KR20190081611A - Catalyst for polymerizing olefin and polyolefin polymerized by using the same - Google Patents

Abstract

The present invention relates to a polyolefin polymerization catalyst capable of manufacturing a polyolefin-based polymer with excellent optical properties, and a polyolefin-based polymer polymerized by using the same. According to the present invention, the polyolefin polymerization catalyst comprises a first transient metal compound represented by chemical formula A-1 and a second transient metal compound represented by chemical formula B-1. In chemical formulas A-1 and B-1, M, X, Q, R^1 to R^7 are as defined in the specification.

Description

TECHNICAL FIELD [0001] The present invention relates to an olefin polymerization catalyst and an olefin polymer polymerized using the olefin polymerization catalyst.

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and an olefin polymer polymerized using the same, and more specifically, to a hybrid catalyst comprising a plurality of transition metal compounds and an olefin polymer polymerized using the same.

A metallocene catalyst, which is one of the catalysts used to polymerize olefins, is a compound in which a ligand such as a cyclopentadienyl group, an indenyl group or a cycloheptadienyl group is coordinated to a transition metal or a transition metal halide compound as a basic form .

It has been known that the olefin polymer polymerized using such a metallocene catalyst has a narrow molecular weight distribution (MWD) as compared with the olefin polymer polymerized by the conventional Ziegler-Natta catalyst, and has a constant comonomer distribution.

A problem to be solved by the present invention is to provide an olefin polymerization catalyst capable of producing an olefin polymer having high activity and excellent optical properties.

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method of manufacturing the same.

In order to solve the above problems, an olefin polymerization catalyst according to an embodiment of the present invention includes a first transition metal compound represented by the following formula A-1 and a second transition metal compound represented by the following formula B-1 .

≪ Formula (A-1) >

<Formula B-1>

In the above Formulas A-1 and B-1, n is an integer of 0 to 5, m and 1 are each an integer of 0 to 4, M is titanium (Ti), zirconium (Zr) or hafnium (Hf) , X is each independently selected from the group consisting of halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C6-20 aryl, C1-20 alkyl C6-20 aryl, C6-20 aryl C1-20 alkyl, (C), silicon (Si), germanium (Ge), or tin (Sn), and R ¹ to R ⁷ are independently an alkyl group having 1 to 20 carbon atoms, Substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-20 aryl, substituted or unsubstituted C1-20 alkyl C6-20 aryl, substituted or unsubstituted C1-20 alkyl, Substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3-20 heteroaryl, substituted or unsubstituted C1-20 alkylamido, substituted or unsubstituted C6 -20 arylamido, substituted or unsubstituted C1-20 aryl A fluoride, or a substituted or unsubstituted C1-20 silyl, R ¹ to R ⁵ are connected to the adjacent groups, each independently may form a substituted or unsubstituted, saturated or unsaturated C4-20 ring.

In the above formulas A-1 and B-1, n, m and 1 are each 1, X is each independently halogen, and R ¹ , R ² and R ³ are each independently C _1-20 alkyl .

Specifically, in the above formulas A-1 and B-1, M is zirconium and Q may be carbon.

More specifically, the above-mentioned formulas A-1 and B-1 may be represented by the following formulas A-2 and B-2, respectively.

&Lt; Formula (A-2) >

<Formula B-2>

The first transition metal compound and the second transition metal compound may be contained in a weight ratio of 0.4 to 2.5: 1.

And a carrier for supporting the first transition metal compound and / or the second transition metal compound.

The carrier may comprise at least one of silica, alumina and magnesia.

The first and second transition metal compounds may be mixed and supported on a single species of the carrier.

The olefin polymerization catalyst according to one embodiment may further comprise a cocatalyst compound comprising at least one of the compound represented by the following formula (1), the compound represented by the formula (2) and the compound represented by the formula (3).

&Lt; Formula 1 >

In the general formula (1), n is an integer of 2 or more, and R _a is a halogen atom, a C _1-20 hydrocarbon group or a C _1-20 hydrocarbon group substituted with halogen.

(2)

R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, a C _1-20 hydrocarbon group substituted with halogen, or a group represented by the formula C _1-20 alkoxy group.

(3)

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

Wherein L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a Group 13 element, and A is independently a substituted or unsubstituted C _{6- 20} aryl group or a substituted or unsubstituted C _1-20 alkyl group.

It can have a catalytic activity of 3500 gPE / gCat · hr or more.

In order to solve the above problems, the olefin polymer according to another embodiment of the present invention is formed by polymerization under the above-mentioned olefin polymerization catalyst.

The olefin-based polymer may be formed by copolymerization of an olefin-based monomer and an olefin-based comonomer.

The olefinic monomer and the olefinic comonomer constituting the olefinic polymer may be ethylene and 1-hexene, respectively.

According to another aspect of the present invention, there is provided a film comprising the olefin-based polymer.

The haze of the film may be 15% or less and the transparency (Clarity) may be 90% or more.

The details of other embodiments are included in the detailed description and drawings.

The embodiments of the present invention have at least the following effects.

The olefin polymerization catalyst of the present invention can be used for producing an olefin polymer having high catalytic activity and excellent optical properties.

The effects according to the embodiments of the present invention are not limited by the contents exemplified above, and more various effects are included in the specification.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

The olefin polymerization catalyst according to an embodiment of the present invention may include at least one selected from the first transition metal compound represented by the following formula A-1 and the second transition metal compound selected from the compound represented by the following formula B-1 have.

&Lt; Formula (A-1) >

<Formula B-1>

In the above Formulas A-1 and B-1, n is an integer of 0 to 5, and m and l may be an integer of 0 to 4, respectively. Specifically, n, m and l may be 1 each.

 M may be titanium (Ti), zirconium (Zr) or hafnium (Hf). Specifically, M may be zirconium.

X is independently selected from the group consisting of halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkyl, amido, may indenyl C _6-20 aryl or C _1-20 amido alkali. Specifically, X may each be a halogen. More specifically, each X may be chlorine (Cl).

Q may be carbon (C), silicon (Si), germanium (Ge), or tin (Sn). Specifically, Q may be carbon.

R ¹ to R ⁷ are each independently a substituted or unsubstituted C _1-20 alkyl, a substituted or unsubstituted C _2-20 alkenyl, a substituted or unsubstituted C _6-20 aryl, a substituted or unsubstituted C _{1 -20} alkyl, C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted Or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl have. Further, each of R ¹ to R ⁵ may independently form an adjacent or adjacent group to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring

Specifically, R ¹ , R ^2, and R ³ may each independently be C _1-20 alkyl. More specifically, R ¹ , R ² and R ³ can each independently be C _1-6 alkyl.

In an exemplary embodiment, the first transition metal compound represented by the above formula (A-1) may be a compound represented by the following formula (A-2). The compound represented by the above formula (B-1) may be a compound represented by the following formula (B-2). However, examples of the olefin polymerization catalyst of the present invention are not limited to the following compounds.

&Lt; Formula (A-2) >

<Formula B-2>

The first transition metal compound and the second transition metal compound may be contained in a weight ratio of 0.4 to 2.5: 1. Specifically, the first transition metal compound and the second transition metal compound may be contained in a weight ratio of 7: 3 to 3: 7. When the content ratio of the first transition metal compound and the second transition metal compound is within the above range, it exhibits a proper supported catalyst activity, which may be advantageous from the viewpoint of maintenance of the activity and economy of the catalyst. In addition, the olefin polymer produced under the olefin polymerization catalyst within the above range can have excellent optical properties.

Olefin polymers containing a small amount of SCB (Short Chain Branch) are generally known to exhibit thermal degradation in optical properties. Olefin polymers containing a large amount of LCB (Long Chain Branch) have an excessively high elasticity, .

As a result, it was confirmed through experimentation that the olefin polymer obtained by using the first transition metal compound alone contained a small amount of SCB, exhibited relatively poor optical properties, and was obtained by using the second transition metal compound alone The olefin polymer thus obtained exhibited excellent properties in terms of optical properties including a large amount of SCB and LCB, but exhibited relatively poor mechanical properties. In addition, when the first transition metal compound was used singly, the catalyst exhibited a lower catalytic activity than the second transition metal compound alone. That is, when the first transition metal compound and the second transition metal compound are used alone, or when the proportion of either the first transition metal compound or the second transition metal compound is excessively high, the catalyst activity, optical property, and mechanical properties It has been confirmed that it is difficult to satisfy all.

On the contrary, the olefin-based polymer provided through the hybrid supported catalyst comprising the first transition metal compound and the second transition metal compound at a weight ratio of 7: 3 to 3: 7 has excellent catalytic activity and excellent optical properties at the same time .

The olefin polymerization catalyst of the present invention may further comprise a cocatalyst compound.

The cocatalyst compound may include at least one of a compound represented by the formula (1), a compound represented by the formula (2), and a compound represented by the formula (3).

&Lt; Formula 1 >

In Formula 1, n is an integer of 2 or more, and R _a may be a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. Specifically, R _a may be methyl, ethyl, n-butyl or isobutyl, but is not limited thereto.

(2)

R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, a C _1-20 hydrocarbon group substituted with halogen, or a group represented by the formula A C _1-20 alkoxy group. Specifically, when D is aluminum, R _b , R _c and R _d may each independently be methyl or isobutyl, and when D is boron, R _b , R _c and R _d are each pentafluoro Phenyl, but is not limited thereto.

(3)

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

Wherein L is a neutral or cationic Lewis base, [LH] ⁺ or [L] ⁺ is a Bronsted acid, Z is a Group 13 element, and A is independently a substituted or unsubstituted C _{6- 20} aryl group or a substituted or unsubstituted C _1-20 alkyl group. Specifically, the [LH] ⁺ may be a dimethylanilinium cation dimethyl, wherein [Z (A) _4] ^- is _{[B (C 6 F 5)} 4] - can be a, the [L] ⁺ is [( C ₆ H ₅ ) ₃ C] ⁺ , but is not limited thereto.

The olefin polymerization catalyst of the present invention may further comprise a carrier carrying a first transition metal compound, a second transition metal compound and a cocatalyst compound.

The carrier may include a substance containing a hydroxyl group on its surface, and preferably a material having a hydroxyl group and a siloxane group having high reactivity and dried on the surface and having moisture removed may 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. Or carbon, zeolite, magnesium chloride, and the like. However, the present invention is not limited thereto, and it is not particularly limited as long as it is capable of supporting the first and second transition metal compounds and the cocatalyst compound.

As a method of supporting a transition metal compound and a promoter compound for an olefin polymerization catalyst on a carrier, a physical adsorption method or a chemical adsorption method may be used.

In an exemplary embodiment, the physical adsorption method includes a method in which a solution in which a transition metal compound is dissolved is contacted with a carrier and then dried, a method in which a solution in which a transition metal compound and a promoter compound are dissolved is contacted with a carrier, A solution in which a metal compound is dissolved is contacted with a carrier and then dried to prepare a carrier carrying the transition metal compound, and separately a solution in which a co-catalyst compound is dissolved is contacted with a carrier, followed by drying to obtain a carrier A method of mixing them, and the like.

In an exemplary embodiment, the chemical adsorption method is a method in which the promoter compound is first supported on the surface of the support, and then the transition metal compound is supported on the promoter compound, or a method in which the functional group on the surface of the support A method of covalently bonding a catalyst compound with a hydroxyl group (-OH) on the surface, and the like.

The total amount of the first and second transition metal compound to be supported may be 0.001 mmol to 1 mmol based on 1 g of the carrier and the amount of the co-catalyst compound to be supported may be 2 mmol to 15 mmol based on 1 g of the carrier.

The carrier may contain one or two or more kinds of carriers, and the first transition metal compound and the second transition metal compound may be both supported on one carrier, and the first transition metal compound and the second transition A metal compound may be supported on the support, and only one of the first transition metal compound and the second transition metal compound may be supported on the support.

In an exemplary embodiment, the olefin polymerization catalyst of the present invention may be a hybrid supported catalyst in which a first transition metal compound, a second transition metal compound, and a promoter compound are supported on silica together. However, the embodiment of the present invention is not limited thereto.

The olefin polymerization catalyst of the present invention can ensure excellent catalytic activity by using a hybrid supported catalyst in which the first transition metal compound and the second transition metal compound are carried together.

The present invention provides an olefin polymer formed by polymerization under the above-mentioned olefin polymerization catalyst according to another embodiment.

The olefin-based polymer of the present invention can be polymerized under the above-mentioned olefin polymerization catalyst, and can have excellent properties in terms of optical properties such as turbidity and sharpness.

The olefin-based polymer of the present invention may be a polymer of an olefin-based monomer or a copolymer of an olefin-based monomer and a comonomer.

The olefinic monomer may be selected from the group consisting of C _2-20 alpha-olefins, C _1-20 diolefins, C _3-20 cyclo-olefins, and C _3-20 cyclodiolefins. And may be one or more selected from the group consisting of

In an exemplary embodiment, the olefinic monomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, , 1-dodecene, 1-tetradecene, 1-hexadecene, and the like, and the olefin-based polymer may be a homopolymer containing only one of the above-exemplified olefin-based monomers or a copolymer containing two or more .

Preferably, the olefin-based polymer may be a copolymer in which ethylene and 1-hexene are copolymerized, but is not limited thereto.

The olefinic polymer of the present invention can be polymerized by polymerization reaction such as, for example, free radical, cationic, coordination, condensation, addition, and the like, It is not.

In an exemplary embodiment, the olefin-based polymer may be produced by gas phase polymerization, solution polymerization, slurry polymerization or the like. Examples of the solvent that can be used when the olefinic polymer is prepared by solution polymerization or slurry polymerization include C _5-12 aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof; Aromatic hydrocarbon solvents such as toluene and benzene; Hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; And mixtures thereof. However, the present invention is not limited to these.

The present invention provides a film produced using the olefinic polymer described above according to another embodiment. The above-mentioned film can have excellent optical properties by being produced by including the olefin-based polymer of the present invention.

Specifically, the film of the present invention may have at least one of the following characteristics (1) and (2).

(One) Haze: Less than 15%

(2) Clarity: 90% or more

In an exemplary embodiment, the haze of the film of the present invention may be about 9% or less, and the transparency may be about 93% or more, but is not limited thereto.

Hereinafter, the hybrid supported catalyst as the olefin polymerization catalyst of the present invention and a specific production example of the olefin based polymer and a specific example of measuring the physical properties of the produced olefin based polymer will be described.

Preparation of hybrid supported catalyst

Production Example 1

The transition metal compound of formula A-2 purchased from sPCI was used without purification, and the electro-metallic compound of B-2 was purchased from MCN and used without further purification.

4.2 mg of the compound of Formula A-2 and 17.7 mg of the compound of Formula B-2 were mixed with 3.97 g of 10% MAO in toluene in a glove box (Al / Zr = 200) and stirred for 1 hour. 1.00 g of XPO-2402 silica and 5 mL of toluene were mixed and the solution was poured into a silica slurry and stirred in an oil bath at 75 캜 for 3 hours. The supported catalyst was washed three times with 5 mL of toluene, and dried at 60 캜 under vacuum for 30 minutes to obtain 1.4 g of mixed carrier catalyst in the form of free-flowing powder.

Production Example 2

Except that the compound ratio of the compound of Formula A-2 and the compound of Formula B-2 was changed to 4: 6 by using 5.6 mg of the compound of Formula A-2 and 15.2 mg of the compound of Formula B-2, A hybrid supported catalyst was obtained in the same manner as in Production Example 1 described above.

Production Example 3

Except that the compound ratio of the compound of Formula A-2 and the compound of Formula B-2 was changed to 5: 5 by using 7.1 mg of the compound of Formula A-2 and 12.7 mg of the compound of Formula B-2, A hybrid supported catalyst was obtained in the same manner as in Production Example 1 described above.

Production Example 4

Except that the composition ratio of the compound of Formula A-2 and the compound of Formula B-2 was changed to 6: 4 by using 8.5 mg of the compound of Formula A-2 and 10.1 mg of the compound of Formula B-2, A hybrid supported catalyst was obtained in the same manner as in Production Example 1 described above.

Production Example 5

Except that the compound ratio of the compound of Formula A-2 and the compound of Formula B-2 was changed to 7: 3 by using 9.9 mg of the compound of Formula A-2 and 7.6 mg of the compound of Formula B-2, A hybrid supported catalyst was obtained in the same manner as in Production Example 1 described above.

Example of olefin polymerization (Production of ethylene / 1-hexene copolymer)

Example 1

An ethylene / 1-hexene copolymer was prepared using a Lab-scale autoclave slurry (2 L) reactor. Specifically, 1 ml of hexane and 0.5 ml of 1M TIBAL and 30 to 100 mg of the catalyst prepared in Preparation Example 1 are injected into a lab-scale autoclave slurry (2 L) reactor in a lab-scale autoclave slurry (2 L) reactor. 30 ml of 1-hexene, which is a comonomer, and 15 cc of hydrogen gas were injected at a rate of 15 kg / min while maintaining the ethylene partial pressure of the reactor at 14 kgf / cm ² and stirring at 1000 rpm, thereby obtaining an ethylene / 1-hexene copolymer.

Example 2

An ethylene / 1-hexene copolymer was obtained in the same manner as in Example 1, except that the hybrid supported catalyst obtained in Preparation Example 2 was used. .

Example 3

An ethylene / 1-hexene copolymer was obtained in the same manner as in Example 1, except that the hybrid supported catalyst obtained in Preparation Example 3 was used.

Example 4

An ethylene / 1-hexene copolymer was obtained in the same manner as in Example 1, except that the hybrid supported catalyst obtained in Preparation Example 4 was used.

Example 5

An ethylene / 1-hexene copolymer was obtained in the same manner as in Example 1 except that the hybrid supported catalyst obtained in Preparation Example 5 was used.

Comparative Example 1

An ethylene / 1-hexene copolymer was obtained in the same manner as in Example 1, except that the transition metal compound of the above formula (A-2) was used alone.

Comparative Example 2

An ethylene / 1-hexene copolymer was obtained in the same manner as in Example 1, except that the transition metal compound of the above formula (B-2) was used alone.

<Experimental Example 1>

The catalyst activity and other physical properties of the polymers prepared in Examples 1 to 5 were measured and are shown in Table 1 below. Catalytic activity and physical properties of Comparative Example 1 and Comparative Example 2 were also measured for comparison.

The catalytic activity was measured in terms of the ratio of the weight of polymer produced (g PE) per used catalyst (g of catalyst) based on unit time (h).

MI
(g / 10 min) MFR Catalytic activity
(gPE / gCat · hr) Cloudiness
(%) transparency
(%) Example 1 0.83 71.4 3533 13.6 90.3 Example 2 2.59 28.6 4543 8.8 94.0 Example 3 2.71 28.1 3500 8.7 93.0 Example 4 1.3 30.7 4343 10.8 90.3 Example 5 0.96 35.0 3633 15.2 85.2 Comparative Example 1 0.9 19 3100 7.1 92.8 Comparative Example 2 1.8 25.7 5933 15.4 87.1

As shown in Table 1, the olefin-based polymer synthesized under mixed supported catalysts containing the structural units A-2 and B-2 at a weight ratio of 7: 3 to 3: 7 satisfies both high catalytic activity and excellent optical properties . On the contrary, the polymer of Comparative Example 1 has excellent optical properties, but the catalytic activity is relatively low, and the polymer of Comparative Example 2 has a high catalytic activity and a comparatively low optical property. That is, the polymer of Comparative Example 1 and the polymer of Comparative Example 2 do not satisfy both high catalytic activity and excellent optical properties at the same time.

Hereinafter, embodiments belonging to the spirit of the invention will be described with reference to the above-described chemical structures, production examples, and the like. However, the spirit of the invention is not limited to the exemplary chemical structures and the production examples, and the ideas of the invention can be variously modified based on the exemplified chemical structures and the manufacturing examples. It is to be understood that both the foregoing general description and the appended claims are intended to provide further understanding of the scope of the inventive concept to those skilled in the art and do not limit the scope of the inventive idea to the scope of the claims . It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (15)

A first transition metal compound represented by the following formula (A-1); And
1. An olefin polymerization catalyst comprising a second transition metal compound represented by the following formula (B-1).
&Lt; Formula (A-1) >

<Formula B-1>

(In the above formulas A-1 and B-1,
n is an integer of 0 to 5, m and l are each an integer of 0 to 4,
M is titanium (Ti), zirconium (Zr), or hafnium (Hf)
X is independently selected from the group consisting of halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C6-20 aryl, C1-20 alkyl C6-20 aryl, C6-20 aryl C1-20 alkyl, C1-20 Alkyl amido, C6-20 aryl amido or C1-20 alkylidene,
Q is carbon (C), silicon (Si), germanium (Ge), or tin (Sn)
Each of R ¹ to R ⁷ is independently a substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-20 aryl, substituted or unsubstituted C1-20 alkyl C6 Substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3-20 heteroaryl, substituted or unsubstituted C1-20 alkyl Substituted or unsubstituted C6-20 arylamino, substituted or unsubstituted C1-20 alkylidene, or substituted or unsubstituted C1-20 silyl,
R ¹ to R ⁵ are each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C4-20 ring) The method according to claim 1,
In the above Formulas A-1 and B-1,
n, m and l are each 1,
X is each independently halogen,
R ¹ , R ² , and R ³ are each independently C _1-20 alkyl. 3. The method of claim 2,
In the above Formulas A-1 and B-1,
M is zirconium,
And Q is a carbon. The method of claim 3,
Wherein said formula (A-1) and (B-1) are respectively the following formulas (A-2) and (B-2).
&Lt; Formula (A-2) >

<Formula B-2>

The method according to claim 1,
Wherein the first transition metal compound and the second transition metal compound are contained in a weight ratio of 0.4 to 2.5: 1. The method according to claim 1,
Wherein the olefin polymerization catalyst further comprises a carrier for carrying the first transition metal compound and / or the second transition metal compound. The method according to claim 6,
Wherein the carrier comprises at least one of silica, alumina and magnesia. The method according to claim 6,
Wherein the first and second transition metal compounds are mixedly supported on the carrier of a single species. The method according to claim 1,
1. A olefin polymerization catalyst further comprising a cocatalyst compound comprising at least one of a compound represented by the formula (1), a compound represented by the formula (2) and a compound represented by the formula (3).
&Lt; Formula 1 >

(Wherein n is an integer of 2 or more,
R _a is a halogen atom, a C _1-20 hydrocarbon group or a C _1-20 hydrocarbon group substituted with halogen)
(2)

(In the above formula (2), D is aluminum (Al) or boron (B)
R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, a C _1-20 hydrocarbon group substituted with halogen, or a C _1-20 alkoxy group)
(3)
^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -
(Wherein L is a neutral or cationic Lewis base,
[LH] ⁺ and [L] ⁺ are Bronsted acids
Z is a Group 13 element,
A is independently a substituted or unsubstituted C _6-20 aryl group or a substituted or unsubstituted C _1-20 alkyl group) The method of claim 1,
An olefin polymerization catalyst having a catalytic activity of 3500 gPE / gCat · hr or more. An olefin-based polymer formed by polymerization under the olefin polymerization catalyst according to any one of claims 1 to 10. 12. The method of claim 11,
An olefin-based polymer formed by copolymerization of an olefin-based monomer and an olefin-based comonomer. 13. The method of claim 12,
Wherein the olefinic monomer and the olefinic comonomer are ethylene and 1-hexene, respectively. A film comprising the olefinic polymer of claim 11. 15. The method of claim 14,
A film having a haze of 15% or less and a transparency (Clarity) of 90% or more.