KR20220101482A - Novel metallocene compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same - Google Patents

Abstract

The present invention relates to a novel metallocene compound, a catalyst composition comprising the same, and a method for manufacturing an olefin polymer using the same. The metallocene compound according to the present invention is a compound having a novel structure, and the catalyst composition containing the same has high copolymerizability and high reaction activity when manufacturing olefin polymers, and is suitable for manufacturing high molecular weight olefin polymers.

Description

A novel metallocene compound, a catalyst composition comprising the same, and a method for producing an olefin polymer using the same

The present invention relates to a novel metallocene compound, a catalyst composition comprising the same, and a method for preparing an olefin polymer using the same. More particularly, it relates to a novel metallocene compound based on a fluorene structure, a catalyst composition including the same, and a method for preparing an olefin polymer using the catalyst composition.

Existing olefin polymerization catalysts can be classified into Ziegler-Natta-based and metallocene-based catalysts. Among them, Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used in the commercial production process. The Ziegler-Natta catalysts have high activity, but because they are multi-site catalysts, the molecular weight distribution of the resulting polymer is wide and the composition distribution of comonomers is It is not uniform, so there is a limit to securing desired physical properties.

Accordingly, in recent years, metallocene catalysts have been developed and widely used in order to overcome the limitations of the Ziegler-Natta catalyst. The metallocene catalyst consists of a combination of a main catalyst which is a transition metal compound including titanium, zirconium, hafnium, and the like, and a cocatalyst including an organometallic compound containing aluminum as a main component. The metallocene catalyst is a single active site catalyst having one type of active site, and a polymer having a narrow molecular weight distribution and a uniform comonomer composition distribution is obtained. In addition, according to the modification of the ligand structure of the catalyst and the change of polymerization conditions, it has the property of changing the stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the polymer.

On the other hand, when molding a polymer into a product, the physical properties of the polymer act as an important factor. When the molecular weight of the polymer is small, processability is improved, but mechanical properties are reduced. Therefore, in order to commercialize a polymer, a polymer having a molecular weight of a certain level or more and a narrow molecular weight distribution is required.

An object of the present invention is to provide a novel novel metallocene compound, a catalyst composition including the metallocene compound, and a method for preparing an olefin polymer using the catalyst composition.

The present invention provides a metallocene compound represented by the following formula (1):

A metallocene compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

M is a Group 4 transition metal,

X ₁ and X ₂ are the same as or different from each other, and are each independently halogen, or C _1-20 alkyl;

Q is carbon, silicon, or germanium, n is an integer from 1 to 20,

R ₁ and R ₂ are the same or different and are each independently hydrogen or C _1-20 alkyl, except that R ₁ and R ₂ are both hydrogen.

R ₃ to R ₆ are hydrogen,

R ₇ to R ₈ are the same as or different from each other and are each independently C _1-20 alkyl, C _6-30 aryl, C _7-30 alkylaryl, or C _7-30 arylalkyl,

R ₉ is C _1-20 alkyl.

In addition, the present invention provides a catalyst composition comprising the metallocene compound of claim 1.

Furthermore, the present invention provides a method for producing an olefin polymer, comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition, and an olefin polymer prepared thereby

The metallocene compound according to the present invention is a compound having a novel structure, and a catalyst composition including the same has high copolymerizability and high reaction activity when preparing an olefin polymer, and is suitable for the preparation of a high molecular weight olefin polymer.

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

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

Hereinafter, the present invention will be described in detail.

The metallocene compound according to an embodiment of the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1,

M is a Group 4 transition metal,

X ₁ and X ₂ are the same as or different from each other, and are each independently halogen, or C _1-20 alkyl;

Q is carbon, silicon, or germanium, n is an integer from 1 to 20,

R ₁ and R ₂ are the same or different and are each independently hydrogen or C _1-20 alkyl, except that R ₁ and R ₂ are both hydrogen.

R ₃ to R ₆ are hydrogen,

R ₇ to R ₈ are the same as or different from each other and are each independently C _1-20 alkyl, C _6-30 aryl, C _7-30 alkylaryl, or C _7-30 arylalkyl,

R ₉ is C _1-20 alkyl.

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

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

C _1-20 alkyl may be straight chain, branched chain or cyclic alkyl. Specifically, the 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 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 It may be a cyclohexyl group or the like.

C _6-30 aryl may mean a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, C _6-30 aryl may be a phenyl group, a naphthyl group, or an anthracenyl group.

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

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

The hydrocarbyl group refers to a monovalent hydrocarbon compound, and includes an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, or an arylalkyl group.

The metallocene compound represented by Formula 1 includes fluorene or a derivative thereof as a ligand, and a nitrogen-containing group (-NR- ₇ ), and each ligand forms a ligand structure crosslinked by a bridging compound.

The fluorene ligand is structurally stable and has electronically rich properties. In particular, the fluorene ligand used in the metallocene compound of the present invention includes a substituent symmetrically at positions 2 and 7 or at positions 3 and 6 of fluorene, respectively. The substituent of the fluorene ligand serves as an electron donating and provides an electron-rich environment compared to the unsubstituted fluorene ligand through an inductive effect. In addition, by symmetrically introducing a substituent, a steric hindrance is formed, and beta-hydride elimination is prevented, so that it can be suitably used for the production of a high molecular weight ethylene polymer.

In addition, in the case of a metallocene compound having an indene ligand in the prior art, a low molecular weight polymer could be prepared, but the metallocene compound in the present invention is a fluorene ligand having a symmetrical substituent through the interaction between the nitrogen atom of the amine derivative. , by inhibiting the hydrogen bonding of beta-hydrogen in the polymer chain during the polymerization process, it is possible to prepare a polymer having a high molecular weight region. In addition, it has excellent copolymerizability by maximizing the bond angle between the ligand and the metal. As such, the ethylene polymer having a high molecular weight and high copolymerizability may have excellent mechanical properties.

One of the substituents of the bridging group (-Q-) connecting the fluorene ligand and the nitrogen-containing group is an alkoxyalkyl group, which forms a structure through chemical bonding with a carrier or co-catalyst compound to be described later, thereby improving the support stability. can

As the central metal (M) of the metallocene compound represented by Formula 1, a Group 4 transition metal may be used, and preferably titanium (Ti).

Preferably, in Formula 1, X ₁ and X ₂ may each independently be C _1-20 alkyl.

Preferably, in Formula 1, X ₁ and X ₂ may each independently be methyl, ethyl, n-propyl, or iso-propyl, more preferably X ₁ and X ₂ may both be methyl.

Preferably, Q in Formula 1 may be silicon.

Preferably, n is an integer of 1-10, More preferably, n is an integer of 4-6.

Preferably, in Formula 1, any one of R ₁ and R ₂ may be hydrogen, and the other may be C _1-10 alkyl. More preferably, any one of R ₁ and R ₂ may be hydrogen, and the other may be methyl, ethyl or t-butyl, and more preferably t-butyl.

Preferably, R ₇ and R ₉ may each independently be t-butyl.

Preferably, the metallocene compound of Formula 1 may be any one selected from the group consisting of Formulas 1-1 and 1-2, but the present invention is not limited thereto:

[Formula 1-1]

[Formula 1-2]

The metallocene compound represented by Chemical Formula 1 may be prepared by, for example, a preparation method as shown in Scheme 1 below, but is not limited thereto, and may be prepared according to a known method for preparing organic compounds and metallocene compounds. The manufacturing method may be more specific in Preparation Examples to be described later.

[Scheme 1]

In Scheme 1, M, X ₁ , X ₂ , Q, n, and R ₁ to R ₉ are as defined in Formula 1 above, X, X ₃ , and X ₄ are halogen, and NBL is n-butyllithium to be.

According to one embodiment of the present invention, there is provided a catalyst composition comprising the metallocene compound represented by Formula 1 above.

The catalyst composition may include the metallocene compound represented by Formula 1 as a single catalyst or may be used together with other metallocene compounds. When the metallocene compound represented by Formula 1 is used alone, the molecular weight distribution of the prepared polymer is narrow, and mechanical properties may be improved. In addition, by using the metallocene compound represented by Formula 1 and another metallocene compound together, an olefin polymer suitable for properties required in the final product may be prepared.

In addition, according to another embodiment of the present invention, in the catalyst composition, the metallocene compound may be used as a single component or may be used in the form of a supported catalyst supported on a carrier. When the metallocene compound is used in the form of a supported catalyst, the morphology and physical properties of the prepared olefin polymer can be further improved, and it can be suitably used for slurry polymerization, bulk polymerization, and gas phase polymerization.

Specifically, as the carrier, a carrier having a hydroxyl group, a silanol group, or a siloxane group having high reactivity on the surface may be used, and for this purpose, a surface modified by calcination or a surface having moisture removed by drying may be used. have. For example, silica prepared by calcining silica gel, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are typically Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ). ₂ and the like oxide, carbonate, sulfate, and nitrate components.

The temperature for calcining or drying the carrier may be 200 to 600 °C, and may be 250 to 600 °C. When the calcination or drying temperature of the carrier is low below 200° C., there is too much moisture remaining in the carrier, so there is a risk that the surface moisture and the co-catalyst may react, and the co-catalyst is loaded due to the excess hydroxyl groups. Although the fertility rate may be relatively high, a large amount of co-catalyst is required. In addition, if the drying or calcination temperature is too high, exceeding 600°C, the pores on the surface of the carrier coalesce and the surface area decreases, a lot of hydroxyl groups or silanol groups disappear on the surface, and only siloxane groups remain, reducing the reaction sites with the promoter. there is a risk of doing

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

Among the above-mentioned carriers, silica, especially silica prepared by calcining silica gel, is supported by chemically bonding the metallocene compound to the silica carrier, so there is almost no catalyst released from the surface of the carrier in the olefin polymerization process. . As a result, when the ethylene polymer is produced by slurry polymerization or gas phase polymerization, fouling, which is caused by agglomeration of the reactor wall or polymer particles, can be minimized.

In addition, when the metallocene compound is included in the form of a supported catalyst in the catalyst composition, the metallocene compound is, for example, 10 μmol or more, or 30 μmol or more, based on 1 g of silica, per carrier weight, 100 It may be supported in a content range of μmol or less, or 80 μmol or less. When supported in the above content range, it may exhibit an appropriate supported catalyst activity, which may be advantageous in terms of maintaining the activity of the catalyst and economic feasibility.

According to another embodiment of the present invention, the catalyst composition may further include a cocatalyst capable of activating the metallocene compound in addition to the metallocene compound and the carrier. As such a cocatalyst, those commonly used in the art to which the present invention pertains may be used without particular limitation. As a non-limiting example, the cocatalyst may be one or more compounds selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4.

[Formula 2]

-[Al(R ₁₁ )-O]a-

In Formula 2,

R ₁₁ is halogen; or C _1-20 hydrocarbyl substituted or unsubstituted with halogen;

a is an integer greater than or equal to 2,

[Formula 3]

D(R ₁₂ ) ₃

In Formula 3,

D is aluminum or boron;

R ₁₂ is halogen; Or halogen-substituted or unsubstituted C _1-20 hydrocarbyl,

[Formula 4]

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Formula 4,

L is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a group 13 element;

A is each independently C _6-20 aryl or C _1-20 alkyl in which one or more hydrogen atoms are substituted with halogen, C _1-20 hydrocarbyl, C _1-20 alkoxy, or phenoxy.

In the compounds represented by Formulas 2 to 4, the hydrocarbyl refers to a monovalent hydrocarbon compound, and includes an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an arylalkyl group, and the like.

C _1-20 alkoxy may be a straight chain, branched chain or cyclic alkoxy group. Specifically, the C _1-20 alkoxy is C _1-20 straight chain alkoxy; C _1-10 alkoxy; C _1-5 straight chain alkoxy group; C _3-20 branched or cyclic alkoxy; C _3-15 branched or cyclic alkoxy; or C _3-20 branched chain or cyclic alkoxy. More specifically, C _1-20 alkoxy is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentoxy group, iso- It may be a pentoxy group, a neo-pentoxy group, or a cyclohexoxy group.

The compound represented by Formula 2 may serve as an alkylating agent and an activator, the compound represented by Formula 3 may serve as an alkylating agent, and the compound represented by Formula 4 may serve as an activator have.

The compound represented by Formula 2 is not particularly limited as long as it is an alkylaluminoxane, but may be, for example, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., preferably methylaluminoxane .

The compound represented by Formula 3 is not particularly limited as long as it is an alkyl metal compound, but for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, Tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc., preferably selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum. can

Examples of the compound represented by Formula 4 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra(p-tolyl). Boron, trimethylammonium tetra(o,p-dimethylphenyl) boron, tributylammonium tetra(p-trifluoromethylphenyl) boron, trimethylammonium tetra(p-trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphoniumtetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammonium tetra(p-tolyl) ) Aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra( p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, di Ethylammonium tetrapentatetraphenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron , tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetrapentafluorophenylboron, and the like. Any one or a mixture of two or more may be used.

Among the above cocatalysts, considering that they can exhibit superior catalytic activity when used with the metallocene compound, the cocatalyst is a compound represented by Formula 3, more specifically, C such as methylaluminoxane It may be an alkylaluminoxane-based compound of _1-20 . The alkylaluminoxane-based compound acts as a scavenger of hydroxyl groups present on the surface of the carrier to improve catalytic activity, and converts the halogen group of the catalyst precursor to a methyl group to promote chain growth during polymerization of ethylene polymer make it

The cocatalyst may be supported in an amount of, for example, 8 mmol or more, or 10 mmol or more, and 25 mmol or less, or 20 mmol or less, based on 1 g of silica per weight of the carrier. When included in the above content range, it is possible to sufficiently obtain the effect of reducing the generation of fine powder together with the effect of improving the catalytic activity according to the use of the cocatalyst.

The catalyst composition according to one embodiment of the present invention described above includes the metallocene compound of Formula 1 and exhibits high catalytic activity when used in polymerization of an olefin monomer. In particular, the olefin polymer prepared using the catalyst composition has a high molecular weight and at the same time shows a narrow molecular weight distribution, and mechanical properties are improved based on these properties.

On the other hand, the present invention provides a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of a catalyst composition comprising the metallocene compound.

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

Specific examples of the olefinic monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene , 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene may include at least one selected from the group consisting of.

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

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

The polymerization reaction of the olefin monomer may be carried out at 10 to 150 °C, preferably at 70 to 100 °C. When the polymerization reaction temperature is too low, the reactivity of the olefin monomer is not high, so it may be difficult to synthesize the olefin polymer. If the polymerization reaction temperature is too high, the olefin monomer may be thermally decomposed.

The polymerization reaction of the olefin monomer may be carried out in a pressure range of 1 to 20 bar, preferably 5 to 10 bar.

On the other hand, according to another embodiment of the present invention, there is provided an olefin polymer prepared by the method for producing the olefin polymer. The olefin polymer may be a copolymer of ethylene and alpha-olefin, and specific examples and contents of each monomer that may be included are the same as described above in the method for preparing the olefin polymer.

The metallocene compound of Formula 1 exhibits high activity in olefin polymerization, and the ethylene-alpha-olefin copolymer exhibits high copolymerizability and high short chain branch (SCB) content. In this case, the term short chain branch (SCB) means branches having 2 to 7 carbon atoms attached to the main chain, and is usually an alpha comonomer having 4 or more carbon atoms, such as 1-butene, 1-hexene, 1-octene, etc. -Means the side branches made when olefins are used. Specifically, the ethylene-1-hexene copolymer prepared in the presence of the metallocene compound of Formula 1 of the present invention has a short-chain branch content of 2.0 or more per 1000 carbon atoms.

The olefin copolymer prepared in the presence of the metallocene compound of Formula 1 has a high molecular weight and a narrow molecular weight distribution, thereby contributing to the improvement of mechanical properties of the final product. Specifically, the weight average molecular weight of the ethylene-alpha-olefin copolymer prepared in the presence of the metallocene compound of Formula 1 is 1,000,000 g/mol or more, 1,200,000 g/mol or more, or 1,400,000 g/mol or more, and 2,000,000 g/mol or more mol or less, 1,800,000 g/mol or less, or 1,500,000 g/mol or less. In addition, the prepared olefin copolymer may have a molecular weight distribution (PDI) of 1.5 or more, 1.8 or more, or 2.0 or more, and 2.6 or less, 2.5 or less, or 2.4 or less.

The weight average molecular weight may be measured using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water). Specifically, as a gel permeation chromatography (GPC) apparatus, a Waters PL-GPC220 instrument may be used, and a Polymer Laboratories PLgel MIX-B 300 mm long column may be used. At this time, the measurement temperature is 160 ℃, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) can be used as a solvent, and the flow rate can be applied at 1 mL/min. Each polypropylene sample was pretreated by dissolving it in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160 ° C. for 10 hours using a GPC analysis device (PL-GP220), and 10 mg/10 mL of It can be measured by preparing it to a concentration and then supplying it in an amount of 200 μL. In addition, the values of Mw and Mn can be derived using a calibration curve formed using a polystyrene standard specimen. The weight average molecular weight of the polystyrene standard specimen is 2,000 g/mol, 10,000 g/mol, 30,000 g/mol, 70,000 g/mol, 200,000 g/mol, 700,000 g/mol, 2,000,000 g/mol, 4,000,000 g/mol, 10,000,000 g Nine types of /mol can be used.

In addition, the molecular weight distribution may be measured as a value obtained by dividing the weight average molecular weight measured using the gel permeation chromatography by the number average molecular weight.

As described above, the olefin polymer according to one embodiment of the present invention has a high molecular weight and a narrow molecular weight distribution, and thus may exhibit improved mechanical properties such as impact strength when molded into various products.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples.

<Example>

<Synthesis of metallocene compound>

Example 1

Step 1: Preparation of Ligand Compound

In a 100 ml Schlenk flask, 2,7-di(t-butyl)fluorene (1 eq) was added as a Cp unit, THF (0.3 M) was added, and then cooled to -20 °C or less. After stirring the cooled mixed solution for 5 minutes, N-butyl lithium (NBL, 2.1 eq) was added and reacted for overnight to prepare lithiated Cp. When the NBL was added, the mixed solution exhibited a brown color.

Dichloro(tert-butoxy)hexyl)methylsilane (1.05eq) as Tether silane was put in a separate 100 ml shrink flask, and THF (0.3M) was added. After the shrink flask was cooled to -20 °C or less, the lithiated Cp prepared above was added dropwise to react. When the reaction was completed, the solvent in the reaction product was removed by distillation under reduced pressure under vacuum, and the resulting salt was removed by filtration using hexane (Hex). After reacting by adding t-BuNH ₂ (4 eq) to the resulting reactant, the resulting precipitate was filtered off using hexane to obtain a ligand compound (yellow oil, yield 99% (molar basis)) .

NMR (400MHz, CDCl ₃ ) 7.82-7.77 (d, 2H), 7.73-7.66 (t, 3H), 7.59 (s, 1H), 3.87 (s, 1H), 3.39-3.23 (m, 2H), 1.58- 1.46 (m, 2H), 1.44-1.40 (m, 6H), 1.36 (s, 18H), 1.34 (s, 9H), 1.18 (s, 9H), 0.07 (s, 3H)

Step 2: Preparation of metallocene compound

Toluene (0.3M) was added to the ligand compound (1 eq) prepared in step 1 in a 100 ml shrink flask, and then cooled to -20 °C or less. After sufficiently cooling through stirring for 5 minutes, NBL (2.1 eq) was added to the resulting mixed solution to perform lithiation. After completion of the lithiation reaction, the resulting reaction solution was cooled to 0 °C, Methyl Magnesium Bromide (MMB, 2.5 eq) was added, and then the temperature was immediately lowered to -20 °C, and TiCl ₄ (1 eq) was added. Smoke was generated upon input, and the reaction solution immediately turned brown. After the addition, stirring was performed overnight, and after completion, salt was removed through a filter to obtain a brown oily metallocene compound (brown oil, yield 86%).

NMR (400 MHz, CDCl ₃ ) 8.02-7.96 (d, 2H), 7.60 (s, 1H), 7.54-7.47 (t, 3H), 3.36-3.31 (t, 2H), 1.97-1.84 (m, 2H), 1.78-1.63 (m, 2H), 1.63-1.50 (m, 6H) 1.39 (s,9H), 1.34 (s, 18H), 1.18 (s, 9H), 0.95-0,84 (m, 2H), 0.79 (s, 3H), -0.50 (s, 3H), -0.51 (s, 3H)

Example 2

Metallocene in the same manner as in Example 1, except that 3,6-di(t-butyl)fluorene was used instead of 2,7-di(t-butyl)fluorene when preparing the ligand compound in Step 1 The compound was prepared.

NMR(400MHz,CDCl ₃ ) 8.03 (s,1H), 7.57-7.36 (m, 5H), 3.39-3.25 (m, 2H), 1.93-1.77 (m, 2H), 1.69-1.40 (m, 8H), 1.44 (s, 9H), 1.40 (s, 9H), 1.38 (s, 9H), 1.18 (s, 9H), 0.75 (s, 3H), 0.00 (s, 3H), -0.50 (s, 3H)

Comparative Example 1

Step 1: Preparation of Ligand Compound

4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-indene (i) (2.9 g, 10 mmol) as a Cp unit was put in a 100 ml Schlenk flask, and tetrahydrofuran (THF) ; 35 ml) and then cooled to -20 °C or less. After stirring the cooled mixed solution for 5 minutes, NBL (4.2 ml, 2.5M in hexane) was added, and reacted overnight to prepare lithiated Cp (lithiated Cp). When the n-butyllithium was added, the mixed solution exhibited a brown color.

Dichloro(tert-butoxy)hexyl)methylsilane (ii) (2.84 g) as tether silane was put in a separate 100 ml shrink flask, and MTBE (methyl tert-butyl ether) (35 ml) was added. After the shrink flask was cooled to -20 °C or less, the lithiated Cp prepared above was added dropwise to react. When the reaction was completed, the solvent in the reaction product was removed by distillation under reduced pressure under vacuum, and the resulting salt was removed by filtration using hexane (Hex). After reacting by adding t-BuNH ₂ (4.5 ml) to the resulting reactant (iii), the resulting precipitate was filtered off using hexane, and 1-(6-(tert-butoxy)hexyl)- A ligand compound of N-(tert-butyl)-1-(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)-1-methylsilanamine (2a) was obtained (yellow oil, 5.50 g, yield 98% (by mole)).

NMR (400 MHz, C ₆ D ₆ ) 7.72-7.65 (m, 2H), 7.59-7.21 (m, 5H), 7.05(s, 1H) 3.73-3.65 (m, 1H), 3.33-3.21 (m, 3H) , 3.11-2.85 (m, 1H), 1.66-1.51 (m, 3H), 1.51-1.34 (m, 4H), 1.26 (s, 9H), 1.12(s, 9H), 1.24-1.18 (m, 6H) , 1.06 (s, 9H), 1.04-0.99 (m, 1H), 0.64-0.58 (m, 1H), 0.54-0.49 (m, 1H), 0.30 (s, 1.5H), 0.19 (s, 1.5H)

Step 2: Preparation of metallocene compound

Into a 100 ml shrink flask, the ligand compound (2a) (4.81 g, 8.6 mmol) prepared in step 1 was put, toluene (43 ml) was added, and then cooled to -20 °C or less. After sufficiently cooling through stirring for 5 minutes, NBL (7.2 ml, 2.5M in Hexane) was added to the resulting mixed solution to perform lithiation. It was confirmed that the color of the mixed solution changed from light yellow to dark yellow after lithiation. After completion of the lithiation reaction, the resulting reaction solution was cooled to 0 °C, MMB (8.6 ml, 3M in ether) was added, and then the temperature was immediately lowered to -20 °C and TiCl ₄ (8.6 ml, 1M in toluene) was added. was put in. Smoke was generated upon input, and the reaction solution immediately turned brown. After the input, o/n stirring was performed, and after completion, salt was removed through a filter to obtain a brown oily metallocene compound (1a) (brown oil, 4.5 g, yield 82% (molar basis)) .

NMR (400 MHz, C ₆ D ₆ ), 7.25-7.75 (m, 8H), 3.20-3.36 (m, 2H), 3.20-2.64 (m, 4H) 2.64-2.74 (m,1H), 1.59-1.71 (m) , 4H), 1.53 (s, 9H), 1.40-1.35 (m, 2H), 1.25 (s, 9H), 1.14 (s, 9H) 1.12 (s, 6H), 0.97 (s, 3H) 0.58 (s, 3H), 0.12 (s, 3H)

Comparative Example 2

In the preparation of the ligand compound in step 1, 7H-benzo[c]fluorene was used instead of 2,7-di(t-butyl)fluorene. In the same manner as in Example 1, an oil phase metal of the above structural formula was used. A strong compound was prepared.

NMR (400 MHz, CDCl ₃ ) 8.83-8.81 (d, 1H), 8.70-8.68 (d, 1H), 7.91-7.90 (d, 1H), 7.79-7.69 (m,2H), 7.69-7.63 (d, 1H) ), 7.62-7.47 (m, 4H), 3.40-3.32 (m, 2H), 1.98-1.84 (m, 2H) 1.79-1.63 (m, 2H), 1.63-1.61 (m, 6H), 1.41 (s, 9H), 1.19 (s, 9H), 0.87 (s, 1.5H), 0.78 (s, 1.5H), -0.42 (s, 3H), -0.64 (s, 1.5H), -0.67 (s, 1.5H) )

Comparative Example 3

An oily metallocene compound of the above structural formula was prepared in the same manner as in Example 1, except that fluorene was used instead of 2,7-di(t-butyl)fluorene when preparing the ligand compound in step 1.

NMR (400MHz, CDCl ₃ ) 7.92-7.85 (d, 2H), 7.56-7.36 (m, 4H), 7.26-7.16 (m, 2H), 3.40-3.25 (m, 2H), 1.95-1.79 (m, 2H) ), 1.73-1.45 (m, 8H), 1.40 (s, 9H), 1.20 (s, 9H), 0.65 (s, 3H), 0.02 (s, 3H), -0.48 (s, 3H)

<Preparation of metallocene supported catalyst>

Example Preparation Example 1

Silica gel (10 g) was put in a glass reactor under argon (Ar), and 55 mL of a 10 wt% methylaluminoxane (MAO) toluene solution (corresponding to 10 mmol per 1 g of Silica) was slowly injected at room temperature at 95 °C for 12 hours. stirred for a while. After completion of the reaction, 60 μmol of the metallocene compound prepared in Example 1 (corresponding to 60 μmol per 1 g of Silica) was dissolved in 10 mL of toluene, and then transferred to the reactor using cannula. After stirring at 80° C. for 2 hours, it was cooled to room temperature and left for 15 minutes to decant the solvent using a cannula. 50 mL of toluene was added, stirred for 1 minute, left for 15 minutes, and decanting the solvent using a cannula was performed twice. In the same way, add 50 mL of hexane, stir for 1 minute and leave for 15 minutes to decant the solvent using a cannula, and 5 ml of a solution of an antistatic agent (Atmer 163™, manufactured by CRODA) dissolved in nucleic acid (antistatic agent content = silica 100) 2 parts by weight) was transferred using a cannula. After stirring at room temperature for 20 minutes, the solvent was removed by transfer through a glass filter. A supported catalyst was obtained by drying at room temperature under vacuum for 5 hours.

Example Preparation 2

A supported catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compound of Example 2 was used instead of the metallocene compound of Example 1.

Comparative Preparation Examples 1 to 3

A supported catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compounds of Comparative Examples 1 to 3 were used instead of the metallocene compound of Example 1.

<Production of Olefin Polymer>

Polymerization Example 1

For the production of olefin polymer, a 600 mL metal alloy reactor equipped with a mechanical stirrer, temperature controllable, and capable of high pressure reaction was prepared. The reactor was vacuum dried at 120° C. and then cooled, and 450 ppm of triethylaluminum (1M solution in Hexane) was added at room temperature, and 7 mg of the metallocene-supported catalyst of Preparation Example 1 was added to the reactor. Thereafter, the temperature of the reactor was gradually increased to 70° C., and 10 ml of 1-hexene was injected, followed by a polymerization process for 0.5 hours. At this time, ethylene gas was continuously injected so that the pressure of the reactor was maintained at about 30 kgf/cm ² . After completion of the reaction, unreacted ethylene was vented.

Polymerization Example 2

The polymerization process of the olefin polymer was performed in the same manner as in Polymerization Example 1, except that the metallocene supported catalyst of Preparation Example 2 was used instead of the metallocene supported catalyst of Preparation Example 1.

Comparative Polymerization Examples 1 to 3

The polymerization process of the olefin polymer was performed in the same manner as in Polymerization Example 1, except that the metallocene-supported catalysts of Comparative Preparation Examples 1 to 3 were used instead of the metallocene-supported catalysts of Preparation Example 1.

test example

The polymerization activity of the supported catalyst containing the metallocene compound of Examples and Comparative Examples and the olefin polymer prepared in the presence of each supported catalyst were evaluated for physical properties in the following manner. The results are shown in Table 1 below.

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

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

(3) SCB (Short Chain Branch) content (branch content of 2 to 7 carbons per 1,000 carbons, unit: ea/1000C): Samples 1 and 2 containing 0.0125% of BHT using PL-SP260VS , After pretreatment by dissolving in 4-Trichlorobenzene at 160 °C for 10 hours, measurements were made at 160 °C using PerkinELmer Spectrum 100 FT-IR connected to high temperature GPC (PL-GPC220).

use catalyst activation
(kg PE/g cat.hr) Mw
(*1000 g/mol) PDI SCB
(pcs/1000 C) Polymerization Example 1 Example 1 2.7 1488 2.1 2.7 Polymerization Example 2 Example 2 2.0 1414 2.1 2.0 Comparative Polymerization Example 1 Comparative Example 1 1.3 974 2.5 1.3 Comparative polymerization example 2 Comparative Example 2 1.8 813 2.7 1.8 Comparative polymerization example 3 Comparative Example 3 1.5 1214 2.3 1.7

Referring to Table 1, the metallocene compound of Formula 1 of the present invention exhibits excellent catalytic activity of 2.0 kg/g cat.hr) or more, and the olefin polymer prepared using the catalyst has a high weight of 1,000,000 g/mol or more. It can be seen that the average molecular weight, PDI of less than 2.5, and high SCB content of 2.0 pieces/1000 C or more.

Claims (13)

A metallocene compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
M is a Group 4 transition metal,
X ₁ and X ₂ are the same as or different from each other, and are each independently halogen, or C _1-20 alkyl;
Q is carbon, silicon, or germanium,
n is an integer from 1 to 20,
R ₁ and R ₂ are the same or different, and are each independently hydrogen or C _1-20 alkyl, except when both R ₁ and R ₂ are hydrogen.
R ₃ to R ₆ are hydrogen,
R ₇ to R ₈ are the same as or different from each other, and each independently represents C _1-20 alkyl, C _6-30 aryl, C _7-30 alkylaryl, or C _7-30 arylalkyl,
R ₉ is C _1-20 alkyl.
According to claim 1,
M is titanium (Ti), X ₁ and X ₂ are each independently C _1-20 alkyl;
metallocene compounds.
According to claim 1,
Q is silicon, n is an integer from 1 to 10,
metallocene compounds.
According to claim 1,
One of R ₁ and R ₂ is hydrogen and the other is C _1-10 alkyl,
metallocene compounds.
According to claim 1,
R ₇ and R ₉ are each independently t-butyl,
metallocene compounds.
According to claim 1,
The metallocene compound of Formula 1 is any one selected from the group consisting of Formula 1-1 and Formula 1-2,
Metallocene compounds:
[Formula 1-1]

[Formula 1-2]

Comprising the metallocene compound of claim 1,
catalyst composition.
8. The method of claim 7,
Further comprising a carrier supporting the metallocene compound,
catalyst composition.
9. The method of claim 8,
The carrier is silica, alumina, magneisa or a mixture thereof,
catalyst composition.
8. The method of claim 7,
The catalyst composition further comprises at least one cocatalyst compound selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4,
Catalyst composition:
[Formula 2]
-[Al(R ₁₀ )-O]a-
In Formula 2,
R ₁₀ is halogen; or C _1-20 hydrocarbyl substituted or unsubstituted with halogen;
a is an integer greater than or equal to 2,
[Formula 3]
D(R ₁₁ ) ₃
In Formula 3,
D is aluminum or boron;
R ₁₁ is halogen; Or halogen-substituted or unsubstituted C _1-20 hydrocarbyl,
[Formula 4]
[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-
In Formula 4,
L is a neutral or cationic Lewis base;
H is a hydrogen atom;
Z is a group 13 element;
A is each independently C _6-20 aryl or C _1-20 alkyl in which one or more hydrogen atoms are substituted with halogen, C _1-20 hydrocarbyl, C _1-20 alkoxy, or phenoxy.
In the presence of the catalyst composition of claim 7, comprising the step of polymerizing an olefin monomer,
A process for producing an olefin polymer.
12. The method of claim 11,
Olefin monomers are 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-penta characterized in that it contains at least one selected from the group consisting of diene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene,
A process for producing an olefin polymer.
13. A method for preparing an olefin polymer according to any one of claims 11 and 12,
olefin polymers.