KR102215024B1 - Method for preparing polyolfin - Google Patents

Abstract

The present invention relates to a method for producing a polyolefin. In more detail, it is to provide a method for producing a polyolefin that enables easier and more effective production of a polyolefin having a high molecular weight and excellent stress cracking resistance (Full Notch Creep Test, FNCT).

Description

Manufacturing method of polyolefin {METHOD FOR PREPARING POLYOLFIN}

The present invention relates to a method for producing a polyolefin.

The olefin polymerization catalyst system can be classified into a Ziegler Natta and a metallocene catalyst system, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler Natta catalysts have been widely applied in conventional commercial processes since their invention in the 50s, but since they are multi-site catalysts with multiple active points, they are characterized by a wide molecular weight distribution of the polymer. There is a problem in that there is a limit to securing desired physical properties because the composition distribution is not uniform.

In particular, when using a Ziegler-Natta catalyst to produce ultra-high molecular weight polyolefins having a weight average molecular weight of 1 million or more, the amount of catalyst residues (Cl component, etc.) is large, so that polyolefin decomposition may occur during molding processing at high temperatures, which reduces the molecular weight of the polyolefin. May be accompanied. For this reason, there is a disadvantage in that excellent physical properties as an ultra-high molecular weight polyolefin cannot be properly expressed.

In contrast, when a high molecular weight polyolefin is obtained using a metallocene catalyst, the molecular weight distribution is relatively small, and thus impact resistance may be improved. In addition, since the Cl component of the catalyst residue is small, decomposition of the polyolefin during molding processing can be greatly suppressed. However, the polyolefin prepared using a metallocene catalyst has a problem of poor processability due to a narrow molecular weight distribution.

In general, the wider the molecular weight distribution, the greater the degree of viscosity decrease according to the shear rate, indicating excellent processability in the processing area.Polyolefins made with metallocene catalysts are relatively narrow in molecular weight distribution, so that at high shear rates. Due to its high viscosity, a lot of load or pressure is applied during extrusion, resulting in lower extrusion productivity, significantly lowering bubble stability during blow molding, and resulting in uneven surface of the manufactured molded product resulting in lowering of transparency.

In addition, in the process of obtaining a high molecular weight polyolefin using a metallocene catalyst, the molecular weight of the polyolefin can be controlled by adjusting the amount of hydrogen gas, and the molecular weight of the polyolefin decreases as the amount of the hydrogen gas is increased. Furthermore, even if the polymerization proceeds without adding hydrogen gas, it is difficult to obtain an ultra-high molecular weight polyolefin having a weight average molecular weight of 1 million or more due to the excellent beta hydrogen removal reaction due to the characteristics of the metallocene catalyst.

On the other hand, polyolefin resins used in large-diameter high-pressure pipes require excellent stress cracking resistance (Full Notch Creep Test, FNCT), which is a characteristic that can withstand high temperature and high pressure.These FNCT properties are due to the content of ultra-high molecular weight polyolefins in the polyolefin resin. It is affected a lot.

Korean Patent Application Publication No. 2015-0037520 discloses a method of polymerizing an ultra-high molecular weight polyolefin using a multistage reactor, and a method of polymerizing by adding a molecular weight modifier and a second olefin-based monomer in a second step reaction. In addition, Korean Patent Application Publication No. 2016-0038589 discloses a method of polymerization by additionally adding a metallocene catalyst and a second olefin-based monomer in a second step reaction.

However, since the above methods are a method of controlling the molecular weight by additionally adding a reactant or a catalyst in the second stage reactor in a multistage-CSTR reactor, the polymerization process becomes complicated, and the FNCT of the polyolefin resin obtained by the method is 200 to 300. In time, research is still needed to obtain a polyolefin resin having a better FNCT while satisfying all physical properties.

Accordingly, the present invention is to provide a method for producing a polyolefin capable of more easily and effectively producing a polyolefin having a high molecular weight and excellent in stress cracking resistance (Full Notch Creep Test, FNCT).

In order to solve the above problems, the present invention is in the presence of a supported metallocene catalyst including at least one metallocene compound having a Group 4 transition metal as a central metal, a cocatalyst compound, and a support and hydrogen gas, A polymerization reaction of polymerizing an olefinic monomer to produce a polyolefin; And

Post reaction of converting the unreacted olefin-based monomer present in the reaction mixture of the polymerization reaction to a polyolefin under a pressure of 1.5 to 3.0 kg/cm ² ;

It provides a method for producing a polyolefin comprising a.

As described above, according to the present invention, by converting the unreacted olefinic monomer present in the polymerization product of the olefinic monomer to a polyolefin under controlled pressure conditions, a polyolefin having improved mechanical properties and stress cracking resistance can be more effectively produced. Can be manufactured.

Hereinafter, a method for producing a polyolefin according to an embodiment of the present invention will be described.

According to an embodiment of the present invention, in the presence of a supported metallocene catalyst including at least one metallocene compound having a Group 4 transition metal as a central metal, a cocatalyst compound, and a carrier and hydrogen gas, an olefinic monomer A polymerization reaction of polymerizing to produce a polyolefin; And further converting the unreacted olefin-based monomer present in the reaction mixture of the polymerization reaction into a polyolefin under a pressure of 1.5 to 3.0 kg/cm ² (post) reaction.

In the method for producing a polyolefin of the present invention, the polymerization reaction is carried out in the presence of a supported metallocene catalyst including at least one metallocene compound having a Group 4 transition metal as a central metal, a cocatalyst compound, and a carrier and a hydrogen gas. This is a step of polymerizing a system monomer to produce a polyolefin.

The polymerization reaction may be performed in a single reactor consisting of one reactor, or a cascade-CSTR reactor including first and second reactors.

During the polymerization reaction, a polyolefin having a desired molecular weight can be polymerized by appropriately adjusting the composition of the supported metallocene catalyst, the amount of comonomer added, the molecular weight modifier, the flow rate of hydrogen gas, the reaction pressure, and the reaction temperature.

The polymerization reaction is a step of polymerizing an olefinic monomer in the presence of a supported metallocene catalyst and hydrogen gas to produce a polyolefin, and due to the high reactivity between the metallocene catalyst and hydrogen gas, most of the olefinic monomers It is converted to polyolefin, and hydrogen gas is almost consumed. However, inevitably, the olefinic monomer remaining in the unreacted state is present in about 2 to about 5% by weight.

According to the method for producing a polyolefin of the present invention, the unreacted olefinic monomer is converted to a polyolefin in the post-reaction so that the conversion rate is substantially 100%, but the unreacted olefinic monomer is distributed in the ultrahigh molecular weight side by adjusting the reaction conditions. It is possible to obtain a polyolefin with improved FNCT by inducing it.

The structure of the metallocene compound used in the method for producing a polyolefin of the present invention is not limited, but at least one metallocene compound suitable for polymerization of a high molecular weight or ultra high molecular weight polyolefin may be used.

According to an embodiment of the present invention, the metallocene compound may include a first metallocene compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to A C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

D is -O-, -S-, -N(R)- or -Si(R)(R')-, wherein R and R'are the same as or different from each other, and each independently hydrogen, halogen, C1 to A C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;

L is a C1 to C10 linear or branched alkylene group;

B is carbon, silicon or germanium;

Q is hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;

M is a Group 4 transition metal;

X ¹ and X ² are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

C ¹ And C ² is the same as or different from each other, and each independently represented by one of the following formulas 2a, 2b, or 2c, provided that C ¹ And Except when C ² is all of Formula 2c;

[Formula 2a]

[Formula 2b]

[Formula 2c]

In Formulas 2a, 2b and 2c, R1 to R17 and R1' to R9' are the same as or different from each other, and each independently hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkyl Silyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, wherein Two or more adjacent to each other among R10 to R17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

In Formula 1, the Group 4 transition metal (M) may include titanium, zirconium, hafnium, etc., but is not limited thereto.

In the first metallocene compound of Formula 1, R1 to R17 and R1' to R9' of Formulas 2a, 2b and 2c are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl Group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, phenyl group, halogen group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, trimethyl It is more preferable that it is a silylmethyl group, a methoxy group, or an ethoxy group, but is not limited thereto.

In the first metallocene compound of Formula 1, L is more preferably a C4 to C8 linear or branched alkylene group, but is not limited thereto. In addition, the alkylene group may be substituted or unsubstituted with a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group.

In the first metallocene compound of Formula 1, A is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert-butoxymethyl group, 1- Although it is preferable that it is an ethoxyethyl group, 1-methyl-1-methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group, it is not limited thereto. In addition, B is preferably silicon, but is not limited thereto.

In addition, B in Formula 1 is preferably silicon, but is not limited thereto.

The first metallocene compound of Formula 1 forms a structure in which indeno indole derivatives and/or fluorene derivatives are crosslinked by a bridge, and a non-shared electron pair capable of acting as a Lewis base in the ligand structure It is supported on the surface having Lewis acid properties of the carrier and exhibits high polymerization activity even when supported. In addition, since the electronically rich indeno indole and/or fluorene group is included, the activity is high, and the hydrogen reactivity is low due to the appropriate steric hindrance and the electronic effect of the ligand, and high activity is maintained even in the presence of hydrogen. In addition, it is possible to polymerize ultra-high molecular weight polyolefins by stabilizing beta-hydrogen in the polymer chain in which the nitrogen atom of the indeno indole derivative grows by hydrogen bonds to inhibit beta-hydrogen elimination.

According to an embodiment of the present invention, specific examples of the first metallocene compound represented by Formula 1 may include compounds represented by one of the following structural formulas, but are not limited thereto.

The first metallocene compound of Formula 1 has excellent activity and can polymerize a high molecular weight polyolefin. In particular, it exhibits high polymerization activity even when used by being supported on a carrier, so that a polyolefin having an ultra high molecular weight can be produced.

In addition, even when used in combination with catalysts having other properties, it is possible to prepare a polyolefin that satisfies the properties of a high molecular weight without deteriorating the activity, so that a polyolefin containing a high molecular weight polyolefin and having a wide molecular weight distribution can be easily prepared. Can

The first metallocene compound of Formula 1 is obtained by connecting an indenoindole derivative and/or a fluorene derivative with a bridge compound to prepare a ligand compound, and then adding a metal precursor compound to perform metallation. However, it is not limited thereto.

The method for preparing the first metallocene compound will be described in detail in Examples to be described later.

According to an embodiment of the present invention, the metallocene compound may further include at least one second metallocene compound selected from compounds represented by the following Chemical Formulas 3 to 5.

[Formula 3]

(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹ _3-n

In Chemical Formula 3,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. One, and these may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ^a and R ^b are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ¹ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;

n is 1 or 0;

[Formula 4]

(Cp ³ R ^c ) _m B ¹ (Cp ⁴ R ^d ) M ² Z ² _3-m

In Chemical Formula 4,

M ² is a Group 4 transition metal;

Cp ³ and Cp ⁴ are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals And these may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ^c and R ^d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ² is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;

B ¹ is at least one of carbon, germanium, silicon, phosphorus or nitrogen atom-containing radicals that cross-link the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or cross-link one Cp ⁴ R ^d ring to M ² Or a combination thereof;

m is 1 or 0;

[Formula 5]

(Cp ⁵ R ^e )B ² (J)M ³ Z ³ ₂

In Chemical Formula 5,

M ³ is a Group 4 transition metal;

Cp ⁵ is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms. Can;

R ^e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl , C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ³ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;

B ² is one or more of carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radicals that bridge the Cp ⁵ R ^e ring and J, or a combination thereof;

J is any one selected from the group consisting of NR ^f , O, PR ^f and S, and R ^f is C1 to C20 alkyl, aryl, substituted alkyl, or substituted aryl.

In Formula 4, when m is 1, it means that the Cp ³ R ^c ring and the Cp ⁴ R ^d ring or the Cp ⁴ R ^d ring and M ² are bridged compound structures crosslinked by B ¹ , and m is 0 In the case of, it means a non-crosslinked compound structure.

The second metallocene compound represented by Formula 3 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

In addition, the compound represented by Formula 4 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

In addition, the compound represented by Formula 5 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

According to an embodiment of the present invention, the supported metallocene catalyst is a second metal selected from at least one of the first metallocene compound represented by Chemical Formula 1 and the compounds represented by Chemical Formulas 3 to 5 It may be a hybrid supported metallocene catalyst in which at least one locene compound is mixedly supported on a carrier together with a cocatalyst compound.

The first metallocene compound represented by Formula 1 of the hybrid supported metallocene catalyst mainly contributes to making a high molecular weight copolymer having a high SCB (short chain branch) content, and is used as a second metal represented by Formula 3 Sen compounds can mainly contribute to making low molecular weight copolymers with low SCB content. In addition, the second metallocene compound represented by Formula 4 or 5 may contribute to making a low molecular weight copolymer having a medium SCB content.

According to an embodiment of the present invention, the hybrid supported metallocene catalyst may include at least one first metallocene compound represented by Formula 1 and at least one second metallocene compound represented by Formula 3.

According to another embodiment of the present invention, the hybrid supported metallocene catalyst is in addition to at least one first metallocene compound of Formula 1 and at least one second metallocene compound of Formula 3, Formula 4 Alternatively, at least one second metallocene compound of Formula 5 may be included.

In the hybrid supported betalocene catalyst of the present invention, the first metallocene compound represented by Chemical Formula 1 and the second metallocene compound selected from the compounds represented by Chemical Formulas 3 to 5 are used. By including at least two types of sen compounds, it is possible to prepare a polyolefin having a high SCB content and having a high SCB content, and at the same time, a polyolefin having excellent physical properties and excellent processability due to a wide molecular weight distribution.

In the method for producing a polyolefin according to the present invention, the cocatalyst compound supported together on a carrier to activate the first and second metallocene compounds is an organometallic compound containing a group 13 metal, and a general metallocene It is not particularly limited as long as it can be used when polymerizing olefins under a catalyst.

According to an embodiment of the present invention, in particular, the cocatalyst compound may include at least one of an aluminum-containing first cocatalyst represented by Formula 6 below and a borate-based second cocatalyst represented by Formula 7 below.

[Formula 6]

-[Al(R ₁₈ )-O-] _k-

In Formula 6, R ₁₈ is each independently halogen, halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,

[Formula 7]

T ⁺ [BG ₄ ] ^-

In Chemical Formula 7, T ⁺ is a +1 valent polyvalent ion, B is boron in a +3 oxidation state, and G is each independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryloxide group, a hydro It is selected from the group consisting of a carbyl group, a halocarbyl group, and a halo-substituted hydrocarbyl group, wherein G has 20 or less carbons, but G is a halide group at only one or less positions.

By using such first and second cocatalysts, the molecular weight distribution of the finally produced polyolefin becomes more uniform, and polymerization activity can be improved.

The first cocatalyst of Formula 6 may be an alkylaluminoxane-based compound in which a repeating unit is bonded in a linear, circular or network type, and specific examples of such a first cocatalyst include methylaluminoxane (MAO), ethylaluminum Noxane, isobutyl aluminoxane, butyl aluminoxane, etc. are mentioned.

In addition, the second cocatalyst of Formula 7 may be a trisubstituted ammonium salt, a dialkyl ammonium salt, or a borate-based compound in the form of a trisubstituted phosphonium salt. Specific examples of such a second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate , Methyltetradecyclooctadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate, N,N-diethylaninium tetraphenylborate, N,N-dimethyl (2,4,6-trimethylaninium )Tetraphenyl borate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium, tetra Kis (pentafluorophenyl) borate, tripropyl ammonium tetrakis (pentafluorophenyl) borate, tri(n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (Pentafluorophenyl) borate, N,N-dimethylaninium tetrakis (pentafluorophenyl) borate, N,N-diethylaninium tetrakis (pentafluorophenyl) borate, N,N-dimethyl (2) ,4,6-trimethylaninium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4) ,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-, Tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylaninium tetrakis (2,3,4,6- Tetrafluorophenyl) borate, N,N-diethylaninium tetrakis(2,3,4,6-tetrafluorophenyl)borate or N,N-dimethyl-(2,4,6-trimethylaninium) Borate compounds in the form of trisubstituted ammonium salts such as tetrakis-(2,3,4,6-tetrafluorophenyl)borate; A borate type of dialkyl ammonium salt such as dioctadecyl ammonium tetrakis (pentafluorophenyl) borate, ditetradecyl ammonium tetrakis (pentafluorophenyl) borate or dicyclohexyl ammonium tetrakis (pentafluorophenyl) borate compound; Or triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate or tri(2,6-, dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) ) Borate compounds in the form of trisubstituted phosphonium salts such as borate.

In the hybrid supported metallocene catalyst, the mass ratio of the total transition metal to the carrier contained in the first metallocene compound represented by Formula 1 and the second metallocene compound represented by Formulas 3 to 5 is 1: 10 to 1: may be 1,000. When the carrier and the metallocene compound are included in the mass ratio, the optimum shape may be exhibited.

In addition, the mass ratio of the cocatalyst compound to the carrier may be 1:1 to 1:100. In addition, the mass ratio of the first metallocene compound represented by Formula 1 to the second metallocene compound represented by Formulas 3 to 5 may be 10: 1 to 1: 10, preferably 5: 1 to 1: 5 have. When the cocatalyst and the metallocene compound are included in the mass ratio, the activity and the polymer microstructure can be optimized.

In the hybrid supported metallocene catalyst, a carrier containing a hydroxyl group on the surface may be used as the carrier, and preferably a carrier having a highly reactive hydroxyl group and a siloxane group from which moisture is removed from the surface by drying. You can use

For example, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are usually oxides, carbonates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) ₂ , It may contain sulfate and nitrate components.

The drying temperature of the carrier is preferably 200 to 800°C, more preferably 300 to 600°C, and most preferably 300 to 400°C. When the drying temperature of the carrier is less than 200°C, there is too much moisture so that the moisture on the surface and the cocatalyst react, and when it exceeds 800°C, the pores on the surface of the carrier are combined and the surface area decreases, and there are many hydroxyl groups on the surface. It is not preferable because it disappears and only siloxane groups remain, and the reaction site with the cocatalyst decreases.

The amount of hydroxy group on the surface of the carrier is preferably 0.1 to 10 mmol/g, and more preferably 0.5 to 5 mmol/g. The amount of hydroxy groups on the surface of the carrier can be controlled by a method and conditions for preparing the carrier or drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than 0.1 mmol/g, the reaction site with the cocatalyst is small, and if it exceeds 10 mmol/g, it is not preferable because it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. not.

In preparing a hybrid supported metallocene catalyst using the first and second metallocene compounds and the first and second cocatalysts described above, the first metallocene compound and the first cocatalyst are supported on the support. Thereafter, the second metallocene compound and the second cocatalyst may be supported, but the present invention is not limited thereto. A washing step using a solvent may be additionally performed between each of these supporting steps.

In the method for producing a polyolefin of the present invention, the polymerization reaction to generate the polyolefin comprises at least one metallocene compound having a Group 4 transition metal as a central metal, a cocatalyst compound, and a supported metallocene catalyst including a carrier. It is carried out by polymerizing an olefin-based monomer in the presence of hydrogen gas, and the supported metallocene catalyst may be a single metallocene supported catalyst or a hybrid metallocene supported catalyst as described above.

In addition, the polymerization reaction may proceed as a single reaction or may be performed by dividing into a first step and a second step reaction using a multistage reactor.

Specific examples of olefinic monomers that can be used include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene and 3-chloromethylstyrene. In one example of such a production method, polyethylene is prepared by using ethylene, or with ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-hexene , 1-heptene, 1-decene, 1-undecene or 1-dodecene may be copolymerized with an alpha olefin to prepare an ethylene-alpha olefin copolymer.

When the polymerization reaction is divided into a first step and a second step reaction, in the second step reaction, the supported metallocene catalyst, a molecular weight modifier, and/or an olefin-based monomer are added to the reaction mixture of the first step. And polymerization can be carried out.

According to an embodiment of the present invention, the molecular weight modifier may include a mixture of a cyclopentadienyl metal compound represented by Formula 8 below and an organoaluminum compound represented by Formula 9 below, or a reaction product thereof.

[Formula 8]

Cp6Cp7M4X'2

In Chemical Formula 8,

Cp6 and Cp7 are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, or a ligand containing a substituted or unsubstituted fluorenyl group, M4 is a Group 4 transition metal element, and X' Is halogen;

[Formula 9]

RfRgRhAl

In Formula 9,

Rf, Rg, and Rh are each independently an alkyl group or halogen having 4 to 20 carbon atoms, and at least one of Rf, Rg, and Rh is an alkyl group having 4 to 20 carbon atoms.

Further, in the first step reaction, the residence time of each raw material may be selected without particular limitation as long as it is a range capable of forming a polyolefin having an appropriate molecular weight distribution and density distribution, but may be about 1 to about 3 hours. If the residence time in the first step reaction is smaller than this, the low molecular weight polyolefin is not properly formed and the molecular weight distribution becomes narrow, so that the processability of the final polyolefin may be deteriorated. Conversely, if the residence time in the first step reaction is too long, it is not preferable in terms of productivity.

Further, the polymerization reaction temperature in the first step reaction may be about 70 to about 90°C. If the polymerization reaction temperature is too low, it is not appropriate in terms of polymerization rate and productivity, and if the polymerization reaction temperature is too high, fouling in the reactor may be caused.

In addition, the polymerization reaction pressure in the first step reaction may be about 7 to about 10 kg/cm ² to maintain a stable continuous process state.

After the polymerization reaction in the first step reaction is performed, a second step reaction may be performed on the slurry reaction mixture in the first step reaction.

At this time, in the second-stage reaction, in addition to the slurry reaction mixture transferred from the first-stage reaction, the above-described supported metallocene catalyst and/or olefinic monomer may be additionally added to proceed with the polymerization process. In this way, a high molecular weight polyolefin can be obtained.

In the second step reaction, the residence time of each raw material may be selected without particular limitation as long as it is a range capable of forming a polyolefin having an appropriate molecular weight distribution and density distribution, but may be about 1 to about 3 hours. If the residence time in the second step reaction is smaller than this, the high molecular weight polyolefin is not formed properly, and the environmental stress cracking resistance or mechanical properties of the final polyolefin may be deteriorated. Conversely, the residence time in the second step reaction If this is too long, it is not preferable from the viewpoint of productivity.

Further, the polymerization reaction temperature in the second step reaction may be about 70 to about 90°C. If the polymerization reaction temperature is too low, it is not appropriate in terms of polymerization rate and productivity, and if the polymerization reaction temperature is too high, fouling in the reactor may be caused.

In addition, the polymerization reaction pressure in the second step reaction may be about 6 to about 9 kg/cm ² to maintain a stable continuous process state.

In addition, the polymerization reaction described above may be carried out by slurry polymerization in an aliphatic hydrocarbon-based solvent such as hexane, butane, or pentane. As already described above, as the metallocene catalysts exhibit excellent solubility in these solvents, they are stably dissolved and supplied to the reaction system, so that the polymerization process can proceed effectively, and polyolefins having a large molecular weight and a wider molecular weight distribution Can be manufactured effectively.

As described above, most of the olefinic monomers, for example about 95 to about 97% by weight of the olefinic monomers, are converted into polyolefins by performing a polymerization reaction using a single reactor or a multistage-CSTR reactor. However, about 2 to about 5% by weight of the olefinic monomer remaining unreacted is still present.

In the polyolefin production method of the present invention, the unreacted olefinic monomer remaining after the polymerization reaction as described above is subjected to a post-reaction to substantially convert the unreacted olefinic monomer to a polyolefin close to 100%. In particular, by adjusting the reaction conditions during the post-reaction, the unreacted olefinic monomer is converted into a high molecular weight polyolefin, thereby further increasing the content of the ultra high molecular weight polyolefin, thereby producing a polyolefin resin having excellent FNCT.

Conventionally, a method of finally producing a polyolefin is known, further including a post reactor for additionally polymerizing unreacted monomers in a slurry reaction mixture that has been polymerized. However, it is not known that FNCT properties can be improved by controlling the reaction conditions in the post reactor.

In addition, in the case of a polymerization process using a conventional Ziegler-Natta catalyst, since the content of hydrogen gas, which is a molecular weight modifier, is high, it is difficult to expect improvement of physical properties by controlling the polymerization conditions. The method to improve physical properties was mainly used.

However, according to the polyolefin production method of the present invention, by adjusting the reaction pressure to be in the range of about 1.5 to about 3.0 kg/cm ² , or about 1.5 to about 2.5 kg/cm ² in the post reaction step, the unreacted olefinic monomer Further reactions can produce ultra-high molecular weight polyolefins. In the post-reaction step, if the reaction pressure is too low, the effect of improving the FNCT of the finally produced polyolefin may be insignificant, and if the reaction pressure is too high, the processability may deteriorate, so it is preferable to adjust the pressure within the above range from this point of view.

In addition, according to an embodiment of the present invention, the reaction temperature in the post-reaction step may be adjusted to be in the range of about 70 to about 78°C, or about 72 to about 78°C. When the reaction temperature in the post-reaction step is within the above-described range, it may be more advantageous to achieve the FNCT improvement effect of the polyolefin.

In addition, in the post-reaction, the reaction may proceed without additional hydrogen gas.

The polyolefin prepared according to the manufacturing method of the above-described embodiment has a high content of ultra-high molecular weight polyolefin resin, and thus has a stress cracking resistance (FNCT) of about 480 hours or more, measured according to ISO 16770 under conditions of a temperature of 80°C and a pressure of 4.0 MPa, About 500 hours or more, or about 550 hours or more may have excellent pressure and heat resistance properties.

In addition, due to a large molecular weight and a wide molecular weight distribution, excellent mechanical properties and processability can be exhibited at the same time.

Hereinafter, preferred examples are presented to aid understanding of the invention, but the following examples are only illustrative of the invention, and the scope of the invention is not limited to the following examples.

<Example>

Synthesis Example of First Metallocene Compound

Synthesis Example 1

1-1 Preparation of Ligand Compound

2 g of fluorene was dissolved in 5 mL MTBE and 100 mL of hexane, and 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath, followed by stirring at room temperature overnight. 3.6 g of (6-(tert-butoxy)hexyl)dichloro(methyl)silane was dissolved in 50 mL of hexane, and the fluorene-Li slurry was transferred for 30 minutes in a dry ice/acetone bath, followed by stirring at room temperature overnight. At the same time, 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole (12 mmol, 2.8 g) was also dissolved in 60 mL of THF to add 5.5 mL of 2.5M n-BuLi hexane solution in a dry ice/acetone bath. It was added dropwise and stirred at room temperature overnight. After confirming the completion of the reaction by NMR sampling the reaction solution of fluorene and (6-(tert-butoxy)hexyl)dichloro(methyl)silane, 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole- Li solution was transferred under a dry ice/acetone bath. It was stirred at room temperature overnight. After the reaction, it was extracted with ether/water to remove residual moisture in the organic layer with MgSO ₄ to obtain a ligand compound (Mw 597.90, 12 mmol), and it was confirmed by 1H-NMR that two isomers were generated.

¹ H NMR (500 MHz, d6-benzene): -0.30 ~ -0.18 (3H, d), 0.40 (2H, m), 0.65 ~ 1.45 (8H, m), 1.12 (9H, d), 2.36 ~ 2.40 ( 3H, d), 3.17 (2H, m), 3.41 to 3.43 (3H, d), 4.17 to 4.21 (1H, d), 4.34 to 4.38 (1H, d), 6.90 to 7.80 (15H, m)

1-2 Preparation of metallocene compound

7.2 g (12 mmol) of the ligand compound synthesized in 1-1 was dissolved in 50 mL of diethylether, and 11.5 mL of a 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath, followed by stirring at room temperature overnight. Vacuum-dried to obtain a brown color sticky oil. It was dissolved in toluene to obtain a slurry. ZrCl ₄ (THF) ₂ was prepared, and 50 mL of toluene was added to prepare a slurry. A 50 mL toluene slurry of ZrCl ₄ (THF) ₂ was transferred in a dry ice/acetone bath. As it was stirred at room temperature overnight, it changed to violet color. The reaction solution was filtered to remove LiCl. After removing toluene in the filtrate by vacuum drying, hexane was added and sonication was performed for 1 hour. The slurry was filtered to obtain 6 g of a dark violet metallocene compound (Mw 758.02, 7.92 mmol, yield 66 mol%) as a filtered solid. Two isomers were observed on 1H-NMR.

¹ H NMR (500 MHz, CDCl ₃ ): 1.19 (9H, d), 1.71 (3H, d), 1.50 ~ 1.70 (4H, m), 1.79 (2H, m), 1.98 ~ 2.19 (4H, m), 2.58 (3H, s), 3.38 (2H, m), 3.91 (3H, d), 6.66 to 7.88 (15H, m)

Synthesis Example 2

2-1 Preparation of Ligand Compound

Add 2.63 g (12 mmol) of 5-methyl-5,10-dihydroindeno[1,2-b]indole to a 250 mL flask, dissolve in 50 mL of THF, and add 6 mL of 2.5M n-BuLi hexane solution to a dr yice/acetone bath. And stirred at room temperature overnight. In another 250 mL flask, 1.62 g (6 mmol) of (6-(tert-butoxy)hexyl)dichloro(methyl)silane was dissolved in 100 mL of hexane to prepare, and then 5-methyl-5,10-dihydroindeno in a dry ice/acetone bath. It was slowly added dropwise to the lithiated solution of [1,2-b]indole, and stirred at room temperature overnight. After the reaction, the reaction mixture was extracted with ether/water, and the residual moisture in the organic layer was removed with MgSO ₄ and dried under vacuum to obtain 3.82 g (6 mmol) of a ligand compound, which was confirmed by 1H-NMR.

¹ H NMR (500 MHz, CDCl3): -0.33 (3H, m), 0.86~ 1.53 (10H, m), 1.16 (9H, d), 3.18 (2H, m), 4.07 (3H, d), 4.12 ( 3H, d), 4.17 (1H, d), 4.25 (1H, d), 6.95~ 7.92 (16H, m)

2-2 Preparation of metallocene compound

After dissolving 3.82 g (6 mmol) of the ligand compound synthesized in 2-1 in 100 mL of toluene and 5 mL of MTBE, 5.6 mL (14 mmol) of 2.5M n-BuLi hexane solution was added dropwise in a dryice/acetone bath overnight at room temperature. Stirred. In another flask, 2.26 g (6 mmol) of ZrCl ₄ (THF) ₂ was prepared, and 100 ml of toluene was added to prepare a slurry. The toluene slurry of ZrCl ₄ (THF) ₂ was transferred to the litiation ligand in a dry ice/acetone bath. It was stirred at room temperature overnight and changed to violet color. After the reaction solution was filtered to remove LiCl, the obtained filtrate was vacuum-dried, hexane was added, and sonication was performed. The slurry was filtered to obtain 3.40 g (yield 71.1 mol%) of a filtered solid dark violet metallocene compound.

¹ H NMR (500 MHz, CDCl3): 1.74 (3H, d), 0.85 to 2.33 (10H, m), 1.29 (9H, d), 3.87 (3H, s), 3.92 (3H, s), 3.36 (2H) , m), 6.48~ 8.10 (16H, m)

Preparation Example of the Second Metallocene Compound

Synthesis Example 3

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

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

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

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

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

<Preparation Example of Supported Catalyst>

Manufacturing Example 1

1-1 Drying of carrier

Silica (SYLOPOL 948 manufactured by Grace Davison) was dehydrated at a temperature of 400° C. for 15 hours under vacuum.

1-2 Preparation of supported catalyst

10 g of dried silica was put into a glass reactor, and 100 mL of toluene was additionally added thereto, followed by stirring. 50 mL of a 10 wt% methylaluminoxane (MAO)/toluene solution was added, and the mixture was slowly reacted with stirring at 40°C. Thereafter, the aluminum compound was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed under reduced pressure. After adding 100 mL of toluene again, 0.25 mmol of the metallocene catalyst prepared in Synthesis Example 2 was dissolved in toluene and added together to react for 1 hour. After the reaction was over, 0.25 mmol of the metallocene catalyst of Synthesis Example 1 was dissolved in toluene and added thereto, and the reaction was further performed for 1 hour. Finally, 0.25 mmol of the metallocene catalyst prepared in Synthesis Example 3 was dissolved in toluene and then added thereto, followed by further reaction for 1 hour. After the reaction was over, the stirring was stopped and the toluene layer was separated and removed, and 1.0 mmol of anilinium borate (N, N-dimethylanilinium tetrakis(pentafluorophenyl)borate, AB) was added, stirred for 1 hour, and then reduced pressure at 50°C. Toluene was removed to prepare a supported catalyst.

<Polymerization Example>

Example 1

A single CSTR reactor with a capacity of 0.2 m ³ was used.

In the reactor, hexane was 31 kg/hr, ethylene was 10 kg/hr, comonomer 1-butene was 0.3 kg/hr, hydrogen was 1.5 g/hr, and triethylaluminum (TEAL) was 23 mmol/hr. Then, the metallocene-supported catalyst prepared in Preparation Example 1 was injected at 0.65 gSiO ₂ /hr. At this time, the reactor was maintained at 80°C, the pressure was maintained at 8 kg/cm ² , the residence time of the reactant was maintained at 3.0 hours, and a slurry reaction mixture containing polyolefin was continuously added to the post reactor while maintaining a constant liquid level in the reactor. The post reaction was carried out by passing it to the (post reactor).

The post reactor was maintained at 78° C. and the pressure at 2.5 kg/cm ² , and the residence time of the reactant was maintained at 2.0 hours without the introduction of hydrogen gas, thereby polymerizing the unreacted monomer. Thereafter, the polymerization product was manufactured into final polyethylene through a solvent removal equipment and a dryer.

Example 2

In Example 1, a polyolefin polymerization process was performed in the same manner as in Example 1 in the same manner, except that the pressure of the post reactor was 1.5 kg/cm ² .

Example 3

In Example 1, the polyolefin polymerization process was carried out in the same manner as in Example 1 in the same manner, except that the temperature of the post reactor was set to 75°C.

Example 4

In Example 1, the pressure in the post reactor was 1.5 kg/cm ² , A polyolefin polymerization process was performed in the same manner as in Example 1 in the same manner, except that the temperature was set to 75°C.

Comparative Example 1

In Example 1, the polymerization process was performed in the same manner, except that the post reaction in the post reactor was not performed.

<Experimental Example>

The properties of the polyethylene prepared in Examples 1 to 4 and Comparative Example 1 were measured by the following method, and the results are shown in Table 1 below.

1) Density: ASTM 1505

2) HLMI: Melt index was measured according to ASTM 1238 at a measurement temperature of 190° C. and a load of 21.6 kg.

3) Stress cracking resistance (FNCT, unit: time): It was measured according to ISO 16770 under the conditions of temperature 80°C and pressure 4.0 MPa.

HLMI
(g/10min) density
(g/cm ³ ) FNCT
(Hr) Example 1 7.0 0.939 550 Example 2 7.1 0.939 480 Example 3 6.9 0.939 580 Example 4 7.0 0.939 500 Comparative Example 1 7.2 0.939 450

Referring to Table 1, the polyolefins of Examples 1 to 4, in which the post-reaction was performed at a constant pressure and temperature range, exhibited high stress cracking resistance without deterioration of other physical properties.

Claims (9)

A polymerization reaction in which an olefin monomer is polymerized to produce a polyolefin in the presence of a supported metallocene catalyst including at least one metallocene compound having a Group 4 transition metal as a central metal, a cocatalyst compound, and a carrier, and hydrogen gas. ; And
A post reaction of converting the unreacted olefinic monomer present in the reaction mixture of the polymerization reaction into a polyolefin further under a pressure of 1.5 to 3.0 kg/cm ² ;
A method for producing a polyolefin comprising a.
The method of claim 1, wherein the polymerization reaction is performed in a single reactor or a cascade-CSTR reactor.
The method of claim 1, wherein the post-reaction is performed in the absence of hydrogen gas.
The method of claim 1, wherein the post reaction is performed at a temperature of 70 to 78°C.
The method of claim 1, wherein the olefinic monomer is ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene , 1-undecene, 1-dodecene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene, and a method of producing a polyolefin comprising at least one monomer selected from the group consisting of 3-chloromethylstyrene.
The method of claim 1, wherein the metallocene compound comprises a first metallocene compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to A C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
D is -O-, -S-, -N(R)- or -Si(R)(R')-, wherein R and R'are the same as or different from each other, and each independently hydrogen, halogen, C1 to A C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;
L is a C1 to C10 linear or branched alkylene group;
B is carbon, silicon or germanium;
Q is hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
M is a Group 4 transition metal;
X ¹ and X ² are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
C ¹ And C ² is the same as or different from each other, and each independently represented by one of the following formulas 2a, 2b, or 2c, provided that C ¹ And Except when C ² is all of Formula 2c;
[Formula 2a]

[Formula 2b]

[Formula 2c]

In Formulas 2a, 2b and 2c, R1 to R17 and R1' to R9' are the same as or different from each other, and each independently hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkyl Silyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, wherein Two or more adjacent to each other among R10 to R17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.
The method of claim 6, wherein the metallocene compound further comprises at least one second metallocene compound selected from compounds represented by the following Formulas 3 to 5:
[Formula 3]
(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹ _3-n
In Chemical Formula 3,
M ¹ is a Group 4 transition metal;
Cp ¹ and Cp ² are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. One, and these may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^a and R ^b are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z ¹ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
n is 1 or 0;
[Formula 4]
(Cp ³ R ^c ) _m B ¹ (Cp ⁴ R ^d ) M ² Z ² _{3 -m}
In Chemical Formula 4,
M ² is a Group 4 transition metal;
Cp ³ and Cp ⁴ are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals And these may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^c and R ^d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z ² is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
B ¹ is at least one of carbon, germanium, silicon, phosphorus or nitrogen atom-containing radicals that cross-link the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or cross-link one Cp ⁴ R ^d ring to M ² Or a combination thereof;
m is 1 or 0;
[Formula 5]
(Cp ⁵ R ^e )B ² (J)M ³ Z ³ ₂
In Chemical Formula 5,
M ³ is a Group 4 transition metal;
Cp ⁵ is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which are substituted with hydrocarbons having 1 to 20 carbon atoms. Can;
R ^e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl , C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z ³ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
B ² is one or more of carbon, germanium, silicon, phosphorus or nitrogen atom-containing radicals that bridge the Cp ⁵ R ^e ring and J, or a combination thereof;
J is any one selected from the group consisting of NR ^f , O, PR ^f and S, and R ^f is C1 to C20 alkyl, aryl, substituted alkyl, or substituted aryl.
The method of claim 6, wherein the first metallocene compound represented by Formula 1 is one of the following structural formulas:

The method of claim 1, wherein the cocatalyst compound comprises at least one selected from the group consisting of a first cocatalyst of Formula 6 below and a second cocatalyst of Formula 7 below:
[Formula 6]
-[Al(R ₁₈ )-O-] _k-
In Formula 6, R ₁₈ is each independently halogen, halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,
[Formula 7]
T ⁺ [BG ₄ ] ^-
In Chemical Formula 7, T ⁺ is a +1 valent polyvalent ion, B is boron in a +3 oxidation state, and G is each independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryloxide group, a hydro It is selected from the group consisting of a carbyl group, a halocarbyl group, and a halo-substituted hydrocarbyl group, wherein G has 20 or less carbons, but G is a halide group at only one or less positions.