KR20220066744A - Hybrid supported catalyst - Google Patents

Abstract

The present invention relates to a hybrid supported catalyst capable of manufacturing polyolefins having high activity in olefin polymerization and excellent processability. The present invention relates to the hybrid supported catalyst comprising: a first transition metal compound represented by chemical formula 1; a second transition metal compound represented by chemical formula 2; a third transition metal compound represented by chemical formula 3; and a carrier supporting the first to third transition metal compounds.

Description

Hybrid supported catalyst {HYBRID SUPPORTED CATALYST}

The present invention relates to a hybrid supported catalyst capable of producing a polyolefin having excellent processability and physical properties and having fewer defects during processing.

Since the Ziegler-Natta catalyst widely applied to the existing commercial process is a multi-site catalyst, the molecular weight distribution of the resulting polymer is wide, and the composition distribution of the comonomer is not uniform, so there is a limit to securing desired properties.

On the other hand, the metallocene catalyst has a narrow molecular weight distribution of the polymer produced as a single active site catalyst with one type of active site, and greatly improves the molecular weight, stereoregularity, crystallinity, and especially the reactivity of the comonomer depending on the structure of the catalyst and ligand. It has the advantage of being adjustable.

The metallocene catalyst system is composed of a combination of a main catalyst containing a transition metal compound centered on a Group 4 metal as a main component and a promoter including an organometallic compound containing a Group 13 metal such as aluminum as a main component. A polymer such as polyolefin having a narrow molecular weight distribution can be prepared according to the single active site characteristic of the catalyst.

The molecular weight and molecular weight distribution of polyolefin are important factors in determining the physical properties of the polymer and the flow and mechanical properties affecting the processability of the polymer. In order to make various polyolefin products, it is an important factor to improve melt processability through molecular weight distribution control. In particular, in the case of polyethylene, toughness, strength, environmental stress resistance characteristics, etc. are very importantly applied.

Accordingly, the mechanical properties and low molecular weight portion of the high molecular weight resin using a hybrid supported catalyst in which two types of a transition metal compound for producing a low molecular weight polyolefin and a transition metal compound for producing a high molecular weight polyolefin are simultaneously supported. A method for improving the processability in

The polyolefin produced by this hybrid supported catalyst has a bimodal molecular weight distribution, and when the degree is extreme, melt fractures such as irregular concave blocks or loss of gloss on the surface during extrusion of polyolefin (melt fracture) may occur.

In order to solve the above problems, an object of the present invention is to provide a hybrid supported catalyst capable of producing a polyolefin capable of minimizing defects during processing while having excellent processability and physical properties.

In addition, the present invention provides a method for producing polyolefin using the hybrid supported catalyst.

According to one embodiment of the present invention,

A first transition metal compound represented by the following formula (1);

a second transition metal compound represented by the following formula (2);

A third transition metal compound represented by the following formula (3); and

a carrier supporting the first to third transition metal compounds;

There is provided a hybrid supported catalyst comprising:

[Formula 1]

In Formula 1,

M ₁ is a Group 4 transition metal,

Cp ₁₁ and Cp ₁₂ are each independently any one ring compound selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl, wherein the ring compound is unsubstituted, or at least one hydrogen of the ring compound is each independently selected from among C1 to C20 alkyl, C2 to C20 alkenyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl substituted with any one of the substituents,

Z ₁₁ and Z ₁₂ are each independently halogen,

[Formula 2]

In Formula 2,

M ₂ is a Group 4 transition metal,

Cp ₂₁ is any one ring compound selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl, the ring compound is unsubstituted, or one or more hydrogens of the ring compound are each independently C1 to 20 Substituted with any one of alkyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl,

X ₂₁ and X ₂₂ are each independently halogen,

B is carbon, silicon, or germanium;

R ₂₁ to R ₂₃ are each independently hydrogen, C1 to C20 alkyl, C2 to C20 alkenyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, Or C7 to C20 arylalkyl,

[Formula 3]

In Formula 3,

M ₃ is a Group 4 transition metal,

X ₃₁ and X ₃₂ are each independently halogen,

R ₃₁ and R ₃₂ are each independently C2 to C20 alkoxyalkyl.

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

The supported hybrid catalyst according to the present invention has high activity for olefin polymerization, and it is possible to prepare polyolefins having high compressive stress while having excellent processability and physical properties.

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

The terminology used herein is used to describe exemplary embodiments only, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In this specification, terms such as "comprises", "comprising" or "have" are intended to designate the presence of an embodied feature, step, element, or a combination thereof, but one or more other features or steps; It should be understood that the possibility of the presence or addition of components, or combinations thereof, is not precluded in advance.

Since the present invention may have various changes and may have various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in detail.

According to one embodiment of the present invention,

A first transition metal compound represented by the following formula (1);

a second transition metal compound represented by the following formula (2);

A third transition metal compound represented by the following formula (3); and

a carrier supporting the first to third transition metal compounds;

There is provided a hybrid supported catalyst comprising:

[Formula 1]

In Formula 1,

M ₁ is a Group 4 transition metal,

Cp ₁₁ and Cp ₁₂ are each independently any one ring compound selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl, wherein the ring compound is unsubstituted, or at least one hydrogen of the ring compound is each independently selected from among C1 to C20 alkyl, C2 to C20 alkenyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl substituted with any one of the substituents,

Z ₁₁ and Z ₁₂ are each independently halogen,

[Formula 2]

In Formula 2,

M ₂ is a Group 4 transition metal,

Cp ₂₁ is any one ring compound selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl, the ring compound is unsubstituted, or one or more hydrogens of the ring compound are each independently C1 to 20 Substituted with any one of alkyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl,

X ₂₁ and X ₂₂ are each independently halogen,

B is carbon, silicon, or germanium;

R ₂₁ to R ₂₃ are each independently hydrogen, C1 to C20 alkyl, C2 to C20 alkenyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, Or C7 to C20 arylalkyl,

[Formula 3]

In Formula 3,

M ₃ is a Group 4 transition metal,

X ₃₁ and X ₃₂ are each independently halogen,

R ₃₁ and R ₃₂ are each independently C2 to C20 alkoxyalkyl.

In the present invention, the substituents of the above formula will be described in more detail as follows.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

C1 to C20 alkyl may be straight chain, branched chain or cyclic alkyl. Specifically, the C1 to C20 alkyl is a straight chain alkyl having 1 to 20 carbon atoms; straight-chain alkyl having 1 to 10 carbon atoms; straight-chain alkyl having 1 to 5 carbon atoms; branched or cyclic alkyl having 3 to 20 carbon atoms; branched or cyclic alkyl having 3 to 15 carbon atoms; Or it may be a branched or cyclic alkyl having 3 to 10 carbon atoms. More specifically, alkyl having 1 to 20 carbon atoms is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, or It may be a cyclohexyl group or the like.

C2 to C20 alkenyl may be straight-chain, branched-chain or cyclic alkenyl. Specifically, the C2 to C20 alkenyl is a straight chain alkenyl having 2 to 20 carbon atoms, a straight chain alkenyl having 2 to 10 carbon atoms, a straight chain alkenyl having 2 to 5 carbon atoms, a branched chain alkenyl having 3 to 20 carbon atoms, and 3 carbon atoms. It may be a branched chain alkenyl having 15 to 15 carbon atoms, a branched chain alkenyl having 3 to 10 carbon atoms, a cyclic alkenyl having 5 to 20 carbon atoms, or a cyclic alkenyl having 5 to 10 carbon atoms. More specifically, the alkenyl having 2 to 20 carbon atoms may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl.

C1 to C20 alkoxy may be a straight chain, branched chain or cyclic alkoxy group. Specifically, the C1 to C20 alkoxy is a straight chain alkoxy group having 1 to 20 carbon atoms; straight-chain alkoxy having 1 to 10 carbon atoms; a straight-chain alkoxy group having 1 to 5 carbon atoms; branched or cyclic alkoxy having 3 to 20 carbon atoms; branched or cyclic alkoxy having 3 to 15 carbon atoms; Or it may be a branched or cyclic alkoxy having 3 to 10 carbon atoms. More specifically, alkoxy having 1 to 20 carbon atoms is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentoxy group, iso It may be a -pentoxy group, a neo-pentoxy group or a cyclohexoxy group.

C2 to C20 alkoxyalkyl may have a structure including -R _y -OR _z and may be a substituent in which one or more hydrogens of alkyl (-R _y ) are substituted with alkoxy (-OR _z ). Specifically, the C2 to C20 alkoxyalkyl group is a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group, tert It may be a butoxyethyl group or a tert-butoxyhexyl group.

C6 to C20 aryl may mean a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, the C6 to C20 aryl may be a phenyl group, a naphthyl group, or an anthracenyl group.

C7 to C20 alkylaryl may mean a substituent in which at least one hydrogen of aryl is substituted with alkyl. Specifically, the C7 to C20 alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl or cyclohexylphenyl.

C7 to C20 arylalkyl may mean a substituent in which at least one hydrogen of the alkyl is substituted with aryl. Specifically, the C7 to C20 arylalkyl may be a benzyl group, phenylpropyl, or phenylhexyl.

Examples of the Group 4 transition metal include titanium, zirconium, and hafnium.

The hybrid supported catalyst according to an embodiment of the present invention includes a low molecular weight, low copolymerizable first transition metal compound, a high molecular weight high copolymerizable second transition metal compound, and the first transition metal compound and the second transition It is a hybrid catalyst simultaneously containing a third transition metal compound exhibiting an intermediate molecular weight and copolymerizability of a metal compound.

Specifically, the first transition metal compound represented by Formula 1 contributes to preparing a low molecular weight polymer having a low short chain branch (SCB) content, and the second transition metal compound represented by Formula 2 has a high SCB content Contributes to making high molecular weight polymers with In addition, the third transition metal compound represented by Chemical Formula 3 may relieve a bimodal molecular weight distribution by preparing a polymer having a medium molecular weight.

Accordingly, the polymer prepared from the supported hybrid catalyst of the present invention has a wide molecular weight distribution, and while the bimodality is reduced, the extrusion stress is improved, so that melt fracture that may occur during extrusion of the polymer can be significantly reduced. Therefore, the polyolefin prepared by the hybrid supported catalyst of the present invention can be suitably used for high pressure heating pipes or PE-RT pipes that require excellent processability and mechanical properties.

Hereinafter, the first, second, and third transition metal compounds included in the supported hybrid catalyst of the present invention will be described in detail.

The first transition metal compound represented by Formula 1 contributes to the preparation of a low molecular weight polymer, and exhibits a relatively low comonomer incorporation rate.

In Formula 1, the central metal M ₁ may be zirconium (Zr).

In Formula 1, Z ₁₁ and Z ₁₂ are each independently halogen, and preferably all of them may be Cl.

In Formula 1, Cp ₁₁ and Cp ₁₂ are each independently any one ring compound selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl. the cyclic compound is unsubstituted, or one or more hydrogens of the cyclic compound are each independently C1 to 6 alkyl, C1 to 6 alkenyl, C2 to C10 alkoxyalkyl, C6 to C12 aryl, or C7 to C12 It may be substituted with any one of the substituents.

Specific examples of the first transition metal compound represented by Formula 1 may include the following compounds:

In the above, Ph means phenyl.

The first transition metal compound represented by the above formula (1) may be synthesized by applying known reactions, and for more detailed synthesis method, refer to Examples.

The second transition metal compound represented by Formula 2 contributes to the preparation of a high molecular weight polymer, and exhibits a relatively high comonomer incorporation rate.

In Formula 2, the central metal M ₂ may be titanium (Ti).

X ₂₁ of Formula 2 and X ₂₂ are each independently halogen, and preferably all of them may be Cl.

In Formula 2, Cp ₂₁ may be cyclopentadienyl, wherein one or more hydrogens of cyclopentadienyl may be substituted with C1 to C4 alkyl. The substituted cyclopentadienyl may exhibit better catalytic activity due to the inductive effect of supplying electrons.

In another embodiment, Cp ₂₁ may be indenyl unsubstituted or substituted with C1 to C4 alkyl, C2 to C10 alkoxyalkyl, or C7 to C20 arylalkyl. Alternatively, Cp ₂₁ may be unsubstituted fluorenyl.

In Formula 2, B may be carbon (C) or silicon (Si), and R ₂₁ and R ₂₂ as a substituent of B may each independently be C1 to C4 alkyl or C5 to C10 alkoxyalkyl.

In a preferred embodiment, any one of R ₂₁ and R ₂₂ is an alkoxyalkyl of -(CH ₂ ) _n R _b (wherein R _b is C3 to C4 alkoxy, n is an integer from 2 to 6), and the other is It may be C1 to C4 alkyl.

In addition, in Formula 2, R ₂₃ may be C1 to C10 alkyl, C2 to C6 alkenyl, C1 to C10 alkoxyalkyl, or C6 to C12 aryl.

Specific examples of the second transition metal compound represented by Formula 2 may include the following compounds:

The second transition metal compound represented by Chemical Formula 2 may be synthesized by applying known reactions, and more detailed synthesis methods may refer to Examples.

The third transition metal compound represented by Formula 3 is a compound including two 4,5,6,7-tetrahydro-1-indene groups, which is higher than that of the polymer prepared by the first transition metal compound, and 2 Contributes to the preparation of a medium-molecular-weight polymer having a lower molecular weight than a polymer prepared by a transition metal compound.

A Group 4 transition metal may be used as the central metal of the third transition metal compound represented by Formula 3, and preferably zirconium (Zr).

Preferably, in Formula 1, both X ₃₁ and X ₃₂ may be Cl.

Preferably, in Formula 1, R ₃₁ and R ₃₂ may be the same as or different from each other, and each independently C2 to C10 alkoxyalkyl. More specifically, R ₁₁ and R ₁₂ may each independently be isopropoxyhexyl, t-butoxypentyl, t-butoxyhexyl, or t-butoxyheptyl, preferably R ₁₁ and R ₁₂ may all be t-butoxyhexyl.

Specific examples of the third transition metal compound represented by Formula 3 include, but are not limited to, a compound represented by Formula 3-1 below:

[Formula 3-1]

The first transition metal compound represented by Chemical Formula 3 may be synthesized by applying known reactions, and for more detailed synthesis method, refer to Examples.

Meanwhile, according to one embodiment of the present invention, the loading amounts of the first transition metal compound, the second transition metal compound, and the third transition metal compound are the same or different from each other, and each independently 0.02 mmol to 1 mmol based on 1 g of the carrier, or 0.024 mmol to 0.2 mmol. When the supported amount of the first, second, and third transition metal compounds satisfies the above range, the activity of the finally prepared hybrid supported catalyst is more excellent, and the physical properties of the polyolefin prepared using the hybrid supported catalyst are can be maintained at a high level.

In addition, the supported hybrid catalyst according to an embodiment of the present invention may be one in which the first transition metal compound, the second transition metal compound, and the third transition metal compound are supported in a molar ratio of 1: 1-2: 1-2. have. That is, the hybrid supported catalyst may be one in which 1 to 2 moles of the second transition metal compound and 1 to 2 moles of the third transition metal compound are supported with respect to 1 mole of the first transition metal compound. Preferably, the first transition metal compound, the second transition metal compound, and the third transition metal compound may be supported in a molar ratio of 1: 1-1.5: 1-1.5, preferably 1:1:1. It can be loaded with rain.

When the molar ratio of each transition metal compound satisfies the above range, the catalyst activity can be maintained excellently, and the bimodality of the molecular weight distribution of the polyolefin prepared using the hybrid supported catalyst is reduced, so that more improved extrusion properties can be exhibited.

As the carrier for supporting the first to third transition metals, a carrier having a hydroxy group, a silanol group or a siloxane group having high reactivity on the surface may be used, and for this purpose, it is surface-modified by calcination, or dried What has been removed from the moisture on the surface can be used.

For example, silica prepared by calcining silica gel, silica such as silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are typically Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg ( oxide, carbonate, sulfate, and nitrate components such as NO ₃ ) ₂ .

The temperature for calcining or drying the carrier may be 200 to 600 °C, and may be 250 to 600 °C. When the calcination or drying temperature of the carrier is lower than 200 °C, there is a risk that the moisture on the surface reacts with the cocatalyst because there is too much moisture remaining on the carrier, and the cocatalyst due to the excess hydroxyl groups The loading rate can be relatively high, but this requires a large amount of co-catalyst. In addition, when the drying or calcination temperature is too high, exceeding 600 °C, the pores on the surface of the carrier are combined and the surface area is reduced, and a lot of hydroxyl groups or silanol groups are lost on the surface, and only siloxane groups are left, which reacts with the promoter. There is a possibility that seats will be reduced.

For example, the amount of hydroxyl groups on the surface of the carrier may be 0.1 to 10 mmol/g, or 0.5 to 5 mmol/g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions or drying conditions of the carrier, such as temperature, time, vacuum or spray drying, and the like. If the amount of the hydroxyl group is too low, there are few reaction sites with the co-catalyst, and if it is too large, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle.

Among the above-mentioned carriers, in the case of silica, since the functional group of the silica carrier and the metallocene compound is supported by chemical bonding, there is almost no catalyst released from the surface of the carrier in the copolymer polymerization process.

When the first to third transition metal compounds are supported on a carrier, the total amount of the first to second transition metal compounds is 0.06 mmol or more, or 0.1 mmol or more, based on 1 g of silica, per weight of the carrier, and , 3 mmol or less, or may be supported in a content range of 2.5 mmol or less. When supported in the above content range, it may exhibit an appropriate supported catalyst activity, which may be advantageous in terms of maintaining the activity of the catalyst and economic feasibility.

In addition, the supported hybrid catalyst according to an embodiment of the present invention may further include a cocatalyst in terms of improving high activity and process stability, in addition to the first to third transition metal compounds and the carrier. The cocatalyst may include at least one of compounds represented by the following Chemical Formula 4, Chemical Formula 5, or Chemical Formula 6.

[Formula 4]

-[Al(R ₄₁ )-O] _m -

In Formula 4,

R ₄₁ is the same as or different from each other, and each independently represents a halogen, a C1 to C20 hydrocarbon, or a halogen-substituted C1 to C20 hydrocarbon;

m is an integer greater than or equal to 2,

[Formula 5]

J(R ₅₁ ) ₃

In Formula 5,

R ₅₁ is the same as or different from each other, and each independently represents a halogen, a C1 to C20 hydrocarbon, or a halogen-substituted C1 to C20 hydrocarbon;

J is aluminum or boron,

[Formula 6]

[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-

In Formula 6,

E is a neutral or cationic Lewis base,

H is a hydrogen atom,

Z is a group 13 element,

Q is the same as or different from each other, and each independently represents C6 to C20 aryl or C1 to C20 alkyl in which one or more hydrogen atoms are unsubstituted or substituted with halogen, C1 to C20 hydrocarbon, alkoxy or phenoxy.

Examples of the compound represented by Formula 4 include aluminoxane-based compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane, any one or mixture of two or more thereof may be used .

Examples of the compound represented by Formula 5 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, and tricyclopentylaluminum. , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and more specifically, may be selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

In addition, examples of the compound represented by Formula 6 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (p- Tolyl) boron, trimethylammonium tetra(o,p-dimethylphenyl) boron, tributylammonium tetra(p-trifluoromethylphenyl) boron, trimethylammonium tetra(p-trifluoromethylphenyl) boron, tributylammonium Umtetrapentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenyl Phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p -Tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium Tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum , diethylammonium tetrapentatetraphenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o, p-dimethylphenyl) ) boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl)boron, or triphenylcarboniumtetrapentafluorophenylboron. and any one or a mixture of two or more thereof may be used.

Among the cocatalysts, considering that better catalytic activity can be exhibited when used in combination with the first to third transition metal compounds, as the cocatalyst, the compound of Formula 4, more specifically, methylaluminoxane It may be an alkyl aluminoxane, such as. The alkylaluminoxane-based cocatalyst acts as a scavenger for hydroxyl groups present on the surface of the carrier to improve activity.

The cocatalyst may be supported in an amount of 1 mmol or more, or 3 mmol or more, and 25 mmol or less, or 20 mmol or less per weight of the carrier, for example, based on 1 g of the carrier. When included in the above content range, it is possible to sufficiently obtain the effect of reducing the generation of fine powder together with the effect of improving the catalytic activity according to the use of the cocatalyst.

The hybrid supported catalyst may be prepared by supporting the first to third transition metal compounds on the support. The first to third transition metal compounds may be supported at the same time, or each may be supported in stages.

When the hybrid supported catalyst further includes the above cocatalyst, the cocatalyst may be supported before or after the first to third transition metal compounds are supported. Alternatively, one or two of the first to third transition metal compounds may be first supported on a carrier, then a promoter may be supported, and then the remaining two or one type of transition metal compound may be supported.

As described above, the hybrid supported catalyst according to an embodiment of the present invention includes different types of transition metal compounds, thereby exhibiting excellent catalytic activity. Accordingly, the supported hybrid catalyst may be suitably used for polymerization of olefinic monomers.

Accordingly, in one embodiment of the present invention, there is provided a method for producing polyolefin, comprising the step of polymerizing an olefin-based monomer in the presence of the hybrid supported catalyst.

The olefinic monomer may be ethylene, alpha-olefin, cyclic olefin, diene olefin or triene olefin having two or more double bonds.

Specific examples of the olefinic monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene , 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc., and may be copolymerized by mixing two or more of these monomers.

The polymerization reaction may be carried out by homopolymerization with one olefinic monomer or copolymerization with two or more types of monomers using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor, or solution reactor.

The hybrid supported catalyst is an aliphatic hydrocarbon solvent having 4 to 12 carbon atoms, for example, isobutane, pentane, hexane, heptane, nonane, decane, and isomers thereof, and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane, chlorobenzene and It can be injected by dissolving or diluting in a hydrocarbon solvent substituted with the same chlorine atom. The solvent used here is preferably used by treating a small amount of alkyl aluminum to remove a small amount of water or air that acts as a catalyst poison, and it is also possible to further use a cocatalyst.

In addition, the polymerization reaction may be carried out at a temperature of 40 °C or higher, or 60 °C or higher, 110 °C or lower or 100 °C or lower, and when the pressure condition is further controlled, 1 bar or more, or 5 bar or more and may be carried out under a pressure of 15 bar or less, or 10 bar or less.

The polyolefin produced by the hybrid supported catalyst of the present invention has a high molecular weight, a wide molecular weight distribution and a relaxed bimodal distribution, so that it has excellent processability and high extrusion stress, resulting in fewer defects during processing.

The supported hybrid catalyst of the present invention may be used for polymerization of polyethylene, for example. Polyethylene prepared from the hybrid supported catalyst exhibits a high weight average molecular weight (Mw) of 500,000 g/mol or more, preferably 550,000 g/mol or more, and has a molecular weight distribution (PDI) in the range of 5 to 15, or 8 to 10 satisfactory, and excellent workability can be exhibited. The upper limit of the weight average molecular weight of the polyethylene is not particularly limited, but may be, for example, 1,000,000 g/mol or less, or 850,000 g/mol or less.

Meanwhile, in the present invention, the weight average molecular weight and molecular weight distribution of the polyethylene may be measured using gel permeation chromatography (GPC). Specifically, after measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn), PDI may be determined as the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn). Methods for measuring the weight average molecular weight and molecular weight distribution will be described in more detail in Examples to be described later.

In addition, the polyethylene may have a characteristic stress of 10 MPa or more, or 12 MPa or more, and 20 MPa or less, or 18 MPa or less. As described above, the polyethylene exhibits a high compressive stress as described above by having a wide molecular weight distribution and a relaxed bimodal distribution, and thus the occurrence of melt fracture during extrusion can be minimized. The method for measuring the intrinsic stress will be described in more detail in Examples to be described later.

As such, the polyolefin prepared by the hybrid supported catalyst of the present invention exhibits a high molecular weight, a broad molecular weight distribution (PDI), and a high compressive stress, thereby exhibiting excellent mechanical properties and processability. Accordingly, the polyolefin may be suitably used for a high-pressure heating pipe or a PE-RT pipe.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that changes and modifications fall within the scope of the appended claims.

[Example]

<Preparation of transition metal compound>

Preparation Example 1: Preparation Example of First Transition Metal Compound

[tBu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ manufacture of

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

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

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

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

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

Preparation Example 2: Preparation Example of the Second Transition Metal Compound

(tBu-O-(CH ₂ ) ₆ )(CH ₃ )Si(C ₅ (CH ₃ ) ₄ )(tBu-N)TiCl ₂ manufacture of

(Step 1)

After adding 50 g of Mg(s) to a 10 L reactor at room temperature, 300 mL of THF was added. After adding about 0.5 g of I ₂ , the temperature of the reactor was maintained at 50 °C. After the reactor temperature was stabilized, 250 g of 6-t-butoxyhexyl chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. As 6-t-butoxyhexyl chloride was added, it was observed that the reactor temperature increased by 4 to 5 °C. The mixture was stirred for 12 hours while continuously adding 6-t-butoxyhexyl chloride. After 12 hours of reaction, a black reaction solution was obtained. After taking 2 mL of the resulting black solution, water was added to obtain an organic layer, and 6-t-butoxyhexane was identified through ¹ H-NMR. It was found that the Grignard reaction proceeded well from the 6-t-butoxyhexane. Thus, 6-t-butoxyhexyl magnesium chloride was synthesized.

After adding 500 g of MeSiCl ₃ and 1 L of THF to the reactor, the temperature of the reactor was cooled to -20 °C. 560 g of the synthesized 6-t-butoxyhexyl magnesium chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. After feeding of the Grignard reagent was completed, the temperature of the reactor was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, it was confirmed that a white MgCl ₂ salt was formed. By adding 4 L of hexane, salt was removed through a labdori to obtain a filter solution. After adding the obtained filter solution to the reactor, hexane was removed at 70°C to obtain a pale yellow liquid. It was confirmed that the obtained liquid was a desired methyl (6-t-butoxy hexyl) dichlorosilane {Methyl (6-t-butoxy hexyl) dichlorosilane} compound through ¹ H-NMR.

¹ H-NMR (CDCl3): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H)

(Step 2)

After adding 1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF to the reactor, the temperature of the reactor was cooled to -20°C. n-BuLi was added to the reactor at a rate of 5 mL/min using a 480 mL feeding pump. After adding n-BuLi, the reactor was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, an equivalent of methyl (6-t-butoxy hexyl) dichlorosilane (326 g, 350 mL) was quickly added to the reactor. After stirring for 12 hours while slowly raising the temperature of the reactor to room temperature, the temperature of the reactor was cooled to 0 °C again, and 2 equivalents of t-BuNH ₂ was added thereto. The reactor was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, THF was removed, and 4 L of hexane was added to obtain a filter solution from which salt was removed through Labdory. After adding the filter solution to the reactor again, hexane was removed at 70 °C to obtain a yellow solution. Confirm that the obtained yellow solution is a compound of methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane (Methyl(6-t-butoxyhexyl) (tetramethylCpH) t-Butylaminosilane) through ¹ H-NMR did

TiCl ₃ (THF) ₃ (10 mmol) was added rapidly. The reaction solution was stirred for 12 hours while slowly raising the temperature from -78 °C to room temperature. After stirring for 12 hours, an equivalent of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution with a bluish color was obtained. After removing THF from the resulting reaction solution, hexane was added to filter the product. After removing hexane from the obtained filter solution, it was confirmed from ¹ H-NMR that it was (tBu-O-(CH ₂ ) ₆ )(CH ₃ )Si(C ₅ (CH ₃ ) ₄ )(tBu-N)TiCl ₂ .

¹ H-NMR (CDCl ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H) , 0.7 (s, 3H)

Preparation Example 3: Preparation Example of the Third Transition Metal Compound

[tBu-O-(CH ₂ ) ₆ -C ₉ H ₁₂ ] ₂ ZrCl ₂ manufacture of

bis(3-(6-(tert-butoxy)hexyl)-1H-inden-1-yl)zirconium(IV) chloride (21 g, 30 mmol), Pd/C (2.4 g, 10 mol) in a dried bombe reactor %) and diluted in 40 mL of DCM. Here, hydrogen was stirred at 20 atmospheres for one day. After transfer to Schlenk flask, dried, substituted with Hexane (20mL), [tBu-O-(CH ₂ ) ₆ -C ₉ H ₁₂ ] ₂ ZrCl ₂ 21.2 g was obtained through a Celite filter.

¹ H NMR (500 MHz, Benzene-D ₆ ): 5.79 (1H, s), 5.69 (1H, s), 5.26 (1H, s), 5.22 (1H, s), 3.31 (4H, m), 3.01-2.90 (4H, m), 2.51-2.31 (8H, m), 1.92 (2H, m), 1.82 (2H, m), 1.65-1.27 (10H, m), 1.15 (18H, s)

<Preparation of supported catalyst>

Example 1

Silica (Grace Davison, SYLOPOL 948) was dehydrated by placing it in a vacuum at 650 °C for 15 h.

4.2 g of the dried silica was put in a 300 mL glass reactor at a temperature of 40 °C, and 50 mL of toluene was added and stirred. Thereafter, 50.5 ml of a 10 wt% methylaluminoxane (MAO)/toluene solution was added to the reactor, the temperature of the reactor was raised to 80 °C, and the mixture was stirred at 200 rpm for 12 hours.

After lowering the reactor temperature to 40 °C, 0.1 mmol of the first transition metal compound prepared in Preparation Example 1, 0.1 mmol of the second transition metal compound prepared in Preparation Example 2, and the third transition prepared in Preparation Example 3 0.1 mmol of a metal compound was dissolved in 10 ml of toluene, and 0.01 mmol of dibutylmagnesium was added, followed by stirring at 40 °C overnight.

After the reaction was completed, the stirring was stopped, the toluene layer was separated and removed, and the residual toluene was removed by reducing the pressure at 40 °C to prepare a hybrid supported catalyst.

Comparative Example 1

In the same manner as in Example 1, except that 0.1 mmol of the first transition metal compound prepared in Preparation Example 1 and 0.1 mmol of the second transition metal compound prepared in Preparation Example 2 were used without using the third transition metal compound. A hybrid supported catalyst was prepared.

Comparative Example 2

In the same manner as in Example 1, except that 0.1 mmol of the first transition metal compound prepared in Preparation Example 1 and 0.1 mmol of the third transition metal compound prepared in Preparation Example 3 were used without using the second transition metal compound. A hybrid supported catalyst was prepared.

Comparative Example 3

In the same manner as in Example 1, except that 0.1 mmol of the second transition metal compound prepared in Preparation Example 2 and 0.1 mmol of the third transition metal compound prepared in Preparation Example 3 were used without using the first transition metal compound. A hybrid supported catalyst was prepared.

Polymerization Example 1: Preparation of homopolyethylene

600 ml of hexane was put into a 2 L autoclave high-pressure reactor under an argon atmosphere, and 2 g of triethylaluminum was added to remove moisture inside the reactor, and then hexane was removed. Then, 600 ml of hexane and 0.2 g of triethylaluminum were added under an argon atmosphere, and 20 mg of the supported hybrid catalyst prepared in Example 1 was added. After venting argon in the reactor, polyethylene was prepared by polymerization at 78° C. and ethylene pressure of 30 bar for 1 hour.

Polymerization Comparative Example 1: Preparation of homopolyethylene

Polyethylene was prepared in the same manner as in Polymerization Example 1, except that the hybrid supported catalyst prepared in Comparative Example 1 was used as the polymerization catalyst.

Polymerization Examples 2 to 4: Preparation of Polyethylene in the Presence of Hydrogen

During polymerization, polyethylene was prepared in the same manner as in Polymerization Example 1, except that hydrogen was added at the content (% by weight) of Table 1 with respect to 100% by weight of ethylene.

Polymerization Comparative Examples 2 to 4: Preparation of polyethylene in the presence of hydrogen

During polymerization, polyethylene was prepared in the same manner as in Comparative Polymerization Example 1, except that hydrogen was added at the content (% by weight) of Table 1 with respect to 100% by weight of ethylene.

Polymerization Comparative Example 5: Preparation of polyethylene in the presence of hydrogen

Polyethylene was prepared in the same manner as in Polymerization Example 2, except that the hybrid supported catalyst prepared in Comparative Example 2 was used as the polymerization catalyst.

Polymerization Comparative Example 6: Preparation of polyethylene in the presence of hydrogen

Polyethylene was prepared in the same manner as in Polymerization Example 2, except that the hybrid supported catalyst prepared in Comparative Example 3 was used as the polymerization catalyst.

test example

The polymerization activity of the supported catalysts of Examples and Comparative Examples and the physical properties of the prepared polyethylene were evaluated by the following method, and the results are shown in Table 1.

(1) Polymerization activity of catalyst (Activity, kg PE/g cat ^. hr): It was calculated as the ratio of the weight (kg PE) of the polymer produced per mass (g) of the supported catalyst used based on the unit time (h).

(2) weight average molecular weight (Mw, g / mol) and molecular weight distribution (PDI, polydispersity index): using gel permeation chromatography (GPC) to measure the weight average molecular weight (Mw) and number average molecular weight (Mn), respectively, Then, the molecular weight distribution was calculated as the ratio of Mw/Mn. Specifically, it was measured using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm long column. At this time, the evaluation temperature was 160 °C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL/min. Samples were prepared at a concentration of 10 mg/10 mL and then supplied in an amount of 200 μL. The values of Mw and Mn were derived using a calibration curve formed using polystyrene standards. The molecular weight (g/mol) of polystyrene standards was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

(3) Melt index (MI): Measured under the conditions of 190 °C and 2.16 kg load according to ASTM D1238 using Dynisco's D4002HV apparatus.

(4) Characteristic Stress (C.S, MPa):

Characteristic stress (C.S.) was measured through a tensile test of stress-strain according to ASTM D 638 method.

Specifically, after obtaining a stress-strain curve for the tensile test under the following test conditions, plot the yield stress and drawig stress according to the strain rate, and extrapolation with a low strain rate, the yield When the stress and the drawing stress were the same, the value was measured as a characteristic stress.

Test : D638

Specimen: D638, Type IV

Strain rate: 0.1, 0.05, 0.01, 0.005 mm/mm s

Yield Stress: The stress at the yield point

Drawing Stress : Stress at 100% Strain (Dutile deformation)

x-axis: ln(strain rate)

y-axis: Stress

(5) Shear viscosity (η _1000, Pa s)

Measurements were made using a capillary at 210 °C and a shear rate of 1/1000 sec.

Specifically, the viscosity was measured at a temperature of 210° C. and a shear rate of 1/1000 second at a die size of 10/2 using a RHEO-TESTER 2000 equipment from Gottfert.

catalyst Amount of hydrogen added during polymerization (%)* catalytic activity
(kg PE/g cat ^. hr) Mw
(g/mol) PDI MI C.S (MPa) shear viscosity
(Pa s) Polymerization Comparative Example 1 Comparative Example 1 - 5.1 588,000 5.9 - - - Polymerization Comparative Example 2 0.1 5.4 545,000 5.1 0.11 13.3 100 Polymerization Comparative Example 3 0.2 5.5 502,000 5.8 0.25 11.6 250 Polymerization Comparative Example 4 0.3 5.0 443,000 5.0 0.47 10.4 250 Polymerization Comparative Example 5 Comparative Example 2 0.1 5.6 412,000 4.0 0.50 8.0 270 Polymerization Comparative Example 6 Comparative Example 3 0.1 4.6 605,000 3.5 0.09 11.5 90 Polymerization Example 1 Example 1 - 6.2 725,000 8.7 - - - Polymerization Example 2 0.1 6.5 677,000 8.6 0.06 15.1 400 Polymerization Example 3 0.2 5.8 611,000 8.3 0.18 13.4 400 Polymerization Example 4 0.3 5.3 556,000 8.3 0.33 12.0 630

* The amount of hydrogen added during polymerization is expressed in weight% compared to 100% by weight of ethylene.

Referring to Table 1, in the case of the supported hybrid catalyst of Example 1 containing the first to third transition metal compounds, high catalytic activity, the produced polyethylene has a high molecular weight, a wide molecular weight distribution, and a low melt index can check that In addition, since the polyolefin prepared from the supported hybrid catalyst of Example 1 has high compressive stress and shear rate, it can be expected that melt fracture does not occur during extrusion.

Claims (14)

A first transition metal compound represented by the following formula (1);
a second transition metal compound represented by the following formula (2);
A third transition metal compound represented by the following formula (3); and
a carrier supporting the first to third transition metal compounds;
A hybrid supported catalyst comprising:
[Formula 1]

In Formula 1,
M ₁ is a Group 4 transition metal,
Cp ₁₁ and Cp ₁₂ are each independently any one ring compound selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl, wherein the ring compound is unsubstituted, or at least one hydrogen of the ring compound is each independently selected from among C1 to C20 alkyl, C2 to C20 alkenyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl substituted with any one of the substituents,
Z ₁₁ and Z ₁₂ are each independently halogen,
[Formula 2]

In Formula 2,
M ₂ is a Group 4 transition metal,
Cp ₂₁ is any one ring compound selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl, the ring compound is unsubstituted, or one or more hydrogens of the ring compound are each independently C1 to 20 Substituted with any one of alkyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl,
X ₂₁ and X ₂₂ are each independently halogen,
B is carbon, silicon, or germanium;
R ₂₁ to R ₂₃ are each independently hydrogen, C1 to C20 alkyl, C2 to C20 alkenyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, Or C7 to C20 arylalkyl,
[Formula 3]

In Formula 3,
M ₃ is a Group 4 transition metal,
X ₃₁ and X ₃₂ are each independently halogen,
R ₃₁ and R ₃₂ are each independently C2 to C20 alkoxyalkyl.
According to claim 1,
In Formula 1,
Cp ₁₁ and Cp ₁₂ are each independently any one ring compound selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl, wherein the ring compound is unsubstituted, or at least one hydrogen of the ring compound is Each independently substituted with any one substituent of C1 to 6 alkyl, C1 to 6 alkenyl, C2 to C10 alkoxyalkyl, C6 to C12 aryl, or C7 to C12 arylalkyl, a hybrid supported catalyst.
According to claim 1,
The first transition metal compound represented by Formula 1 is any one selected from the group consisting of, a hybrid supported catalyst:

According to claim 1,
In Formula 2,
Cp ₂₁ is cyclopentadienyl substituted with one or more C1 to C4 alkyl; unsubstituted indenyl; indenyl substituted with C1 to C4 alkyl, C2 to C10 alkoxyalkyl, or C7 to C20 arylalkyl; or unsubstituted fluorenyl, a hybrid supported catalyst.
According to claim 1,
In Formula 2,
B is carbon or silicon,
R ₂₁ and R ₂₂ are each independently C1 to C4 alkyl or C5 to C10 alkoxyalkyl.
The second transition metal compound represented by Formula 2 is any one selected from the group consisting of the following, a hybrid supported catalyst:

According to claim 1,
In Formula 3, R ₃₁ and R ₃₂ are the same as or different from each other, and each independently C2 to C10 alkoxyalkyl.
According to claim 1,
In Formula 3, M ₁ is Zr, and R ₃₁ and R ₃₂ are both t-butoxyhexyl, a hybrid supported catalyst.
According to claim 1,
Wherein Formula 3 is represented by the following Formula 3-1, a hybrid supported catalyst:
[Formula 3-1]

According to claim 1,
The supported amounts of the first transition metal compound, the second transition metal compound, and the third transition metal compound are the same or different from each other and each independently 0.02 mmol to 1 mmol based on 1 g of the carrier, a hybrid supported catalyst.
According to claim 1,
The molar ratio of the first transition metal compound, the second transition metal compound, and the third transition metal compound is 1: 1-2: 1-2, a hybrid supported catalyst.
According to claim 1,
The carrier is silica, alumina, magnesia, or a mixture thereof, a hybrid supported catalyst.
According to claim 1,
A hybrid supported catalyst further comprising one or more cocatalysts selected from the group consisting of compounds of Formulas 4 to 6:
[Formula 4]
-[Al(R ₄₁ )-O] _m -
In Formula 4,
R ₄₁ is the same as or different from each other, and each independently represents a halogen, a C1 to C20 hydrocarbon, or a halogen-substituted C1 to C20 hydrocarbon;
m is an integer greater than or equal to 2,
[Formula 5]
J(R ₅₁ ) ₃
In Formula 5,
R ₅₁ is the same as or different from each other, and each independently represents a halogen, a C1 to C20 hydrocarbon, or a halogen-substituted C1 to C20 hydrocarbon;
J is aluminum or boron,
[Formula 6]
[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-
In Formula 6,
E is a neutral or cationic Lewis base,
H is a hydrogen atom,
Z is a group 13 element,
Q is the same as or different from each other, and each independently represents C6 to C20 aryl or C1 to C20 alkyl, in which one or more hydrogen atoms are unsubstituted or substituted with halogen, C1 to C20 hydrocarbon, alkoxy or phenoxy.
A method for producing polyolefin, comprising the step of polymerizing an olefinic monomer in the presence of a supported hybrid catalyst according to any one of claims 1 to 13.