KR102821274B1 - Hybrid supported catalyst - Google Patents

Abstract

The present invention relates to a hybrid supported catalyst capable of producing a polyolefin having high activity in olefin polymerization, a high BOCD index and melt flow rate, and excellent stress cracking resistance.

Description

Hybrid Supported Catalyst {HYBRID SUPPORTED CATALYST}

The present invention relates to a hybrid supported catalyst capable of producing a polyolefin having a high BOCD index and excellent mechanical properties and processability.

Polyolefin resins used in large-diameter high-pressure pipes generally require high pressure resistance and excellent processability. High pressure resistance is a property that can generally be expressed in the high-density region, and this is because the higher the crystallinity in the polyolefin resin, the higher the strength (modulus), which increases the ability to withstand high pressure. Pipes generally must have long-term pressure stability for at least 50 years, but if the density is high, the resistance to brittle fracture is low, which has the disadvantage of low long-term pressure resistance. In addition, if the molecular weight is low or the molecular weight distribution is narrow, the large-diameter pipes are difficult to process due to the sagging phenomenon (melt sagging phenomenon) during processing, so polyolefin resins with high molecular weight and very wide molecular weight distribution must be applied to solve these problems. In particular, if the molecular weight is high, the extrusion load is high, and the pipe appearance is poor, so a very wide molecular weight distribution is absolutely required.

Many efforts are being made to improve these problems, and for example, Korean Patent Application Nos. 2003-7007276, 1999-0064650, 2006-7005524, and 2003-7004360 disclose isotropic polyethylene resins for application to blow molded products, compositions containing isotropic polyethylene resins, catalysts for producing the same, etc. However, there is a problem that both physical properties and processability of the products cannot be satisfied at the same time.

Against this backdrop, there is a constant demand for the manufacture of better products with a good balance between properties and processability, and in particular, improvement in stress crack resistance is more necessary.

The present invention provides a hybrid supported catalyst capable of producing a polyolefin having excellent olefin polymerization activity and high BOCD and processability.

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 chemical formula 1;

A second transition metal compound represented by the following chemical formula 2; and

A carrier carrying the first and second transition metal compounds;

As a hybrid supported catalyst comprising:

A hybrid supported catalyst is provided, wherein the molar ratio of the first transition metal compound and the second transition metal compound is 1:4 to 1:10:

[Chemical Formula 1]

In the above chemical formula 1,

M ₁ is a group 4 transition metal;

X ₁₁ and X ₁₂ are the same or different from each other, and each independently is a halogen;

R ₁₁ and R ₁₂ are the same or different and are each independently alkoxyalkyl having C2 to C20,

[Chemical formula 2]

In the above chemical formula 2,

M ₂ is a group 4 transition metal;

Cp is any one cyclic compound selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl, and at least one hydrogen of the cyclic compound may be independently substituted with any one substituent selected from the group consisting of C1 to C20 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 the same or different from each other, and each independently represents halogen, C1 to C20 alkyl, C2 to C10 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl;

B is carbon, silicon, or germanium;

R ₂₁ to R ₂₃ are the same or different, and 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.

The hybrid supported catalyst according to the present invention has high activity in olefin polymerization, has excellent processability due to high BOCD index and melt flow rate, and can produce a polyolefin having excellent stress cracking resistance.

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

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. It should be understood that, as used herein, the terms "comprises," "includes," or "has" are intended to specify the presence of a feature, step, component, or combination thereof implemented, but do not preclude the possibility of the presence or addition of one or more other features, steps, components, or combinations thereof.

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

Hereinafter, 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 chemical formula 1;

A second transition metal compound represented by the following chemical formula 2; and

A carrier carrying the first and second transition metal compounds;

As a hybrid supported catalyst comprising:

A hybrid supported catalyst is provided, wherein the molar ratio of the first transition metal compound and the second transition metal compound is 1:4 to 1:10:

[Chemical Formula 1]

In the above chemical formula 1,

M ₁ is a group 4 transition metal;

X ₁₁ and X ₁₂ are the same or different from each other, and each independently is a halogen;

R ₁₁ and R ₁₂ are the same or different and are each independently alkoxyalkyl having C2 to C20,

[Chemical formula 2]

In the above chemical formula 2,

M ₂ is a group 4 transition metal;

Cp is any one cyclic compound selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl, and at least one hydrogen of the cyclic compound may be independently substituted with any one substituent selected from the group consisting of C1 to C20 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 the same or different from each other, and each independently represents halogen, C1 to C20 alkyl, C2 to C10 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl;

B is carbon, silicon, or germanium;

R ₂₁ to R ₂₃ are the same or different, and 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.

In the present invention, the substituents of the chemical formula are described more specifically as follows.

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

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

The C2 to C20 alkenyl can be a straight chain, branched chain or cyclic alkenyl. Specifically, the C2 to C20 alkenyl can be 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, a branched chain alkenyl having 3 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 can be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl.

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

Alkoxyalkyl having C2 to C20 may be a substituent having a structure containing -R _y -OR _z in which at least one hydrogen of alkyl (-R _y ) is replaced with alkoxy (-OR _z ). Specifically, the alkoxyalkyl having C2 to C20 carbon atoms may be a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhectyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, or a tert-butoxyhexyl group.

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

C7 to C20 alkylaryl may refer to a substituent in which one or more hydrogens of an aryl are replaced by alkyl. Specifically, the C7 to C20 alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, or cyclohexylphenyl.

Arylalkyl having C7 to C20 may refer to a substituent in which one or more hydrogens of alkyl are replaced by aryl. Specifically, the arylalkyl having C7 to C20 may be a benzyl group, phenylpropyl, or phenylhexyl.

The above group 4 transition metals include titanium, zirconium, and hafnium.

The hybrid supported catalyst according to one embodiment of the present invention is a hybrid catalyst comprising a first transition metal compound having a low molecular weight and low polymerizability and a second transition metal compound having a high molecular weight and high polymerizability.

Specifically, the first transition metal compound represented by the chemical formula 1 contributes to producing a low molecular weight copolymer having a low SCB (short chain branch) content, and the second transition metal compound represented by the chemical formula 2 contributes to producing a high molecular weight copolymer having a high SCB content.

Accordingly, the hybrid supported catalyst of the present invention can exhibit high copolymerizability in polyolefins in a high molecular weight range due to the second transition metal compound, while exhibiting low copolymerizability in polyolefins in a low molecular weight range due to the action of the first transition metal compound. As a result, it is very advantageous in the production of polyolefins having a BOCD (broad orthogonal co-monomer distribution) structure in which the content of a comonomer such as an alpha olefin is concentrated in a high molecular weight backbone, that is, a structure in which the SCB content increases as it goes toward the high molecular weight.

In addition, the polyolefin produced by the hybrid supported catalyst has excellent stress cracking resistance, and at the same time, has a BOCD structure with a high SCB (Short Chain Branch) content in the high molecular weight range and a high melt flow rate ratio, so that it can exhibit excellent processability and extrusion properties. Accordingly, the polyolefin produced by the hybrid supported catalyst of the present invention can be suitably used for high-pressure heating pipes or PE-RT pipes, which require high pressure resistance properties and excellent processability in addition to basic mechanical properties.

The first transition metal compound represented by the above chemical formula 1 is a compound containing two 4,5,6,7-tetrahydro-1-indene groups, and exhibits better hydrogen reactivity compared to compounds containing conventional indene groups, thereby enabling a reduction in the amount of hydrogen input during an olefin polymerization reaction, and as a result, improving process stability.

The first transition metal compound represented by the above chemical formula 1 contains an alkoxy alkyl group as a substituent in the 4,5,6,7-tetrahydro-1-indene group, and can exhibit a low conversion rate for the comonomer when producing a polyolefin using an alpha olefin comonomer.

A Group 4 transition metal may be used as the central metal of the first transition metal compound represented by the above chemical formula 1, and preferably, it may be zirconium (Zr).

Preferably, in the chemical formula 1, both X ₁₁ and X ₁₂ can be Cl.

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

Specific examples of the first transition metal compound represented by the above chemical formula 1 include, but are not limited to, the following compounds:

(A)

(A)

The first transition metal compound represented by the above chemical formula 1 can be synthesized by applying known reactions, and more detailed synthesis methods can be found in the examples.

The second transition metal compound represented by the above chemical formula 2 contributes to the production of a high molecular weight copolymer and exhibits a relatively high comonomer incorporation rate compared to the first transition metal compound.

Specifically, in the chemical formula 2, the central metal M ₂ may be titanium (Ti).

Preferably, X ₂₁ of the chemical formula 2 and X ₂₂ are halogen groups, more preferably both can be Cl.

In addition, in the chemical formula 2, B may be silicon (Si), and one of R ₂₁ and R ₂₂ , which are substituents of B, may be an alkoxyalkyl of -(CH ₂ ) _n- R _b (wherein R _b is a C3 to C6 alkoxy, and n is an integer from 2 to 10), and the other may be a C1 to C4 alkyl.

In the above chemical formula 2, Cp may be cyclopentadienyl, and at least one hydrogen of cyclopentadienyl may be substituted with C1 to C4 alkyl. Cyclopentadienyl substituted in this way may exhibit better catalytic activity due to the inductive effect of supplying electrons.

In another embodiment, Cp can be indenyl substituted with C1 to C4 alkyl, C1 to C10 alkoxyalkyl, or C7 to C20 arylalkyl. Alternatively, Cp can be, but is not limited to, unsubstituted fluorenyl.

Additionally, in the chemical formula 2, R ₂₃ may be C1 to C10 alkyl, or C1 to C10 alkoxyalkyl.

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

The second transition metal compound represented by the above chemical formula 2 can be synthesized by applying known reactions, and more detailed synthesis methods can be found in the examples.

The hybrid supported catalyst of the present invention contains the first and second transition metal compounds in a molar ratio of 1:4 to 1:10. When the above-described mixing ratio is satisfied, the activity of the catalyst is excellently maintained, and the polyolefin produced from the hybrid supported catalyst can have the BOCD structure as described above and exhibit high melt flow rate ratio and stress cracking resistance. If the mixing ratio of the first and second transition metal compounds is out of the above range and the first transition metal compound is excessively abundant, it may be difficult to secure stress cracking resistance and BOCD structure. On the other hand, if the second transition metal compound is excessively abundant, the catalytic activity is reduced, and the processability of the produced polyolefin is reduced, and there may be a problem that it is difficult to secure stress cracking resistance and BOCD structure.

As a carrier supporting the first and second transition metals, a carrier having a highly reactive hydroxyl group, silanol group or siloxane group on the surface can be used. For this purpose, a carrier whose surface has been modified by calcination or whose surface moisture has been removed by drying can be used.

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

The calcination or drying temperature for the carrier may be 200 to 600°C, and may be 250 to 600°C. If the calcination or drying temperature for the carrier is low, such as below 200°C, there is a concern that the moisture remaining in the carrier may be too much and the moisture on the surface may react with the cocatalyst, and although the cocatalyst loading rate may be relatively high due to the excessive presence of hydroxyl groups, this requires a large amount of cocatalyst. In addition, if the drying or calcination temperature is excessively high, exceeding 600°C, the pores on the surface of the carrier merge together, the surface area may decrease, many hydroxyl groups or silanol groups may disappear on the surface, and only siloxane groups may remain, which may reduce the reaction sites with the cocatalyst.

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 manufacturing method and conditions of the carrier or the drying conditions, such as temperature, time, vacuum or spray drying. If the amount of hydroxyl groups is too low, there are few reaction sites with the cocatalyst, and if it is too large, it may be caused by moisture other than the hydroxyl groups present on the surface of the carrier particles.

Among the above-mentioned carriers, in the case of silica, since the silica carrier and the functional group of the metallocene compound are chemically bonded and supported, almost no catalyst is liberated from the carrier surface during the copolymer polymerization process.

When the first and second transition metal compounds are supported on a carrier, the total amount of the first and second transition metal compounds may be supported in a content range of 0.05 mmol or more, or 0.1 mmol or more, and 10 mmol or less, or 0.5 mmol or less, based on 1 g of silica. When supported in the content range, it may exhibit appropriate supported catalytic activity, which may be advantageous in terms of maintaining the activity of the catalyst and economic efficiency.

In addition, the hybrid supported catalyst according to one embodiment of the invention may further include a cocatalyst in addition to the first and second transition metal compounds and the support in terms of improving high activity and process stability. The cocatalyst may include at least one of the compounds represented by the following chemical formula 3, chemical formula 4, or chemical formula 5.

[Chemical Formula 3]

-[Al(R ₃₁ )-O] _m -

In the above chemical formula 3,

R ₃₁ are the same or different and each independently represent halogen; a C1 to C20 hydrocarbon; or a C1 to C20 hydrocarbon substituted by halogen;

m is an integer greater than or equal to 2;

[Chemical Formula 4]

J(R ₃₂ ) ₃

In the above chemical formula 4,

R ₃₂ are the same or different and each independently represent halogen; a C1 to C20 hydrocarbon; or a C1 to C20 hydrocarbon substituted by halogen;

J is aluminum or boron;

[Chemical Formula 5]

[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-

In the above chemical formula 5,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a group 13 element;

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

Examples of compounds represented by the above chemical formula 3 include aluminoxane compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane, and one or a mixture of two or more of these may be used.

Examples of the compound represented by the above chemical formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, and more specifically, the compound may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum. there is.

In addition, examples of the compound represented by the chemical formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, Trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium 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-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, Examples thereof include triethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarbonium tetra(p-trifluoromethylphenyl)boron, or triphenylcarbonium tetrapentafluorophenylboron, and one or a mixture of two or more thereof may be used.

Considering that among the above-mentioned cocatalysts, a better catalytic activity can be exhibited when used in combination with the above-mentioned first and second transition metal compounds, the cocatalyst may be a compound of the above-mentioned chemical formula 3, more specifically, an alkyl aluminoxane such as methylaluminoxane. The alkylaluminoxane-based cocatalyst acts as a scavenger for the hydroxyl groups present on the surface of the carrier, thereby improving the activity.

The above-mentioned 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, based on the weight of the carrier, for example, 1 g of the carrier. When included in the above-mentioned content range, the effect of improving catalytic activity according to the use of the cocatalyst and the effect of reducing fine particle generation can be sufficiently obtained.

The above hybrid supported catalyst can be prepared by supporting the first and second transition metal compounds on the above-described carrier. When the above-described hybrid supported catalyst further includes the above-described cocatalyst, the cocatalyst can be supported before or after supporting the first and second transition metal compounds. Alternatively, one of the first or second transition metal compounds can be supported on the carrier first, then the cocatalyst can be supported, and then the remaining one of the transition metals can be supported.

For example, when the hybrid supported catalyst further comprises a cocatalyst, the hybrid supported catalyst of the present invention can be produced by a production method including the steps of: supporting a first transition metal compound on a support; supporting a cocatalyst on the support on which the first transition metal compound is supported; and supporting a second transition metal compound on the support on which the first transition metal compound and the cocatalyst are supported.

The structure of the supported catalyst determined according to the loading/processing order can affect the catalytic activity and process stability during polymer production. As described above, when the first transition metal compound, cocatalyst, and second transition metal compound are loaded sequentially, a structure having excellent processability and physical properties can be secured.

As described above, the hybrid supported catalyst according to one embodiment of the invention can exhibit excellent catalytic activity by including different types of transition metal compounds. Accordingly, the hybrid supported catalyst can be suitably used for the polymerization of olefin monomers.

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

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

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

The above polymerization reaction can be carried out by homopolymerizing one olefin monomer or copolymerizing two or more monomers using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

The above hybrid supported catalyst can be dissolved or diluted and injected into an aliphatic hydrocarbon solvent having 4 to 12 carbon atoms, such as isobutane, pentane, hexane, heptane, nonane, decane, and isomers thereof; an aromatic hydrocarbon solvent such as toluene and benzene; a hydrocarbon solvent substituted with a chlorine atom, such as dichloromethane and chlorobenzene. It is preferable to use the solvent used here after removing a small amount of water or air, which act as catalyst poisons, by treating it with a small amount of alkyl aluminum, and it is also possible to perform the process using a cocatalyst.

In addition, the polymerization reaction can be performed at a temperature of 40 °C or higher, or 60 °C or higher, and 110 °C or lower, or 100 °C or lower, and when the pressure conditions are further controlled, it can be performed under a pressure of 1 bar or higher, or 5 bar or higher, and 15 bar or lower, or 10 bar or lower.

The polyolefin produced by the hybrid supported catalyst of the present invention has a BOCD structure, exhibits a high melt flow rate ratio, and has excellent stress crack resistance, so that it exhibits excellent mechanical properties as well as processability. In a preferred embodiment, the polyolefin may be an ethylene-1-butene copolymer.

Specifically, the polyolefin manufactured using the hybrid supported catalyst may have a Broad Orthogonal Comonomer Distribution index (BOCD index) of 1.0 to 3.0.

The above BOCD structure means a structure in which the content of a comonomer such as alpha-olefin is concentrated on the high molecular weight main chain, that is, a structure in which the content of short chain branches (SCB) increases as the high molecular weight increases. Here, the term short chain branches (SCB) refers to branches having 2 to 6 carbon atoms attached to the main chain, and usually refers to side branches created when an alpha-olefin having 4 or more carbon atoms, such as 1-butene, 1-hexene, and 1-octene, is used as a comonomer.

The BOCD index can be measured according to the standard method using a GPC-FTIR device. Specifically, when a molecular weight distribution curve is drawn with the logarithm value (log M) of the molecular weight (M) as the x-axis and the molecular weight distribution (dwt/dlog M) for the logarithm value as the y-axis, the SCB (Short Chain Branch) content (branch content having 2 to 7 carbon atoms per 1,000 carbon atoms, unit: branches/1,000C) is measured at the left and right boundaries of the middle 60% excluding the left and right ends of the total area, and the BOCD index can be calculated according to the following mathematical equation 1. At this time, the high molecular weight SCB content and the low molecular weight SCB content mean the SCB content values at the right and left boundaries of the middle 60% range, respectively. The method for measuring BOCD will be described in more detail in the examples described below.

[Mathematical formula 1]

BOCD index = (SCB content on the high molecular weight side - SCB content on the low molecular weight side) / (SCB content on the low molecular weight side)

If the BOCD index is less than 0, it can be seen as a polymer that does not have a BOCD structure, and if it is greater than 0, it can be seen as a polymer that has a BOCD structure. The larger the value, the better the BOCD characteristics. Polymers with a BOCD structure can exhibit better properties by concentrating tie molecules such as SCB in the high molecular weight portion, which is relatively responsible for the properties, rather than in the low molecular weight portion.

In the present invention, by concentrating SCB in a high molecular weight portion while simultaneously implementing a small amount of SCB in a low molecular weight portion by using the hybrid supported catalyst described above, the physical properties and processability of the polyolefin produced are further improved. Specifically, the polyolefin according to one embodiment of the invention has a BOCD index of 1.0 to 3.0, or 1.5 to 2.0.

In addition, the polyolefin can exhibit a melt flow rate ratio (MFRR) of 30 to 70, more specifically, 40 to 60 (MFR _21.6 /MFR _2.16 ), together with a BOCD index within the above range by controlling the mixing ratio of the transition metal compound in the hybrid supported catalyst and the polymerization conditions during polymerization. When the MFRR of the polyolefin is less than 30, there is a concern of deterioration in processability, and when it exceeds 70, there is a concern of deterioration in mechanical strength. The polyolefin according to one embodiment of the invention can exhibit excellent processability by having an MFRR within the above range.

In the present invention, the MFRR of the polyolefin is the ratio of MFR _2.16 measured under the condition of 2.16 kg load at 190°C to MFR 21.6 measured under the condition of 21.6 kg load at 190°C (MFR _21.6 /MFR _2.16 ), where MFR _21.6 and MFR _2.16 can be measured under the conditions of 21.6 kg load and _2.16 kg load at 190°C, respectively, using a D4002HV device from Dynisco according to ASTM D1238.

In addition, the polyolefin exhibits a high weight average molecular weight (Mw) of 80,000 g/mol, preferably 100,000 g/mol or more, and a molecular weight distribution (PDI) of 10 to 15. By satisfying such ranges, excellent processability can be exhibited.

Meanwhile, in the present invention, the weight average molecular weight and molecular weight distribution of the polyolefin can be measured using gel permeation chromatography (GPC). Specifically, PDI can be determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn), and then determining the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn). The method for measuring the weight average molecular weight and molecular weight distribution will be described in more detail in the examples described below.

In addition, the polyolefin has a stress cracking resistance (unit: time) of 1,000 to 6,000 hours as measured by a full notch creep test (FNCT) according to ISO 16770 at 4.0 MPa and 80°C, so that excellent mechanical properties can be maintained for a long time. More preferably, the stress cracking resistance is 1,000 hours or more, or 1,200 hours or more, or 1,300 hours or more, or 1,500 hours or more, or 1,700 hours or more, or 2,000 hours or more. In addition, since the value of the stress cracking resistance is higher, the physical properties are better, and there is no practical limitation on the upper limit thereof, but for example, it may be 6,000 hours or less, or 5,000 hours or less, or 4,000 hours or less.

In this way, the polyolefin produced by the hybrid supported catalyst of the present invention has a narrow molecular weight distribution (PDI), a wide melt flow ratio, and a large BOCD index, thereby exhibiting excellent processability and excellent stress crack resistance. As a result, it can be suitably used for high-pressure heating pipes or PE-RT pipes that require excellent processability and durability in addition to mechanical properties.

Hereinafter, preferred examples are presented to help understand the present invention, but the following examples are only 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 technical idea of the present invention, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[Example]

<Production of Transition Metal Compounds>

Manufacturing Example 1: Manufacturing of Compound A

(A)

(A)

Bis(3-(6-(tert-butoxy)hexyl)-1H-inden-1-yl)zirconium(IV) chloride (21 g, 30 mmol) and Pd/C (2.4 g, 10 mol%) were added to a dried bomb reactor and diluted with 40 mL of DCM. The mixture was stirred at 20 atm with hydrogen for one day. Afterwards, the mixture was transferred to a Schlenk flask, dried, replaced with hexane (20 mL), and filtered through a Celite filter to obtain 21.2 g of the target compound.

^1H NMR (500MHz, 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)

Manufacturing Example 2: Manufacturing of Compound B

(B)

(B)

(Step 1)

At room temperature, 50 g of Mg(s) was added to a 10 L reactor, and then 300 mL of THF was added. About 0.5 g of I ₂ was added, and the reactor temperature was maintained at 50 °C. After the reactor temperature stabilized, 250 g of 6-t-butoxyhexyl chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. It was observed that the reactor temperature increased by about 4 to 5 °C as 6-t-butoxyhexyl chloride was added. 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. 2 mL of the generated black solution was taken, water was added, and an organic layer was obtained, and 6-t-butoxyhexane was confirmed through ¹ H-NMR. It was found that the Grignard reaction proceeded well from the above 6-t-butoxyhexane. Thus, 6-t-buthoxyhexyl magnesium chloride was synthesized.

After adding 500 g of MeSiCl ₃ and 1 L of THF to the reactor, the reactor temperature 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 the feeding of the Grignard reagent was completed, the reactor temperature was slowly increased to room temperature and the mixture was stirred for 12 hours. After 12 hours of reaction, it was confirmed that a white MgCl ₂ salt was produced. 4 L of hexane was added, and the 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. The obtained liquid was confirmed to be the desired methyl(6-t-buthoxy 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)

1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, and the reactor temperature was cooled to -20°C. 480 mL of n-BuLi was added to the reactor at a rate of 5 mL/min using a feeding pump. After adding n-BuLi, the reactor temperature was slowly increased to room temperature and the mixture was stirred for 12 hours. After 12 hours of reaction, an equivalent amount of methyl(6-t-buthoxy hexyl)dichlorosilane (326 g, 350 mL) was rapidly added to the reactor. The reactor temperature was slowly increased to room temperature and the mixture was stirred for 12 hours. After cooling the reactor temperature to 0°C, 2 equivalents of t-BuNH ₂ were added. The reactor temperature was slowly increased to room temperature and the mixture was stirred for 12 hours. After 12 hours of reaction, THF was removed, 4 L of hexane was added, and a filter solution was obtained by removing the salt through a labdori. The filter solution was added back to the reactor, and hexane was removed at 70°C to obtain a yellow solution. The obtained yellow solution was confirmed to be a methyl(6-t-buthoxyhexyl)(tetramethylCpH)t-butylaminosilane compound through ¹ H-NMR.

TiCl ₃ (THF) ₃ (10 mmol) was rapidly added to the dilithium salt of the ligand synthesized from n-BuLi and the ligand dimethyl(tetramethylCpH) t-butylaminosilane in a THF solution at -78°C. The reaction solution was stirred for 12 hours while slowly warming from -78°C to room temperature. After 12 hours of stirring, an equivalent amount of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After 12 hours of stirring, a dark black solution with a bluish tinge was obtained. After removing THF from the resulting reaction solution, hexane was added, and the product was filtered. After removing hexane from the obtained filter solution, it was confirmed to be (tBu-O-(CH ₂ ) ₆ )(CH ₃ )Si(C ₅ (CH ₃ ) ₄ )(tBu-N)TiCl ₂ by ¹ H-NMR.

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

<Manufacture of supported catalyst>

Example 1

Silica (Grace Davison, SYLOPOL 948) was dehydrated at 650 °C for 15 hours under vacuum. 10 g of the dried silica was placed in a 300 mL glass reactor at 40 °C, 100 mL of toluene was added, and the mixture was stirred. 0.01 mmol of the transition metal compound (A) prepared in Manufacturing Example 1 was dissolved in 10 mL of toluene, placed into the reactor, and stirred for 2 hours. Thereafter, 50 mL of a 10 wt% methylaluminoxane (MAO)/toluene solution was placed into the reactor, the temperature was increased to 60 °C, and stirred for 12 hours. After lowering the reactor temperature to 40 °C, stirring was stopped, and the mixture was allowed to settle for 10 minutes, and then the reaction solution was decantated. Toluene was added to the 100 mL line of the reactor, 0.1 mmol of the transition metal compound (B) prepared in Manufacturing Example 2 was dissolved in 10 mL of toluene, added to the reactor, and stirred for 2 hours. After stopping the stirring and separating the toluene layer, toluene was removed under reduced pressure at 50 °C, thereby preparing a hybrid supported catalyst.

Example 2

A hybrid supported catalyst was prepared in the same manner as in Example 1, except that 0.03 mmol of the transition metal compound (A) prepared in Manufacturing Example 1 was used.

Example 3

A hybrid supported catalyst was prepared in the same manner as in Example 1, except that 0.04 mmol of the transition metal compound (A) prepared in Manufacturing Example 1 was used.

Comparative Example 1

A hybrid supported catalyst was prepared in the same manner as in Example 1, except that 0.03 mmol of a transition metal compound (C) having the following structure was used instead of the transition metal compound (A) prepared in Manufacturing Example 1.

(C)

(C)

Comparative Example 2

Magnesium ethylate (500 kg) was dispersed in sufficient hexane, and titanium tetrachloride (1700 kg) was slowly added dropwise at 85 °C over 5.5 hours, followed by tempering at 120 °C. Thereafter, unreacted by-products including titanium compounds were removed until the titanium concentration of the total solution became 500 mmol, and then pre-activated by contact with triethylaluminum at 120 °C for 2 hours, and unreacted by-products were removed to obtain a Ziegler-Natta (Z/N) catalyst.

Comparative Example 3

A hybrid supported catalyst was prepared in the same manner as in Example 1, except that 0.05 mmol of the transition metal compound (A) prepared in Manufacturing Example 1 was used.

Comparative Example 4

A hybrid supported catalyst was prepared in the same manner as in Example 1, except that 0.005 mmol of the transition metal compound (A) prepared in Manufacturing Example 1 was used.

Catalyst type Molar ratio of transition metal compounds in the catalyst Example 1 A:B = 1:10 Example 2 A:B = 3:10 Example 3 A:B = 4:10 Comparative Example 1 C:B = 3:10 Comparative Example 2 Z/N catalyst Comparative Example 3 A:B = 5:10 Comparative Example 4 A:B = 0.5:10

<Production of ethylene-1-butene copolymer>

2 ml (1.0 M hexane) of triethylaluminum (TEAL), each of the hybrid supported catalysts manufactured in the above examples and comparative examples, and hexane were placed in a vial in a 2 L autoclave high-pressure reactor and placed into the reactor. 0.8 kg of hexane was added, and the temperature was raised to 80 °C while stirring at 500 rpm. When the internal temperature of the reactor reached 80 °C, ethylene and 10 g of butene were reacted for 1 hour while stirring at 500 rpm under a pressure of 9 bar. After completion of the reaction, the obtained polymer was filtered to remove hexane first, and then dried in a vacuum oven at 80 °C for 4 hours.

Exam example

The polymerization activity of the hybrid supported catalysts manufactured in the above examples and comparative examples, as well as the physical properties of the manufactured ethylene-1-butene copolymers, were evaluated by the following method. The results are shown in Table 2 below.

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

(2) Melt Flow Rate Ratio (MFRR, MFR _21.6 /MFR _2.16 ): The ratio is calculated by dividing MFR _21.6 (190°C, 21.6 kg load) by MFR _2.16 (190°C, 2.16 kg load). The MFR _21.6 and MFR _2.16 were measured under the conditions of 21.6 kg load and 2.16 kg load at 190°C, respectively, using a D4002HV device from Dynisco according to ASTM D1238.

(3) Weight-average molecular weight (Mw, g/mol) and molecular weight distribution (PDI, polydispersity index): The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured using gel permeation chromatography (GPC), and then the molecular weight distribution was calculated by the ratio of Mw/Mn. Specifically, the measurement was performed 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. The sample was 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 a polystyrene standard. The molecular weights (g/mol) of polystyrene standards were 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000, nine types.

(4) BOCD index: Measured according to the standard method using a PerkinElmer Spectrum 100 FT-IR connected to GPC (PL-GPC220).

Specifically, when a molecular weight distribution curve was drawn with the logarithm value (log M) of the molecular weight (M) as the x-axis and the molecular weight distribution (dwt/dlog M) for the logarithm value as the y-axis, the SCB (Short Chain Branch) content (branch content of 2 to 7 carbon atoms per 1,000 carbon atoms, unit: units/1,000C) was measured at the left and right boundaries of the middle 60% excluding the left and right ends of the total area, and the BOCD index was calculated according to the following mathematical equation 1.

At this time, the high molecular weight SCB content and the low molecular weight SCB content mean the SCB content values at the right and left boundaries of the middle 60% range, respectively, and the sample was pretreated by melting it in 1, 2, 4-trichlorobenzene containing 0.0125% BHT at 160°C for 10 hours using PL-SP260, and then measured at 160°C using Perkin Elmer Spectrum 100 FT-IR connected to high temperature GPC (PL-GPC220).

[Mathematical formula 1]

BOCD index = (SCB content on the high molecular weight side - SCB content on the low molecular weight side) / (SCB content on the low molecular weight side)

(5) FNCT (Full Notch Creep Test):

It was measured according to ISO 16770 which is described in the literature [M. Fleissner in Kunststoffe 77 (1987), pp. 45 et seq.] and is still in force. At 80 °C and 4.0 MPa of tensile force, the stress crack accelerating medium IGEPAL CO-630 (Etoxilated Nonylphenol, Branched) 10 % concentration, the failure time was shortened due to the shortening of the stress initiation time by the notch (1.5 mm/safety razor blade). The specimens were manufactured by sawing three specimens with the dimensions 10 mm wide, 10 mm long and 100 mm long from a compressed nameplate with a thickness of 10 mm. A central notch was provided in the specimen using a safety razor blade in a notch device specifically manufactured for this purpose. The notch depth was 1.5 mm. The time until the specimen broke was measured.

catalyst
amount used*
(mmol) Catalytic activity
(kg PE/g cat ^. hr) MFRR Mw
(g/mol) PDI BOCD index FNCT
(hr) Example 1 0.01/0.1 10 60 150,000 12.5 1.5 1500 Example 2 0.03/0.1 15 50 100,000 13.4 2.0 3200 Example 3 0.04/0.1 17 43 85,000 14.3 1.7 2700 Comparative Example 1 0.03/0.1 10 35 100,000 9.5 0.6 2000 Comparative Example 2 0.1 6 30 70,000 14.0 0.3 1000 Comparative Example 3 0.05/0.1 10 25 50,000 11.8 0.6 500 Comparative Example 4 0.005/0.1 3 10 80,000 8.7 0.2 100

* The amount of catalyst used is listed in the order of first transition metal compound/second transition metal compound.

Referring to Table 2 above, in the case of a hybrid supported catalyst including a transition metal compound of Chemical Formula 1 and a transition metal compound of Chemical Formula 2, it can be confirmed that the catalyst activity is equivalent or higher than that of existing catalysts, and that a polyolefin copolymer having high MFRR and BOCD indices and excellent stress crack resistance can be produced. The polyolefin exhibiting high MFRR and copolymerizability as described above has excellent processability as well as physical properties, and can be suitably used as a material for PE-RT pipes, etc. Meanwhile, referring to Comparative Examples 3 and 4, it can be confirmed that in order to secure the above properties, the transition metal compound of Chemical Formula 1 and the transition metal compound of Chemical Formula 2 must be included at a predetermined molar ratio.

Claims (12)

A first transition metal compound represented by the following chemical formula 1;
A second transition metal compound represented by the following chemical formula 2; and
A carrier carrying the first and second transition metal compounds;
As a hybrid supported catalyst comprising:
A hybrid supported catalyst wherein the molar ratio of the first transition metal compound and the second transition metal compound is 1:10 to 4:10:
[Chemical Formula 1]

In the above chemical formula 1,
M ₁ is a group 4 transition metal;
X ₁₁ and X ₁₂ are the same or different from each other, and each independently is a halogen;
R ₁₁ and R ₁₂ are the same or different and are each independently alkoxyalkyl having C2 to C20,
[Chemical formula 2]

In the above chemical formula 2,
M ₂ is a group 4 transition metal;
Cp is any one cyclic compound selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl, and at least one hydrogen of the cyclic compound may be independently substituted with any one substituent selected from the group consisting of C1 to C20 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 the same or different from each other, and each independently represents halogen, C1 to C20 alkyl, C2 to C10 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl;
B is carbon, silicon, or germanium;
R ₂₁ to R ₂₃ are the same or different, and 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.
In the first paragraph,
A hybrid supported catalyst, wherein in the chemical formula 1, R ₁₁ and R ₁₂ are the same as or different from each other and each independently represent a C2 to C10 alkoxyalkyl.
In the first paragraph,
A hybrid supported catalyst wherein in the above chemical formula 1, M ₁ is Zr, and R ₁₁ and R ₁₂ are both t-butoxyhexyl.
In the first paragraph,
The above chemical formula 1 is a hybrid supported catalyst represented by the following chemical formula A:
[Chemical Formula A]

In the first paragraph,
A hybrid supported catalyst, wherein in the above chemical formula 2, Cp is cyclopentadienyl substituted with at least one C1 to C4 alkyl.
In the first paragraph,
A hybrid supported catalyst, wherein in the above chemical formula 2, B is silicon, one of R ₂₁ and R ₂₂ is an alkoxyalkyl of -(CH ₂ ) _n -R _b (wherein R _b is C3 to C6 alkoxy and n is an integer from 2 to 10), and the other is C1 to C4 alkyl.
In the first paragraph,
The second transition metal compound represented by the above chemical formula 2 is a hybrid supported catalyst selected from the group consisting of:


In the first paragraph,
The above-mentioned carrier is a hybrid supported catalyst comprising silica, alumina, magnesia or a mixture thereof.
In the first paragraph,
A hybrid supported catalyst further comprising at least one cocatalyst selected from the group consisting of compounds of the following chemical formulas 3 to 5.
[Chemical Formula 3]
-[Al(R ₃₁ )-O] _m -
In the above chemical formula 3,
R ₃₁ are the same or different and each independently represent halogen; a C1 to C20 hydrocarbon; or a C1 to C20 hydrocarbon substituted by halogen;
m is an integer greater than or equal to 2;
[Chemical Formula 4]
J(R ₃₂ ) ₃
In the above chemical formula 4,
R ₃₂ are the same or different and each independently represent halogen; a C1 to C20 hydrocarbon; or a C1 to C20 hydrocarbon substituted by halogen;
J is aluminum or boron;
[Chemical Formula 5]
[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-
In the above chemical formula 5,
E is a neutral or cationic Lewis base;
H is a hydrogen atom;
Z is a group 13 element;
Q is the same or different and each independently represents a C6 to C20 aryl or a C1 to C20 alkyl, wherein one or more hydrogen atoms are substituted or unsubstituted with halogen, a C1 to C20 hydrocarbon, alkoxy or phenoxy.
In the first paragraph,
A hybrid supported catalyst, wherein the total amount of the first and second transition metal compounds supported on the carrier is 0.05 to 10 mmol per 1 g of the carrier.
A method for producing a polyolefin, comprising a step of polymerizing an olefin monomer in the presence of a hybrid supported catalyst according to any one of claims 1 to 10,
A method for producing a polyolefin, wherein the above olefin monomer is ethylene, alpha-olefin, cyclic olefin, diene olefin, or triene olefin. delete