WO2020149643A1 - Supported hybrid metallocene catalyst and method for preparing olefin polymer by using same - Google Patents

Abstract

According to the present invention, provided are a catalyst composition and a method for preparing an olefin polymer by using the catalyst composition, the catalyst composition being capable of contributing to catalyst cost saving by exhibiting high activity in an olefin polymerization reaction, and being capable of exhibiting excellent processability and long-term properties by exhibiting high copolymerizing ability, thereby being suitable for providing a polymer for pipes.

Description

Hybrid supported metallocene catalyst and method for producing olefin polymer using same

Cross-citation with relevant application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0006226 filed on January 17, 2019 and Korean Patent Application No. 10-2019-0172478 filed on December 20, 2019. All content disclosed in the literature is incorporated as part of this specification.

The present invention relates to a hybrid supported metallocene catalyst having high activity and high polymerizability and a method for producing an olefin polymer using the same.

Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used in the commercial manufacturing process of the existing olefin polymers. Although the Ziegler-Natta catalysts have high activity, the molecular weight distribution of the resulting polymer is wide due to the high activity catalyst. Since the composition distribution of the monomers is not uniform, there is a limit to securing desired physical properties.

Accordingly, recently, a metallocene catalyst in which a transition metal such as titanium, zirconium or hafnium and a ligand including a cyclopentadiene functional group are combined has been developed and widely used. Metallocene compounds are generally activated by using aluminoxane, borane, borate or other activators. For example, a metallocene compound having a ligand including a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. The metallocene catalyst is a single active point catalyst having one kind of active point, and the molecular weight distribution of the resulting polymer is narrow, and the molecular weight, stereoregularity, crystallinity, and especially the reactivity of the comonomer can be adjusted depending on the structure of the catalyst and ligand. There are advantages. However, an olefin polymer polymerized with a metallocene catalyst has a low melting point and a narrow molecular weight distribution, and thus, when applied to some products, there is a problem in that it is difficult to apply in the field, such as a significant drop in productivity due to the effect of extrusion load.

Particularly, in the case of the existing PE-RT (Polyethylene-Raised Temperature) pipe product, it is an ethylene copolymer using a metallocene catalyst, and has a narrow molecular weight distribution, thereby obtaining desired properties. On the other hand, due to the narrow molecular weight distribution, there is a problem that long-term physical properties and processability such as stress cracking resistance (FNCT) are inferior to existing PE-RT pipes.

The present invention compensates for shortcomings in product processing by improving the Broad Orthogonal Comonomer Distribution (BOCD) and melt flow rate ratio (MFRR), and can manufacture olefin polymers for pipes with excellent physical properties. It is to provide a method for producing a hybrid supported metallocene catalyst and an olefin polymer using the same.

According to an embodiment of the present invention, the first metallocene compound represented by Formula 1 below, the second metallocene compound represented by Formula 2 below, and the carrier supporting the first and second metallocene compounds It provides a hybrid supported metallocene catalyst comprising a.

[Formula 1]

In Chemical Formula 1,

X ₁ and X ₂ are each independently halogen,

R ₁ and R ₅ are each independently C _6-20 aryl substituted with C _1-20 alkyl,

R ₂ to R ₄ and R ₆ to R ₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 Alkoxysilyl, C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

A is carbon, silicon or germanium,

R ₉ and R ₁₀ are each independently C _1-2 straight chain alkyl; Or C _3-10 straight chain alkyl substituted with C _1-10 alkoxy, at least one of R ₉ and R ₁₀ is C _3-10 straight chain alkyl substituted with C _1-10 alkoxy,

[Formula 2]

In Chemical Formula 2,

X ₃ and X ₄ are each independently halogen,

R ₁₁ to R ₂₀ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _{1- 20} ether, C _1-20 silyl ether, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

At least one of R ₁₁ and R ₁₂ is C _2-20 alkoxyalkyl,

At least one of R ₁₇ to R ₂₀ is C _1-20 alkyl.

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

According to another embodiment of the present invention, it is produced by the method for producing the olefin polymer, the melt flow rate ratio (MFRR; Melt flow rate ratio) is 22 to 50, stress cracking resistance (FNCT; Full Notch Creep Test) Provided is an olefin polymer having a 1000 to 3000 hr and a Bio Orthogonal Comonomer Distribution (BOCD) index of 0.8 to 3.0.

According to the present invention, as well as exhibiting high activity and polymerizability in the production of olefin polymers, it is possible to secure excellent processability and long-term properties by broadening the molecular weight distribution of synthesized olefin polymers, and contributing to reducing catalyst costs. A supported metallocene catalyst and a method for producing an olefin polymer using the hybrid supported metallocene catalyst may be provided. Therefore, the olefin polymer prepared according to the method of the present invention is suitable for use in pipes because of its excellent processability and long-term physical properties.

Hereinafter, a hybrid supported metallocene catalyst according to a specific embodiment of the present invention, a method for producing an olefin polymer using the same, and an olefin polymer will be described.

According to the above embodiment, a first metallocene compound represented by the following Chemical Formula 1, a second metallocene compound represented by the following Chemical Formula 2, and a carrier supporting the first and second metallocene compounds A hybrid supported metallocene catalyst is provided.

[Formula 1]

In Chemical Formula 1,

X ₁ and X ₂ are each independently halogen,

R ₁ and R ₅ are each independently C _6-20 aryl substituted with C _1-20 alkyl,

R ₂ to R ₄ and R ₆ to R ₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 Alkoxysilyl, C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

A is carbon, silicon or germanium,

R ₉ and R ₁₀ are each independently C _1-2 straight chain alkyl; Or C _3-10 straight chain alkyl substituted with C _1-10 alkoxy, at least one of R ₉ and R ₁₀ is C _3-10 straight chain alkyl substituted with C _1-10 alkoxy,

[Formula 2]

In Chemical Formula 2,

X ₃ and X ₄ are each independently halogen,

R ₁₁ to R ₂₀ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _{1- 20} ether, C _1-20 silyl ether, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

At least one of R ₁₁ and R ₁₂ is C _2-20 alkoxyalkyl,

At least one of R ₁₇ to R ₂₀ is C _1-20 alkyl.

Meanwhile, the following terms may be defined as follows, unless otherwise specified.

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

C _1-20 alkyl may be straight chain, branched chain or cyclic alkyl. Specifically, C _1-20 alkyl is C _1-20 straight chain alkyl; C _1-10 straight chain alkyl; C _1-5 straight chain alkyl; C _3-20 branched chain or cyclic alkyl; C _3-15 branched or cyclic alkyl; Or C _3-10 branched chain or cyclic alkyl. More specifically, C _1-20 alkyl 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 cyclo Hexyl group and the like.

C _2-20 The alkenyl can be straight chain, branched chain or cyclic alkenyl. Specifically, C _2-20 alkenyl is C _2-20 straight chain alkenyl, C _2-10 straight chain alkenyl, C _2-5 straight chain alkenyl, C _3-20 branched chain alkenyl, C _3-15 branched chain alkenyl Kenyl, C _3-10 branched chain alkenyl, C _5-20 cyclic alkenyl or C _5-10 cyclic alkenyl. More specifically, C _2-20 alkenyl may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl, and the like.

C _6-20 aryl may mean a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, C _6-20 aryl may be a phenyl group, a naphthyl group or anthracenyl group.

C _7-20 Alkylaryl may mean a substituent in which one or more hydrogens of aryl are substituted by alkyl. Specifically, C _7-20 alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, or cyclohexylphenyl.

C _7-20 Arylalkyl may mean a substituent in which one or more hydrogens of alkyl are substituted by aryl. Specifically, C _7-20 The arylalkyl may be a benzyl group, phenylpropyl or phenylhexyl.

C _1-20 Examples of the alkoxy include methoxy group, ethoxy group, phenyloxy group, cyclohexyloxy group, and tert-butoxyhexyl group.

The above-mentioned substituents are optionally composed of hydroxy, halogen, alkyl, heterocycloalkyl, alkoxy, alkenyl, silyl, sulfonate, sulfone, aryl and heteroaryl within the range of exerting the same or similar effect as the desired effect. It may be substituted with one or more substituents selected from.

The hybrid supported metallocene catalyst according to the embodiment may exhibit high activity and polymerizability by using together the first metallocene compound represented by Chemical Formula 1 and the second metallocene compound represented by Chemical Formula 2 In addition, the molecular weight distribution of the synthesized olefin polymer is somewhat widened to improve bio-CD (BOCD) and melt flow rate ratio (MFRR) to ensure excellent processability. In addition, long-term physical properties such as stress cracking resistance (FNCT) of the olefin polymer to be synthesized can be secured. The olefin polymer may be suitable for use in pipes.

Specifically, in the first metallocene compound represented by Chemical Formula 1, the two positions of the two indenyl groups which are ligands are substituted with methyl, and the positions of four (R ₁ and R ₅ ) are each substituted with alkyl phenyl. By being substituted with, it can exhibit better catalytic activity by an inductive effect capable of supplying sufficient electrons.

In addition, the first metallocene compound contains zirconium (Zr) as a central metal, and thus has more orbitals capable of accepting electrons compared to other group 14 elements such as hafnium (Hf). It can exhibit a characteristic that can be easily combined with a monomer with a higher affinity, thereby exhibiting a better catalytic activity improvement effect.

More specifically, in Formula 1, R ₁ and R ₅ may each independently be C _6-12 aryl substituted with C _1-10 alkyl or phenyl substituted with C _3-6 branched chain alkyl, and more specifically May be tert-butyl phenyl. In addition, the substitution position of the alkyl group with respect to the phenyl group may be the 4th position corresponding to the R ₁ or R ₅ position and the para position bonded to the indenyl group.

In addition, in Chemical Formula 1, R ₂ to R ₄ and R ₆ to R ₈ may be hydrogen, and X ₁ and X ₂ may be chloro.

In addition, in Chemical Formula 1, A may be silicon.

In addition, the substituents R ₉ and R _{10 of A} are each independently methyl; Or C _5-9 straight chain alkyl substituted with tert-butoxy, but may be C _5-9 straight chain alkyl substituted with at least tert-butoxy among R ₉ and R ₁₀ . More specifically, R ₉ is methyl, and R ₁₀ may be normal-hexyl substituted with tert-butoxy. By introducing different substituents to each other as the substituents of the bridge, it is possible to exhibit catalytic activity with excellent loading reactivity. Specifically, in the R ₉ or R ₁₀ , when the R ₉ and R ₁₀ are the same as each other, a poor solubility in preparing the supported catalyst may cause a problem of poor supported reactivity.

A representative example of the first metallocene compound represented by Chemical Formula 1 may be Chemical Formula 1-1.

[Formula 1-1]

The first metallocene compound represented by Chemical Formula 1 may be synthesized by applying known reactions, and detailed examples of synthesis may be referred to Examples.

On the other hand, the second metallocene compound represented by Chemical Formula 2 has a structure in which an indenyl group and a cyclopentadienyl group are non-crosslinked, and can easily control the electronic/stereoscopic environment around the transition metal zirconium (Zr). As a result, properties such as the chemical structure, molecular weight distribution, and mechanical properties of the olefin polymer to be produced can be easily adjusted.

In addition, the second metallocene compound contains zirconium (Zr) as the central metal, and thus has more orbitals capable of accepting electrons compared to other group 14 elements such as hafnium (Hf). It can exhibit a characteristic that can be easily combined with a monomer with a higher affinity, thereby exhibiting a better catalytic activity improvement effect.

More specifically, in Chemical Formula 2, C _2-20 alkoxyalkyl may be substituted at least one position (one of R ₁₁ to R ₁₆ ) of the indenyl group, and specifically, to R ₁₁ or R ₁₂ C _2-20 alkoxyalkyl may be substituted, and more specifically, R ₁₁ or R ₁₂ may be substituted with C _5-9 straight chain alkyl substituted with tert-butoxy or hexyl substituted with tert-butoxy. C _2-20 alkoxyalkyl is substituted on at least one of the indenyl groups, thereby affecting the copolymerization of an alpha olefin comonomer such as 1-butene or 1-hexene. , Specifically, it is possible to secure excellent processability and long-term physical properties by slightly widening the molecular weight distribution of the synthesized olefin polymer. Furthermore, the C _2-20 alkoxyalkyl substituted with the indenyl group can form a covalent bond through close interaction with the silanol group on the silica surface used as a support, thereby enabling stable supported polymerization.

In addition, C _1-20 alkyl may be substituted at at least one position (one of R ₁₇ to R ₂₀ ) of the cyclopentadienyl group, specifically, one of R ₁₈ and R ₁₉ may be C _1-20 alkyl It may be substituted, and more specifically, one of R ₁₈ and R ₁₉ may be substituted with normal-butyl.

In addition, in Chemical Formula 2, R ₁₁ , R ₁₃ to R ₁₇ , R ₁₉ and R ₂₀ may be hydrogen, and X ₃ and X ₄ may be chloro.

A representative example of the second metallocene compound represented by Chemical Formula 2 may be Chemical Formula 2-1.

[Formula 2-1]

The second metallocene compound represented by Chemical Formula 2 may be synthesized by applying known reactions, and detailed examples of synthesis may be referred to Examples.

On the other hand, the first and second metallocene compounds have the above structural characteristics and can be stably supported on a carrier.

As the carrier, a carrier containing a hydroxy group or a siloxane group on the surface may be used. Specifically, as the carrier, a carrier containing a hydroxy group or a siloxane group having high reactivity may be used by drying at a high temperature to remove moisture on the surface. More specifically, as the carrier, silica, alumina, magnesia or a mixture thereof can be used. The carrier may be dried at a high temperature, and these may typically include oxides, carbonates, sulfates, and nitrate components such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ and Mg(NO ₃ ) ₂ .

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

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

When the amount of the hydroxy group is less than 0.1 mmol/g, there are few reaction sites with the cocatalyst, and if it exceeds 10 mmol/g, it is not preferable because it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. not.

The hybrid supported metallocene catalyst according to the above embodiment may further include a cocatalyst to activate the metallocene compound as a catalyst precursor. The cocatalyst is an organometallic compound containing a Group 13 metal, and is not particularly limited as long as it can be used when polymerizing an olefin under a general metallocene catalyst. Specifically, the cocatalyst may be one or more compounds selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5.

[Formula 3]

In Chemical Formula 3,

R ₂₁ , R ₂₂ and R ₂₃ are each independently hydrogen, halogen, C _1-20 hydrocarbyl group, or C _1-20 hydrocarbyl group substituted with halogen,

n is an integer of 2 or more,

[Formula 4]

In Chemical Formula 4,

D is aluminum or boron,

R ₂₄ are each independently halogen, C _1-20 hydro-car invoking, C _1-20 hydro-car bilok group, or substituted C _1-20 hydro-car invoking by halogen,

[Formula 5]

In Chemical Formula 5,

L is a neutral or cationic Lewis base,

H is a hydrogen atom,

W is a group 13 element,

A is each independently a C _1-20 hydrocarbyl group; C _1-20 hydrocarbyloxy group; And one or more substituents in which one or more hydrogen atoms of these substituents are substituted with one or more substituents among halogen, C _1-20 hydrocarbyloxy group and C _1-20 hydrocarbyl(oxy)silyl group.

In the present specification, unless otherwise specified, the following terms may be defined as follows.

The hydrocarbyl group is a monovalent functional group in which hydrogen atoms are removed from the hydrocarbon, and an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkylaryl group, an alkenylaryl group, and an alkyl group And a nilaryl group. Further, the hydrocarbyl group having 1 to 20 carbon atoms may be a hydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. Specifically, the hydrocarbyl group 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, n-hexyl group , n-heptyl group, cyclohexyl group, such as a straight chain, branched chain or cyclic alkyl group; Or it may be an aryl group such as a phenyl group, naphthyl group, or anthracenyl group.

The hydrocarbyloxy group is a functional group in which the hydrocarbyl group is bonded to oxygen. Specifically, the hydrocarbyloxy group having 1 to 20 carbon atoms may be a hydrocarbyloxy group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. More specifically, the hydrocarbyloxy group having 1 to 20 carbon atoms is 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 , straight-chain, branched-chain or cyclic alkoxy groups such as n-hexoxy group, n-heptoxy group and cyclohexoxy group; Or it may be an aryloxy group such as a phenoxy group or a naphthalenoxy group.

The hydrocarbyl (oxy) silyl group is a functional group in which 1-3 hydrogens of -SiH ₃ are substituted with 1 to 3 hydrocarbyl groups or hydrocarbyloxy groups. Specifically, the hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms may be a hydrocarbyl (oxy) silyl group having 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms. More specifically, hydrocarbyl (oxy) silyl groups having 1 to 20 carbon atoms include alkyls such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group and dimethylpropylsilyl group. Silyl group; Alkoxysilyl groups such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group and dimethoxyethoxysilyl group; And alkoxyalkylsilyl groups such as methoxydimethylsilyl group, diethoxymethylsilyl group, and dimethoxypropylsilyl group.

Non-limiting examples of the compound represented by Chemical Formula 3 may include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, or tert-butyl aluminoxane. In addition, non-limiting examples of the compound represented by Chemical Formula 4 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-sec-butyl aluminum, To tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide or dimethyl aluminum And thoxide. Finally, non-limiting examples of the compound represented by Formula 5 include trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis( Pentafluorophenyl)borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate, N,N-dimethylanilinium Tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2,3 ,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis (Pentafluorophenyl) borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl )Borate, hexadecyldimethylammonium tetrakis(pentafluorophenyl)borate, N-methyl-N-dodecylanilinium tetrakis(pentafluorophenyl)borate or methyldi(dodecyl)ammonium tetrakis(pentafluoro) And phenyl) borate.

The use content of the co-catalyst can be appropriately adjusted according to the properties or effects of the desired hybrid supported metallocene catalyst.

The hybrid supported metallocene catalyst according to the above embodiment is prepared, for example, by supporting a cocatalyst on a carrier and supporting a first and second metallocene compound as a catalyst precursor on a cocatalyst carrier. Can be.

Specifically, in the step of supporting the co-catalyst on the carrier, the co-catalyst supported carrier can be prepared by adding the co-catalyst to the carrier dried at high temperature and stirring it at a temperature of about 20 to 120°C.

In addition, in the step of supporting the catalyst precursor on the co-catalyst carrier, the first and second metallocene compounds are added to the co-catalyst carrier obtained in the step of supporting the co-catalyst on the carrier, which is again about 20 to 120°C. It can be prepared by stirring at a temperature of the supported catalyst.

In the step of supporting the catalyst precursor on the cocatalyst carrier, the first and second metallocene compounds are added to the cocatalyst carrier and stirred, and then a cocatalyst is further added to prepare a supported catalyst.

The content of the carrier, cocatalyst, cocatalyst carrier, and transition metal compound used in the hybrid supported metallocene catalyst according to the above embodiment may be appropriately adjusted according to the properties or effects of the desired supported catalyst.

Specifically, in the hybrid supported metallocene catalyst, the molar ratio of the first metallocene compound and the second metallocene compound may be 1:1 to 15:1. By including the first and second metallocene compounds in the mixing molar ratio described above, it is possible to provide a hybrid supported metallocene catalyst having high activity and high polymerizability compared to the prior art. In addition, when the olefin polymer is prepared using the hybrid basal metallocene catalyst, the molecular weight distribution can be widened to improve long-term physical properties such as stress cracking resistance (FNCT), and bioCD (BOCD) and melt flow rate ratio. The workability can be improved by improving (MFRR).

However, if the molar ratio of the first metallocene compound and the second metallocene compound is less than 1:1, copolymerizability and processability may be deteriorated, and when the molar ratio exceeds 15:1, activity and physical properties may be deteriorated. .

In addition, in the hybrid supported metallocene catalyst according to the embodiment, the weight ratio of the total metallocene compound and the carrier including the first and second metallocene compounds is 1:10 to 1:1,000 or 1: 10 to 1:500. When the carrier and the metallocene compound are included in the above-described range of rangrang ratio, an optimum shape may be exhibited.

In addition, when the hybrid supported metallocene catalyst further includes a cocatalyst, the weight ratio of the cocatalyst and the carrier may be 1:1 to 1:100 or 1:1 to 1:50. When the cocatalyst and carrier are included in the above weight ratio, it is possible to optimize the active and polymer microstructure.

As a reaction solvent in preparing the hybrid supported catalyst, hydrocarbon solvents such as pentane, hexane, and heptane; Alternatively, an aromatic solvent such as benzene or toluene may be used.

For a specific method of manufacturing the supported catalyst, reference may be made to Examples described later. However, the manufacturing method of the supported catalyst is not limited to the contents described in the present specification, and the manufacturing method may further employ a step conventionally employed in the technical field to which the present invention pertains, and the step of the manufacturing method ( The field(s) can be modified by the step(s), which are usually changeable.

On the other hand, according to the other embodiment, in the presence of the hybrid supported metallocene catalyst, a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer is provided.

As described above, the hybrid supported metallocene catalyst has a broad molecular weight distribution compared to an olefin polymer polymerized using a conventional metallocene compound catalyst due to a specific structure, thereby providing excellent processability and long-term physical properties. Can provide.

Examples of the olefin monomer polymerizable with the hybrid supported catalyst include ethylene, alpha-olefin, cyclic olefin, and the like, and diene olefin monomer or triene olefin monomer having two or more double bonds may also be polymerized. Specific examples of the monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-atocene, norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like, and may be copolymerized by mixing two or more of these monomers. When the olefin polymer is a copolymer of ethylene and another comonomer, the comonomer is one or more comonomers selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. It is preferred.

For the polymerization reaction of the olefin monomer, various polymerization processes known as polymerization reactions of olefin monomers, such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process, or an emulsion polymerization process, may be employed, and more specifically , The polymerization reaction can be carried out in a semi-batch reactor.

Specifically, the polymerization reaction may be performed under a temperature of about 50 to 110°C or about 60 to 100°C and a pressure of about 1 to 100kgf/cm ² or about 1 to 50 kgf/cm ² .

In addition, in the polymerization reaction, the hybrid supported catalyst may be used in a dissolved or diluted state in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like. At this time, by treating the solvent with a small amount of alkyl aluminum or the like, a small amount of water or air, which may adversely affect the catalyst, can be removed in advance.

The olefin polymer prepared by the above method has a somewhat wider molecular weight distribution as it is prepared using the above-mentioned hybrid supported metallocene catalyst, and improves bio-CD (BOCD) and melt flow rate ratio (MFRR) to ensure excellent processability It is also possible to secure long-term physical properties such as stress cracking resistance (FNCT) of the olefin polymer to be synthesized.

Specifically, the olefin polymer has a melt flow rate ratio (MFRR) of 22 to 50 or 25 to 32, and a stress cracking resistance (FNCT; Full Notch Creep Test) of 1000 to 3000 hr or 1000 to 2000 hr, The Bio Orthogonal Comonomer Distribution (BOCD) index may be 0.8 to 3.0 or 0.9 to 1.4.

Further, when the polymer to be polymerized using the above-mentioned hybrid supported catalyst is, for example, an ethylene-alpha olefin copolymer, preferably an ethylene-1-butene polymer, the above physical properties can be more appropriately met.

Hereinafter, the operation and effects of the invention will be described in more detail through specific examples of the invention. However, this is provided as an example of the invention, and the scope of the invention is not limited in any way.

Preparation Example 1: Preparation of the first metallocene compound (A)

Step 1: Preparation of ((6-(t-butoxy)hexyl)methylsilane-diyl)-bis((2-methyl-4-t-butyl-phenylindenyl)silane

2-Methyl-4-t-butyl-phenylindene (10.0 g, compound 1) was dissolved in 76.2 mL of diethyl ether (Et ₂ O) and cooled to -25 °C. Then, 16.0 mL of n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise, and then stirred at room temperature for 4 hours. Thereafter, the mixture was cooled to -25°C, 1 mol% of copper cyanide (CuCN) was added, and 2.92 mL of (6-(t-butoxy)hexyl)methyldichlorosilane was dissolved in 38 mL of diethyl ether and slowly added dropwise. , Stirred at room temperature for 16 hours. Then, dichloromethane (DCM) and water were added to separate the organic layer, and then the organic layer was removed with magnesium sulfate (MgSO ₄ ), filtered, and the solvent was distilled under reduced pressure to give ((6-(t-butoxy )Hexyl)methylsilane-diyl)-bis((2-methyl-4-t-butyl-phenylindenyl)silane.

Step 2: Preparation of [((6-(t-butoxy)hexyl)methylsilane-diyl)-bis((2-methyl-4-t-butyl-phenylindenyl)]zirconium dichloride

The ((6-(t-butoxy)hexyl)methylsilane-diyl)-bis((2-methyl-4-t-butyl-phenylindenyl)silane prepared in step 1 above is diethyl ether (Et ₂ O ) Dissolved in 95.3 mL and cooled to -25° C. 8 mL of n-butyllithium solution (2.5 M) was slowly added dropwise, followed by stirring at room temperature for 4 hours, then cooled to -25° C. and zirconium. 3.59 g of tetrachloride tetrahydrofuran complex [ZrCl ₄ ·2THF] was added dropwise and stirred for 16 hours at room temperature After removing the solvent of the reaction solution under reduced pressure, dichloromethane was added and filtered, and the filtrate was distilled off under reduced pressure. Recrystallization using dichloromethane [((6-(t-butoxy)hexyl)methylsilane-diyl)-bis((2-methyl-4-t-butyl-phenylindenyl)]zirconium dichloride (1.0 g, yield 14%).

Preparation Example 2: Preparation of second metallocene compound (B)

Step 1: Preparation of 3-(6-(t-butoxy)hexyl)-1H-indene

10.8 g (100 mmol) of chlorohexanol was added to a dried 250 mL shrink flask, followed by addition of 10 g of molecular sieve and 100 mL of MTBE (methyl t-butyl ether), and 20 g of Sulfuric acid was slowly added over 30 minutes. The reaction mixture slowly turned pink over time and poured into saturated sodium bicarbonate solution chilled with ice after 16 hours. The mixture was extracted four times using 100 mL of ether, and the combined organic layer was dried with MgSO ₄ , filtered, and then the solvent was removed under vacuum reduced pressure to obtain a yellow liquid in the form of 1-(t-butoxy)-6-chlorohexene. 10 g (60% yield) was obtained.

To a dried 250 mL shrink flask, 4.5 g (25 mmol) of the above synthesis 1-(t-butoxy)-6-chlorohexene was added and dissolved in 40 mL of THF. After slowly adding 20 mL of sodium indenide THF solution, the mixture was stirred overnight. The reaction mixture was quenched by adding 50 mL of water, extracted with ester (50 mL x 3), and then the collected organic layer was sufficiently washed with brine. The remaining moisture was dried with MgSO ₄ , filtered, and then the solvent was removed under reduced pressure in vacuo to give 3-(6-(t-butoxy)hexyl)-1H-indene, a dark brown viscous product, in quantitative yield. Obtained.

Step 2: Preparation of 3-(6-(t-butoxy)hexyl)-1H-inden-1-yl)(3-butylcyclopenta-2,4-dien-1-yl) zirconium dichloride

To the dried 250 mL shrink flask, 4.57 g (20 mmol) of 3-(6-(t-butoxy)hexyl)-1H-indene prepared above was added and dissolved in 60 mL of ether and 40 mL of THF. To this, 13 mL of n-BuLi 2.0M hexane solution was added, stirred for one day, and then a toluene solution (concentration 0.378 mmol/g) of n-butyl cyclopentadiene ZrCl ₃ was slowly added at -78°C. When the reaction mixture was raised to room temperature, it turned from a clear brown solution to a white suspension floating with a yellow solid. After 12 hours, 100 mL of hexane was added to the reaction mixture to generate additional precipitation. Then filtered under argon to obtain a yellow filtrate, which was dried to give the desired compound 3-(6-(t-butoxy)hexyl)-1H-inden-1-yl)(3-butylcyclopenta-2,4 -Dien-1-yl) It was confirmed that zirconium dichloride was produced.

Preparation Example 3: Preparation of Ziegler-Natta catalyst (Z/N catalyst)

To prepare a Ziegler-Natta catalyst, 500 kg of magnesium ethylate was dispersed in sufficient hexane, and then 1700 kg of tetrachloride titanium was slowly added dropwise over a period of 5.5 hours at 85°C, followed by tempering at 120°C. Thereafter, the unreacted by-products including the titanium compound were removed until the titanium concentration of the total solution became 500 mmol, and then pre-activated by contacting with triethyl aluminum at 120° C. for 2 hours, and the unreacted by-products were removed to remove the final catalyst. Got.

Example 1: Preparation of hybrid supported catalyst and olefin polymer using the same

(1) Preparation of hybrid supported catalyst

Silica (SYLOPOL 948 manufactured by Grace Davison) was dehydrated at a temperature of 200° C. for 15 hours under vacuum. 10 g of dried silica was placed in a glass reactor, and 100 mL of toluene was further added and stirred. 50 mL of a 10% by weight methylaluminoxane (MAO)/toluene solution was added, and the temperature was raised to 60° C., followed by reaction for 12 hours with stirring. After the temperature of the reactor was lowered to 40° C., stirring was stopped, and after being set for 10 minutes, the reaction solution was decanted. Toluene was filled up to 100 mL of the reactor, and 0.01 mmol of the first metallocene compound (A) of Preparation Example 1 was dissolved in 10 ml of toluene and added together, followed by reaction for 1 hour. After the reaction was over, 0.01 mmol of the second metallocene compound (B) of Preparation Example 2 was dissolved in 10 ml of toluene and added together, followed by further reacting for 1 hour.

(2) Preparation of olefin polymer

TEAL 2ml (1.0M hexane), 1-butene 10g was added to a 2L autoclave high-pressure reactor, and 0.8kg of hexane was added, followed by stirring at 500rpm and raising the temperature to 80°C.

50 mg of the supported catalyst prepared above and hexane were put in a 50 mL vial and then put into the reactor, and when the internal temperature of the reactor reached 78°C, the mixture was reacted for 1 hour while stirring at 500 rpm under 9 bar of ethylene pressure. After the reaction was completed, hexane was first removed through a filter, and dried in a vacuum oven at 80° C. for 4 hours to obtain an olefin polymer.

Example 2: Preparation of hybrid supported catalyst and olefin polymer using the same

In Example 1, a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that the first metallocene compound (A) of Preparation Example 1 was used as 0.05 mmol.

Example 3: Preparation of hybrid supported catalyst and olefin polymer using same

In Example 1, a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that the first metallocene compound (A) of Preparation Example 1 was used in 0.1 mmol.

Example 4: Preparation of hybrid supported catalyst and olefin polymer using the same

In Example 1, a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that 0.15 mmol of the first metallocene compound (A) of Preparation Example 1 was used.

Comparative Example 1: Preparation of hybrid supported catalyst and olefin polymer using the same

In Example 1, instead of the first and second metallocene compound composition (A/B), the second metallocene compound (B) of Preparation Example 2 was set to be the molar ratio (1/1) of Table 1 below. A hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that 0.01 mmol and 0.01 mmol of the metallocene compound (C) represented by Formula C below were used.

[Chemical Formula C]

Comparative Example 2: Preparation of olefin polymer using Ziegler-Natta catalyst

An olefin polymer was prepared in the same manner as in Example 1, except that the Ziegler-Natta catalyst of Preparation Example 3 (Z/N catalyst) was used as 0.1 mmol.

Comparative Example 3: Preparation of supported catalyst and olefin polymer using the same

In Example 1, a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that only the first metallocene compound (A) of Preparation Example 1 was used in 0.1 mmol.

Comparative Example 4: Preparation of supported catalyst and olefin polymer using the same

In Example 1, a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that only the second metallocene compound (B) of Preparation Example 2 was used in 0.1 mmol.

Comparative Example 5: Preparation of hybrid supported catalyst and olefin polymer using same

In Example 1, instead of the first and second metallocene compound composition (A/B), the second metallocene compound (B) of Preparation Example 2 was set to be the molar ratio (1/1) of Table 1 below. A hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that 0.01 mmol and 0.01 mmol of the metallocene compound (D) represented by the following Chemical Formula D were used.

[Formula D]

Comparative Example 6: Preparation of hybrid supported catalyst and olefin polymer using same

Instead of the first and second metallocene compound composition (A/B) in Example 1, the metallocene compound (E) 0.01 represented by the following Chemical Formula E is set to be the molar ratio (1/1) of Table 1 below. A hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that mmol and 0.01 mmol of the metallocene compound (F) represented by Formula F below were used.

[Formula E]

[Formula F]

Test Example: Evaluation of activity of hybrid supported catalyst and physical properties of olefin polymer

The catalyst activity, melt index, melt flow rate ratio (MFRR), stress cracking resistance (FNCT), and bioCD index of the catalysts and olefin polymers of Examples 1 to 4 and Comparative Examples 1 to 5 were measured by the following methods, The results are shown in Table 1 below.

(1) Catalytic activity (kg PE / g SiO ₂ )

: It was calculated as the ratio of the weight (kg PE) of the resulting olefin polymer per catalyst content (g SiO ₂ ) used per unit time (h).

(2) Polymer melt index (MI 2.16)

: According to ASTM D 1238, the melt index (MI2.16) was measured at 190°C under a load of 2.16 kg, and it was expressed as the weight (g) of the polymer melted for 10 minutes.

(3) Melt flow rate ratio (MFRR: MFR ₂₀ /MFR ₂ ): The ratio of MFR ₂₀ melt index (MI, 21.6kg load) divided by MFR ₂ (MI, 2.16kg load).

(4) BOCD Index ( Broad Orthogonal Co-monomer Distribution index) : SCB in the range of 30% (60% total) on the left and right of the molecular weight distribution (MWD) based on the weight average molecular weight (Mw) in the interpretation of the GPC-FTIR measurement results. By measuring the content (unit: dogs/1,000C), the bioCD index was obtained using Equation 1 below.

[Equation 1]

(5) Stress cracking resistance (FNCT, hr): As an evaluation for molded products of olefin polymers, a method for testing stress cracking resistance is described in M. Flissner in Kunststoffe 77 (1987), pp. 45 et seq.], and corresponds to ISO/FDIS 16770 which has been in effect so far. In ethylene glycol, a stress crack promoting medium using a tension of 3.5 Mpa at 80° C., the break time was shortened due to the shortening of the stress initiation time by the notch (1.6 mm/safety razor blade).

For the preparation of the specimens, 750 ppm of primary antioxidants (Irganox 1010, CIBA), 1500 ppm of secondary antioxidants (Irgafos 168, CIBA) and processing aids (SC110, Ca-St, two minutes) were added to the olefin polymers of each Example and Comparative Example. Emulsification Co., Ltd.) was added at 1000 ppm and granulated at an extrusion temperature of 170 to 220°C using a twin screw extruder (W&P Twin Screw Extruder, 75 pi, L/D = 36). Extrusion test of the processability of the resin was tested by using a Haake Single Screw Extruder (19 pi, L/D = 25) under conditions of 190 to 220°C (Temp. profile (°C): 190/200/210/220). . In addition, the pipe molding was extruded to a standard of 32 mm outer diameter and 2.9 mm thick at an extrusion temperature of 220° C. using a single-screw extruder (Battenfeld Pipe M/C, 50 pi, L/D=22, compression ratio=3.5). .

Thereafter, three specimens of 10 mm in width, 10 mm in length, and 90 mm in length were sawed from the compressed name plate having a thickness of 10 mm for the molded article. For this purpose, a central notch is provided to the specimen using a safety razor blade in a specifically manufactured notch element. The notch depth is 1.6 mm.

As shown in Table 1 above, it can be confirmed that the polymers of Examples 1 to 4 of the present application show high activity using a supported catalyst using a combination of specific precursors. In addition, the polymers of Examples 1 to 4 are all excellent in MFRR, BOCD, and FNCT compared to the comparative example, and thus can provide a polymer for pipes with improved processability and long-term physical properties.

Claims (15)

1. A first metallocene compound represented by Formula 1 below;

   A second metallocene compound represented by Formula 2 below; And

   Hybrid supported metallocene catalyst comprising a carrier supporting the first and second metallocene compounds:

   [Formula 1]

   

   In Chemical Formula 1,

   X ₁ and X ₂ are each independently halogen,

   R ₁ and R ₅ are each independently C _6-20 aryl substituted with C _1-20 alkyl,

   R ₂ to R ₄ and R ₆ to R ₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 Alkoxysilyl, C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

   A is carbon, silicon or germanium,

   R ₉ and R ₁₀ are each independently C _1-2 straight chain alkyl; Or C _3-10 straight chain alkyl substituted with C _1-10 alkoxy, at least one of R ₉ and R ₁₀ is C _3-10 straight chain alkyl substituted with C _1-10 alkoxy,

   [Formula 2]

   

   In Chemical Formula 2,

   X ₃ and X ₄ are each independently halogen,

   R ₁₁ to R ₂₀ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _{1- 20} ether, C _1-20 silyl ether, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

   At least one of R ₁₁ and R ₁₂ is C _2-20 alkoxyalkyl,

   At least one of R ₁₇ to R ₂₀ is C _1-20 alkyl.
2. According to claim 1,

   The R ₁ and R ₅ are each independently phenyl substituted with C _3-6 branched chain alkyl, a hybrid supported metallocene catalyst.
3. According to claim 1,

   R ₉ and R ₁₀ are each independently methyl; Or are a C _5-9 straight chain alkyl substituted with a tert- butoxy, R ₉ and R ₁₀ and of a C _5-9 straight-chain alkyl substituted with at least tert- butoxy, the hybrid supported metallocene catalyst metal.
4. According to claim 1,

   The first metallocene compound represented by Chemical Formula 1 is a compound represented by the following Chemical Formula 1-1, and a mixed supported metallocene catalyst:

   [Formula 1-1]

   
5. According to claim 1,

   R ₁₂ is C _5-9 straight chain alkyl substituted with tert-butoxy, a hybrid supported metallocene catalyst.
6. According to claim 1,

   A hybrid supported metallocene catalyst, wherein one of R ₁₈ and R ₁₉ is normal-butyl.
7. According to claim 1,

   The second metallocene compound represented by Formula 2 is a compound represented by the following Formula 2-1, a hybrid supported metallocene catalyst:

   [Formula 2-1]

   
8. According to claim 1,

   The first metallocene compound and the second metallocene compound have a molar ratio of 1:1 to 15:1, and the mixed supported metallocene catalyst.
9. According to claim 1,

   The carrier comprises a mixture of any one or two or more selected from the group consisting of silica, alumina and magnesia, a hybrid supported metallocene catalyst.
10. According to claim 1,

    A hybrid supported metallocene catalyst further comprising at least one cocatalyst selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5:

    [Formula 3]

    

    In Chemical Formula 3,

    R ₂₁ , R ₂₂ and R ₂₃ are each independently hydrogen, halogen, C _1-20 hydrocarbyl group, or C _1-20 hydrocarbyl group substituted with halogen,

    n is an integer of 2 or more,

    [Formula 4]

    

    In Chemical Formula 4,

    D is aluminum or boron,

    R ₂₄ are each independently halogen, C _1-20 hydro-car invoking, C _1-20 hydro-car bilok group, or substituted C _1-20 hydro-car invoking by halogen,

    [Formula 5]

    

    In Chemical Formula 5,

    L is a neutral or cationic Lewis base,

    H is a hydrogen atom,

    W is a group 13 element,

    A is each independently a C _1-20 hydrocarbyl group; C _1-20 hydrocarbyloxy group; And one or more substituents in which one or more hydrogen atoms of these substituents are substituted with one or more substituents among halogen, C _1-20 hydrocarbyloxy group and C _1-20 hydrocarbyl(oxy)silyl group.
11. A method for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the hybrid supported metallocene catalyst of claim 1.
12. The method of claim 11,

    The polymerization reaction is carried out in a semi-batch reactor, a method for producing an olefin polymer.
13. The method of claim 11,

    The olefin monomer is 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-atocene, norbornene, norbornadiene, ethylidene novoden, phenyl novoden, vinyl novoden, dicyclopentadiene, 1,4-butadiene, 1,5- A method for producing an olefin polymer comprising at least one member selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.
14. It is manufactured by the manufacturing method of claim 11,

    Melt flow rate ratio (MFRR) is 22 to 50,

    Stress crack resistance (FNCT; Full Notch Creep Test) is 1000 to 3000hr,

    An olefin polymer having a Broad Orthogonal Comonomer Distribution (BOCD) index of 0.8 to 3.0.
15. The method of claim 14,

    An olefin polymer, which is an ethylene-1-butene polymer.