KR20220055863A - 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 preparing olefin polymer using the same. The metallocene compound is represented by chemical formula 1. According to the present invention, a catalyst composition comprising the metallocene compound is adequate to prepare LLDPE for a film with excellent material properties and processability.

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 comprising benzofluorene and a cyclopentadiene ligand, a catalyst composition comprising 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, a Ziegler-Natta catalyst of titanium or vanadium compounds has been widely used in the commercial production process. The Ziegler-Natta catalyst has high activity, but because it is a multi-site catalyst, the molecular weight distribution of the resulting polymer is wide and the composition distribution of the comonomer 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 to overcome the limitations of Ziegler-Natta catalysts. 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, while linear low density polyethylene (LLDPE) synthesized from a metallocene catalyst has excellent physical properties, it has a problem of low processability. In order to improve processability, a technology of blending LDPE (low density polyethylene) has been developed. However, as the amount of LDPE used increases, there is a problem in that the physical properties of LLDPE decrease.

Accordingly, the ethylene polymer containing an appropriate amount of long chain branch (LCB) in the LLDPE can have excellent physical properties without kneading with the LDPE and improve processability at the same time. Accordingly, there is a continuing demand for the development of a novel catalyst having high polymerization activity while including LCB in an appropriate amount.

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 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 hydrogen, halogen, or C _1-20 alkyl;

Q ₁ and Q ₂ are the same or different and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkoxyalkyl, or C _6-30 aryl;

R ₁ to R ₄ are the same or different, and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, or two adjacent substituents thereof are connected to each other and substituted or unsubstituted C _6-30 form an aryl;

R ₅ to R ₈ are the same or different and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, or C _1-20 alkoxy;

R ₉ to R ₁₄ are the same or different, and each independently represent hydrogen, C _1-20 alkyl.

In addition, the present invention provides a catalyst composition comprising the metallocene compound represented by Formula 1 above.

Furthermore, the present invention provides a method for preparing 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 of a novel structure, and the catalyst composition including the compound shows high activity in ethylene polymerization reaction, and contains a high content of LCB, and has excellent properties and processability. suitable for

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

Hereinafter, the present invention will be described in detail.

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 hydrogen, halogen, or C _1-20 alkyl;

Q ₁ and Q ₂ are the same or different and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkoxyalkyl, or C _6-30 aryl;

R ₁ to R ₄ are the same or different, and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, or two adjacent substituents thereof are connected to each other and substituted or unsubstituted C _6-30 form an aryl;

R ₅ to R ₈ are the same or different and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, or C _2-20 alkoxy;

R ₉ to R ₁₄ are the same or different, and each independently represent hydrogen or C _1-20 alkyl.

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

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

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, It may be n-hexyl, or a cyclohexyl group.

C _2-20 alkenyl may be straight chain, branched chain or cyclic alkenyl. Specifically, the 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, 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 _6-30 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 _2-20 alkoxyalkyl may have a structure including -Ra-O-Rb and may be a substituent in which at least one hydrogen of alkyl (-Ra) is substituted with alkoxy (-O-Rb). Specifically, C _2-20 alkoxyalkyl is a methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, iso-propoxyethyl group, iso-propoxyhexyl group, tert-butoxymethyl group, tert- part It may be a toxyethyl group or a tert-butoxyhexyl group.

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 metallocene compound represented by Formula 1 includes benzofluorene, cyclopentadiene, or a derivative thereof as a ligand, and each ligand forms a cross-linked structure by a bridging compound. Benzofluorene, cyclopentadiene or a derivative thereof provides an electronically rich environment and has high polymerization activity. In addition, they have low hydrogen reactivity due to appropriate steric hindrance and a negative effect of the ligand, and high activity is maintained even in the presence of hydrogen.

The benzofluorene ligand has a structure in which benzene is fused to fluorene, and additionally forms a resonance structure in the existing fluorene ligand. The formation of such a resonance structure provides an abundant electronic environment and provides a vacant site to the central metal based on a flat and wide three-dimensional structure, so that an oligomer of an appropriate length is easily inserted, which is advantageous for LCB formation. Furthermore, when the benzofluorene and cyclopentadiene ligands have a substituent, the effect can be increased by an inductive effect, and an appropriate steric hindrance is formed to play an advantageous role in polymerization activity and LCB generation.

In addition to the structural characteristics of the ligand, the metallocene compound of the present invention includes a bridging group other than the transition metal compound. The bridging group facilitates copolymerization of the oligomer so that the bond angle between the central metal and the reactant is properly maintained. In this way, along with the role of increasing the accessibility of monomers and oligomers, they interact with carriers and cocatalysts to be described later, thereby improving loading stability. In the case of an element smaller than Si that provides an appropriate angle or if the angle is large, such as an ethylene bridge, the accessibility of the oligomer is lowered, and thus the reaction activity or LCB formation may be adversely affected.

As described above, the metallocene compound of the present invention is suitable for the production of LLDPE having a high LCB content when used as a catalyst because the characteristic ligand, bridge compound, and transition metal interact, and the prepared ethylene polymer can have improved physical properties and processability .

A Group 4 transition metal may be used as the central metal (M) of the metallocene compound represented by Formula 1, and preferably zirconium (Zr) or hafnium (Hf).

Preferably, in Formula 1, X ₁ and X ₂ may each independently be halogen, and more preferably, both X ₁ and X ₂ may be chloro (Cl).

Preferably, in Formula 1, Q ₁ and Q ₂ are the same or different, and each independently may be methyl, ethyl, propyl, butyl, tert-butoxyhexyl, or phenyl.

Preferably, in Formula 1, R ₁ to R ₄ are the same or different, and each independently hydrogen, methyl, or two adjacent substituents thereof may be connected to each other to form a benzene ring, and the benzene ring may be It may be unsubstituted or substituted with phenyl.

Preferably, in Formula 1, R ₅ to R ₈ are the same or different, and each independently may be hydrogen, methyl, or methoxy.

Preferably, R ₉ to R ₁₄ are the same or different, and each independently may be hydrogen.

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

The metallocene compound represented by Formula 1 may be prepared by, for example, a manufacturing 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 ₁ , Q ₂ , R ₁ to R ₁₄ are as defined in Formula 1 above.

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 Chemical Formula 1 as a single catalyst. When the metallocene compound represented by Formula 1 is used alone, LLDPE including a high content of LCB while exhibiting high reaction activity can be prepared.

Further, 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 olefin polymer to be prepared may be further improved, and may 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 a 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. there is. 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 moisture on the surface and the co-catalyst may react, and the co-catalyst is loaded due to excess hydroxyl groups. Although the fertility rate may be relatively high, a large amount of co-catalyst is required. In addition, when the drying or calcination temperature is excessively 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 co-catalyst, and if it is too large, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. 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 transition metal 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 transition metal compound is included in the form of a supported catalyst in the catalyst composition, the transition metal compound is 30 μmol or more, or 50 μmol or more, and 200 μmol or less per carrier weight, for example, based on 1 g of silica. , or may be supported in a content range of 150 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 at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4.

[Formula 2]

-[Al(R ₁₅ )-O]a-

In Formula 2,

R ₁₅ 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 ₁₆ )3

In Formula 3,

D is aluminum or boron;

R ₁₆ 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.

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 there is.

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, 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 Tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethylammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) ) Aluminum, tripropylammonium tetra(p-tolyl)aluminum, 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, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron , tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetrapentafluorophenylboron, and the like, and these Any one or a mixture of two or more may be used.

Among the cocatalysts, in consideration of the fact that they can exhibit superior catalytic activity when used with the transition metal compound, the cocatalyst is a compound represented by Formula 3, more specifically C ₁ such as methylaluminoxane _-20 may be an alkylaluminoxane-based compound. The alkylaluminoxane-based compound acts as a scavenger of hydroxyl groups on the surface of the carrier to improve catalytic activity, and converts the halogen group of the catalyst precursor into 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 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, an alpha-olefin, a cyclic olefin, a diene olefin having two or more double bonds, or a triene olefin.

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

The 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 ℃, preferably 40 to 120 ℃. 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 50 bar, preferably 20 to 40 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 polymer prepared by using it as a catalyst has a low melting point and a high molecular weight, has a narrow molecular weight distribution, and contains an appropriate amount of LCB to provide physical properties and processability. This was improved.

Specifically, the ethylene-1-hexene copolymer prepared in the presence of the metallocene compound of Formula 1 has a melting point of less than 125° C. and a weight average molecular weight of 100,000 g/mol or more, 120.000 g/mol or more, or 150,000 g/mol or more, and may be 1,000,000 g/mol or less, 750,000 g/mol or less, or 600,000 g/mol 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 °C, 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 the 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 ethylene-1-hexene copolymer prepared in the presence of the metallocene compound of Formula 1 exhibits a high content of short chain branch (SCB) as well as long chain branch (LCB). . In this case, the term short chain branch (SCB) refers to branches having 2 to 6 carbon atoms attached to the main chain, and alpha-olefins having 4 or more carbon atoms, such as 1-butene, 1-hexene, etc., are usually used as comonomers. It means the side branches that are created in case. In addition, the term long chain branch (LCB) usually refers to branches having 7 or more carbons attached to the main chain. Specifically, the ethylene-1-hexene copolymer prepared in the presence of the transition metal compound of Formula 1 of the present invention has an SCB content of 0.5 or more, 1.0 or more, or 1.2 or more per 1000 carbon atoms, and an LCB content of at least 1.2 carbon atoms. It may be 0.017 or more, 0.020 or more, or 0.025 or more per 1000 pieces.

As described above, it can be seen that the ethylene copolymer according to an embodiment of the present invention has a low melting point, a high molecular weight, and includes an appropriate amount of LCB, thereby improving both processability and physical properties.

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

Preparation of dimethylsilanediyl(7H-benzo[c]fluoren-7-yl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

After TMCP (tetramethylcyclopentadiene) (1 equiv) was dissolved in THF (0.3 M), n-BuLi (1.05 eq) was slowly added dropwise at -25 °C, followed by stirring at room temperature for 3 hours. Thereafter, dichloro dimethyl silane (1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. After dissolving 7H-benzo[c]fluoren-7-yl (1 eq) in Toluene/THF (3/2, 0.5M) in another reactor, n-BuLi (1.05 eq) was slowly added dropwise at -25 °C, The mixture was stirred at room temperature for 3 hours. After CuCN (2 mol%) was added and stirred for 30 minutes, a mono-Si solution as the first reactant was added thereto. After that, the mixture was stirred at room temperature overnight, worked-up using water, and dried to obtain a ligand.

The ligand was dissolved in Toluene/Diethyl ether (2/1, 0.53M), n-BuLi (2.05 eq) was added at -25 °C, and stirred at room temperature for 5 hours. ZrCl ₄ (1 eq) was added to the flask to make slurry in toluene (0.17 M), and then stirred at room temperature overnight. Upon completion of the reaction, the solvent was vacuum dried, dichloromethane (DCM) was re-injected, LiCl was removed through a filter, etc., the filtrate was vacuum dried, and DCM/Hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and vacuum dried to obtain a solid metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.91 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.33-7.38 (t, 2H), 7.09 (d, 1H), 2.12 (s, 6H), 1.79 (s, 6H), 1.00 (s, 6H) ppm

Example 2

Preparation of diethylsilanediyl(7H-benzo[c]fluoren-7-yl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that dichloro diethyl silane was used instead of dichloro dimethyl silane.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.91 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.33-7.38 (t, 2H), 7.09 (d, 1H), 2.12 (s, 6H), 1.79 (s, 6H), 0.94 (t, 6H), 0.66 ( m, 4H) ppm

Example 3

Preparation of methylpropylsilanediyl(7H-benzo[c]fluoren-7-yl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that dichloro methylpropyl silane was used instead of dichloro dimethyl silane.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.91 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.33-7.38 (t, 2H), 7.09 (d, 1H), 2.12 (s, 6H), 1.79 (s, 6H), 1.29 (m, 2H), 0.96 ( t, 3H), 0.61 (t, 2H), 0.43 (s, 3H) ppm

Example 4

Preparation of dipropylsilanediyl(7H-benzo[c]fluoren-7-yl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that dichloro dipropyl silane was used instead of dichloro dimethyl silane.

¹ H-NMR (500 MHz, CDCl3): 8.88 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t, 1H), 7.43 (t, 1H), 7.33-7.38 (t, 2H), 7.09 (d, 1H), 2.12 (s, 6H), 1.79 (s, 6H), 1.29 (m, 4H), 0.94 (t) , 6H), 0.62 (t, 4H) ppm

Example 5

Preparation of diphenylsilanediyl(7H-benzo[c]fluoren-7-yl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that dichloro diphenyl silane was used instead of dichloro dimethyl silane.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.90 (d, 1H), 8.24 (d, 1H), 8.09 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.39-7.46 (m, 10), 7.33-7.38 (t, 2H), 7.09 (d, 1H), 2.12 (s, 6H), 1.79 (s, 6H) ppm

Example 6

Preparation of 6-tertButoxyhexylmethylsilanediyl(7H-benzo[c]fluoren-7-yl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that dichloro 6-tertButoxyhexylmethyl silane was used instead of dichloro dimethyl silane.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.92 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.33-7.38 (t, 2H), 7.09 (d, 1H), 2.12 (s, 6H), 1.79 (s, 6H), 1.2-1.5 (m, 10H), 1.12 (s, 9H), 0.92 (t, 2H), 0.83 (s, 3H) ppm

Example 7

Preparation of methylphenylsilanediyl(7H-benzo[c]fluoren-7-yl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that dichloro methylphenyl silane was used instead of dichloro dimethyl silane.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.90 (d, 1H), 8.24 (d, 1H), 8.09 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.39-7.46 (m, 5), 7.33-7.38 (t, 2H), 7.09 (d, 1H), 2.12 (s, 6H), 1.79 (s, 6H), 0.98 (s, 3H) ppm

Example 8

Preparation of dimethylsilanediyl(7H-benzo[c]fluoren-7-yl)(2,3,4,5-tetramethyl cyclopentadienyl) hafnium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that HfCl ₄ was used instead of ZrCl ₄ .

¹ H-NMR (500 MHz, CDCl ₃ ): 8.93 (d, 1H), 8.22 (d, 1H), 8.07 (d, 1H), 7.90 (d, 1H), 7.75 (d, 1H), 7.58 (t) , 1H), 7.43 (t, 1H), 7.31-7.38 (t, 2H), 7.09 (d, 1H), 2.12 (s, 6H), 1.79 (s, 6H), 0.99 (s, 6H) ppm

Example 9

Preparation of dimethylsilanediyl(7H-benzo[c]fluoren-7-yl)cyclopentadienyl zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that cyclopentadiene (CP) was used instead of TMCP.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.91 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.33-7.38 (t, 2H), 7.09 (d, 1H), 6.38-6.5 (m, 4H), 1.02 (s, 6H) ppm

Example 10

Preparation of dimethylsilanediyl(7H-benzo[c]fluoren-7-yl)(2,4-dimethylcyclopentadienyl)zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that 2,4-dimethylcyclopentadiene was used instead of TMCP.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.9 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.33-7.38 (t, 2H), 7.09 (d, 1H), 6.26 (s, 1H), 6.2 (d, 1H), 2.1 (s, 3H), 1.82 ( s, 3H), 0.89 (s, 6H) ppm

Example 11

Preparation of dimethylsilanediyl(7H-benzo[c]fluoren-7-yl)indenyl zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that indene was used instead of TMCP.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.91 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.33-7.38 (t, 2H), 7.2-7.35 (m, 4H), 7.09 (d, 1H), 6.58 (d, 1H), 6.4 (d, 1H), 0.99 (s, 6H) ppm

Example 12

Preparation of dimethylsilanediyl(7H-benzo[c]fluoren-7-yl)2-methylindenyl zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that 2-methylindene was used instead of TMCP.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.85 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.33-7.38 (t, 2H), 7.2-7.35 (m, 4H), 7.09 (d, 1H), 6.36 (d, 1H), 1.8 (s, 1H), 1.03 (s, 6H) ppm

Example 13

Preparation of dimethylsilanediyl(7H-benzo[c]fluoren-7-yl)2-methyl-4-phenylindenyl zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that 2-methyl-4-phenylindene was used instead of TMCP.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.94 (d, 1H), 8.29 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d , 1H), 7.57 (t, 1H), 7.42-7.51 (m, 7H), 7.43 (t, 1H), 7.33-7.38 (t, 2H), 7.09 (d, 1H), 6.38 (d, 1H), 1.77 (s, 1H), 1.03 (s, 6H) ppm

Example 14

Preparation of dimethylsilanediyl(7H-benzo[c]fluoren-7-yl)4-phenylindenyl zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that 4-phenylindene was used instead of TMCP.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.91 (d, 1H), 8.35 (d, 1H), 8.22 (d, 1H), 8.05 (d, 1H), 7.9 (d, 1H), 7.79 (d , 1H), 7.57 (t, 1H), 7.42-7.51 (m, 7H), 7.43 (t, 1H), 7.33-7.38 (t, 2H), 7.09 (d, 1H), 6.59 (d, 1H), 6.38 (d, 1H), 1.03 (s, 6H) ppm

Example 15

Preparation of dimethylsilanediyl(7H-benzo[c]fluoren-7-yl)9H-fluorenyl zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that fluorene was used instead of TMCP.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.90 (d, 1H), 8.24 (d, 1H), 8.03 (d, 1H), 7.90 (m, 2H), 7.85 (d, 1H), 7.79 (d , 1H), 7.57 (t, 1H), 7.28-7.53 (m, 6H), 7.43 (t, 1H), 7.09 (d, 1H), 1.03 (s, 6H) ppm

Example 16

Preparation of dimethylsilanediyl(9-methyl-7H-benzo[c]fluoren-7-yl)(2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that 9-methylbenzofluorene was used instead of benzofluorene.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.91 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.35 (t, 1H), 7.09 (d, 1H), 2.31 (s, 1H), 2.16 (s, 6H), 1.75 (s, 6H), 1.00 (s, 6H) ppm

Example 17

Preparation of dimethylsilanediyl(9-methoxy-7H-benzo[c]fluoren-7-yl)(2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride

A metallocene compound was obtained in the same manner as in Example 1, except that 9-methoxybenzofluorene was used instead of benzofluorene.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.91 (d, 1H), 8.24 (d, 1H), 8.07 (d, 1H), 7.88 (d, 1H), 7.75 (d, 1H), 7.57 (t) , 1H), 7.43 (t, 1H), 7.35 (t, 1H), 7.09 (d, 1H), 3.71 (s, 1H), 2.12 (s, 6H), 1.79 (s, 6H), 1.00 (s, 6H) ppm

Comparative Example 1

A metallocene compound was obtained in the same manner as in Example 1, except that Benzoindene was used instead of Benzofluorene.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.86-7.80 (m, 4H), 7.55 (t, 1H), 7.36 (t, 1H), 7.21 (d, 1H), 6.62 (d, 1H), 6.42 (d, 1H), 2.16 (s, 6H), 1.82 (s, 6H), 0.96 (s, 6H) ppm

Comparative Example 2

A metallocene compound was obtained in the same manner as in Example 1, except that flurorene was used instead of benzofluorene.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.82 (d, 2H), 7.56 (d, 2H), 7.43-7.29 (m, 4H), 2.18 (s, 6H), 2.12 (s, 6H), 0.95 (s, 6H) ppm

Comparative Example 3

A metallocene compound was obtained in the same manner as in Example 1, except that indene was used instead of benzofluorene.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.40-7.35 (m, 3H), 7.21 (t, 1H), 6.61 (d, 1H), 6.43 (d, 1H), 2.17 (s, 6H), 2.11 (s, 6H), 0.95 (s, 6H) ppm

Comparative Example 4

Dimethylfulvene was dissolved in Toluene (0.5 M), benzofluorene (1.0 eq) was dissolved in Toluene/THF (volume ratio 3:1, 0.37 M) in another flask, and n-BuLi (1 eq) was slowly added at -25 ° C. Then, at room temperature After stirring for 3 hours, the previously prepared dimethylfulvene solution was added and stirred overnight. The ligand was obtained purely using column chromatography, and the solvent was dried. The ligand was dissolved in Toluene/Diethyl ether (volume ratio 3:1, 0.5 M), ZrCl ₄ was made into a Toluene (0.17 M) slurry in another flask and added at -25 ° C. Then, the solvent of the crude solution was dried and filtered with DCM to remove LiCl. The filtrate was dried and crystallized with Hexane to form a solid metal. A strong compound was obtained.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.93 (d, 1H), 8.22 (d, 1H), 8.07 (d, 1H), 7.90 (d, 1H), 7.75 (d, 1H), 7.58 (t) , 1H), 7.43 (t, 1H), 7.31-7.38 (t, 2H), 7.09 (d, 1H), 2.11 (s, 6H), 1.77 (s, 6H), 0.99 (s, 6H) ppm

<Preparation Example of Supported Catalyst>

Example Preparation Example 1

Silica gel (SYLOPOL 2408HT, calcinated under 250 ℃, 10 g) was put in a 0.25 L reactor under argon (Ar), and methylaluminoxane (MAO in Toluene, 10wt%, 760 ml) was slowly injected at room temperature for 15 hours at 90 ℃. stirred for a while. After completion of the reaction, it was cooled to room temperature and left for 15 minutes to decant the solvent using a cannula. Toluene (400 ml) was added, stirred for 1 minute, and left for 15 minutes to decant the solvent using a cannula. The metallocene compound of Example 1 (700 μmol) was dissolved in toluene (400 ml), and then transferred to the reactor using cannula. After stirring at 50 °C for 5 hours, it was cooled to room temperature and left for 15 minutes to decant the solvent using a cannula. Toluene (400 ml) 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 hexane (400 ml), stir for 1 minute, leave for 15 minutes, use cannula to decant the solvent, dissolve antistatic agent (Atmer 163, 3 g) in hexane (400 ml), and use cannula in the reactor transferred. After stirring at room temperature for 20 minutes, the solvent was removed by transferring to a glass filter. A supported catalyst was obtained by drying at room temperature and vacuum for 5 hours, and vacuum drying at 45° C. for 4 hours.

Examples Preparation Examples 2 to 17

A supported catalyst was obtained in the same manner as in Preparation Example 1, except that the metallocene compounds of Examples 2 to 17 were respectively used instead of the metallocene compound of Example 1.

Comparative Preparation Examples 1 to 4

A supported catalyst was obtained in the same manner as in Preparation Example 1, except that the metallocene compounds of Comparative Examples 1 to 4 were respectively used instead of the metallocene compound of Example 1.

<Example of polymerization of ethylene-1-hexene copolymer>

Polymerization Example 1

After vacuum drying a 2 L stainless steel reactor at 70 °C, it was cooled, and triisobutylaluminum (TIBAL in Hexane, 1 M, 3 ml) was added at room temperature, and stirred for 5 minutes. Example The supported catalyst of Preparation Example 1 (30 mg) was put into the reactor under argon pressure. Thereafter, the reactor temperature was gradually raised to 70° C., 1-hexene (10 ml) was added, ethylene (30 bar), and hydrogen were added to perform a polymerization process for 30 minutes. After completion of the reaction, unreacted ethylene was vented.

Polymerization Examples 2 to 17

A PE polymerization process was performed in the same manner as in Polymerization Example 1, except that the supported catalysts of Preparation Examples 2 to 17 were respectively used instead of the supported catalyst of Preparation Example 1.

Comparative Polymerization Examples 1 to 4

A PE polymerization process was performed in the same manner as in Polymerization Example 1, except that the supported catalysts of Comparative Preparation Examples 1 to 4 were respectively used instead of the supported catalysts of Preparation Example 1.

The polymerization activity of the supported catalyst containing the metallocene compound of Examples and Comparative Examples and the ethylene-1-hexene copolymer 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/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) Melting point (Tm)

The melting point (Tm) of the ethylene-1 hexene copolymer was measured using a differential scanning calorimeter (Differential Scanning Calorimeter, DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, after heating the polymer to 200 °C by increasing the temperature, it is maintained at that temperature for 5 minutes, then lowered to 30 °C, and then the temperature is increased again to obtain the top of the DSC (Differential Scanning Calorimeter, TA) curve. It was set as the melting point. At this time, the rate of temperature rise and fall was 10 °C/min, and the melting point was measured in the section where the second temperature rose.

(3) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (MWD)

The weight average molecular weight (Mw) and the number average molecule (Mn) were respectively measured using gel permeation chromatography (GPC), and the molecular weight distribution was calculated as the ratio of Mw/Mn.

Specifically, as a gel permeation chromatography (GPC) apparatus, a Waters PL-GPC220 instrument was used, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. At this time, the measurement temperature was 160 °C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) was used as a solvent, and the flow rate was 1 mL/min. Polymer samples according to Examples and Comparative Examples were each pretreated by dissolving them in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160 ° C. for 10 hours using a GPC analysis device (PL-GP220). , was prepared at a concentration of 10 mg/10mL, and then supplied in an amount of 200 μL. The values of Mw and Mn were derived using a calibration curve formed using a polystyrene standard 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 species of /mol were used.

(4) SCB content (branch content of 2 to 6 carbon atoms per 1,000 carbons, unit: ea/1000 C)

The sample was pretreated by dissolving it in 1,2,4-Trichlorobenzene containing 0.0125% of BHT using PL-SP260VS at 160 °C for 10 hours, and then using PerkinElmer Spectrum 100 FT-IR connected to high-temperature GPC (PL-GPC220). and measured at 160 °C.

(5) LCB content (branch content of 7 or more carbons per 1,000 carbons, unit: ea/1000 C)

The LCB content was measured according to KR10-2017-0112184. More specifically, the rheological properties and molecular weight distribution of the sample were measured using a rotational rheometer and GPC. And an arbitrary value of the number of LCBs in the sample was calculated. Thereafter, the rheological properties and molecular weight distribution are predicted from the random values, and a random value with an error of less than 5% of the predicted value and the measured value is derived as a definite value, and the rheological property predicted value and the actual value are compared from the process of setting the random value again Thus, the process of deriving a definite value was repeated. Through this, the average value of the confirmed fixed values was obtained and the number of LCBs was calculated.

use
metallocene
catalyst activation
(kg PE/g cat.hr) Tm
(℃) Mw
(g/mol) MWD Number of SCBs
(pcs/1000 C) Number of LCBs
(pcs/1000 C) Polymerization Example 1 Example 1 8.40 122.9 464,608 2.45 2.9 0.041 Polymerization Example 2 Example 2 8.53 128.2 472,509 2.69 1.2 0.048 Polymerization Example 3 Example 3 8.58 123.5 472,811 2.62 2.2 0.035 Polymerization Example 4 Example 4 8.46 124.6 481,310 2.66 1.8 0.035 Polymerization Example 5 Example 5 5.49 124.9 564,390 2.61 2.4 0.041 Polymerization Example 6 Example 6 10.39 123.5 466,827 2.29 1.6 0.047 Polymerization Example 7 Example 7 5.60 123.4 460,371 2.69 2.9 0.042 Polymerization Example 8 Example 8 6.80 124.8 418.563 3.02 1.8 0.036 Polymerization Example 9 Example 9 6.21 124.4 432,815 2.40 1.3 0.039 Polymerization Example 10 Example 10 6.25 124.6 443,208 2.43 1.2 0.033 Polymerization Example 11 Example 11 7.85 123.0 223,459 2.68 2.1 0.043 Polymerization Example 12 Example 12 9.13 122.8 254,813 2.55 2.4 0.041 Polymerization Example 13 Example 13 8.67 122.9 222,123 2.23 3.2 0.038 Polymerization Example 14 Example 14 8.80 122.7 223,456 2.68 3.7 0.028 Polymerization Example 15 Example 15 10.11 123.1 157,456 2.71 1.8 0.033 Polymerization Example 16 Example 16 8.12 123.8 481,414 2.74 2.6 0.032 Polymerization Example 17 Example 17 8.56 123.2 489,157 2.70 2.1 0.040 Comparative polymerization example 1 Comparative Example 1 5.22 125.0 221,909 3.15 2.8 0.010 Comparative polymerization example 2 Comparative Example 2 3.25 129.7 190,148 3.05 3.4 0.015 Comparative polymerization example 3 Comparative Example 3 3.66 128.8 70,040 5.36 3.3 0.008 Comparative Polymerization Example 4 Comparative Example 4 5.24 125.1 126.515 3.11 1.1 0.019

Referring to Table 1, the metallocene compound of Formula 1 of the present invention exhibits high activity in preparing ethylene polymer. In addition, it can be seen that the ethylene polymer prepared by using the metallocene compound according to the present invention as a catalyst has a low melting point, a high molecular weight, a narrow molecular weight distribution, and a high LCB content.

Claims (14)

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 hydrogen, halogen, or C _1-20 alkyl;
Q ₁ and Q ₂ are the same or different and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkoxyalkyl, or C _6-30 aryl;
R ₁ to R ₄ are the same or different, and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, or two adjacent substituents thereof are connected to each other and substituted or unsubstituted C _6-30 form an aryl;
R ₅ to R ₈ are the same or different and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, or C _1-20 alkoxy;
R ₉ to R ₁₄ are the same or different, and each independently represent hydrogen or C _1-20 alkyl.
The method of claim 1,
M is zirconium (Zr), or hafnium (Hf),
X ₁ and X ₂ are each independently halogen;
metallocene compounds.
The method of claim 1,
Q ₁ and Q ₂ are the same or different and are each independently methyl, ethyl, propyl, butyl, tert-butoxyhexyl, or phenyl;
metallocene compounds.
The method of claim 1,
R ₁ to R ₄ are the same or different, and each independently hydrogen, methyl, or two adjacent substituents thereof may be connected to each other to form a benzene ring,
The benzene ring may be unsubstituted or substituted with phenyl,
metallocene compounds.
According to claim 1,
R ₅ to R ₈ are the same or different, and are each independently hydrogen, methyl, or methoxy;
metallocene compounds.
The method of claim 1,
R ₉ to R ₁₄ are the same or different, and are each independently hydrogen,
metallocene compounds.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of the following compounds,
Metallocene compounds:

Comprising the metallocene compound of claim 1,
catalyst composition.
9. The method of claim 8,
Further comprising a carrier supporting the metallocene compound,
catalyst composition.
10. The method of claim 9,
The carrier is silica, alumina, magnesia or a mixture thereof,
catalyst composition.
9. The method of claim 8,
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 ₁₅ )-O]a-
In Formula 2,
R ₁₅ 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 ₁₆ ) ₃
In Formula 3,
D is aluminum or boron;
R ₁₆ 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 8, comprising the step of polymerizing an olefin monomer,
A process for producing an olefin polymer.
14. The method of claim 13,
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-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5- Characterized in that it contains at least one selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene,
A process for producing an olefin polymer.
A method for producing an olefin polymer according to any one of claims 12 and 13,
olefin polymers.