KR20190058864A - Catalyst for polymerizing olefin and polyolefin polymerized by using the same - Google Patents

Abstract

Provided are an olefin polymerization catalyst, an olefin-based polymer, and a film. The olefin polymerization catalyst comprises a first transition metal compound represented by chemical formula A-1 and a second transition metal compound represented by chemical formula B-1. Specific details of chemical formula A-1 and chemical formula B-1 are described in the specification. The olefin polymerization catalyst of the present invention can be used for manufacturing the olefin-based polymer having an excellent melt tension and high processability at the same time.

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.

On the other hand, it is generally known that the melt tension and high-speed processability of a polymer are in a trade-off relationship in which one is increased and the other is decreased. For example, when the polymer is synthesized / processed to have a large amount of LCB (Long Chain Branch), the melt tension is improved but the high-speed processability may deteriorate.

A problem to be solved by the present invention is to provide an olefin polymerization catalyst capable of producing an olefin polymer having excellent melt tension and high processability simultaneously.

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.

The olefin polymerization catalyst according to one 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 is an integer of 0 to 2, 1 is an integer of 0 to 8, M is titanium (Ti), zirconium Hafnium (Hf), X is each 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 alkylamido, C _6-20 arylamido or C _1-20 alkylidene, and Q is carbon (C), silicon (Si), germanium (Ge ) Or tin (Sn), R ¹ to R ⁸ each independently represents a substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl , 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 group, a substituted or unsubstituted C _1-20 alkyl, amido, substituted or unsubstituted C _6-20 aryl amino , Substituted or unsubstituted, and a C _1-20 unsubstituted alkylidene, substituted or unsubstituted C _1-20 silyl group, R ¹ to R ⁶ are each is independently of the adjacent groups are connected by a substituted or unsubstituted, saturated or unsaturated C _{4- 20} rings can be formed.

In the above formulas A-1 and B-1, n is 1, X is each independently halogen, and R ¹ , R ² , R ⁷ and R ⁸ are each independently C _1-20 alkyl.

In the above Formulas A-1 and B-1, m and l are each 0, M is zirconium, and Q may be silicon.

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

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

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

The olefin-based monomer and the olefin-based comonomer may be ethylene and 1-hexene, respectively.

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

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 excellent melt tension and high processability simultaneously.

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.

As used herein, the term " C _AB " means " the number of carbon atoms is not less than A and not more than B &quot;, and the terms " A to B ""inthe" substituted "means" at least one hydrogen of the hydrocarbon compound or a hydrocarbon derivative 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, C _6-20 aryl or C _1-20 amido substituted with alkylidene "means, and" unsubstituted "means" hydrocarbon compounds or at least one hydrogen, halogen, C _1-20 alkyl hydrocarbon derivatives, 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 alkylamido, C _6-20 arylamido or C _1-20 alkylidene ".

The olefin polymerization catalyst according to an embodiment of the present invention may include 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.

&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 is an integer of 0 to 2, and 1 may be an integer of 0 to 8. Specifically, n is 1, and m and l may be 0, respectively.

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 silicon.

R ¹ to R ⁸ 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 ⁶ 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 , R ⁷ and R ⁸ may each independently be C _1-20 alkyl. More specifically, R ¹ and R ² may each be C _1-6 alkyl, and R ⁷ and R ⁸ may each be methyl.

In an exemplary embodiment, the first and second transition metal compounds may be compounds represented by the following formulas A-2 and B-2, respectively. 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, an olefin polymer having excellent melt tension and high-speed processability can be produced as described later.

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, it 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 the compound is dissolved is brought into contact with a carrier and then dried to prepare a carrier carrying the transition metal compound; separately from the solution in which the co-catalyst compound is dissolved, the carrier is contacted with the carrier, And then mixing them, or 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 present invention provides an olefin polymer formed by polymerization under the above-mentioned olefin polymerization catalyst according to another embodiment.

As the olefin polymer of the present invention is polymerized under the olefin polymerization catalyst described above, an LCB (Long Chain Branch) having an optimal number and shape can be introduced. As a result, a high melt index (MI) But also excellent melt tension (MT) and maximum machining speed (Velocity at break) at the same time.

Specifically, the olefin polymer of the present invention may have a melt tension (MT) of 80 mN or more and a maximum processing speed (Velocity at break) of 200 mm / s or more.

The maximum processing speed means the speed measured immediately before the polymer is cut at the time of processing the polymer at a high speed, and can be an index indicating the high-speed processability of the olefin-based polymer. Specifically, as the processing speed increases, the polymer chain is relaxed as it is stretched in a single axis. The larger the main chain of the polymer is, the longer the polymer chains are loosened at high speed, and the polymer chains may be intertwined longer. Therefore, the fact that the maximum processing speed is high may mean that the ratio of the polymer having a large main chain is high.

On the other hand, the olefinic polymer of the present invention may have a melt index (MI) of 0.5 to 1.7 g / 10 min and include LCB (Long Chain Branch). As described above, the olefinic polymer of the present invention has LCB The melt tension and the maximum machining speed can be high at the same time even though the melt index is high. The melt index may be a value measured according to ASTM D1238 (2.16 Kg, 190 DEG C).

LCB is a long carbon branch attached to the main chain of the olefinic polymer and may particularly refer to branches having about 8 or more carbon atoms. Usually, comonomers include 1-butene, 1-hexene, 1- Lt; RTI ID = 0.0 &gt; alpha-olefins. &Lt; / RTI &gt;

The olefin polymer of the present invention may have an LCB ratio of 1 to 3, and may satisfy the following formula (1).

[Formula 1]

In the formula 1, Mn, Mw and Mz mean a number-average molecular weight, a weight-average molecular weight and a Z-average molecular weight, respectively.

The above equation 1 means that the ratio of high molecular weight among the whole polymer distribution is larger, thereby increasing the entanglement and elasticity, which may mean that LCB is concentrated on the high molecular weight polymer chain. That is, although the number of LCBs is not excessively large, the olefinic polymer of the present invention may have a high value at the same time as the melt tension and the maximum processing speed, as described above, due to the specificity of its existence form.

The LCB ratio may be substantially the same as the peak ratio calculated according to the following formulas 2 to 5.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

The higher the peak ratio in Equation (5), the more LCBs can be counted.

The melt strength, the maximum machining speed, and a length 30 mm, diameter 2 mm, shear rate 72 / s of the capillary (capillary) and / or the initial speed of 18 mm / s, the wheel acceleration 12 mm / s ² (wheel) &Lt; / RTI &gt;

Specifically, the melt index, melt tension, LCB ratio and maximum processing speed of the olefinic polymer of the present invention can be as follows.

(1) Melt index: 1.0 to 1.6 g / 10 min

(2) Melting tension: 100 to 200 mN

(3) LCB ratio: 1.5 to 2.5

(4) Maximum machining speed: 350 to 450 mm / s

In a more specific embodiment, the olefinic polymer of the present invention may have a density of 0.91 to 0.93 g / cc, and may satisfy the following formula (6).

[Formula 6]

In the formula 6, Mw and Mz mean a weight-average molecular weight and a Z-average molecular weight, respectively.

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 olefinic polymer of the present invention may have a unimodal molecular weight distribution. That is, the olefin-based polymer of the present invention can have a relatively narrow molecular weight distribution by including a single component. Such a polymer may be one in which only one peak is observed when the molecular weight is measured by gel permeation chromatography (GPC).

The present invention provides a film produced using the olefinic polymer described above according to another embodiment. The film may have excellent haze, clarity, modulus and the like 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) to (5).

(1) Turbidity: 15% or less

(2) Sharpness: 90% or more

(3) Young's modulus: more than 15,000 (MD), more than 17,000 (TD)

(4) 1% Secant Modulus: 3,000 or more (MD, TD)

(5) 2% Secant Modulus: 2,500 or more (MD), 2,800 or more (TD)

In an exemplary embodiment, the haze of the film of the present invention is less than about 7%, the clarity is greater than about 95%, the Young's modulus (MD) is greater than about 15,900, the 1% Secant modulus (TD) The modulus (MD) may be at least about 2,500, 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 Example 1] Preparation of hybrid supported catalyst

The transition metal compound of Formula A-2 purchased from sPCI was used without purification and the transition metal compound of Formula B-2 was prepared by the method disclosed in U.S. Patent No. 5,883,275.

1.99 g of the compound of the above formula A-2 and 2.25 g of the compound of the above formula B-2 were mixed with 838 g of MAO in the glove box (Al / Zr = 150) and stirred in 2 L of RBF for 1 hour. 212 g of XPO-2402 silica and 500 mL of toluene were mixed in 3 L (RBF), and the above solution was injected into the silica slurry and stirred in an oil bath at 75 캜 for 3 hours. The supported catalyst was washed three times with 500 mL of toluene and dried at 60 캜 under vacuum for 30 minutes to obtain 283 g of a mixed supported catalyst in the form of free-flowing powder (Production Example 1-1).

Further, a hybrid supported catalyst (Production Example 1-2) was obtained in the same manner as described above, except that 2.78 g and 1.35 g of the compound of the above formulas A-2 and B-2 were used, respectively.

[Preparation Example 2] Preparation of ethylene / 1-hexene copolymer

An ethylene / 1-hexene copolymer was prepared using a gas phase fluidized bed pilot reactor. Specifically, the catalyst prepared in the above Preparation Example was continuously fed into a gas phase fluidized bed pilot reactor, and the temperature and the partial pressure of ethylene were maintained at 80 ° C. and 14 kgf / cm ² , respectively, and MI and Density were measured. To obtain about 10 kg / hr of ethylene / 1-hexene copolymer continuously.

Table 1 summarizes the respective polymerization conditions using the hybrid supported catalyst of Production Example 1 above.

Example catalyst 1-hexene charge
(ml) Hydrogen input amount
(cc / min) Catalytic activity
(gPE / gCat? hr) One 1-1 50 One 4340 2 1-2 50 One 4800

[Experimental Example] Measurement of physical properties of ethylene / 1-hexene copolymer

The properties of the ethylene / 1-hexene copolymer (Examples 1 and 2) synthesized in Preparation Example 2 were measured and shown in Table 2 below. For comparison, conventional ethylene / 1-hexene copolymers (Comparative Examples 1 to 3) were obtained and their physical properties were measured.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 MI
(g / 10 min) 1.3 1.5 1.11 1.1 1.0 MFR 20.4 20.6 16.14 30.2 23.2 density
(g / cc) 0.923 0.923 0.920 0.918 0.920 Mn
(g / mol) 30,890 43,000 41,000 26230 48,620 Mw
(g / mol) 119,080 114,590 109,400 90,380 127,220 Mz
(g / mol) 489,040 354,840 227,150 195,270 288,910 PDI
(Mw / Mn) 3.85 2.66 2.61 3.45 2.2 Mz / Mw 4.11 3.10 2.07 2.16 2.27 η ₀ 16,300 14,600 7,100 60,800 33,200 MT
(mN) 166 164 70 101 114 Maximum machining speed
(mm / s) 380 396 367 398 208 LCB ratio 1.83 1.70 0.85 3.6 20.2

As shown in Table 2, the olefin polymer synthesized under the olefin polymerization catalyst of the present invention has a relatively high melt index (MI), a molecular weight characteristic (Mz / Mw) and the like, (MT) and the maximum machining speed 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 will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or scope of the inventive concept. . It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (13)

A first transition metal compound represented by the following formula (A-1); And
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 is an integer of 0 to 2, 1 is an integer of 0 to 8,
M is titanium (Ti), zirconium (Zr), or hafnium (Hf)
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, C _6-20 aryl or C _1-20 amido FIG alkylidene,
Q is carbon (C), silicon (Si), germanium (Ge), or tin (Sn)
R ¹ to R ⁸ 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 a substituted or unsubstituted C _1-20 alkylamino, a substituted or unsubstituted C _6-20 arylamino, a substituted or unsubstituted C _1-20 alkylidene, or a substituted or unsubstituted C _1-20 silyl,
R ¹ to R ⁶ are each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring) The method according to claim 1,
In the above Formulas A-1 and B-1,
n is 1,
X is each independently halogen,
R ¹ , R ² , R ⁷ and R ⁸ are each independently C _1-20 alkyl. 3. The method of claim 2,
In the above Formulas A-1 and B-1,
m and l are each 0,
M is zirconium,
Q is a silicon-containing olefin polymerization catalyst. 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) An olefin-based polymer formed by polymerization under the olefin polymerization catalyst of any one of claims 1 to 9. 11. The method of claim 10,
An olefin-based polymer formed by copolymerization of an olefin-based monomer and an olefin-based comonomer. 12. The method of claim 11,
Wherein the olefinic monomer and the olefinic comonomer are ethylene and 1-hexene, respectively. A film comprising the olefinic polymer of claim 10.