KR101903245B1 - Polyolefin catalyst and preparing method of polyolefin using same - Google Patents

Abstract

A catalyst having a high molecular weight using a novel metallocene catalyst and a process for producing a polyolefin using the same. The present invention provides a transition metal compound represented by the following formula (1).
[Chemical Formula 1]

Description

TECHNICAL FIELD [0001] The present invention relates to a polyolefin catalyst and a method for producing the polyolefin using the same,

The present invention relates to a polyolefin catalyst and a process for producing a polyolefin using the same, and more particularly, to a process for producing a polyolefin having a high molecular weight using a metallocene catalyst.

Conventionally, the preparation of olefin polymers has generally employed the so-called Ziegler-Natta catalyst system consisting of the main catalyst component of a titanium or vanadium compound and the cocatalyst component of an alkyl aluminum compound. However, although the Ziegler-Natta catalyst system is a multi-active catalyst having a plurality of active species, the molecular weight distribution of the polymer is broad, but the composition distribution of the comonomer is not uniform.

Since the metallocene catalyst system composed of the metallocene compound of the transition metal of the periodic table group 4, such as titanium, zirconium, and hafnium, and methylaluminoxane, which is a cocatalyst, is a homogeneous catalyst having a single catalytic active site, - Natta catalyst system, the molecular weight distribution of the polymer is narrow, the composition distribution of the comonomer is uniform, and the characteristics of the polymer can be changed according to the modification of the ligand structure of the catalyst.

On the other hand, the metallocene catalyst is more expensive than the conventional Ziegler-Natta catalyst but has high activity and is economically valuable. Especially, since the reactivity to the comonomer is good, the amount of the comonomer There is an advantage that the incorporated polymer can be obtained with high activity. Even if the same amount of comonomer is used, a polymer having a higher molecular weight with a more uniform composition distribution can be produced, so that it can be applied as a film or an elastomer having good physical properties. In addition, since the wax-like extract of low molecular weight is hardly generated in the copolymer, it can be applied to applications requiring medical hygiene.

In general, it is known that an anthra-metallocene compound, which is a transition metal compound containing two bridged catalysts, that is, two ligands connected to each other by a bridge group, is excellent in reactivity with respect to comonomers, and is useful for preparing olefin homopolymers or copolymers Have been used as catalysts. In particular, it is known that an anisma-metallocene compound comprising a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, thereby controlling the microstructure of the polypropylene.

Despite the development of such catalysts, there is a need in the art to develop olefin polymerization methods using catalysts that exhibit more effective catalysts, more improved polymerization performance, and especially, catalysts with higher molecular weight.

[Prior Patent Literature]

- Korean Patent Publication No. 2015-0029368 (2015.03.18)

Korean Laid-Open Patent No. 2014-0133343 (November 19, 2014)

- U.S. Patent No. 7226886 (Jun. 2007)

- European Patent No. 0416815 (Mar. 13, 1991)

- European Patent No. 0420436 (Apr. 03, 1991)

- European Patent No. 0842939 (May 20, 1998)

The present invention provides a catalyst having a high molecular weight using a novel metallocene catalyst and a process for producing a polyolefin using the catalyst.

In order to solve the above problems, the present invention provides a transition metal compound represented by the following general formula (1).

[Chemical Formula 1]

(In formula 1, M is a Group 4 transition metal; Q ¹ and Q ² is halogen, (C ₁ -C ₂₀ each independently represent) alkyl, (C ₂ -C ₂₀₎ alkenyl, (C ₂ -C ₂₀₎ alkynyl, (C ₆ -C ₂₀₎ aryl, (C ₁ -C ₂₀₎ alkyl (C ₆ -C ₂₀₎ aryl, (C ₆ -C ₂₀₎ aryl (C ₁ -C ₂₀₎ alkyl, (C ₁ - C ₂₀₎ alkyl, amido, (C ₆ -C ₂₀₎ aryl amido or (C ₁ -C ₂₀₎ alkylidene and; R ^1, R ^2, R ³ and R ⁴ are each independently hydrogen, acetal, ketal or (C ₁ -C ₂₀ ) alkyl with or without an ether group, (C ₂ -C ₂₀ ) alkenyl with or without an acetal, ketal or ether group, (C ₂ -C ₂₀ ) ₁ -C ₂₀₎ alkyl (C ₆ -C ₂₀₎ aryl, acetal, ketal or ether which does not contain or contains a group (C ₆ -C ₂₀₎ aryl (C ₁ -C ₂₀₎ alkyl, acetal, ketal or ether groups (C ₁ -C ₂₀ ) silyl, with or without R ¹ , R ² , R ³ and R ⁴ Two or more of which may be linked to each other to form an aliphatic ring or aromatic ring; R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Or (C ₁ -C ₂₀ ) silyl, with or without an acetal, ketal or ether group; R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ Two or more of which may be linked to each other to form an aliphatic ring or aromatic ring.

And at least one of R ¹ , R ² , R ³ and R ⁴ is hydrogen and the others are independently selected from the group consisting of (C ₁ -C ₂₀ ) alkyl, (C ₂ -C ₂₀ ) alkenyl, (C ₆ -C ₂₀ ) C ₂₀₎ aryl, or an acetal, which does not include or include a ketal or ether (C ₁ -C ₂₀₎ may be substituted with a silyl group; At least ^{two of} R ¹ , R ² , R ³ and R ⁴ may be connected to each other to form an aliphatic ring or aromatic ring.

Wherein at least one of R ¹ , R ² , R ³ and R ⁴ is hydrogen and the others are independently substituted with (C ₁ -C ₂₀ ) alkyl.

And at least two of R ¹ , R ² , R ³ and R ⁴ are hydrogen and the others are independently selected from the group consisting of (C ₁ -C ₂₀ ) alkyl, (C ₂ -C ₂₀ ) alkenyl, (C ₆ -C ₂₀ ) C ₂₀₎ aryl, or an acetal, which does not include or include a ketal or ether (C ₁ -C ₂₀₎ may be substituted with a silyl group; The R ¹ , R ² , R ³ and R ⁴ Wherein at least two of R < 1 > and R < 2 > are linked to each other to form an aliphatic ring or an aromatic ring.

And at least two of R ¹ , R ² , R ³ and R ⁴ are hydrogen and the rest of the R ¹ , R ² , R ³ and R ⁴ are independently selected from (C ₁ -C ₂₀ ) alkyl.

The transition metal compound; And at least one promoter compound selected from the group consisting of an aluminum compound represented by the following formula (2), an alkyl metal compound represented by the following formula (3), and a boron compound represented by the following formula (4).

(2)

- [Al (R17) -O] n-

(Wherein R 17 is the same or different and each independently represents a hydrocarbyl radical having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen radical or a halogen; and n is an integer of 2 or more).

(3)

A (R18) 3

(Wherein A is aluminum or boron; R18 is the same or different and each independently is a hydrocarbyl radical having 1 to 20 carbon atoms, which is substituted or unsubstituted with a halogen radical or a halogen.)

[Chemical Formula 4]

^{[LH] + [Z (B} ) 4] - or ^{[L] + [Z (B} ) 4] -

(Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom;

Z is a Group 13 element; B each independently represent an aryl or alkyl radical having from 6 to 20 carbon atoms in which at least one hydrogen atom is replaced by halogen, hydrocarbyl, alkoxy, or phenoxy radical having 1 to 20 carbon atoms.

Also, the aluminum compound promoter may be one or a mixture of two or more selected from alkylaluminoxane or organoaluminum, and may be selected from the group consisting of methylaluminoxane, modified methylaluminoxane, tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum, Trioctyl aluminum, and the boron compound co-catalyst is selected from the group consisting of tris (pentafluorophenyl) borane, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and triphenylmethyllinium Tetrakis (pentafluorophenyl) borate, or a mixture thereof.

According to another aspect of the present invention, there is provided a process for producing a polyolefin comprising polymerizing propylene or ethylene in the presence of the transition metal catalyst composition.

The novel metallocene catalysts according to the present invention enable production of high molecular weight polyolefins with high activity compared to existing catalysts.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as "including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

The present invention discloses a transition metal compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, M is a Group 4 transition metal; Q ¹ and Q ² are each independently selected from the group consisting of halogen, (C ₁ -C ₂₀ ) alkyl, (C ₂ -C ₂₀ ) alkenyl, (C ₂ -C ₂₀ ) alkynyl, (C ₆ -C ₂₀ ) C ₁ -C ₂₀₎ alkyl (C ₆ -C ₂₀₎ aryl, (C ₆ -C ₂₀₎ aryl (C ₁ -C ₂₀₎ alkyl, (C _{1 also, (C 6 -C 20 -C 20} ) alkyl amido ) Arylamido or (C ₁ -C ₂₀ ) alkylidene; R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Or (C ₁ -C ₂₀ ) silyl, with or without an acetal, ketal or ether group; R ¹ , R ² , R ³ and R ⁴ Two or more of which may be linked to each other to form an aliphatic ring or aromatic ring; R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Or (C ₁ -C ₂₀ ) silyl, with or without an acetal, ketal or ether group; R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ Two or more of which may be linked to each other to form an aliphatic ring or aromatic ring.

The term " alkyl " as used herein refers to a monovalent straight or branched saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms. Examples of such alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Butyl, pentyl, hexyl, octyl, dodecyl, and the like.

The term " cycloalkyl " as used in the present invention means a monovalent alicyclic alkyl radical consisting of one ring, examples of which include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, But are not limited to, cyclononyl, cyclodecyl, and the like.

The term " alkenyl " as used herein also refers to straight or branched chain hydrocarbon radicals containing one or more carbon-carbon double bonds, including ethenyl, propenyl, butenyl, pentenyl and the like, But is not limited to.

The term " aryl ", as defined in the present invention, is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, including a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyreneyl, perylenyle, klycenyl, naphthacenyl, fluoranthenyl and the like.

The term " alkoxy " as used in the present invention means an -O-alkyl radical where 'alkyl' is as defined above. Examples of such alkoxy radicals include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.

The term " halogen " as used in the present invention means a fluorine, chlorine, bromine or iodine atom.

In the present invention, the transition metal compound is a cyclopentadiene derivative ligand connected with a bridge group of silicon or alkenylene and an anisole derivative ligand in which the aryl is substituted at the 4-position, And has an ansa-metallocene structure.

Thus, the transition metal compound has an aldehyde derivative ligand in which aryl is substituted at the 4-position, and has superior catalytic activity and copolymerization as compared with a transition metal compound having an aryl group-unsubstituted ligand at the 4-position of indene .

In the transition metal compound according to the present invention, at least one or more, preferably two or more, of R ¹ , R ² , R ³ and R ⁴ in the structure of Formula (1) are hydrogen and the rest are independently of each other (C ₁ - (C ₁ -C ₂₀ ) alkyl, (C ₂ -C ₂₀ ) alkenyl, (C ₆ -C ₂₀ ) aryl or (C ₁ -C ₂₀ ) silyl with or without an acetal, ketal or ether group; The R ¹ , R ² , R ³ and R ⁴ More preferably two or more of R ¹ , R ² , R ^3, and R ⁴ may be connected to each other to form an aliphatic ring or aromatic ring, more preferably at least one, Is hydrogen and the others are independently substituted with (C ₁ -C ₂₀ ) alkyl, it is possible to produce a polyolefin having excellent activity and high molecular weight when olefin polymerization using propylene or ethylene as a monomer is excellent.

On the other hand, the transition metal compound represented by the general formula (1) can be used as an active catalyst component used in the olefin polymerization. The transition metal compound can be obtained by extracting a ligand in the transition metal compound and cationizing the center metal, The compounds represented by 2 to 4 function together as a cocatalyst.

Accordingly, the present invention relates to the above transition metal compound; And at least one promoter compound selected from the group consisting of an aluminum compound represented by the following formula (2), an alkyl metal compound represented by the following formula (3), and a boron compound represented by the following formula (4).

(2)

- [Al (R17) -O] n-

In the general formula (2), R 17 is the same or different and each independently represents a hydrocarbyl radical having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen radical or a halogen; n is an integer of 2 or more.

(3)

A (R18) 3

In Formula 3, A is aluminum or boron; R18 are the same or different and each independently represent a hydrocarbyl radical having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen radical or a halogen.

[Chemical Formula 4]

^{[LH] + [Z (B} ) 4] - or ^{[L] + [Z (B} ) 4] -

In Formula 4, L is a neutral or cationic Lewis acid; H is a hydrogen atom;

Z is a Group 13 element; B are each independently an aryl or alkyl radical having from 6 to 20 carbon atoms in which at least one hydrogen atom is replaced by halogen, hydrocarbyl having from 1 to 20 carbon atoms, alkoxy, or phenoxy radical.

In order to allow the above-mentioned promoter compound to exhibit a more excellent activation effect, the compound represented by the above-mentioned formula (2) is not particularly limited as long as it is alkylaluminoxane, and preferred examples thereof include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, Aluminoxane, and the like. Particularly preferred compounds are methylaluminoxane.

The alkyl metal compound represented by the general formula (3) is not particularly limited, but preferred examples thereof include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, t-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p- Particularly preferred compounds are selected from among trimethylaluminum, triethylaluminum and triisobutylaluminum. Preferred examples of the compound include trimethylaluminum, trimethylaluminum, trimethylaluminum, trimethylaluminum, triethylaluminum, have.

Furthermore, in the co-catalyst compound represented by the above formula (4), the [LH] ⁺ is dimethylanilinium cation dimethyl, wherein [Z (A) 4] ^- is [B (C6F5) 4] ^-, and it is preferably, the [ L] ⁺ is [(C6H5) 3C] ⁺ , and [Z (A) 4] ^- is [B (C6F5) 4] ^- . Herein, the co-catalyst compound represented by Formula 4 is not particularly limited, but examples thereof include triethylammonium tetraphenyl borate, tributylammonium tetraphenyl borate, trimethylammonium tetraphenyl borate, tripropylammonium tetraphenyl (O, p-dimethylphenyl) borate, triethylammoniumtetra (p-tolyl) borate, tripropylammoniumtetra (p- tolyl) borate, trimethylammoniumtetra Phenyl) borate, tributylammoniumtetra (ptrifluoromethylphenyl) borate, trimethylammoniumtetra (p-trifluoromethylphenyl) borate, tributylammonium tetrapentafluorophenylborate, N, Amylidium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrapentafluorophenyl Borate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, triphenylcarboniumtetra (p-trivoloromethylphenyl) borate, triphenylcarbonium Tetrapentafluorophenyl borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, and the like.

The catalyst composition may be prepared by using the compounds of Formulas 1 to 4 and then used for olefin polymerization.

First, when Q1 and Q2 of the transition metal compound represented by Formula 1 are halogen, the compound represented by Formula 2 is contacted. Secondly, a transition metal compound in the case where Q1 and Q2 in the above formula (1) are alkyl radicals and a compound represented by the above formulas (3) and (4) are contacted to prepare a catalyst composition, It is also said.

The addition amount of the above-mentioned co-catalyst compound can be determined in consideration of the addition amount of the transition metal compound represented by the above-mentioned formula (1) and the amount necessary for sufficiently activating the above promoter compound. The content of the co-catalyst compound may be 1: 1 to 100,000, based on the molar ratio of the metal contained in the co-catalyst compound to 1 mole of the transition metal contained in the transition metal compound represented by the formula (1) 1: 1 to 10,000, more preferably 1: 1 to 5,000.

More specifically, in the case of the first method, the compound represented by Formula 2 is preferably used in a molar ratio of 1:10 to 5,000, more preferably 1:50 to 1,000, to the transition metal compound represented by Formula 1 , And most preferably from 1: 100 to 1,000 molar ratio. When the molar ratio of the compound represented by the formula (2) to the transition metal compound represented by the formula (1) is less than 1:10, the amount of the aluminoxane is so small that the activation of the metal compound may not proceed completely, The excess aluminoxane acts as a catalyst poison to prevent the polymer chain from growing well.

In the case of the second method, when A is boron in the co-catalyst compound represented by Formula 3, the transition metal compound represented by Formula 1 is used at a ratio of 1: 1 to 100, preferably 1: 1 to 10 , More preferably in a molar ratio of 1: 1 to 3. In the co-catalyst compound represented by Formula 3, when A is aluminum, the amount of water may vary depending on the amount of water in the polymerization system. However, the amount of the transition metal compound represented by Formula 1 is preferably 1: 1 to 1000, : 1 to 500, and more preferably 1: 1 to 100.

The promoter compound represented by Formula 4 is supported on the transition metal compound represented by Formula 1 at a molar ratio of 1: 0.5 to 30, preferably 1: 0.7 to 20, more preferably 1: 1 to 10, . When the ratio of the promoter compound represented by Formula 4 is less than 1: 0.5, the amount of the activator is relatively small and activation of the metal compound is not completely performed, : 30, the activation of the metal compound is completely performed. However, there is a problem that the unit cost of the catalyst composition is not economical due to an excess amount of the remaining activator, or the purity of the produced polymer is lowered.

Meanwhile, the catalyst according to the present invention may further include a carrier in the compound represented by Formula 1 and the co-catalyst compound.

As the carrier, inorganic or organic carrier used in the production of the catalyst in the technical field of the present invention may be used without limitation, for example, SiO ₂ , Al ₂ O ₃ , MgO, MgCl ₂ , CaCl ₂ , ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , SiO ₂ -Al ₂ O ₃ , SiO ₂ -MgO, SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -CrO ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, bauxite, zeolite, starch, cyclodextrine, synthetic polymer and the like can be used. Preferably, the carrier comprises a hydroxy group on the surface, and may be at least one carrier selected from the group consisting of silica, silica-alumina and silica-magnesia.

The method of supporting the transition metal compound and the promoter compound on the carrier includes a method of directly supporting the transition metal compound on a dehydrated carrier, a method of pretreating the carrier with the promoter compound, A method in which the transition metal compound is supported on the support, followed by post treatment with a promoter compound, a method in which the transition metal compound is reacted with a cocatalyst compound, and then a carrier is added and reacted.

The solvent usable in the above carrying method may be an aromatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent or a mixture thereof. The aliphatic hydrocarbon solvent may include, but is not limited to, pentane, hexane, heptane, octane, nonane, decane, undecane, Dodecane and the like. Examples of the aromatic hydrocarbon solvents include, but are not limited to, benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene. Examples of the halogenated aliphatic hydrocarbon solvent include, but are not limited to, dichloromethane, trichloromethane, dichloroethane, and trichloroethane

The step of carrying the transition metal compound and the co-catalyst compound on the carrier is carried out at a temperature of -70 to 200 ° C, preferably -50 to 150 ° C, more preferably 0 to 100 ° C, .

According to the embodiment of the present invention, the copolymer produced through the polymerization process which is carried out by directly contacting the propylene or the ethylene compound is a condition in which the catalyst site is relatively insoluble and / or fixed and the polymer chain is rapidly immobilized according to this information ≪ / RTI > by propylene or ethylene polymerization. Such immobilisation can be carried out, for example, by using a solid insoluble catalyst and by performing copolymerization in a medium in which the resulting copolymer is generally insoluble and keeping the polymerization reactants and products below the crystalline melting point of the copolymer.

The metallocene catalyst composition described above is preferred for copolymerization of propylene or ethylene. Thus, the present invention discloses a process for producing polyolefins comprising polymerizing propylene or ethylene in the presence of said transition metal catalyst composition. That is, the process for producing a polyolefin according to the present invention is characterized in that the transition metal compound represented by the formula (1), the aluminum compound represented by the formula (2), the alkyl metal compound represented by the formula (3), and the boron compound represented by the formula In the presence of a transition metal catalyst composition comprising at least one cocatalyst compound selected from the group consisting of ethylene and propylene.

Suitable polymerization processes for the copolymerization of propylene are well known to those skilled in the art and include bulk polymerization, solution polymerization, slurry polymerization and low pressure gas phase polymerization. The metallocene catalyst compositions are particularly useful in known operating forms employing fixed bed, moving bed or slurry processes carried out in single, series or parallel reactors.

When the polymerization reaction is carried out in a liquid phase or a slurry, a solvent or propylene or ethylene monomer itself can be used as a medium.

Since the catalyst composition presented in the present invention is present in a uniform form in a polymerization reactor, it is preferable to apply to a solution polymerization process carried out at a temperature above the melting point of the polymer. However, it may also be used for slurry polymerization or gas phase polymerization in the form of a non-uniform catalyst composition obtained by supporting the transition metal catalyst and cocatalyst on a porous metal oxide support as disclosed in U.S. Patent No. 4,752,597. Therefore, when the catalyst composition of the present invention is used together with an inorganic carrier or an organic polymer carrier, it can be applied to a slurry or a gas phase process. That is, the transition metal compound and the promoter compound may be supported on an inorganic carrier or an organic polymer carrier.

The solvent usable in the polymerization reaction may be an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent or a mixture thereof. The aliphatic hydrocarbon solvent may include, but is not limited to, butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, Decane, undecane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, and the like can be given. The aromatic hydrocarbon solvent may include, but not limited to, benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, chlorobenzene, (Chlorobenzene), and the like. The halogenated aliphatic hydrocarbon solvent may include, but not limited to, dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, 1,2-dichloroethane, 1,2-dichloroethane, and the like.

According to an embodiment of the present invention, a method for producing a polypropylene resin can be produced by polymerizing propylene and an ethylene compound in the presence of the above transition metal catalyst composition. At this time, the transition metal catalyst and the cocatalyst component may be separately introduced into the reactor, or the respective components may be premixed and introduced into the reactor, and there are no particular restrictions on the mixing conditions such as the order of introduction, temperature or concentration. At this time, the ethylene may be contained in an amount of 0.01 to 10 wt%, preferably 0.1 to 8 wt%, and more preferably 0.5 to 5 wt%. If the content is out of the above range, the catalytic activity may be lowered or the fouling phenomenon may occur in the process.

On the other hand, the amount of the catalyst added in the polymerization reaction of the present invention is not particularly limited because it can be determined within a range in which the polymerization reaction of the monomers can sufficiently take place in accordance with slurry, liquid, vapor or massive processes. However, the amount of the catalyst and is based on the concentration of the central metal (M) in the main catalyst compound per unit volume (L) of the monomer (transition metal compound) 10 ^-8 to preferably a 1 mol / L, 10 ^-7 to 10 ^-1 mol / L it is more preferred, and 10 ^-7 to 10 ^-2 mol / L of it is further more preferable.

The polymerization reaction of the present invention may be carried out in a batch type, a semi-continuous type or a continuous type, preferably a continuous reaction.

The temperature and pressure conditions of the polymerization reaction of the present invention can be determined in consideration of the efficiency of the polymerization reaction depending on the kind of the reaction to be applied and the type of the reaction. However, the polymerization temperature is preferably 40 to 150 ° C, And the pressure may be 1 to 100 atm, preferably 5 to 50 atm.

The polyolefin produced in accordance with the present invention can enhance the polymerization activity of propylene or ethylene monomers and exhibit high molecular weight using a catalyst comprising a main catalyst compound and a cocatalyst compound.

At this time, the polyolefin may have a weight average molecular weight (Mw) of 10,000 to 1,000,000, preferably 100,000 to 800,000, and more preferably 300,000 to 700,000.

The polyolefin may have a molecular weight distribution (Mw / Mn) of 1 to 15, preferably 1.5 to 10, more preferably 1.5 to 5.

Hereinafter, a specific embodiment of the present invention will be described.

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

The polymerization solvent, n-hexane, was passed through a tube filled with 5A molecular sieve and activated alumina and bubbled with high purity nitrogen to sufficiently remove water, oxygen and other catalyst poison substances. All the polymerization was carried out by introducing the required amount of solvent, co-catalyst, monomers to be polymerized, etc. in a high-pressure reactor (autoclave) completely blocked with the external air and then adding the catalyst. The polymerized polymer was analyzed according to the following method.

(1) Melt index

After heating each cylinder at a temperature of 0 to 230 ° C in accordance with ASTM D 1238, a piston of 2.16 kg was placed in the cylinder and the weight of the resin passed through the orifice (inner diameter: 2.09 mm, length: 8 mm) And converted into the amount of passage for 10 minutes.

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

PL Mixed-BX2 + preCol-loaded PL210 GPC at 135 ° C at a rate of 1.0 mL / min in 1,2,3-trichlorobenzene solvent, and the molecular weight was corrected using a PL polystyrene standard material.

(3) Melting point (Tm) analysis

Dupont DSC2910 at a rate of 10 ° C / min under nitrogen atmosphere.

(4) Analysis of ethlylene content

13C-NMR analysis using Bruker 300 MHz.

[ Example  One]

The transition metal compound (4-butyl-2- Methylcyclopentadienyl Dimethylsilyl  2- methyl -4- (4-t-butylphenyl) Indeny  zirconium Dichloride (4-butyl-2- methylcyclopentadienyl  dimethylsilyl 2-methyl-4- (4- tert - butylphenyl ) indenyl Zr  dichloride

1) Synthesis of dimethyl 4-butyl-2-methylcyclopentadienyl chlorosilane (Dimethyl 4-butyl-2-methylcyclopentadienyl chlorosilane)

Butyllithium (600 ml) and 1-butyl-3-methylcyclopentadiene (50 g) were placed in a 2 L flask and n-BuLi (2.5 M hexane solution) (170 ml) was slowly dropped And the mixture was reacted at room temperature for 12 hours with stirring. The temperature of the reaction solution was lowered to -10 ° C again, and then dimethyldichlorosilane (170 g) was added thereto. The mixture was stirred at room temperature for 12 hours for reaction, and then the reaction product was vacuum-dried. To the reaction mixture was added n-hexane (500 ml) to dissolve the reaction product. The reaction mixture was filtered through a Celite filter. The filtered solution was vacuum-dried to obtain 70 g of dimethyl 4-butyl-2-methylcyclopentadienylchlorosilane (Yield: 70%).

2) Synthesis of dimethyl 4-butyl-2-methylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenylsilane (Dimethyl 4-butyl-2-methylcyclopentadienyl 2-methyl- -butylphenyl) indenyl silane)

The flask charged with toluene (200 ml), tetrahydrofuran (40 ml) and 2-methyl-4- (4-t-butylphenyl) indene (50 g) was cooled to -10 ° C and n-BuLi M hexane solution) (76 ml) was slowly added dropwise thereto, followed by stirring at room temperature for 12 hours. The temperature of the reaction mixture was lowered to -10 DEG C again, and dimethyl 4-butyl-2-methylcyclopentadienylchlorosilane (38 g) was added thereto and reacted at room temperature for 12 hours with stirring. After the completion of the reaction, water (400 ml) was added thereto, and the mixture was stirred at room temperature for 1.5 hours. Then, the mixture was extracted with toluene and vacuum dried to obtain dimethyl 4-butyl-2-methylcyclopentadienyl 2-methyl- - (4-t-butylphenyl) indenylsilane (yield: 95%).

3) Preparation of 4-butyl-2-methylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenylzirconium dichloride 4-tert-butylphenyl) indenyl Zr dichloride)

Butyl-2-methylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenylsilane (50 g), toluene (300 ml) and diethyl ether (100 ml) After cooling to -10 ° C, n-BuLi (2.5 M hexane solution) (90 mL) was slowly added dropwise. After dropwise addition, the reaction temperature was raised to room temperature, stirred for 48 hours, and then filtered. The resulting filtrate was vacuum-dried to obtain 40 g (yield: 80%) of 4-butyl-2-methylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t- butylphenyl) indenyldilithium salt in solid form And used directly in the next reaction without purification.

Butyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyldilithium salt (40 g), toluene (40 ml) and ether (10 ml) 1 and stirred. In Flask # 2, a mixture of toluene (30 ml) and ZrCl ₄ (20 g) was prepared. The mixture of flask # 2 was slowly dropped into flask # 1 with a cannula, and then stirred at room temperature for 24 hours. After stirring, the mixture was vacuum-dried, extracted with methylene chloride (500 ml), filtered through a Celite filter, and then the filtrate was vacuum-dried. The resulting solid was washed with a 1: 3 mixture of methylene chloride and n-hexane (50 ml) and vacuum dried to obtain 4-butyl-2-methylcyclopentadienyldimethylsilyl 2- - (4-t-butylphenyl) indenylzirconium dichloride (yield: 60%).

Supported catalyst preparation

Silica (manufacturer: Grace, product name: XPO-2412, 2.0 g) was placed in a Schlenk flask (100 ml) in a glove box, and 10 ml of anhydrous toluene solution was added thereto. Then, about 10.2 ml of methylaluminoxane (10 wt% solution of methylaluminoxane in toluene, 15 mmol of Al, manufactured by Albemarle) was slowly added dropwise at 10 DEG C, and the mixture was stirred at 0 DEG C for about 1 hour, , Stirred for 3 hours and cooled to 25 < 0 > C. Separately, the synthesized transition metal compound (0.060 g, 100 μmol) synthesized in the above formula (1) was placed in another 100 ml Schlenk flask and taken out of the glove box, followed by addition of 10 ml of anhydrous toluene solution. The solution containing the transition metal compound was slowly added to the solution containing silica and methylaluminoxane at 10 DEG C, and then the temperature was raised to 70 DEG C and stirred for 1 hour, then cooled to 25 DEG C for about 24 hours Lt; / RTI > The resulting reaction product was dried in a vacuum to obtain 2.70 g of a supported catalyst of Free Flowing.

Polymer manufacture

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

[ Example  2]

After the supported catalyst was synthesized in the same manner as in Example 1, polymerization was carried out using the supported catalyst as described below.

Polymer manufacture

The inside of a stainless steel autoclave having an internal capacity of 2 L at room temperature was completely replaced with nitrogen. Triisobutylaluminum (2 ml of a 1M solution in hexane) and 500 g of propylene were injected while maintaining nitrogen purging, and then 10 ppm of hydrogen was injected through the MFC. Thereafter, 50 mg of the supported catalyst compound was dispersed in 5 ml of hexane and introduced into the reactor using high-pressure nitrogen. Thereafter, polymerization was carried out at 70 DEG C for 60 minutes. After completion of the polymerization, the reactor was cooled to room temperature and the excess propylene was removed through a discharge line to obtain a white powdery solid. The resulting white solid powder was dried for 15 hours or more while heating to 80 캜 using a vacuum oven to prepare a final polypropylene resin.

[ Example  3]

After the supported catalyst was synthesized in the same manner as in Example 1, polymerization was carried out using the supported catalyst as described below.

Polymer manufacture

The inside of a stainless steel autoclave having an internal capacity of 2 L at room temperature was completely replaced with nitrogen. Triisobutylaluminum (2 ml of a 1 M solution in hexane) and 500 g of propylene were injected while keeping the nitrogen purging, and then 60 ppm of hydrogen was injected through the MFC. Thereafter, 50 mg of the supported catalyst compound was dispersed in 5 ml of hexane and introduced into the reactor using high-pressure nitrogen. Thereafter, polymerization was carried out at 70 DEG C for 60 minutes. After completion of the polymerization, the reactor was cooled to room temperature and the excess propylene was removed through a discharge line to obtain a white powdery solid. The resulting white solid powder was dried for 15 hours or more while heating to 80 캜 using a vacuum oven to prepare a final polypropylene resin.

[ Example  4]

The transition metal compound (2,4- Dimethylcyclopentadienyl Dimethylsilyl  2- methyl -4- (4-t- part Butylphenyl) Indeny  zirconium Dichloride (2,4- dimethylcyclopentadienyl  dimethylsilyl 2-methyl-4- (4- tert - butylphenyl ) indenyl Zr  dichloride

1) Synthesis of dimethyl 2,4-dimethylcyclopentadienyl chlorosilane (Dimethyl 2,4-dimethylcyclopentadienyl chlorosilane)

(600 mL) and 1,3-dimethylcyclopentadiene (50 g) were placed in a 2 L flask, n-BuLi (2.5 M hexane solution) (170 mL) was slowly added dropwise at -10 캜 in a nitrogen atmosphere The mixture was reacted at room temperature for 12 hours with stirring. The temperature of the reaction solution was lowered to -10 ° C again, and then dimethyldichlorosilane (170 g) was added thereto. The mixture was stirred at room temperature for 12 hours for reaction, and then the reaction product was vacuum-dried. To the reaction mixture was added n-hexane (500 ml) to dissolve the reaction product. The reaction mixture was filtered through a Celite filter, and the filtrate was vacuum-dried to obtain 70 g of dimethyl 2,4-dimethylcyclopentadienylchlorosilane in the form of a yellow oil (Yield: 70%).

2) Preparation of dimethyl 2,4-dimethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenylsilane (Dimethyl 2,4- dimethylramethylcyclopentadienyl 2-methyl- 4- Synthesis of silane

The flask charged with toluene (200 ml), tetrahydrofuran (40 ml) and 2-methyl-4- (4-t-butylphenyl) indene (50 g) was cooled to -10 ° C and n-BuLi M hexane solution) (76 ml) was slowly added dropwise thereto, followed by stirring at room temperature for 12 hours. The temperature of the reaction mixture was lowered to -10 DEG C again, and dimethyl 2,4-dimethylcyclopentadienylchlorosilane (38 g) was added thereto, followed by stirring at room temperature for 12 hours. After completion of the reaction, water (400 ml) was added, and the mixture was stirred at room temperature for 1.5 hours. Then, the mixture was extracted with toluene and vacuum dried to obtain dimethyl 2,4-dimethylcyclopentadienyl 2-methyl- 4-t-butylphenyl) indenylsilane (yield: 95%).

3) Preparation of 2,4-dimethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenylzirconium dichloride (2,4-dimethylcyclopentadienyl dimethylsilyl 2-methyl- 4- butylphenyl) indenyl Zr dichloride

50 g of dimethyl 2,4-dimethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenylsilane, 300 ml of toluene and 100 ml of diethyl ether were charged into a flask, , And then n-BuLi (2.5 M hexane solution) (90 ml) was slowly added dropwise. After dropwise addition, 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 2,4-dimethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyldilithium salt as a solid, It was used directly for the next reaction without purification.

40 g of 2,4-dimethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyldilithium salt, 40 ml of toluene and 10 ml of ether were placed in a flask # And stirred. In Flask # 2, a mixture of toluene (30 ml) and ZrCl ₄ (20 g) was prepared. The mixture of flask # 2 was slowly dropped into flask # 1 with a cannula, and then stirred at room temperature for 24 hours. After stirring, the mixture was vacuum-dried, extracted with methylene chloride (500 ml), filtered through a Celite filter, and then the filtrate was vacuum-dried. The resulting solid was washed with a 1: 3 mixture of methylene chloride and n-hexane (50 ml), and then vacuum dried to obtain 2,4-dimethylcyclopentadienyldimethylsilyl 2-methyl-4- ( 4-t-butylphenyl) indenyl zirconium dichloride (yield: 60%).

Supported catalyst preparation

Silica (manufacturer: Grace, product name: XPO-2412, 2.0 g) was placed in a Schlenk flask (100 ml) in a glove box, and 10 ml of anhydrous toluene solution was added thereto. Then, about 10.2 ml of methylaluminoxane (10 wt% solution of methylaluminoxane in toluene, 15 mmol of Al, manufactured by Albemarle) was slowly added dropwise at 10 DEG C, and the mixture was stirred at 0 DEG C for about 1 hour, , Stirred for 3 hours and cooled to 25 < 0 > C. Separately, the synthesized transition metal compound (0.060 g, 100 μmol) synthesized in the above formula (1) was placed in another 100 ml Schlenk flask and taken out of the glove box, followed by addition of 10 ml of anhydrous toluene solution. The solution containing the transition metal compound was slowly added to the solution containing silica and methylaluminoxane at 10 DEG C, and then the temperature was raised to 70 DEG C and stirred for 1 hour, then cooled to 25 DEG C for about 24 hours Lt; / RTI > The resulting reaction product was dried in a vacuum to obtain 2.70 g of a supported catalyst of Free Flowing.

Polymer manufacture

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

[ Example  5]

After the supported catalyst was synthesized in the same manner as in Example 4, polymerization was carried out using the supported catalyst as described below.

Polymer manufacture

The inside of a stainless steel autoclave having an internal capacity of 2 L at room temperature was completely replaced with nitrogen. Triisobutylaluminum (2 ml of a 1M solution in hexane) and 500 g of propylene were injected while maintaining nitrogen purging, and then 10 ppm of hydrogen was injected through the MFC. Thereafter, 50 mg of the supported catalyst compound was dispersed in 5 ml of hexane and introduced into the reactor using high-pressure nitrogen. Thereafter, polymerization was carried out at 70 DEG C for 60 minutes. After completion of the polymerization, the reactor was cooled to room temperature and the excess propylene was removed through a discharge line to obtain a white powdery solid. The resulting white solid powder was dried for 15 hours or more while heating to 80 캜 using a vacuum oven to prepare a final polypropylene resin.

[ Example  6]

After the supported catalyst was synthesized in the same manner as in Example 4, polymerization was carried out using the supported catalyst as described below.

Polymer manufacture

The inside of a stainless steel autoclave having an internal capacity of 2 L at room temperature was completely replaced with nitrogen. Triisobutylaluminum (2 ml of a 1 M solution in hexane) and 500 g of propylene were injected while keeping the nitrogen purging, and then 60 ppm of hydrogen was injected through the MFC. Thereafter, 50 mg of the supported catalyst compound was dispersed in 5 ml of hexane and introduced into the reactor using high-pressure nitrogen. Thereafter, polymerization was carried out at 70 DEG C for 60 minutes. After completion of the polymerization, the reactor was cooled to room temperature and the excess propylene was removed through a discharge line to obtain a white powdery solid. The resulting white solid powder was dried for 15 hours or more while heating to 80 캜 using a vacuum oven to prepare a final polypropylene resin.

[ Example  7]

Transition metal compound ( Tetramethylcyclopentadienyl Dimethylsilyl  2- methyl -4- (4-t- Butylphenyl ) Indeny  zirconium Dichloride ( Tetramethylcyclopentadienyl  dimethylsilyl 2-methyl-4- (4- tert - butylphenyl ) indenyl Zr  dichloride

1) Synthesis of dimethyl tetramethylcyclopentadienyl chlorosilane (Dimethyl 2,4-dimethylcyclopentadienyl chlorosilane)

N-BuLi (2.5 M hexane solution) (170 ml) was slowly added dropwise at -10 ° C under a nitrogen atmosphere, followed by dropwise addition of 12 (trimethylsilyl) methylene chloride Lt; / RTI > for 1 hour. The temperature of the reaction solution was lowered to -10 ° C again, and then dimethyldichlorosilane (170 g) was added thereto. The mixture was stirred at room temperature for 12 hours for reaction, and then the reaction product was vacuum-dried. Hexane (500 ml) was added thereto to dissolve the reaction product. The reaction product was filtered through a Celite filter, and the filtered solution was vacuum-dried to obtain 70 g of dimethyl tetramethylcyclopentadienyl chlorosilane in the form of yellow oil (yield: 80%).

2) Synthesis of dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenyl silane (Dimethyl Tetramethylmethylcyclopentadienyl 2-methyl-4-

The flask charged with toluene (200 ml), tetrahydrofuran (40 ml) and 2-methyl-4- (4-t-butylphenyl) indene (50 g) was cooled to -10 ° C and n-BuLi M hexane solution) (76 ml) was slowly added dropwise thereto, followed by stirring at room temperature for 12 hours. The temperature of the reaction mixture was lowered to -10 DEG C again, and then dimethyltetramethylcyclopentadienylchlorosilane (38 g) was added thereto, followed by stirring at room temperature for 12 hours. After completion of the reaction, water (400 ml) was added thereto, and the mixture was stirred at room temperature for 1.5 hours. Then, the mixture was extracted with toluene and vacuum dried to obtain dimethyltetramethylcyclopentadienyl 2- -Butylphenyl) indenylsilane (yield: 95%).

3) Synthesis of tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenylzirconium dichloride (Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4- synthesis

Dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenylsilane (50 g), toluene (300 ml) and diethyl ether (100 ml) , And n-BuLi (2.5 M hexane solution) (90 ml) was slowly added dropwise. After dropwise addition, 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 tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyldilithium salt as a solid, The next reaction was used.

Tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyldilithium salt (40 g), toluene (40 ml) and ether (10 ml) were placed in a flask . In Flask # 2, a mixture of toluene (30 ml) and ZrCl ₄ (20 g) was prepared. The mixture of flask # 2 was slowly dropped into flask # 1 with a cannula, and then stirred at room temperature for 24 hours. After stirring, the mixture was vacuum-dried, extracted with methylene chloride (500 ml), filtered through a Celite filter, and then the filtrate was vacuum-dried. The resulting solid was washed with a 1: 3 mixture of methylene chloride and n-hexane (50 ml) and vacuum dried to obtain tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t -Butylphenyl) indenyl zirconium dichloride (yield: 60%).

Supported catalyst preparation

Silica (manufacturer: Grace, product name: XPO-2412, 2.0 g) was placed in a Schlenk flask (100 ml) in a glove box, and 10 ml of anhydrous toluene solution was added thereto. Then, about 10.2 ml of methylaluminoxane (10 wt% solution of methylaluminoxane in toluene, 15 mmol of Al, manufactured by Albemarle) was slowly added dropwise at 10 DEG C, and the mixture was stirred at 0 DEG C for about 1 hour, , Stirred for 3 hours and cooled to 25 < 0 > C. Separately, the synthesized transition metal compound (0.060 g, 100 μmol) synthesized in the above formula (1) was placed in another 100 ml Schlenk flask and taken out of the glove box, followed by addition of 10 ml of anhydrous toluene solution. The solution containing the transition metal compound was slowly added to the solution containing silica and methylaluminoxane at 10 DEG C, and then the temperature was raised to 70 DEG C and stirred for 1 hour, then cooled to 25 DEG C for about 24 hours Lt; / RTI > The resulting reaction product was dried in a vacuum to obtain 2.70 g of a supported catalyst of Free Flowing.

Polymer manufacture

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

[ Example  8]

After the supported catalyst was synthesized in the same manner as in Example 7, polymerization was carried out using the supported catalyst as described below.

Polymer manufacture

The inside of a stainless steel autoclave having an internal capacity of 2 L at room temperature was completely replaced with nitrogen. Triisobutylaluminum (2 ml of a 1M solution in hexane) and 500 g of propylene were injected while maintaining nitrogen purging, and then 10 ppm of hydrogen was injected through the MFC. Thereafter, 50 mg of the supported catalyst compound was dispersed in 5 ml of hexane and introduced into the reactor using high-pressure nitrogen. Thereafter, polymerization was carried out at 70 DEG C for 60 minutes. After completion of the polymerization, the reactor was cooled to room temperature and the excess propylene was removed through a discharge line to obtain a white powdery solid. The resulting white solid powder was dried for 15 hours or more while heating to 80 캜 using a vacuum oven to prepare a final polypropylene resin.

[ Example  9]

After the supported catalyst was synthesized in the same manner as in Example 7, polymerization was carried out using the supported catalyst as described below.

Polymer manufacture

The inside of a stainless steel autoclave having an internal capacity of 2 L at room temperature was completely replaced with nitrogen. Triisobutylaluminum (2 ml of a 1 M solution in hexane) and 500 g of propylene were injected while keeping the nitrogen purging, and then 60 ppm of hydrogen was injected through the MFC. Thereafter, 50 mg of the supported catalyst compound was dispersed in 5 ml of hexane and introduced into the reactor using high-pressure nitrogen. Thereafter, polymerization was carried out at 70 DEG C for 60 minutes. After completion of the polymerization, the reactor was cooled to room temperature and the excess propylene was removed through a discharge line to obtain a white powdery solid. The resulting white solid powder was dried for 15 hours or more while heating to 80 캜 using a vacuum oven to prepare a final polypropylene resin.

The physical properties of the polymers prepared according to the above examples were measured, and the results are shown in Table 1 below.

Referring to Table 1, it can be seen that, in the production of a polymer by direct contact of propylene or ethylene using a specific metallocene catalyst system according to the present invention, a polymer having excellent catalytic activity and a high molecular weight can be produced. However, in the case of using a catalyst in which at least two of R ¹ , R ² , R ³ and R ⁴ are hydrogen in the structure of the formula (1) in the polymerization of propylene or ethylene (Examples 1 to 6) It is confirmed that it can be implemented.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (8)

A transition metal compound for propylene polymerization represented by the following formula (1)
[Chemical Formula 1]

In formula (1)
M is a Group 4 transition metal;
Q ₁ and Q ₂ are each independently halogen;
_{Two of} R ₁ , R ₂ , R ₃ and R ₄ are hydrogen and the other two are independently of each other (C ₁ -C ₂₀ ) alkyl;
R ₅ , R ₆ and R ₇ are methyl;
R ₈ is hydrogen;
R ₉ , R ₁₀ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are hydrogen;
R < ₁₁ > is tert-butyl. delete delete delete delete A transition metal compound of claim 1; And
At least one promoter compound selected from the group consisting of an aluminum compound represented by the following formula (2), an alkyl metal compound represented by the following formula (3) and a boron compound represented by the following formula (4);
≪ / RTI > wherein the transition metal catalyst is a transition metal catalyst.
(2)
- [Al (R17) -O] n-
(Wherein R 17 is the same or different and each independently represents a hydrocarbyl radical having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen radical or a halogen; and n is an integer of 2 or more).
(3)
A (R18) 3
(Wherein A is aluminum or boron; R18 is the same or different and each independently is a hydrocarbyl radical having 1 to 20 carbon atoms, which is substituted or unsubstituted with a halogen radical or a halogen.)
[Chemical Formula 4]
^{[LH] + [Z (B} ) 4] - or ^{[L] + [Z (B} ) 4] -
(Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom;
Z is a Group 13 element; B each independently represent an aryl or alkyl radical having from 6 to 20 carbon atoms in which at least one hydrogen atom is replaced by halogen, hydrocarbyl, alkoxy, or phenoxy radical having 1 to 20 carbon atoms. The method according to claim 6,
Wherein the aluminum compound co-catalyst is one or a mixture of two or more selected from alkylaluminoxane or organoaluminum, and is selected from the group consisting of methylaluminoxane, modified methylaluminoxane, tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum, Octyl aluminum, and the boron compound promoter is selected from the group consisting of tris (pentafluorophenyl) borane, N, N-dimethyl anilinium tetrakis (pentafluorophenyl) borate and triphenylmethyl nitrite tetra Kiss (pentafluorophenyl) borate, or a mixture thereof. A process for producing a polyolefin comprising polymerizing propylene or ethylene in the presence of the transition metal catalyst composition of claim 6.