more halogen groups Bound aromatic compounds; And
Including; a carrier supporting the main catalyst, the cocatalyst and the aromatic compound, and a functional group is bonded to the surface,
The molar ratio of the functional group to the alkyl aluminum is 0.7 or more and 3.5 or less,
A supported catalyst for olefin polymerization, wherein the molar ratio of the aromatic compound to the alkyl aluminum is 0.5 or more and 1.9 or less. The method according to claim 1,
The content of the functional group bound to the carrier is 0.3 mmol/g or more and less than 2.0 mmol/g, the molar ratio of the functional group to the alkyl aluminum is 0.7 or more and 1.5 or less, and the molar ratio of the aromatic compound to the alkyl aluminum is 0.7 or more 1.7 A supported catalyst for olefin polymerization, characterized in that the following. The method according to claim 1,
The content of the functional group bonded to the carrier is 2.0 mmol/g or more and 5.0 mmol/g or less, the molar ratio of the functional group to the alkyl aluminum is 0.9 or more and 3.5 or less, and the molar ratio of the aromatic compound to the alkyl aluminum is 0.5 or more 1.5 A supported catalyst for olefin polymerization, characterized in that the following. The method according to claim 1,
The functional group, characterized in that it comprises any one selected from the group consisting of silanol group, hydroxy group, amine group and thiol group, supported catalyst for olefin polymerization. The method according to claim 1,
The carrier is a supported catalyst for olefin polymerization, characterized in that it comprises silica having a silanol group (Si-OH) content of 0.3 mmol/g or more and 5.0 mmol/g or less. The method according to claim 1,
The alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloroaluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, tri At least one selected from the group consisting of isopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, and dimethyl aluminum ethoxide. A supported catalyst for olefin polymerization, characterized in that it contains species. The method according to claim 1,
The aluminoxane compound is a supported catalyst for olefin polymerization, characterized in that it comprises a compound containing a unit represented by the following formula (1):
Formula 1

In Formula 1,
b is an integer of 2 or more,
Al is aluminum,
O is oxygen,
Ra is a halogen group; Or a halogen group substituted or unsubstituted (C ₁ -C ₂₀ ) Hydrocarbyl group. As a method for producing a catalyst for olefin polymerization according to any one of claims 1 to 7,
(1) preparing a carrier having a functional group bonded to the surface;
(2) supporting the alkyl aluminum on the carrier prepared according to the step (1);
(3) A polar group selected from a hydroxy group (-OH), an amine group (-NH ₂ ), a thiol group (-SH), a carboxyl group (-COOH), and an amide group (-CONH ₂ ) on the carrier after step (2) Supporting the aromatic compound having two or more bonds and one or more halogen groups bonded thereto;
(4) supporting a cocatalyst containing an aluminoxane compound on the carrier passed through the step (3); And
(5) supporting a main catalyst containing a metallocene-based compound on the carrier passed through the step (4); Including,
The molar ratio of the functional group to the alkyl aluminum is 0.7 or more and 3.5 or less,
The method for producing a supported catalyst for olefin polymerization, characterized in that the molar ratio of the aromatic compound to the alkyl aluminum is 0.5 or more and 1.9 or less. A method for producing a polyolefin comprising the step of polymerizing an olefin in the presence of a supported catalyst according to any one of claims 1 to 7.