KR20180046291A - Ethylene/alpha-olefin copolymer having an excellent environmental stress crack resistance - Google Patents

Abstract

The present invention relates to an ethylene / alpha-olefin copolymer and the ethylene / alpha-olefin copolymer according to the present invention has excellent environmental stress cracking properties and can be applied to various products.

Description

(Ethylene / alpha-olefin copolymer having an excellent environmental stress crack resistance)

The present invention relates to an ethylene / alpha-olefin copolymer having excellent environmental stress cracking resistance.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to conventional commercial processes since the invention of the 50's. However, since the Ziegler-Natta catalyst is a multi-site catalyst containing a plurality of active sites, the molecular weight distribution of the polymer is broad, There is a problem that the desired physical properties can not be secured.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst, . The polymer has a narrow molecular weight distribution according to the single active site property and a homogeneous composition distribution of the comonomer is obtained. According to the modification of the ligand structure and the polymerization conditions of the catalyst, the stereoregularity of the polymer, Crystallinity and so on.

U.S. Patent No. 5,914,289 discloses a method of controlling the molecular weight and molecular weight distribution of a polymer by using a metallocene catalyst supported on each support. However, the amount of the solvent used for preparing the supported catalyst and the preparation time are long , And the metallocene catalyst used had to be carried on the carrier, respectively.

Korean Patent Application No. 2003-12308 discloses a method for controlling the molecular weight distribution by carrying a double-nucleated metallocene catalyst and a single nuclear metallocene catalyst together with an activating agent in a carrier to change and polymerize the combination of catalysts in the reactor have. However, this method has a limitation in simultaneously realizing the characteristics of the individual catalysts, and also disadvantageously causes fouling in the reactor due to liberation of the metallocene catalyst portion in the carrier component of the finished catalyst.

Accordingly, there is a continuing need for a process for preparing an olefin polymer of desired properties by preparing a hybrid supported metallocene catalyst having excellent activity in order to solve the above-mentioned disadvantages.

On the other hand, the linear low density polyethylene is a resin which is produced by copolymerizing ethylene and an alpha olefin at a low pressure using a polymerization catalyst, has a short molecular weight distribution and a short chain length and has no long chain branch. Linear low density polyethylene film has high tensile strength and elongation as well as general polyethylene characteristics, and has excellent tear strength and falling impact strength. Therefore, it is used for stretch film and overlap film which are difficult to apply low density polyethylene or high density polyethylene .

However, linear low density polyethylene using 1-butene or 1-hexene as a comonomer is mostly prepared in a single gas phase reactor or a single loop slurry reactor, and productivity is high compared to the process using 1-octene comonomer. Due to limitations of catalyst technology and process technology, there is a problem that the physical properties are considerably weaker than when using 1-octene comonomer, and the molecular weight distribution is narrow, resulting in poor processability. Much effort has been made to improve these problems,

U.S. Patent No. 4,935,474 discloses a process for preparing polyethylene having a broad molecular weight distribution using two or more metallocene compounds. U.S. Patent No. 6,828,394 discloses a process for producing polyethylene which is excellent in processability using a mixture of a monomer having good comonomer binding property and a monomer having no comonomer binding property and is particularly suitable for a film. In addition, U.S. Patent No. 6,841,631 and U.S. Patent No. 6,894,128 disclose that a polyethylene having at least two kinds of metal compounds is used as a metallocene-based catalyst and has a molecular weight distribution of at least two, and is used for films, blow molding, It is reported that it is applicable. However, these products have improved processability, but the dispersed state of the unit particles in molecular weight is not uniform, so that the extrusion appearance is rough and the physical properties are not stable even under relatively good extrusion conditions.

In this background, there is a continuing need for the production of superior products having a balance between physical properties and processability, and in particular, there is a need for a polyethylene copolymer having excellent environmental stress cracking resistance.

The inventors of the present invention confirmed that the ethylene / alpha-olefin copolymer had an excellent resistance to environmental stress cracking when the content of the high molecular weight region and the content of the tie molecule exceeded a certain level, Completed.

The present invention is to provide an ethylene / alpha-olefin copolymer excellent in environmental stress cracking resistance.

In order to solve the above problems, the present invention provides an ethylene / alpha-olefin copolymer satisfying the following conditions:

A weight average molecular weight (g / mol) of 100,000 to 250,000,

A molecular weight distribution (PDI) of 3 or more,

A density (g / cm ³ ) of 0.948 to 0.956,

in the GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw, the integral value of the region where log Mw is 5.0 or more is 20% or more of the integral value of the x-

The Tie molecule fraction is 4 or more.

Environmental stress crack resistance (ESCR) is known to be one of the most important properties of polymers used in food containers. It can be used to judge the stability and resistance of polymers to oils and fats contained in foods, etc. As an indicator, it is important to ensure the continuous performance of the polymer.

Generally, it is known that the higher the molecular weight of a polymer, the better the mechanical properties. Thus, the environmental stress cracking resistance of an ethylene / alpha-olefin copolymer can be improved as the molecular weight of the copolymer increases. In particular, even when the molecular weight is similar, the content of the linking molecule can be increased in the case of increasing the ultrahigh molecular weight portion, thereby further improving the environmental stress cracking resistance.

The 'Tie molecule' refers to a molecule linking one lamellar crystal and another lamellar crystal in the ethylene / alpha-olefin copolymer. More specifically, the ethylene / alpha-olefin copolymer is a spherulite semi-crystalline polymer formed by assembling a plurality of lamella in which a plurality of chains of folded polymers are formed, It consists of a crystalline part and an amorphous part. In this case, the crystalline portion means the inside of the lamellar crystal, and the amorphous portion means the portion outside the lamellar crystal. Also, the amorphous part is composed of i) a cilia in which the chain starts at the crystalline part and ends in the amorphous part, ii) a loose loop in which the chain connects one lamellar crystal, and iii) an inter-lamellar link, and one of these inter-lamellar links is a linking molecule between two lamellar crystals.

Thus, the ethylene / alpha-olefin copolymers contain linking molecules linking them in the amorphous portion, i.e. between one lamellar crystal and another lamellar crystal. The content of such linking molecules is particularly important because it imparts a bonding force to the amorphous portion to improve the physical properties of the whole copolymer.

Accordingly, the present invention provides an ethylene / alpha-olefin copolymer having an increased content of ultrahigh molecular weight region and an increased content of linking molecules linking the lamellar crystal structures in the copolymer to increase environmental stress cracking resistance It is characterized by. Specifically, when the content of the linking molecules is increased, the crystalline portions may be bonded well, and even if they have the same molecular weight, the physical properties of the ethylene / alpha-olefin copolymer, especially the environmental stress cracking property, can be improved.

Hereinafter, the present invention will be described in more detail.

The ethylene / alpha-olefin copolymer according to the present invention is a polymer having a weight average molecular weight (g / mol) of 100,000 to 250,000 and a molecular weight distribution (PDI) of 3 or more and a density (g / cm ³ ) of 0.948 to 0.956 to be.

In order to have a high environmental stress cracking property, such an ethylene / alpha-olefin copolymer has an integral value of a log Mw of 5.0 or more in a GPC curve graph having an x-axis of log Mw and a y-axis of dw / dlogMw, It represents more than 20% of the integral value. In the above, Mw denotes a weight-average molecular weight, and w denotes a weight fraction.

Also, in the GPC curve graph, an area having a log Mw of 5.0 or more is an important point for confirming the formation of a linking molecule. Generally, the linking molecule is formed when the content of the high molecular weight region is above a certain level. For example, in general, a linking molecule is generated when the weight average molecular weight is 40,000, and the content of the linking molecule is increased as the content of the high molecular weight region is higher. Accordingly, when the ethylene / alpha-olefin copolymer exhibits a high molecular weight region content as described above, it can have a content of a connecting molecule of a certain level or higher, thereby further improving environmental stress cracking resistance.

Specifically, the ethylene / alpha-olefin copolymer has an integral value of a log Mw of 5.0 or more in a GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw is 20% to 30% Lt; / RTI > When the value is less than 20%, it is difficult to exhibit a desired level of environmental stress cracking resistance (ESCR). When the value is more than 30%, the high molecular weight content is high and workability is deteriorated. This can be difficult.

In addition, the ethylene / alpha-olefin copolymer has a Tie molecule fraction of 4 or more. If the ethylene / alpha-olefin copolymer has a connecting molecular content of less than 4, the desired level of environmental stress cracking (ESCR) can not be achieved. Specifically, the linking molecule content may be at least 4.1, at least 4.2, at least 4.3, or at least 4.4, and the upper limit may be less than 6.3, less than 6.2, less than 6.1, or less than 6.0. If the molecular weight of the linker exceeds 6.3, the environmental stress cracking resistance (ESCR) is high, but the workability may be deteriorated.

At this time, the molecular weight of the ethylene / alpha-olefin copolymer can be measured through a graph of a Tie molecule fraction distribution graph in which the x-axis is log Mw and the y-axis is nPdM.

The Tie molecule fraction distribution graph can be obtained from the data of the GPC curve graph. Specifically, the log Mw of the x-axis is the same as the x-axis of the GPC curve graph. Further, the y-axis nPdM can be calculated from the data obtained in the GPC curve graph. In the nPdM, n is dw / 10 log Mw, P can be calculated from the following equation 1, dM is dlogMw <x axis data of GPC curve, X n + 1> - d logMw <x axis data of GPC curve, X n >.

[Equation 1]

In the above equation (1)

r is an end-to-end distance of a random coil of the random coil,

b ² is 3/2 < r &^gt; ² ,

l _c is the crystal thickness,

l _a is the amorphous layer thickness.

In the above formula (1), l _c can be calculated from the following equation (2), where Tm is the melting point of the ethylene / alpha-olefin copolymer.

&Quot; (2) &quot;

In Equation (2)

T _m ⁰ is 415K, σ _e is 60.9 × 10 ^{- 3} is Jm ^-2, Δh _m is 2.88 × 10 ³ Jm ^-3,

In Equation (1), l _a can be calculated from the following Equation (3), and <r> can be calculated as 2 x l _c + l _a .

&Quot; (3) &quot;

In Equation (3)

ρ _c is the density of the crystalline, 1000 kg / m ³ ,

ρ _a is the density of the amorphous phase, which is 852 kg / m ³ ,

ω ^c is the weight fraction crystallinity and can be measured by DSC.

)을 계산할 수 있다.From the value of P obtained from the above-mentioned formula (1), Tie molecule fraction

) Can be calculated.

&Quot; (4) &quot;

The ethylene / alpha-olefin copolymer having the above-mentioned characteristics has an environmental stress cracking resistance (ESCR) of 10 hours or more as measured according to ASTM D 1693. If the environmental stress cracking resistance is less than 10 hours, the stability and resistance of the copolymer may be poor, which may not be easy for commercial application. More specifically, the environmental stress cracking resistance (ESCR) of the ethylene / alpha-olefin copolymer is at least 20 hours, at least 30 hours, at least 40 hours, at least 50 hours, at least 100 hours, at least 120 hours, or at least 150 hours The higher the ESCR value is, the higher the ESCR value is, and the upper limit is not limited. For example, the ESCR value may have a value of 550 hours or less.

In the GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw, the integral value of the log Mw of 5.5 or more may be 10% or more of the integral value of the x-axis in the ethylene / alpha-olefin copolymer .

In the GPC curve graph, a region having a log Mw of 5.5 or more means the content of ultrahigh molecular weight molecules in the copolymer. Considering the tendency that the higher the molecular weight, the more the ESCR increases, the GPC curve graph It is important that the region where the log Mw is 5.5 or more shows a value higher than a certain level.

Specifically, the ethylene / alpha-olefin copolymer has an integral value of a log Mw of 5.5 or more in a GPC curve graph having an x-axis of log Mw and a y-axis of dw / dlogMw of 10% %, 12%, or 13%, and the upper limit may be 20% or less, for example. If the value is more than 20%, the ultrahigh molecular weight content is high, and the processability may be deteriorated.

In addition, the ethylene / alpha-olefin copolymer may have a molecular weight distribution (PDI) of 10 to 25. And, the ethylene / alpha-olefin copolymer can exhibit a multimodal molecular weight distribution or a bimodal molecular weight distribution.

Specifically, when the ethylene / alpha-olefin copolymer exhibits a multimodal molecular weight distribution or a bimodal molecular weight distribution, one of the peaks is a GPC curve graph with the x axis of log Mw and the y axis of dw / dlogMw Of log Mw is 5.0 or more.

On the other hand, the ethylene / alpha-olefin copolymer can be prepared by polymerizing ethylene and an alpha-olefin in the presence of a metallocene catalyst.

Examples of the alpha-olefin monomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, , 1-tetradecene, 1-hexadecene, and 1-aidocene may be used. Among them, the use of 1-butene, 1-hexene, or 1-octene is preferable in terms of resistance to environmental stress cracking and workability.

At this time, the content of the comonomer alpha-olefin is not particularly limited, and can be appropriately selected according to the use, purpose, etc. of the copolymer. More specifically, it may be more than 0 and 99 mol% or less.

More specifically, the ethylene / alpha-olefin copolymer may include at least one first metallocene compound represented by the following formula (1): And in the presence of one or more second metallocene compounds selected from compounds represented by the following formulas (3) to (5): &lt; EMI ID =

[Chemical Formula 1]

In Formula 1,

A is selected from the group consisting of hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, C _7-20 arylalkyl, C _1-20 alkoxy, C _2-20 alkoxy Alkyl, C _3-20 heterocycloalkyl, or C _5-20 heteroaryl;

D is -O-, -S-, -N (R) - or -Si (R) (R ') - , in which R and R' are the same or different from each other, each independently hydrogen, halogen, C _{1 -20} alkyl, C _2-20 alkenyl, or C _6-20 aryl;

L is C _1-10 linear or branched alkylene;

B is carbon, silicon or germanium;

Q is hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl;

M is a Group 4 transition metal;

X ¹ and X ² are the same or different and are each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, nitro, amido, C _1-20 alkylsilyl, C _{1 -20} alkoxy, or C _1-20 sulfonate;

C ¹ And C ² are the same or different and each independently represents one of the following formulas (2a), (2b) or (2c) below, with the proviso that C ¹ And Except that the case where all of C ² is the formula 2c;

(2a)

(2b)

[Chemical Formula 2c]

Wherein R ₁ to R ₁₇ and R ₁ 'to R ₉ ' are the same or different from each other and each independently represents hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 alkyl silyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 alkyl and aryl, wherein R _At least two adjacent to each other of R ₁₀ to R ₁₇ may be connected to form a substituted or unsubstituted aliphatic or aromatic ring;

(3)

(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹³ _-n

In Formula 3,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ^a and R ^b are the same or different and each independently hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;

Z ¹ is halogen, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene, Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;

n is 1 or 0;

[Chemical Formula 4]

(Cp ³ R ^c ) _m B ¹ (Cp ⁴ R ^d ) M ² Z ² _3-m

In Formula 4,

M ² is a Group 4 transition metal;

Cp &lt; ³ &gt; and Cp &lt; ⁴ &gt; are the same or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical , Which may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ^c and R ^d are the same or different from each other and each independently represents hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;

Z ² is halogen, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene, Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;

B ¹ is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom containing radical which bridges the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or cross-links one Cp ⁴ R ^d ring to M ² Or a combination thereof;

m is 1 or 0;

[Chemical Formula 5]

(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂

In Formula 5,

M ³ is a Group 4 transition metal;

Cp &lt; ⁵ &gt; is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, which are substituted with hydrocarbons having 1 to 20 carbon atoms ;

R ^e is hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl , C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;

Z ³ represents halogen, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene, Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;

B ² is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radical which cross-links the Cp ⁵ R ^e ring with J, or a combination thereof;

J is any one selected from the group consisting of NR ^f , O, PR ^f and S, and R ^f is C _1-20 alkyl, aryl, substituted alkyl or substituted aryl.

The first metallocene compound of Formula 1 forms a structure in which an indeno indole derivative and / or a fluorene derivative is bridged by a bridge, and a non-covalent electron pair which can act as a Lewis base in the ligand structure Thereby supporting the carrier on the surface having Lewis acid properties and exhibiting high polymerization activity even when carried. In addition, the activity is high due to the electron enrichment of the indenoindole group and / or the fluorene group, and not only the hydrogen reactivity is low due to the appropriate steric hindrance and the electronic effect of the ligand, and the high activity is maintained even in the presence of hydrogen. In addition, it is possible to stabilize the beta-hydrogen of the polymer chain in which the nitrogen atom of the indenoindole derivative grows by hydrogen bonding to inhibit beta-hydrogen elimination and polymerize the ultra-high molecular weight polyolefin. In particular, even when used on a carrier, it exhibits a high polymerization activity, and thus an ethylene / alpha-olefin copolymer having an ultra-high molecular weight can be produced.

Further, in addition to the first metallocene compound, a second metallocene compound selected from the compounds represented by the general formulas (3) to (5) is further included, that is, at least two or more kinds of metallocene compounds It is possible to produce a polyolefin which is a high molecular weight polyolefin having a high side-chain content and at the same time has a broad molecular weight distribution and is excellent in physical properties as well as in processability.

For example, the first metallocene compound may be selected from compounds represented by Formula 6:

[Chemical Formula 6]

In Formula 6,

A is hydrogen, or C _1-20 alkyl;

D is -O-;

L is C _1-10 linear or branched alkylene;

B is carbon, silicon (Si) or germanium;

Q is hydrogen, or C _1-20 alkyl;

M is a Group 4 transition metal;

X ¹ and X ² are the same or different and are each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, nitro, amido, C _1-20 alkylsilyl, C _{1 -20} alkoxy, or C _1-20 sulfonate;

R ₁ to R ₁₇ are the same or different from each other, and each independently hydrogen or C _1-20 alkyl.

Also, the second metallocene compound may be selected from compounds represented by the following general formula (7): &lt; EMI ID =

(7)

In Formula 7,

M ⁴ is a Group 4 transition metal;

B ^' is carbon, germanium, silicon, phosphorus, or nitrogen;

Z ²¹ to Z ²³ are the same or different and each is independently halogen, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, Substituted or unsubstituted C _1-20 alkylidene, substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;

R ^c1 to R ^c4 and R ^d1 to R ^d4 are the same as or different from each other and each independently hydrogen or C _1-20 alkyl, and R ^c1 to R ^c4 and R ^d1 to R ^d4 Two or more of which are adjacent to each other may be connected to form a substituted or unsubstituted aliphatic or aromatic ring.

When the ethylene / alpha-olefin copolymer is produced in the presence of at least one first metallocene compound represented by Formula 6 and at least one second metallocene compound selected from the compound represented by Formula 7, Due to the interaction of two or more kinds of catalysts, the polymer chains in the high molecular weight region can be contained in a higher content, while the molecular weight distribution as a whole is wide, so that the above conditions can be satisfied, It can indicate the sex.

The substituents of the above formulas (1) to (7) will be more specifically described below.

Examples of the halogen include a halogen atom such as fluoro, bromo, chloro, or iodo.

Examples of the C _1-20 alkyl include linear or branched alkyl, and specifically methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, , But is not limited thereto.

The C _2-20 alkenyl includes straight or branched chain alkenyl, and specific examples thereof include, but are not limited to, allyl, ethenyl, propenyl, butenyl, pentenyl and the like.

The C _6-20 aryl includes aryl of a monocyclic or condensed ring, and specifically includes, but is not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, and the like.

The C _5-20 heteroaryl includes a heteroaryl of a monocyclic or condensed ring and includes a heteroaryl such as carbazolyl, pyridyl, quinoline, isoquinoline, thiophenyl, furanyl, imidazole, oxazolyl, thiazolyl, Tetrahydropyranyl, tetrahydropyranyl, tetrahydrofuranyl, and the like, but are not limited thereto.

Examples of the C _1-20 alkoxy include, but are not limited to, methoxy, ethoxy, phenyloxy, cyclohexyloxy, and the like.

Examples of the Group 4 transition metal include, but are not limited to, titanium, zirconium, and hafnium.

Wherein A in Formula 6 is hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, methoxymethyl, tert-butoxymethyl, 1-ethoxyethyl, Ethyl, but is not limited thereto.

Further, L in Formula 6 is more preferably C _4-8 straight chain or branched alkylene, but is not limited thereto.

B in the formula (6) is preferably silicon, but is not limited thereto.

Q in Formula 6 is preferably hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl.

In Formula 6, X ¹ and X ² may each independently be halogen, but are not limited thereto.

R ₁ to R ₁₇ in Formula 6 are each independently preferably hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl It is not.

For example, specific examples of the first metallocene compound represented by Formula 6 include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

The first metallocene compound of Formula 6 may be prepared by ligating an indenoindole derivative and / or a fluorene derivative with a bridging compound to prepare a ligand compound, and then adding a metal precursor compound to carry out metallation . The method for producing the first metallocene compound will be described in the following Examples.

B 'in the above formula (7) is preferably silicon, but is not limited thereto.

In formula (7), Z ²¹ to Z ²³ each independently represent halogen, but are not limited thereto.

R ^c1 to R ^c4 and R ^d1 to R ^d4 in Formula 7 are each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert- butyl, pentyl, hexyl, heptyl, R ^c1 to R ^c4 and R ^d1 to R ^d4 Is preferably an aromatic ring which is unsubstituted or substituted by methyl or phenyl, but is not limited thereto.

For example, specific examples of the second metallocene compound represented by Formula 7 include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

The metallocene catalyst used in the present invention may be one in which at least one of the first metallocene compounds and at least one of the second metallocene compounds are supported on a carrier together with a promoter compound.

In addition, the supported metallocene catalyst can induce the formation of LCB (Long Chain Branch) in the ethylene / alpha-co-copolymer to be produced.

In the supported metallocene catalyst according to the present invention, the co-catalyst to be supported on the support for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and the olefin is polymerized under a general metallocene catalyst It is not particularly limited as long as it can be used in the case of the above.

More specifically, the promoter may be at least one member selected from the group consisting of compounds represented by the following formulas (8) to (10):

[Chemical Formula 8]

_{- [Al (R 21) -O} ] c -

In Formula 8,

Each R &lt; ₂₁ &gt; is independently halogen, _C1-20 alkyl or _C1-20 haloalkyl,

c is an integer of 2 or more,

[Chemical Formula 9]

D (R _{22) 3}

In the above formula (9)

D is aluminum or boron,

R ₂₂ are each independently, a substituted C _1-20 hydrocarbyl hydrogen, halogen, C _1-20 hydrocarbyl or a halogen,

[Chemical formula 10]

^{[LH] + [Q (E} ) 4] - or ^{[L] + [Q (E} ) 4] -

In Formula 10,

L is a neutral or cationic Lewis base,

[LH] ⁺ is Bronsted acid,

Q is Br &lt; ^{3 +} &gt; or Al &lt; ³⁺

Wherein each E is independently C _6-20 aryl or C _1-20 alkyl, wherein said C _6-20 aryl or C _1-20 alkyl is unsubstituted or substituted with one or more groups selected from halogen, C _1-20 alkyl, C _1-20 alkoxy and Lt; / RTI &gt; is substituted by one or more substituents selected from the group consisting of phenoxy.

The compound represented by Formula 8 may be, for example, alkylaluminoxane such as modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like.

The alkyl metal compound represented by the formula (9) is, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, Aluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, Aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like.

The compound represented by Formula 10 may be, for example, triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra (p- (O, p-dimethylphenyl) boron, tributylammonium tetra (p-tolyl) boron, triethylammoniumtetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphine Tetramethylammonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl ) Aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetra Pentafluorophenyl aluminum, diethylammonium tetrapentafluorophenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetra (P-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, and the like can be used in the present invention. have.

The amount of the promoter to be supported may be 5 mmol to 20 mmol based on 1 g of the carrier.

In the supported metallocene catalyst according to the present invention, a carrier containing a hydroxy group on its surface can be used as the carrier, and preferably has a hydroxy group and a siloxane group which are dried and have moisture removed from the surface and have high reactivity Can be used.

Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. If the drying temperature of the carrier is less than 200 ° C, moisture is excessively large and the surface moisture reacts with the cocatalyst. When the temperature exceeds 800 ° C, the pores on the surface of the carrier are combined to reduce the surface area. And only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.

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

If the amount of the hydroxyl group is less than 0.1 mmol / g, the number of sites of reaction with the co-catalyst is small. If the amount is more than 10 mmol / g, the hydroxyl group may be present in the water other than the hydroxyl group present on the surface of the carrier particle. not.

On the other hand, the ethylene / alpha-olefin copolymer according to the present invention can be produced by polymerizing ethylene and alpha-olefin in the presence of the above-described supported metallocene catalyst.

The polymerization can be carried out by copolymerizing ethylene and alpha-olefins using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

The polymerization temperature may be about 25 to about 500 캜, preferably about 25 to about 200 캜, and more preferably about 50 to about 150 캜. The polymerization pressure may be from about 1 to about 100 Kgf / cm ^2, preferably about 1 to about 50 Kgf / cm ^2, more preferably from about 5 to about 30 Kgf / cm ^2.

The supported metallocene catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane and chlorobenzene A chlorine atom-substituted hydrocarbon solvent, or the like. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

As described above, the ethylene / alpha-olefin copolymer according to the present invention contains a first metallocene compound that mainly polymerizes a high molecular weight polymer chain and a second metallocene compound that mainly polymerizes a low molecular weight polymer chain , &Lt; / RTI &gt; ethylene and alpha-olefin monomers. For example, the first metallocene compound and the second metallocene compound may be supported at a molar ratio of 5: 1 to 1: 5 based on 1 g of the support. Due to the interaction of these two or more catalysts, it is possible to produce an ethylene / alpha-olefin copolymer having excellent environmental stress cracking properties, while having a broad molecular weight distribution as a whole.

The ethylene / alpha-olefin copolymer according to the present invention has excellent environmental stress cracking property and can be usefully applied to various products.

Fig. 1 shows the GPC curves of the ethylene / 1-hexene copolymer produced in Examples 1 to 5 and Comparative Example 1. Fig.
Fig. 2 is an enlarged view of a region where log Mw is 5.0 or more in Fig.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

Manufacturing example  A: First Metallocene  Preparation of compound (A)

9.7 mmol of the starting material, n-butyl-indenoindole derivative, was dissolved in 250 ml of schlenk flask and dissolved in 100 ml of hexane and 38.8 mmol of methyl tert-butyl ether. Then, 2.5 M n -BuLi Hexane solution (4.3 ml, 10.7 mmol) was added dropwise and the mixture was stirred at room temperature overnight. Another 250 ml schlenk flask was placed in a glove box and 2.6 g (9.7 mmol) of (6-tert-butoxyhexyl) dichloro (methyl) silane was taken out from the glove box and dissolved in 50 ml of hexane , Lithiated slurry of n-butyl-indenoindole derivative in dryice / acetone bath was dropwise added dropwise via cannula. The temperature of the mixture was slowly raised to room temperature and stirred overnight. At the same time, 1.6 g (9.7 mmol) of Fluorene was also dissolved in 100 ml of THF, and 4.3 ml (10.7 mmol) of 2.5 M n-BuLi Hexane solution was added dropwise in a dryice / acetone bath and stirred overnight at room temperature. The synthesized intermediate was used in the next reaction without ¹ H NMR confirmation. (6-tert-butoxyhexyl) dichloro (methyl) silane was slowly added dropwise in a dryice / acetone bath and stirred overnight at room temperature. After the reaction, the residue was extracted with ether / water to remove residual water in the organic layer with MgSO ₄ , and the solvent was removed under vacuum decompression to obtain 9 mmol of the compound in an oily state.

To the above compound was added slowly the equivalent of n-BuLi 2, then the temperature was raised to room temperature, and the reaction was carried out for at least 8 hours to give a suspension solution of ZrCl ₄ (THF) ₂ (1 equivalent) / THF The synthesized lithium salt solution was slowly added and reacted at room temperature for 6 hours.

All volatile materials were vacuum dried, and toluene solvent was added to the obtained oily liquid material for filtering. The filtered solution was vacuum dried to give the title compound.

^{1 H NMR (500 MHz, CDCl} 3): 7.90-6.98 (15H, m), 4.31-3.55 (2H, m), 3.18 (2H, m), 2.37 (3H, d), 1.33-1.25 (9H, m ), 1.15 (9H, s), 0.91 (8H, m).

Manufacturing example  B: 2nd Metallocene  Preparation of compound (B)

One equivalent of Tetramethylcyclopentadiene (TMCp) was dissolved in THF at -78 ° C, n-BuLi was added slowly, the temperature was raised to room temperature, and the reaction was allowed to proceed for 8 hours. The solution was dropwise added dropwise to a flask containing 1 equivalent of (6-tert-butoxyhexyl) dichloro (methyl) silane at -78 ° C. overnight. At the same time, one equivalent of Cyclopentadiene (Cp) was dissolved in THF at -78 ° C in another flask, n-BuLi was added slowly, the temperature was raised to room temperature, and the reaction was allowed to proceed for 8 hours. The TMCp reaction mixture was dropwise added dropwise to the flask containing the Cp reaction mixture at -78 ° C., and the temperature was raised to room temperature, followed by overnight reaction.

To the above final reaction mixture was slowly added n-BuLi 2 equivalents, then warmed to room temperature and reacted for at least 8 hours to suspend ZrCl ₄ (THF) ₂ (1 equivalent) / THF (30 mL) The lithium salt solution prepared in the solution was added slowly and further reacted at room temperature for 6 hours.

All volatile materials were vacuum dried, and hexane solvent was added to the obtained oily liquid substance to be filtered. The filtered solution was vacuum dried to give the title compound.

¹ H NMR (500 MHz, CDCl ₃ ): 6.69-5.49 (4H, m), 3.28 (2H, m), 1.80-1.22 (9H, m), 1.11 (9H, s), 0.80

Manufacturing example  1: hybrid bearing Metallocene  Preparation of Catalyst (A + B)

The high-pressure reactor was charged with 100 ml of toluene solution, and the reactor temperature was maintained at 40 占 폚. 9 g of silica dehydrated under a vacuum at a temperature of 600 ° C for 12 hours was charged into the reactor and sufficiently dispersed in the silica. Then, the first metallocene compound (A) prepared in Preparation Example A was added to 0.10 mmol / g SiO ₂ , And the mixture was reacted by stirring at 40 DEG C for 2 hours.

Then, 50 mL of 10 wt% methylaluminoxane (MAO) / toluene solution was added, and the mixture was stirred at 40 ° C and 200 rpm for 12 hours.

The second metallocene compound prepared in Preparation Example B was dissolved in toluene at a ratio of 0.20 mmol / g SiO ₂ , and the mixture was stirred at 40 ° C and 200 rpm for 12 hours.

After the completion of the reaction, stirring was stopped, and the reaction solution was washed with a sufficient amount of toluene. Then, 50 ml of toluene was added thereto. After stirring for 10 minutes, the solution was stopped and washed with a sufficient amount of toluene to remove unreacted compounds. Thereafter, 50 ml of hexane was added and stirred, and then the hexane slurry was transferred to a filter and filtered. This was dried at 40 DEG C under reduced pressure for 4 hours to prepare 8 g of hybrid supported catalyst.

Manufacturing example  2: hybrid bearing Metallocene  Preparation of Catalyst (A + B)

Except that the metallocene compound (B) prepared in Preparation Example B was added in an amount of 0.15 mmol / g SiO ₂ and the metallocene compound (A) prepared in Preparation Example A was added in an amount of 0.15 mmol / g SiO ₂ , A mixed supported metallocene catalyst was prepared using the same method as in Production Example 1 above.

Manufacturing example  3: Hybrid support Metallocene  Preparation of Catalyst (A + B)

Except that the metallocene compound (B) prepared in Preparation Example B was added in an amount of 0.12 mmol / g SiO ₂ and the metallocene compound (A) prepared in Preparation Example A was added in an amount of 0.12 mmol / g SiO ₂ , A mixed supported metallocene catalyst was prepared using the same method as in Production Example 1 above.

Manufacturing example  4: Hybrid support Metallocene  Preparation of Catalyst (A + B)

Except that the metallocene compound (B) prepared in Preparation Example B was added in an amount of 0.12 mmol / g SiO ₂ , and the metallocene compound (A) prepared in Preparation Example A was added in an amount of 0.15 mmol / g SiO ₂ , A mixed supported metallocene catalyst was prepared using the same method as in Production Example 1 above.

Manufacturing example  5: Hybrid support Metallocene  Preparation of Catalyst (A + B)

Except that the metallocene compound (B) prepared in Preparation Example B was added in an amount of 0.10 mmol / g SiO ₂ and the metallocene compound (A) prepared in Preparation Example A was added in an amount of 0.20 mmol / g SiO ₂ , A mixed supported metallocene catalyst was prepared using the same method as in Production Example 1 above.

Example  1: Ethylene / 1- Hexen  Preparation of Copolymer

50 mg of the mixed supported metallocene catalyst prepared in Preparation Example 1 was quantitatively measured in a dry box and packed in a 50 mL glass bottle, sealed with a rubber septum, and taken out from a dry box to prepare a catalyst to be injected. The polymerization was carried out in a temperature controlled, 2 L metal alloy reactor at high pressure equipped with a mechanical stirrer.

1 L of hexane containing 1.0 mmol of triethylaluminum and 10 cc of 1-hexene were fed into the reactor, and the respective supported catalysts prepared above were introduced into the reactor without air contact, and then gaseous ethylene monomer And polymerized for 1 hour while continuously adding thereto a pressure of 9 Kgf / cm ² . The termination of the polymerization was completed by first stopping the stirring and then removing ethylene by evacuation. The polymerization solvent was removed from the obtained polymer by filtration and dried in a vacuum oven at 80 캜 for 4 hours.

Example  2 to 5

Except that the mixed supported metallocene catalysts prepared in Preparation Examples 2 to 5 were used in place of the mixed supported metallocene catalysts prepared in Preparation Example 1, -Hexene copolymer.

Comparative Example  One

SM800 polyethylene commercially available from LG Chemical Co., Ltd. was prepared.

Test Example : Ethylene / 1- Hexen  Evaluation of physical properties of copolymer

The properties of the ethylene / 1-hexene copolymer prepared in the above Examples and Comparative Examples were evaluated by the following methods.

1) Density: ASTM 1505

2) Melt Index (MI, 2.16 kg / 10 min): Measuring temperature 190 占 폚, ASTM D1238

3) Mn, Mw, PDI and GPC curves: The sample was pre-treated with 1,2-trichlorobenzene containing 0.0125% of BHT at 160 ° C for 10 hours using PL-SP260 and measured with PL-GPC220 The number average molecular weight and the weight average molecular weight were measured at 160 캜. PDI is represented by the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight.

4) ESCR: Time to F50 (50% destruction) was measured under a condition of 50 ° C using 10% Igepal CO-630 Solution according to ASTM D 1693.

5) Melting point (Tm), and ω ^c (weight fraction crystallinity): after increasing the temperature to 200 ℃, maintained at that temperature for 5 minutes, the down and then up to 30 ℃, by increasing the back temperature DSC (Differential Scanning Calorimeter , Manufactured by TA Corporation), and the top of the curve was taken as the melting point. At this time, the temperature rise and fall speed was 10 ° C / min, and the melting point was measured at the second temperature rise.

6) Tie Molecule Fraction: The data and the melting point of the measured GPC curve were used to calculate the molecular weight by the above-described formula (4).

The results are shown in Table 1 below. The GPC curve of each copolymer is shown in Fig. 1, and an enlarged view of a region having a log Mw of 5.0 or more is shown in Fig.

Mw PDI MI _2.16 density Log Mw 5.0
Above Area
(GPC curve) Log Mw 5.5
Above Area
(GPC curve) connect
molecule
content ESCR unit - - g / 10 min g / cm ³ % % - hr Example 1 142,000 12.9 0.42 0.953 21.06 13.89 4.4 180 Example 2 190,000 15.1 0.25 0.952 22.19 14.23 5.5 270 Example 3 200,000 10.6 0.22 0.951 23.94 14.54 5.6 380 Example 4 182,000 20.2 0.22 0.952 24.13 15.15 5.8 400 Example 5 165,000 14.6 0.29 0.953 25.41 15.25 5.9 500 Comparative Example 1 106,000 7.5 1.62 0.952 16.44 7.07 2.7 8

As shown in Table 1 and Figs. 1 and 2, the ethylene / 1-hexene copolymer of the Example exhibited remarkably improved environmental stress cracking resistance due to the high proportion of the high molecular weight region and the high molecular weight of the connecting molecule. .

Claims (10)

A weight average molecular weight (g / mol) of 100,000 to 250,000,
A molecular weight distribution (PDI) of 3 or more,
A density (g / cm ³ ) of 0.948 to 0.956,
in the GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw, the integral value of the region where log Mw is 5.0 or more is 20% or more of the integral value of the x-
A Tie molecule fraction of 4 or more,
Ethylene / alpha-olefin copolymer.
The method according to claim 1,
Having an environmental stress cracking resistance (ESCR) of 10 hours or more as measured according to ASTM D 1693,
Ethylene / alpha-olefin copolymer.
The method according to claim 1,
in the GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw, the integral value of the log Mw of 5.5 or more is 10% or more of the integral value of the x-
Ethylene / alpha-olefin copolymer.
The method according to claim 1,
Wherein said molecular weight distribution (PDI) is from 10 to 25,
Ethylene / alpha-olefin copolymer.
The method according to claim 1,
in the GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw, the integral value of the region where log Mw is 5.0 or more is 20% to 30%
Ethylene / alpha-olefin copolymer.
The method according to claim 1,
Wherein the Tie molecule fraction is between 4 and 6.3,
Ethylene / alpha-olefin copolymer.
The method according to claim 1,
The alpha-olefin is preferably selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-tetradecene, 1-hexadecene, and 1-aidocene.
Ethylene / alpha-olefin copolymer.
The method according to claim 1,
Wherein the ethylene / alpha-olefin copolymer comprises at least one first metallocene compound represented by the following formula (1); And at least one second metallocene compound selected from compounds represented by the following general formulas (3) to (5): &lt; EMI ID =
Ethylene / alpha-olefin copolymer:
[Chemical Formula 1]

In Formula 1,
A is selected from the group consisting of hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, C _7-20 arylalkyl, C _1-20 alkoxy, C _2-20 alkoxy Alkyl, C _3-20 heterocycloalkyl, or C _5-20 heteroaryl;
D is -O-, -S-, -N (R) - or -Si (R) (R ') - , in which R and R' are the same or different from each other, each independently hydrogen, halogen, C _{1 -20} alkyl, C _2-20 alkenyl, or C _6-20 aryl;
L is C _1-10 linear or branched alkylene;
B is carbon, silicon or germanium;
Q is hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl;
M is a Group 4 transition metal;
X ¹ and X ² are the same or different and are each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, nitro, amido, C _1-20 alkylsilyl, C _{1 -20} alkoxy, or C _1-20 sulfonate;
C ¹ And C ² are the same or different and each independently represents one of the following formulas (2a), (2b) or (2c) below, with the proviso that C ¹ And Except that the case where all of C ² is the formula 2c;
(2a)

(2b)

[Chemical Formula 2c]

Wherein R ₁ to R ₁₇ and R ₁ 'to R ₉ ' are the same or different from each other and each independently represents hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 alkyl silyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 alkyl and aryl, wherein R _At least two adjacent to each other of R ₁₀ to R ₁₇ may be connected to form a substituted or unsubstituted aliphatic or aromatic ring;
(3)
(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹³ _-n
In Formula 3,
M ¹ is a Group 4 transition metal;
Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^a and R ^b are the same or different and each independently hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;
Z ¹ is halogen, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene, Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;
n is 1 or 0;
[Chemical Formula 4]
(Cp ³ R ^c ) _m B ¹ (Cp ⁴ R ^d ) M ² Z ² _3-m
In Formula 4,
M ² is a Group 4 transition metal;
Cp &lt; ³ &gt; and Cp &lt; ⁴ &gt; are the same or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical , Which may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^c and R ^d are the same or different from each other and each independently represents hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;
Z ² is halogen, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene, Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;
B ¹ is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom containing radical which bridges the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or cross-links one Cp ⁴ R ^d ring to M ² Or a combination thereof;
m is 1 or 0;
[Chemical Formula 5]
(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂
In Formula 5,
M ³ is a Group 4 transition metal;
Cp &lt; ⁵ &gt; is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, which are substituted with hydrocarbons having 1 to 20 carbon atoms ;
R ^e is hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl , C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;
Z ³ represents halogen, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene, Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;
B ² is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radical which cross-links the Cp ⁵ R ^e ring with J, or a combination thereof;
J is any one selected from the group consisting of NR ^f , O, PR ^f and S, and R ^f is C _1-20 alkyl, aryl, substituted alkyl or substituted aryl.
9. The method of claim 8,
Wherein the first metallocene compound is selected from compounds represented by the following general formula (6)
Ethylene / alpha-olefin copolymer:
[Chemical Formula 6]

In Formula 6,
A is hydrogen, or C _1-20 alkyl;
D is -O-;
L is C _1-10 linear or branched alkylene;
B is carbon, silicon (Si) or germanium;
Q is hydrogen, or C _1-20 alkyl;
M is a Group 4 transition metal;
X ¹ and X ² are the same or different and are each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, nitro, amido, C _1-20 alkylsilyl, C _{1 -20} alkoxy, or C _1-20 sulfonate;
R ₁ to R ₁₇ are the same or different from each other, and each independently hydrogen or C _1-20 alkyl.
9. The method of claim 8,
Wherein the second metallocene compound is selected from compounds represented by the following general formula (7)
Ethylene / alpha-olefin copolymer:
(7)

In Formula 7,
M ⁴ is a Group 4 transition metal;
B ^' is carbon, germanium, silicon, phosphorus, or nitrogen;
Z ²¹ to Z ²³ are the same or different and each is independently halogen, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, Substituted or unsubstituted C _1-20 alkylidene, substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;
R ^c1 to R ^c4 and R ^d1 to R ^d4 are the same as or different from each other and each independently hydrogen or C _1-20 alkyl, and R ^c1 to R ^c4 and R ^d1 to R ^d4 Two or more of which are adjacent to each other may be connected to form a substituted or unsubstituted aliphatic or aromatic ring.

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