WO2016093580A1 - Ethylene/alpha-olefin copolymer having excellent processability - Google Patents

Abstract

The present invention relates to an ethylene/alpha-olefin copolymer having excellent processability. The ethylene/alpha-olefin copolymer according to the present invention has excellent processability by having a low complex viscosity at a high shear velocity, thereby enabling the copolymer to be applied to a large-caliber pipe or a complex pipe and the like.

Description

 [Name of invention]

 Ethylene / alpha-lephine copolymer with excellent processability

 [Cross Reference with Related Application (s)]

 This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0174985, dated December 8, 2014, and Korean Patent Application No. 10—2015-0161159, filed November 17, 2015. All content disclosed in the literature of the applications is included as part of this specification.

 Technical Field

 The present invention relates to an ethylene / alpha-olepin copolymer having excellent processability.

 Background Art

The olefin polymerization catalyst system _may, be divided into Ziegler-Natta and metallocene catalyst systems, the high activity catalyst systems of these two has been developed according to its characteristics. Ziegler-Natta catalysts have been widely applied to existing commercial processes since the invention in the 50s, but are characterized by a wide molecular weight distribution of polymers because they are multi-active catalysts with multiple active sites. Since the composition distribution of the comonomer is not uniform, there is a problem that there is a limit in securing the desired physical properties. ^' Meanwhile, the metallocene catalyst is composed of a combination of a main catalyst composed mainly of transition metal compounds and a cocatalyst composed of organometallic compounds composed mainly of aluminum. Such a catalyst is a homogeneous complex catalyst, which is a single active site catalyst (s ingle si). te catalyst), single _. The polymer has a narrow molecular weight distribution and a homogeneous composition distribution of the comonomer according to the active site characteristics, and the stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the polymer can be obtained by changing the ligand structure of the catalyst and changing the polymerization conditions. It has the property to change. U.S. Patent No. 5,914,289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount and time of solvent used in preparing the supported catalyst This takes a lot, The hassle of having to support each of the metallocene catalysts to be used on a carrier was followed. Korean Patent Application No. 10-2003-0012308 discloses a method of controlling molecular weight distribution by supporting a double-nucleated metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing the combination of catalysts in the reactor. Is starting. However, this method is limited in realizing the characteristics of each catalyst at the same time, and also has the disadvantage that the metallocene catalyst portion is released from the carrier component of the finished catalyst causing fouling in the reactor. Therefore, in order to solve the above disadvantages, there is a continuous need for a method of preparing a common supported phthalocene catalyst having excellent activity and preparing a olefinic polymer of desired physical properties. On the other hand, linear low density polyethylene is prepared by copolymerizing ethylene and alpha olepin at low pressure using a polymerization catalyst, and has a narrow molecular weight distribution, a short chain branch of a constant length, and a long chain branch. The linear low density polyethylene film has the characteristics of general polyethylene, and has high breaking strength and elongation, and excellent tearing strength and fall stratification strength, so that the use of stretch film or overlap film, which is difficult to apply to the existing low density polyethylene or high density polyethylene, increases. Doing. By the way, linear low-density polyethylene using 1-butene or 1-nuxene as comonomers is mostly produced in a single gas phase reactor or a single loop slurry reactor, and is more productive than a process using 1-octene comonomers. Due to the limitation of the catalyst technology and the process technology used, there is a problem that the physical properties are inferior to that of using the 1-octene comonomer, and the processability is poor because the molecular weight distribution is narrow. Many efforts are being made to improve this problem, and US Patent No. 4, 935, 474 reports two or more metallocene compounds used for producing polyethylene having a wide molecular weight distribution. have. U.S. Patent No. 6,828,394 reports a method for producing polyethylene which has good comonomer binding properties and those which do not have good processability and is particularly suitable for films. In addition, US Pat. No. 6,841,631 and US Pat. No. 6,894,128 produce polyethylene having bimodal or polycrystalline molecular weight distribution with a metallocene catalyst using at least two kinds of metal compounds to form films, blow moldings, and pipes. It is reported that it can be applied to such applications. However, these products have improved processability, but there is a problem in that the extrusion appearance is coarse and the physical properties are not stable even under relatively good extrusion conditions because the dispersion state by molecular weight in unit particles is not uniform. Against this background, there is a constant demand for producing a better product having a balance between physical properties and processability, and in particular, a need for a polyethylene copolymer having excellent processability is further required.

 [Content of invention]

 [Problem to solve]

 In order to solve the problems of the prior art, the present invention is to provide an ethylene / alpha-olefin copolymer excellent in processability.

 [Measures of problem]

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

 Density (g / otf) is from 0.930 to 0.950,

MFR ₅ (g / 10 min, 19 (measured by ASTM 1238 in C)) is 0.1 to

5

Melt flow rate ratio (MFR2i. ₆ / MFR ₅ , measured by ASTM 1238 at 19CTC) is 10 to 200,

When the complex viscosity (H * [Pa.s]) graph according to the frequency (frequency, co [rad / s]) is fit to the power law of Equation 1 below, the d value is 250,000 to 400,000. , C ₂ value is -0.7 to -0.5, Ci value is 1,500,000 to 2,500, 000, C ₂ value is 3 to 10, C ₃ value is 0.2 to 0.3 persons Ethylene / Alpha-olefin-Polymer

 [Equation 1]

 ᅳ ^ 2

[Equation 2]

C

Fully elastic materials deform in proportion to the elastic shear force (el ast ic shear st ress), which is called Hook's law. In addition, in the case of pure viscous liquid, deformation occurs in proportion to the _v i _scous shear stress, which is called Newton's law. The material of the fully elastic can be deformed again when the elastic energy is accumulated and the elastic shear force is removed, and the fully viscous material does not recover even if the viscous shear force is removed, since the energy is all lost to the deformation. In addition, the viscosity of the material itself does not change. However, polymers in the molten state have a property of between a material of full elasticity and a viscous liquid, which is called viscoelastic (vi scoelast ici ty). In other words, when the polymer receives a shear force in the molten state, the deformation is not proportional to the shear force, and the viscosity varies according to the shear force, which is also called a non-Newtonian fluid. This property is due to the complexity of the deformation due to shear forces due to the large molecular size and complex intermolecular structure of the polymer. In particular, when manufacturing a molded article using a polymer, shear thinning is considered to be important among the characteristics of non-Newtonian fluids. Shear fluidization phenomenon means that as the shear rate increases It means a phenomenon that the viscosity of the polymer is reduced, the molding method of the polymer is determined according to the shear fluidization characteristics. In particular, when manufacturing large molded articles such as large diameter pipes or composite pipes or molded articles requiring high-speed polymer extrusion, such as the present invention, considerable pressure must be applied to the molten polymer, so that it is difficult to manufacture such molded articles unless they exhibit shear fluidization characteristics. Fluidization characteristics are considered important.

. Accordingly, in the present invention, shear fluidization characteristics are measured through a graph of complex viscosity (ri * [Pa.s]) according to frequency (frequency, to [rad / s]). Equations 1 and 2 are models for quantitatively evaluating the 'shear fluidization characteristics of the ethylene / alpha-olefin copolymer according to the present invention, and apply complex viscosity data according to frequency to complex at high frequencies. To predict the viscosity. First, Equation 1 is a Power Law model, x means frequency, y means complex viscosity, and two variables, ^ and C _2, are required. (^ Is the consistency index, C ₂ is the CV index, C ₂ is the slope of the graph. The higher the complex viscosity at low frequencies, the better the physical properties, and the higher the complex viscosity. The lower the better the workability, the smaller the C ₂ value, that is, the larger the negative slope of the graph, the above Equation 2 is Cross Model, x is frequency, y is complex viscosity, The two variables d, C ₂ and C ₃ are required (^ is the zero-shear viscosty, C ₂ is the material constant and C ₃ is the flow behavior index). In particular, the smaller the value of C ₃ , that is, the larger the negative slope of the graph, the lower the complex viscosity at the high frequency, thereby providing excellent shear fluidization characteristics. As a method of fitting the complex viscosity graphs according to the frequencies by Equations 1 and 2, TA Orchestrator, which is an ARES measurement program of TA Instruments, may be used. Accordingly, when the complex viscosity graph according to the frequency of the ethylene / alpha-olefin copolymer according to the present invention is fitted with p _Lawer Law of Equation 1, C ₂ value is -0.7 to -0.5, and Cross of Equation 2 is When fitting with a model, the value of C ₃ is 0.2 to 0.3. In addition, the d value of the above formula (2) is preferably a zero point viscosity

It has a value ranging from 1,500,000 to 2,500,000. In the case of more than 2,500,000, the zero-point viscosity value is too high and the complex viscosity value is high at a high frequency, and if it is less than 1,500,000, the negative slope of the graph of Equation 2 is low, and the complex viscosity value is also high at a high frequency. Appears high. In addition, the C ₂ value of Equation 2 has a value in the range of 3 to 10 as the material constant, preferably has a value in the range of 5 to 8. In addition, by substituting the obtained d, C ₂ and C ₃ value into the above equation (2) to predict the complex viscosity value at high frequencies, namely 800 rad / s and 1,200 rad / s, the ethylene / It is possible to predict the shear fluidization properties of the alpha-lepinin copolymer. Specifically, when X is 800 in Equation 2, the value of y is 3,000 to

It is characterized in that 5,000. More preferably, when X is 800 in Equation 2, the value of y is 4,000 to 4,900, and most preferably 4,000 to 4,500. Further, when X is 1,200 in Equation 2, the value of y is 3,000 to It is characterized by being 3,800. More preferably, when X is 1,200 in Equation 2, the value of y is 3,000 to 3,700, and most preferably 3,000 to 3,200. According to one embodiment of the present invention, when X is 800 and 1,200 in Equation 2, the complex viscosity value is lower than that of the comparative example, respectively, which is a high shear of the ethylene / alpha-olefin copolymer according to the present invention. Low viscosity in speed means that the workability is remarkably excellent. Preferably, the ethylene / alpha-olefin copolymer is. Density (g / cii)

0.931 or more, 0.932 or more, 0.933 or more, 0.934 or more, 0.935 or more, 0.936 or more 0.937 or more, 0.938 or more, 0.939 or more, 0.940 or more, 0.941 or more, or 0.942 or more, 0.949 or less, 0.948 or less, 0.947 or less, 0.946 or less, or 0.945 or less. Also preferably, the ethylene / alpha-olefin copolymer has an increased average molecular weight (g / mol) of 10,000 to 40,000. More preferably, the weight average molecular weight is 100,000 or more, 120,000 or more, 140,000 or more, 160,000 or more, 180,000 or more, or 200,000 or more, 380,000 or less, 360,000 or less, 340,000 or less, 320,000 or less, 300,000 or less, 280,000 or less, 260,000 or less Or 240,000 or less. Also preferably, the ethylene / alpha-olepin copolymer has a molecular weight distribution (Mw / Mn, PDI) of 5 to 30. More preferably, the molecular weight distribution is 7 or more, 9 or more, 11 or more, 13 or more, 15 or more, or 17 or more, 29 or less, 28 or less, 27 or less, 26 or less, 25 or less, 24 or less, 23 or less, Or 22 or less. The alpha -olepin that can be used for the copolymerization of the above ethylene / alpha-olephine is -butene, 1-pentene, 1-nuxene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene , One- Any one or more selected from the group consisting of tetradecene, 1-nuxadecene, 1-octadecene, and 1-eicosene can be used. In the ethylene / alpha-olepin copolymer, the content of alpha-lephine may be about 0.5% to about 10% by weight, preferably about 1% to about 5% by weight, but is not limited thereto. The ethylene / alpha-olefin copolymer as described above may be prepared using a metallocene catalyst. The metallocene catalyst that can be used includes at least one first metallocene compound represented by Formula 1 below; And a mixture of one or more second metallocene compounds selected from compounds represented by the following Chemical Formulas 3 to 5.

[Formula 1]

 In Chemical Formula 1,

A is hydrogen, halogen, alkyl, CHO, C ₂ - ₂₀ alkenyl, C ₆ -20 aryl, C ₇ - ₂₀ alkylaryl, C ₇ - ₂₀ aryl-alkyl, d-20 alkoxy, C ₂ - ₂₀ alkoxyalkyl, C ₂₀ heterocyclic cycloalkyl, or C ₅ - ₂₀ membered heteroaryl;

D is -0-, -S-, -N (R)-or -S RKR ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, d- ₂₀ alkyl, C ₂ - ₂₀ alkenyl, or C ₆ - ₂₀ aryl;

 L is d-) straight or branched alkylene;

 B is carbon, silicon or germanium;

Q is hydrogen, halogen, d-20 alkyl, C ₂ - ₂₀ alkenyl, C ₆ - ₂₀ aryl, and C ₂₀ alkylaryl, or C ₇ - ₂₀ aryl-alkyl;

 M is a Group 4 transition metal;

X ¹ and X ² are the same or different and are each independently halogen, d-20 alkyl, C ₂ - alkenyl ₂₀ Al, C ₆ - ₂₀ aryl, nitro, amido, d-20 alkyl silyl, d-20-alkoxy Or C-20 sulfonate; c ¹ and c ² are the same as or different from each other, and are each independently represented by one of the following Formulas 2a, 2b, or 2c, except that C ¹ and C ² are both Formula 2c;

 [Formula 2a]

[Formula 2c]

 In Chemical Formulas 2a, 2b and 2c,

Ri to R ₁₇ and "to" are the same or different and are each independently hydrogen, halogen, ₍₂₀ alkyl, C ₂ - ₂₀ alkenyl, d- ₂₀ alkyl silyl, alkyl silyl, alkoxysilyl CHO, d- ₂₀ alkoxy , C ₆ - ₂₀ aryl, C ₇ - ₂₀ alkylaryl, or C ₇ -2o aryl-alkyl, wherein ₀ to R ₁₇ of the two or more adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring Can do it;

 [Formula 3]

 In Chemical Formula 3,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;

R ^a and R ^b are the same or different, each independently represent a hydrogen, an alkyl, an alkoxy, and C ₂ of each other - 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 a halogen atom, an alkyl C ₂ -io alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₆ - ₂₀ aryl, optionally substituted d-20 alkylidene, substituted or unsubstituted amino, C ₂ - ₂₀ alkyl, an alkoxy, or a C ₇ - ₄₀ aryl-alkoxy;

 n is 1 or 0;

[Formula 4] In Chemical Formula ⁴ ,

M ² is a Group 4 transition metal;

Cp ³ and Cp ⁴ are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4 5 6 7-tetrahydro-1-indenyl and fluorenyl radicals, which are May be substituted with a hydrocarbon having 1 to 20 carbon atoms;

R ^c and R ^d are the same or different and each is independently hydrogen, alkyl, Cwo alkoxy, C ₂ of each other - 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 a halogen atom, alkyl, C ₂ - ₁₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₆ - ₂₀ aryl, alkyl substituted or unsubstituted alkylidene, substituted or unsubstituted amino, C ₂ - ₂₀ alkyl, an alkoxy, or C ₇ - ₄₀ aryl-alkoxy;

B ¹ is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp¾ ^c ring with the Cp ⁴ R ^d ring or crosslinks one Cp ⁴ R ^d ring with M ² ; Combination;

 m is 1 or 0;

 [Formula 5]

(Cp¾ ^e ) B ² (J) M ³ Z ³ ₂

 In Chemical Formula 5,

M ³ is a Group 4 transition metal;

Cp ⁵ is any one selected from the group consisting of cyclopentadienyl, indenyl, 4 5 6, 7-tetrahydro— 1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms, ;

R ^e is hydrogen, d- ₂₀ alkyl, Cwo 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 is a halogen atom, alkyl, C ₂ - ₁₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₆ - ₂₀ aryl, optionally substituted d-20 alkylidene, optionally substituted are amino, C ₂ - ₂₀ alkyl, an alkoxy, or C ₇ - ₄₀ aryl-alkoxy; B ² is at least one or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp ⁵ R ^e ring and J;

J is any one selected from the group consisting of R ^f , 0, PR ^f and S, wherein R ^f is d-20 alkyl, aryl, substituted alkyl or substituted aryl. Hereinafter, the substituents of Chemical Formulas 1, 3, 4, and 5 will be described in more detail. The ( ₂₀ alkyl) includes a linear or branched alkyl, specifically methyl, ethyl, propyl, isopropyl, η-butyl, tert- butyl, pentyl, nuclear chamber, heptyl, octyl, etc. but it not limited to the C ₂ -. ₂₀ alkenyl include, including alkenylene of straight or branched chain, and allyl specifically, ethenyl, propenyl, butenyl, pen, but the like ethenyl, whereby only not limited to a C ₆ -. ₂₀ aryl include, includes monocyclic or condensed ring aryl ol and, but, and the like More specifically, phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, whereby only limited but not the C ₅ -. ₂₀ heteroaryl group include a monocyclic or condensed ring includes heteroaryl, carbazolyl, pyridyl, quinoline, isoquinoline, thiophenyl, furanyl, imidazole, oxazolyl, thiazolyl, bit Azine, tetrahydropyranyl, tetrahydrofuranyl, etc., but is not limited thereto .. Examples of the alkoxy include methoxy, ethoxy, phenyloxy, cyclonuxyloxy, and the like. Examples of the Group 4 transition metal include titanium, zirconium, hafnium, and the like, but are not limited thereto. In Formulas 2a, 2b, and 2c to R ₁₇ and I to 'are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, phenyl, halogen, More preferably, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, mesooxy, or ethoxy are not limited thereto. L of the general formula (1) is C ₄ - ₈ straight or branched chain alkylene of one to more preferred, but is not limited thereto only. Further, the alkylene group d-20 alkyl, C ₂ - may be substituted or unsubstituted aryl as ₂₀ - ₂₀ alkenyl, or C _6. In addition, in Formula 1, A is hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, mesoxymethyl, tert-butoxymethyl, 1-ethoxyethyl, 1 ᅳ methyl— 1-meth Preferred is methoxyethyl, tetrahydropyranyl, or tetrahydrofuranyl, but is not limited thereto. In addition, B of Formula 1 is preferably silicon, but is not limited thereto. The crab 1 metallocene compound of Formula 1 may be a structure in which an indeno indol derivative and / or a fluorene derivative are crosslinked by a bridge, and may act as a Lewis base to the ligand structure. By having a non-covalent electron pair, it is supported on the surface having the Lewis acid characteristic of the carrier and shows high polymerization activity even when supported. In addition, it is highly active as it contains an electronically rich indeno indole group and / or fluorene group, and due to appropriate steric hindrance and the electronic effect of the ligand, the hydrogen reactivity is low and high activity is maintained even in the presence of hydrogen. In addition, the beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno indole derivative grows is stabilized by hydrogen bonding, thereby inhibiting beta-hydrogen el iminat ion, and thus, an ultra high molecular weight olefin type The polymer can be polymerized. According to an embodiment of the present invention, specific examples of the compound represented by Chemical Formula 2a may include a compound represented by one of the following structural formulas.

According to one embodiment of the present invention, specific examples of the compound represented by Chemical Formula 2b include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

According to one embodiment of the present invention, specific examples of the compound represented by Chemical Formula 2c may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

According to one embodiment of the present invention, specific examples of the first metallocene compound represented by Chemical Formula 1 may include a compound represented by one of the following structural formulas, but is not limited thereto.

LI

ZCCTO / SlOZaM / X3d 08SC60 / 9T0Z OAV

The Crab 1 metallocene compound of Chemical Formula 1 has excellent activity and may polymerize high molecular weight ethylene / alpha-lepin copolymer. In particular, even when used on a carrier, it shows high polymerization activity, and thus an ultra high molecular weight ethylene / alpha-lephine co-polymer can be prepared. In addition, even when the polymerization reaction including hydrogen to produce an ethylene / alpha olefin copolymer having a high molecular weight and a wide molecular weight distribution at the same time, the first metallocene compound of formula 1 according to the present invention is low hydrogen It exhibits reactivity and still allows high polymerization of ultra high molecular weight ethylene / alpha-olefin copolymers. Therefore, an ethylene / alpha-olefin copolymer that satisfies high molecular weight characteristics can be produced without deterioration of activity even when used in combination with a catalyst having other characteristics, while containing an ethylene / alpha-olefin copolymer of a polymer. Ethylene / alpha-olefin copolymers having a wide molecular weight distribution can be readily prepared. The C1 metallocene compound of Chemical Formula 1 is prepared as a ligand compound by connecting an innoindol derivative and / or a fluorene derivative with a bridge compound, and then a metal precursor is added to perform metallization. Can be obtained. The manufacturing method of the said 1st metallocene compound is concretely demonstrated to the Example mentioned later. Examples of the compound represented by Formula 3 include one of the following structural formulas

In Formula 4, when m is 1, it means that a Cp ³ R ^c ring and a Cp ⁴ R ^d ring or a Cp ⁴ R ^d ring and M ² is a bridge compound structure cross-linked by B ¹ , and m is 0. In the case of, it means a non-crosslinked compound structure. The compound represented by Chemical Formula 4 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

In addition, the compound represented by Formula 5 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

The metallocene catalyst used in the present invention may be at least one of the first metallocene compounds represented by Formula 1, and one of the metallocene compounds selected from the compounds represented by Formulas 3 to 5. The above may be supported on the carrier together with the cocatalyst compound. In addition, the supported metallocene catalyst may induce the formation of a long chain branch (LCB) in the ethylene / alpha—lepin copolymer prepared. In the supported metallocene catalyst according to the present invention, the cocatalyst supported on the carrier for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and polymerizes the olefin under a general metallocene catalyst. If it can be used when it is not particularly limited. Specifically, the cocatalyst compound may include at least one of an aluminum-containing first cocatalyst of Formula 6, and a borate-based 2 cocatalyst of Formula 7 below.

 [Formula 6]

R ₁₈ in Formula 6 is each independently a halogen, a halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and k is an integer of 2 or more, [Formula 7]

T ⁺ [BG ₄ ] ^"

In formula (7), T ⁺ is a + monovalent polyatomic ion, B is boron in +3 oxidation state, G is independently hydride, dialkylamido, halide, alkoxide, aryl oxide, hydrocarbyl, halocarbyl And. Selected from the group consisting of halo-substituted hydrocarbyl, wherein G has up to 20 carbons, but at up to one position G is a halide. By using such first and second cocatalysts, the molecular weight distribution of the finally produced polyethylene copolymer can be made more uniform, and the polymerization activity can be improved. . The first cocatalyst of Chemical Formula 6 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular or reticulated form. Specific examples of the promoter include methyl aluminoxane (MA0), ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane. In addition, the second cocatalyst of Formula 7 may be a borate-based compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt. Specific examples of such a second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate ， Methyltetracyclooctadecylammonium tetraphenylborate ， Ν, Ν-dimethylaninium tetraphenylborate, Ν, Ν-diethylaninynium tetraphenylborate, Ν, Ν-dimethyl (2, 4, 6-trimethylaninium Tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium, tetra Keith (pentafluorophenyl) borate

Tripropylammonium tetrakis (pentafluorophenyl) borate, tri (η-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate, N , Ν-dimethylaninium tetrakis (pentafluorophenyl) borate ， Ν, Ν-diethylaninium tetrakis (pentafluorophenyl) borate ， ^^ dimethyl (2,4,6-trimethylaninynium) tetrakis (Pentafluorophenyl) borate ，

Trimethylammonium tetrakis (2, 3, 4, 6-tetrafluorophenyl) borate,

Triethylammonium tetrakis (2, 3, 4, 6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2 ᅳ 3, 4, 6-tetrafluorophenyl) borate, tri (η ᅳ butyl) ammonium tetra Keith (2, 3, 4, 6 ᅳ, tetrafluorophenyl) borate, dimethyl ( _t -butyl) ammonium tetrakis (2, 3, 4, 6-tetrafluorophenyl) borate, Ν, Ν-dimethylaninynium Tetrakis (2,3,4,6-tetrafluorophenyl) borate, Ν, Ν-diethylaninynium tetrakis (2,3,4,6-tetrafluorophenyl) borate or Ν, Ν—dimethyl- (2,4,6-trimethylaninynium) tetrakis- (2,3,4,6- Borate compounds in the form of trisubstituted ammonium salts of tetrafluorophenyl) borate; Borates in the form of dialkylammonium salts, such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorofluorophenyl) borate or dicyclonucleoammonium tetrakis (pentafluorophenyl) borate System compounds; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) Borate compounds in the form of trisubstituted phosphonium salts, such as a borate, etc. are mentioned. In the supported metallocene catalyst according to the present invention, the mass ratio of the total transition metal to the carrier included in the first metallocene compound represented by the formula (1), or the C2 metallocene compound represented by the formulas (3) to (5) is 1 : May be from 1 to 1,000. When the carrier and the metallocene compound are included in the mass ratio, the optimum shape can be exhibited. In addition, the mass ratio of the promoter compound to the carrier may be from 1: 1 to 1: 100. In the supported metallocene catalyst according to the present invention, the carrier may be a carrier containing a hydroxy group on the surface, preferably a dry semi-reactive hydroxy group and a siloxane group which have been dried to remove moisture on the surface. The carrier which has is used. For example, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, and these are usually oxides, carbonates, sulfates, such as Na ₂ 0, ₂ C0 ₃ , BaS0 ₄ , and Mg (N0 ₃ ) ₂ . And nitrate components. The drying temperature of the carrier is preferably 200 to 80CTC, more preferably 300 to 600 ^° C, and most preferably 300 to 400 ^° C. When the drying temperature of the carrier is less than 200 ^° C, the moisture is too much and the surface of the carrier reacts with the promoter, and when it exceeds 800 ^° C, pores on the surface of the carrier It is not preferable because the surface area is reduced as they are combined, and also a lot of hydroxyl groups are left on the surface and only siloxane groups are left to decrease the reaction site with the promoter. The amount of hydroxy groups on the surface of the carrier is preferably from 0.1 to 10 kPa / g, more preferably from 0.5 to 5 mmol / g. The amount of hydroxy groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying. If the amount of the hydroxy group is less than 0.1 dl ol / g, the reaction site with the promoter is small, and if it exceeds 10 dl ol / g, it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. On the other hand, the ethylene / alpha-olefin copolymer according to the present invention can be produced by polymerizing ethylene and alpha-lepin in the presence of the supported metallocene catalyst described above. The polymerization reaction may be performed by copolymerizing ethylene and alpha-olefin using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor. And, the polymerization temperature is about 25 to about 500 ^° C, preferably about 25 to about _. About 200 ^° C., more preferably about 50 to about 15 CTC. In addition, the polymerization pressure may be about 1 to about 100 Kgf / citf, preferably about 1 to about 50 Kgf / ciii ² , more preferably about 5 to about 30 Kgf / cuf. The supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, nucleic acid, heptane, nonane, decane, isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane and chlorobenzene. The solution may be dissolved or diluted in a hydrocarbon solvent substituted with the same chlorine atom. The solvent used herein is preferably used by removing a small amount of water, air, or the like acting as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter. Ethylene / alpha-lepine copolymer according to the present invention is a combination of the catalyst of formula 3 to 5 to polymerize low-molecular-weight polymer chains, and the catalyst of formula 1 mainly to polymerize high-molecular weight polymer chain, ethylene and Prepared by copolymerizing alpha-olefin monomers. Due to the interaction of these two or more catalysts, the overall low molecular weight and molecular weight distribution increases. As a result, the ethylene / alpha-olefin copolymer may exhibit, for example, a molecular weight distribution curve as shown in FIG. 1 and may exhibit excellent processability. Due to the above-described physical layer, the ethylene / alpha -olefin copolymer according to the present invention can be preferably applied to large diameter pipes or composite pipes.

 【Effects of the Invention】

 The ethylene / alpha-olefin copolymer ^ according to the present invention is excellent in workability and can be applied to large diameter pipes or composite pipes.

 [Brief Description of Drawings]

 1 shows the GPC curves of the copolymers prepared in Examples and Comparative Examples of the present invention.

 Figure 2 shows the result of fitting the complex viscosity graph according to the frequency of the copolymer prepared in Example 2 of the present invention, Power Law and Cross Model.

 Figure 3 shows the result of fitting the complex viscosity graph according to the frequency of the copolymer prepared in Examples and Comparative Examples of the cross model.

 [Specific contents to carry out invention]

Hereinafter, preferred embodiments of the present invention are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

[First Metallocene Compound]

 1-1) Preparation of Ligand Compound

2 g of fluorene was dissolved in 5 mL MTBE and 100 mL of hexane, and 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred at room temperature overnight. (3.6 g of 6- (tert-butoxy) hexyl) dichloro (methyl) silane was dissolved in .50 mL of nucleic acid (hexane), and then dried in a dry ice / acetone bath) to transfer the slurry of fluorene 1 Li for 30 minutes and stirred at room temperature overnight. It was. At the same time 5, 8-di met hy 1 -5, 10-di hydr oi ndeno [1, 2-b] i ndo 1 e (12 mmol, 2.8 g) also dissolved in 60 m THF 2.5 M n-BuLi hexane 5.5 mL of solution was added dropwise in a dry ice / acetone bath and stirred overnight in silver. NMR sampling the reaction solution of fluorene with (6- (tert 一 butoxy) hexyl) dichloro (methyl) silane to confirm the reaction was completed, 5,8-ditnethyl-5,10-dihydroindeno [l, 2-b] inck) le ᅳ Li solution was transferred under dry ice / acetone bath. Stir overnight at room temperature. After the reaction was extracted with ether / water (extract ion) to remove the residual moisture of the organic layer with MgS0 ₄ and to obtain a ligand compound (Mw 597.90, 12 匪 ol) and two isomers were formed in-顺 R was confirmed. .

¾ 匪 R (500 MHz, de-benzene): -0.30--0.18 (3H, d), 0.40 (2H, m), 0.65-1.45 (8H, m), 1.12 (9H, d), 2.36-2.40 ( 3H, d), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21 (1H, d), 4.34-4.38 (1H, d), 6.90-7.80 (15H, m) 1-2) Preparation of Metallocene Compound

7.2 g (12 ′ ol) of the ligand compound synthesized in 1-1 was dissolved in 50 mL of diethylether, and 11.5 mL of 2.5 M n-BuL i hexane solution was added dropwise in a dry ice / acetone bath, followed by stirring at room temperature overnight. Drying in vacuo gave a brown colored sticky oil. It was dissolved in toluene to obtain a slurry. ZrCl ₄ (THF) ₂ was prepared, and 50 mL of toluene was added to prepare a slurry. 50 mL of ZrCl ₄ (THF) ₂ was transferred to a luene slurry in a dry ice / acetone bath. The solution was changed to violet color at room temperature overnight. The reaction solution was filtered to remove LiCl. The toluene of the filtrate was removed by vacuum drying, and the nucleic acid was added and sonicated for 1 hour. The slurry was filtered to give 6 g (Mw 758.02, 7.92 mmol, yield 66 mol%) of a dark violet metallocene compound as a filtered solid. Two isomers were observed on ¾-NMR.

 ¾ 赚 (500 MHz, CDCla): 1.19 (9H, d), 1.71 (3H, d), 1.50 to

1.70 (4H, m), 1.79 (2H, m), 1.98-2.19 (4H, m), 2.58 (3H, s), 3.38 (2H, m), 3.91 (3H, d), 6.66-7.88 (15H, m) Art 2

 2-1) Preparation of Ligand Compound

Into a 250 mL flask, add 2.63 g (12 誦 ol) of 5-methyl-5, l ()-dihydroindeno [l, 2-b] indole, dissolve in 50 mL of THF, and dr yice 6 mL of 2.5 M n-BuLi hexane solution. It was added dropwise in the / acetone bath and stirred overnight at room temperature. In addition In another 250 tnL flask, 1.62 g (6 画 ol) of (6- (ter t-butoxy) hexyl) dichloro (methyl) si lane was dissolved in 100 mL of hexane and prepared under 5-methyl-5, 10 under a dry ice / acetone bath. -Dihydroindeno [l, 2-b] indole ^ 1 ithiated solution was slowly added dropwise and stirred overnight at room temperature. After the reaction was extracted with ether / water to remove the residual moisture of the organic layer to ¾¾50 ₄ and dried in vacuo to obtain 3.82 g (6 mmol) of the ligand compound was confirmed in ¾- 丽 R.

¾ NMR (500 MHz, CDC1 ₃ ): -0.33 (3H, ni), 0.86- 1.53 (10H, m), 1.16 (9H, d), 3.18 (2H, m), 4.07 (3H, d), 4.12 ( 3H, d), 4.17 (1H, d), 4.25 (1H, d), 6.95-7.92 (16H, m)

2-2) Preparation of Metallocene Compound

3.82 g (6 醒 ol) of the ligand compound synthesized in 2-1 above was dissolved in 100 mL of toluene and 5 mL of MTBE, and 5.6 mL (14 隱 ol) of 2.5M n-BuLi hexane solution was added dropwise in a dryice / acetone bath. Stir overnight at. In another flask, 2.26 g (6 mmol) of ZrCl ₄ (THF) 2 was prepared, and 100 mL of toluene was added to prepare a sultry. Toluene slurry of ZrCl ₄ (THF) ₂ was transferred to litiated ligand in a dry ice / acetone bath. It stirred at room temperature overnight and it changed into violet color. The reaction solution was filtered to remove LiCl, and the filtrate was dried in vacuo to add hexane and sonicat ion. ^'The slurry was filtered to obtain 3.40 g (yield 71.1 mol%) of a metallocene compound of dark violet as a filtered solid.

¾ 匪 R (500 MHz, CDC1 ₃ ): 1.74 (3H, d), 0.85-2.23 (10H, m), 1.290H, d), 3.87 (3H, s), 3.92 (3H, s), 3.36 (2H , m), 6.48-8.10 (16H, m)

Second Metallocene Compound

 Preparation Example 3 Preparation of [tBiHHCI ^ Csiy ^ rC ^

6-Chlorohexanol was used to prepare t_Butyl-0- (CH ₂ ) ₆ -Cl using the method presented in Tetrahedron Lett. 2951 (1988), whereupon NaCp was reacted to t- Buty 卜 0— (CH ₂ ) ₆ ᅳ C ₅ ¾ (yield 60%, bp 80 VI 0.1 隱 Hg). Further, t-ButyK)-(C¾) ₆ -C ₅ ¾ at -78t: was dissolved in THF, and normal butyllithium (n-BuLi) was slowly added, and the reaction mixture was heated to room temperature for 8 hours. The solution was slowly added to a lithium salt solution pre-synthesized in a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 μl) / THF (30 ml) at -78 ^° C. It was added and reacted further for 6 hours at room temperature. ^ Den _. The volatiles were dried in vacuo and a hexane solvent was added to the resulting oily liquid material to filter out. The filtered solution was dried in vacuo and nucleic acid was added to induce precipitate ^at low temperature (-20 ^° C.). The precipitate obtained was filtered off at low temperature to give [tBu-0- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound as a white solid (yield 92%):

¾ NMR (300 MHz, CDC1 ₃ ): 6.28 (t, J = 2 ^* .6 Hz, 2H), 6.19 (t, J =

2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J = 8 Hz), 1.7-1.3 (m, 8H), 1.17 (s, 9H)

¹³ C NMR (CDCls): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00

[Supported Catalyst]

 Examples 1 and 2

3.0 kg of toluene solution was added to a 20 L sus high pressure reactor, and the reactor temperature was maintained at 40 ^° C. 500 g of silica (Grace Davison, SP2212) was added to the reactor, and after sufficient dispersion of silica, 2.78 kg of 10 wt methylaluminoxane (MAO) / luluene solution was added and the temperature was reduced to 8 (C at 15 rpm at 200 rpm). After further stirring, the reactor temperature was lowered to 40 ^° C., and 300 g of 7.5 wt% catalyst Preparation Example 2 / luene solution was added to the reactor and stirred at 200 rpm for 1 hour. 250 g of a 1 / luene solution was added to a reactor and stirred at 200 rpm for 1 hour Catalyst Preparation Example 3 (20 g) was dissolved in toluene, charged into the reactor, and stirred at 200 rpm for 2 hours. 70 g of the cocatalyst (ani 1 inium tetrakis (pentaf luorophenyl) borate) was diluted in toluene and added to the reaction vessel, followed by stirring at 200 rpm for 15 hours or more. After the reaction temperature was lowered to room temperature, stirring was stopped and sett ling was applied for 30 minutes, and then the reaction solution was decantat i on. The toluene slurry was transferred to a fil ter dryer and filtered. 3.0 kg of toluene was added and stirred for 10 minutes, and then stirring was stopped and filtered. 3.0 kg of nucleic acid was added to the reactor and stirred for 10 minutes, and then the stirring was stopped and filtered. Drying under reduced pressure at 50 ^° C. for 4 hours to prepare a 500g-Si0 ₂ supported catalyst.

[Ethylene / 1-butene copolymer]

 The olefin polymer was prepared by bimodal operation of two common supported metallocene catalysts prepared in Examples 1 and 2 using two hexane slurry slurry tank polymerizers. 1-butene was used as comonomer. In Examples 1 and 2, polymerization conditions using respective common supported metallocene catalysts are summarized in Table 1 below.

 Table 1

[Comparative Examples 1 to 3]

 In order to compare with the polymer prepared by using each of the common supported metallocene catalysts in Examples 1 and 2, the following copolymer having a similar density was used as a comparative example.

 Comparative Example 1: LyondellBasell's Hostalene 473 IB

 Comparative Example 2: Total T-70

 Comparative Example 3: XP9020 of Daelim Industrial [Evaluation of Physical Properties of Copolymer]

 Physical properties of the copolymer prepared in Example and the copolymer of Comparative Example were evaluated in the following manner.

1) Density: ASTM 1505 ^'

 2) Melt Index (MFR, 5 kg / 21.6 kg): Measurement Temperature 19CTC, ASTM 1238

3) MFRR (MFR _{21 .6} / MFR ₅ ): MFR ₂₁ . ₆ Melt index (MI ᅳ 21.6kg load) divided by MFR ₅ (MI, 5kg lower).

4) Mn, Mw, 匿 D, GPC curve: Melt the sample in l, 2,4-Trichlorobenzene containing 0.0125% of BHT using PL-SP260 for 160 ^° C for 10 hours, and use PL-GPC220. The number average molecular weight and the weight average molecular weight were measured at a measurement temperature of 160 ^° C. The molecular weight distribution was expressed as the ratio of weight average molecular weight and number average molecular weight. -

5) Complex viscosity graph with frequency, fitting with Power Law and Cross Model :. Complex viscosity was measured by ARES (Advanced Rheometric Expansion System) of TA instruments. Samples were made to have a gap of 2.0 mm3 using parallel plates of 25: 0 mm diameter at 190 ^° C. In the dynamic strain frequency sweep mode, 5% strain, 0.05 rad / s to 500 rad / s, and 10 points in each decade were measured. Power law and Cross Model fitting was performed using TA Orchestrator, a measurement program. First, the results regarding the physical properties of the copolymer are shown below. In addition, the GPC curve of each copolymer is shown in FIG.

 Table 2

Next, a graph of the complex viscosity according to the frequency of the copolymer prepared in Example 2 and a result of fitting this to the power law and the cross model are shown in FIG. 2. As shown in FIG. 2, it was confirmed that the results of fitting the complex viscosity graph according to the frequency of the copolymer prepared in Example 2 and the result of fitting the power law and the cross model were very similar. It was confirmed that the model is suitable for quantitatively evaluating the flow characteristics of the copolymer according to the invention. The copolymers prepared in Examples and Comparative Examples were fitted to Power Law and Cross Mode, and the values of the variables obtained are shown in Table 3 below. In addition, based on the obtained variable values, the complex viscosity (complex vi scosi ty) values at the frequencies of 800 / s and 1, 200 / s in the Cross Model are also shown in Table 3 below. TABLE 3

214950 187 270 205 150 360090 337500

Power law

c ₂ -0.5111 -0.4978 -0.4446 -0.6141 -0.6277

Ci 645 230 590 910 376790 1978 500 1958 600

Cross Model c ₂ 1.81966 2.22020 0.33886 6.57477 7.09718

c ₃ 0.33584 0.36301 0.25547 0.29941 0.28975

800 rad / s 5075.7 4988.3 5727.0 4879.7 4222.2

₇ _ high 03

 1200 rad / s 3884.6 3860.3 4251.5 3675.2 3160.6

When a polyethylene copolymer is applied to a large diameter pipe or a composite pipe, since it receives a strong pressure, it can be evaluated that workability is so high that a complex viscosity in the high frequency area is low. Therefore, it can be predicted that the lower the value of the complex viscosity at 800 rad / s and 1,200 rad / s, which are high frequencies in the cross model, the better the processability. Thus, as shown in Table 3, it was confirmed that the complex viscosity value of the Example is lower than the comparative example when 800 rad / s and 1,200 rad / s. Therefore, the polyethylene co-polymer according to the present invention is excellent in processability at high shear rate, and can be preferably applied to large diameter pipe or composite pipe processing.

Claims

[Patent Claims] [Claim 1] Density (g / cirf) is 0.930 to 0.950, MFR5 (g / 10 min, measured by ASTM 1238 at 190 ° C.) is 0.1 to 5, and melt flow rate ratio (MFR2L6). / MF¾, measured according to ASTM 1238 at 190 ° C.) and a graph of complex viscosity (* [Pa.s]) according to frequency (frequency, ω [rad / s]) 6 \}. The d value is 250,000 to 400,000 when fit with the power law of Equation 1 below, the C2 value is -0.7 to -0.5, and the d value is 1,500,000 to 2, 500 when fit with the cross model of Equation 2 , 000, C2 value of 3 to 10, C3 value of 0.2 to 0.3, ethylene / alpha-lephine copolymer:

 [Equation 1]

_{¾ ^} ^C l

'^' C Λ-

[Equation 2]

 I 、 1 尋)

1 + (c ₂ )

[Claim 2]

 The method of claim 1,

 In the above Equation 2, when X is 800, the value of y is characterized in that 3,000 to 5,000,

 Ethylene / alpha-olefin copolymers.

[Claim 3]

The method of claim 2, Characterized in that the value of y is 4,000 to 4,900,

 Ethylene / Alpha—Lepin Copolymer.

[Claim 4]

 The method of claim 1,

 When x is 1,200 in Equation 2, y is 3,000 to 3,800, characterized in that

 Ethylene / Alpha-Lepine Copolymer.

[Claim 5]

 According to claim 4,

 Characterized in that the value of y is 3,000 to 3,700,

 Ethylene / Alpha-olefin Copolymers.

[Claim 6]

 The method of claim 1,

Characterized in that the C ₂ value of the formula (2) is 5 to 8,

 Ethylene / alpha-olefin copolymers.

[Claim 7]

 The method of claim 1, wherein the ethylene / alpha olefin copolymer is

 The weight average molecular weight (g / mol) is 10,000 to 400,000,

 Ethylene / alpha-lephine copolymer, characterized in that the molecular weight distribution (Mw / Mn, PDI) is 5 to 30.

[Claim 8]

 The method of claim 1,

The alpha-olephine is 1-butene, 1-pentene, 1-nuxene, 4-methyl-1-pentene, 1-oxane 1pydecene, 1-dodecene, 1-tetradecene, 1-nuxadecene, 1- At least one selected from the group consisting of octadecene and 1-eicosene Characteristic ，

 Ethylene / Alpha-olefin Copolymers.

[Claim 9]

 The method of claim 1,

 入 / ethylene / alpha-olepin copolymer is at least one first metallocene compound represented by the formula (1); And a second metallocene compound selected from compounds represented by the following Chemical Formulas 3 to 5, prepared by polymerizing ethylene and alpha-ole ¾,

 Ethylene / Alpha—Lepin Copolymer:

 In Chemical Formula 1,

A is hydrogen, halogen, alkyl, C ₂ - ₂₀ alkenyl Al, C ₆ - ₂₀ aryl, alkyl aryl, C ₇ - ₂₀ aryl-alkyl, d-20 alkoxy, C ₂ -20 alkoxyalkyl, by interrogating cycloalkyl, or C ₅ — ₂₀ heteroaryl;

D is -E, -S-, -N (R)-or -S i (RKR ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, d- ₂₀ alkyl, C ₂ - ₂₀ alkenyl, or C ₆ - ₂₀ aryl;

 L is Cwo straight or branched alkylene;

 B is carbon, silicon or germanium;

Q is hydrogen, halogen, d- ₂₀ alkyl, C ₂ - ₂₀ alkenyl, C ₆ - ₂₀ aryl, C ₇ - ₂₀ alkylaryl, or C ₂₀ The aryl alkyl;

 M is a Group 4 transition metal;

X ¹ and X ² are the same or different and are each independently halogen, d-20 alkyl, C ₂ - ₂₀ alkenyl, C ₆ - ₂₀ aryl, nitro, amido, ₂₀ alkylsilyl, d-20 alkyl, or CHO sulfonate;

C ¹ and C ² are the same as or different from each other, and each independently 2a, 2b, or 2c, except that C ¹ and C ² are all 2c;

[Formula 2a]

In Chemical Formulas 2a, 2b and 2c,

Ri to R ₁₇ and IV to "are the same or different, each independently represent hydrogen, halogen, alkyl, and C ₂ of each other - ₂₀ alkenyl, d- ₂₀ alkylsilyl, d-20 alkyl silyl group, alkoxysilyl group CHO, alkoxy, C ₆ - ₂₀ aryl, C _20, and the alkyl aryl, or C ₇ -20 aryl-alkyl, wherein 0-7 of the two or more adjacent to each other are connected to each other may form a substituted or unsubstituted aliphatic or aromatic ring;

 [Formula 3] In Formula 3,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;

R ^a and R ^b are the same or different and each is independently hydrogen, Cuo alkyl, 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 a halogen atom, C - ₂₀ alkyl, C ₂ - ₁₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₆ - ₂₀ aryl, alkylidene, substituted or unsubstituted substituted or unsubstituted are amino, C ₂ - ₂₀ alkyl, alkoxy, aryl, or C T ₄₀ alkoxy;

 n is 1 or 0;

 [Formula 4] In Formula 4,

M ² is a Group 4 transition metal;

Cp ³ and Cp ⁴ are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, gtetrahydro-1-indenyl and fluorenyl radicals; They may be substituted with a hydrocarbon having 1 to 20 carbon atoms; R ^C and R ^d are the same or different from each other, each independently hydrogen, d-20 alkyl, an alkoxy, C ₂ -20 alkoxyalkyl, C ₆ - ₂₀ aryl, C ₆ - ₁₀ aryloxy, C ₂ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₈ - ₄₀ arylalkenyl, or C ₂ - ₁₀ alkynyl;

Z ² is a halogen atom, ₍₂₀ alkyl, C ₂ - ₁₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₆ - ₂₀ aryl, optionally substituted C -20 alkylidene, substituted or unsubstituted amino, C ₂ - ₂₀ alkyl, an alkoxy, or a C ₇ - ₄₀ aryl-alkoxy;

B ¹ is one or more of a carbon germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp¾ ^c ring with the Cp ⁴ R ^d ring or crosslinks one Cp ⁴ R ^d ring with M ² or Combination; .

 m is 1 or 0;

 [Formula 5]

(Cp ⁵ R ^e ) B ² (J) M¾ ³ 2

 In Chemical Formula 5,

M ³ is a Group 4 transition metal;

Cp ⁵ is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms Can be;

R ^e is hydrogen, C ₂₀ alkyl, d- ₁₀ alkoxy, C ₂ - ₂₀ alkoxyalkyl, C ₆ - ₂₀ aryl, C ₆ - 10 aryloxy, C ₂ - ₂₀ alkenyl, the alkyl, aryl, C ₇ - ₄₀ aryl alkyl, C ₈ - ₄₀ arylalkenyl, or C ₂ - ₁₀ alkynyl;

Z ³ is a halogen atom, alkyl, C ₂ - ₁₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₆ - ₂₀ aryl, optionally substituted ₍₂₀ alkylidene, substituted or unsubstituted amino, C ₂ - ₂₀ alkyl, an alkoxy, or a C ₇ - ₄₀ aryl-alkoxy;

B ² is at least one or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp¾ ^e ring and J;

J is any one selected from the group consisting of NR ^f , 0, PR ^f and S, wherein R ^f is alkyl, aryl, substituted alkyl or substituted aryl of d-20.