KR20170057965A

KR20170057965A - Supported metallocene catalyst and method for preparing polyolefin by using the same

Info

Publication number: KR20170057965A
Application number: KR1020150161531A
Authority: KR
Inventors: 허은정; 양혜림; 박란화; 양송희; 정동욱
Original assignee: 한화케미칼 주식회사
Priority date: 2015-11-18
Filing date: 2015-11-18
Publication date: 2017-05-26
Also published as: WO2017086597A1; KR101784689B1

Abstract

The present invention relates to a supported metallocene catalyst in which at least one first metallocene compound of the compounds represented by chemical formula 1, at least one second metallocene compound of the compounds represented by chemical formula 2, and a cocatalyst compound are supported on a carrier; and to a method for preparing polyolefin which is characterized by polymerizing olefin monomers in the presence of the supported metallocene catalyst. In the chemical formulas 1 and 2, M, X, Q, and R^1 to R^14 are as specified in the present specification. According to the present invention, polyolefin having improved mechanical properties can be provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a metallocene supported catalyst and a method for producing the olefin polymer using the metallocene supported catalyst.

The present invention relates to a metallocene supported catalyst and a process for producing an olefin polymer using the metallocene supported catalyst.

Unlike the conventional Ziegler-Natta catalyst, a resin polymerized with a metallocene catalyst has a narrow molecular weight distribution and excellent mechanical properties because a polymer is grown at a single active site. Based on these excellent properties, metallocene catalysts are gradually expanding in the polyethylene (PE) and polypropylene (PP) industries. However, the resin polymerized with the metallocene catalyst is disadvantageous in that it has a lower processability than the resin polymerized with the Ziegler-Natta catalyst.

The present invention provides a metallocene supported catalyst capable of providing an olefin polymer improved in processability and mechanical properties, and a process for producing an olefin polymer using the metallocene supported catalyst.

The metallocene supported catalyst according to the present invention comprises a support, at least one first metallocene compound among compounds represented by the following general formula (1) carried on the support, compounds represented by the following general formula (2) At least one second metallocene compound, and a co-catalyst compound supported on said support:

(Formula 1)

(2)

M is any one of titanium (Ti), zirconium (Zr) or hafnium (Hf), and Q is at least one element selected from the group consisting of carbon (C), silicon (Si), germanium (Ge) Sn), and X is each independently any one of halogen, C _1-10 alkyl group, and C _2-10 alkenyl group.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently selected from the group consisting of hydrogen, C _1-20 alkyl, or one of the C _3-6 cycloalkyl group (cycloalkyl group), C _6-14 aryl group (aryl group), R ^m (m is from 1 to 12) among them, two adjacent R ⁿ and R ⁿ ⁺¹ (n is from 1 to 11), the C _1-4 alkyl group is substituted or unsubstituted C _1-15 when forming a ring compound, wherein C _1-4 alkyl group is substituted or unsubstituted C _1-15 membered ring R ^< ^m ^> and R < ⁿ ^{+ 1} ^> are independently hydrogen, a _C1-20 alkyl group, a _C3-6 cycloalkyl group or a _C6-14 aryl group.

In the formulas (1) and (2), R ¹³ and R ¹⁴ are each independently a C _1-10 alkyl group or a C _6-14 aryl group.

The process for preparing an olefin polymer according to the invention is characterized in that the olefin monomers are polymerized in the presence of a metallocene supported catalyst.

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

The metallocene supported catalyst and the process for producing an olefin polymer according to the present invention can provide an olefin polymer improved in processability and mechanical properties.

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

1 is a graph showing the weight average molecular weight of an olefin polymer measured by gel permeation chromatography-infrared spectroscopy (GPC-IR).
2 is a graph of the melt strength versus the pull-off speed of the olefin polymer.
Figure 3 is a graph of melt strength versus melt flow ratio (MFR) of olefin polymers.
FIG. 4 is a graph of melt strength versus number of long chain branches (LCB / 10 ⁴ C) per total 10,000 carbon atoms.

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. Like reference numerals refer to like elements throughout the specification. The dimensions and relative sizes of layers and regions in the figures may be exaggerated for clarity of illustration.

Although the first, second, etc. are used to describe various components, it goes without saying that these components are not limited by these terms. These terms are used only to distinguish one component from another. Therefore, it goes without saying that the first component mentioned below may be the second component within the technical scope of the present invention.

As used herein, the term "C _AB " means that the number of carbon atoms is A or more and B or less.

In the present specification, "A to B" means A or more and B or less.

Hereinafter, the metallocene supported catalyst according to the invention will be described in detail.

The metallocene supported catalyst according to the invention comprises a support, a first metallocene compound supported on the support, a second metallocene compound supported on the support, and a promoter compound supported on the support.

The carrier is not particularly limited as long as it is capable of supporting the first metallocene compound, the second metallocene compound and the promoter compound, and examples thereof include carbon, silica, alumina, zeolite, magnesium chloride, etc. .

The co-catalyst compound is not particularly limited as long as it is widely used in the metallocene catalyst field, and includes, for example, a first co-catalyst compound of at least one compound represented by the following formula A-1, And at least one of a mixture of the first co-catalyst compound and the second co-catalyst compound.

(A-1)

(A-2)

In the above formulas A-1 and A-2, Ra is a halogen, a substituted or unsubstituted C _1-20 alkyl group, a C _3-6 cycloalkyl group, or a C _6-14 aryl group; n is an integer of 2 or more; D is aluminum or boron; Rb to Rd are the same or different from each other and each independently represents a C _1-20 alkyl group, a C _3-6 cycloalkyl group, or a C _6-14 aryl group substituted or unsubstituted with hydrogen, halogen, or halogen.

As the method of carrying the first metallocene compound, the second metallocene compound and the co-catalyst compound on the carrier, known physical adsorption method or known chemical adsorption method may be used.

The physical adsorption method includes, for example, a method in which a solution in which the first metallocene compound and the second metallocene compound are dissolved is contacted with the carrier and then dried, or a method in which the first metallocene compound and the A method in which a solution in which the second metallocene compound and the co-catalyst compound are dissolved is contacted with the carrier and then dried, or a method in which a solution in which the first metallocene compound and the second metallocene compound are dissolved is contacted with the carrier And drying the resultant to prepare a carrier on which the first metallocene compound and the second metallocene compound are supported. In addition, a solution in which the co-catalyst compound is dissolved is contacted with the carrier, followed by drying, A method of mixing the carrier with the carrier, and the like.

The chemical adsorption method includes, for example, a method in which the promoter compound is first supported on the surface of the support, and then the first metallocene compound and the second metallocene compound are supported on the promoter compound, Or a method of covalently bonding the metallocene compound to the functional group on the surface of the support (for example, in the case of silica, the hydroxyl group (-OH) on the silica surface).

The sum of the amount of the first metallocene compound and the amount of the second metallocene compound may be 0.001 mmol to 1 mmol based on 1 g of the carrier and the amount of the co- And may be from 2 mmol to 15 mmol.

The first metallocene compound and the second metallocene compound can be used together with the co-catalyst compound to be used as a polymerization catalyst for polyolefins.

The first metallocene compound and the second metallocene compound will be described in more detail below.

The first metallocene compound is one of compounds represented by the following formula (1).

(Formula 1)

The second metallocene compound is one of the compounds represented by the following general formula (2).

(2)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 in} Formula 1 and Formula 2 , R < ¹³ > and R < ¹⁴ >

M may be any one of titanium (Ti), zirconium (Zr), and hafnium (Hf).

Q may be any one of carbon (C), silicon (Si), germanium (Ge), and tin (Sn).

X may each independently be any one of halogen, C _1-10 alkyl group, and C _2-10 alkenyl group.

^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11 and R ¹² are each independently hydrogen, C _1-20 alkyl, C _{3- A} cycloalkyl group, a C _6-14 aryl group, or R ^m (m is 1 to 12), two adjacent R ⁿ and R ⁿ ⁺¹ (n is an integer of 1 to 6) 11) when a is C _1-4 alkyl group to form a substituted or unsubstituted C _1-15 membered ring, two adjacent R to the C _1-4 alkyl group form a substituted or unsubstituted C _1-15 membered ring ^The remaining R ^m other than ⁿ and R ^{n + 1} may independently be one of hydrogen, a C _1-20 alkyl group, a C _3-6 cycloalkyl group, and a C _6-14 aryl group.

R ¹³ and R ¹⁴ may each independently be a C _1-10 alkyl group or a C _6-14 aryl group.

The C _1-15 monocyclic compound may be a monocyclic compound of an aliphatic cyclic compound or a monocyclic compound of an aromatic cyclic compound and the C _1-15 multicyclic compound may be a cyclic compound of an aliphatic cyclic compound, Or a multi-cyclic compound of the aliphatic cyclic compound and the aromatic cyclic compound.

The first metallocene compound and the second metallocene compound may be prepared in a predetermined composition ratio through partial hydrogenation of at least one of the compounds represented by the following formula (B). For example, the partial hydrogenation reaction can be achieved by controlling the content of the hydrogenation catalyst.

(Formula B)

In Formula B, M, Q, X, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , And R < ¹⁴ > are the same as described in the above Chemical Formulas 1 and 2, respectively.

The first metallocene compound and the second metallocene compound may be prepared by, for example, putting the base compound and the predetermined hydrogenation catalyst in a reactor, injecting hydrogen into the reactor, , Stirring the base compound and the hydrogenation catalyst, terminating the reaction, and removing the solvent in the reactor.

Examples of the hydrogenation catalyst include at least one of nickel (Ni), platinum (Pt), ruthenium (Ru), rhodium (Rh), and palladium (Pd). The content of the hydrogenation catalyst may be in the range of 0.10 part by weight to 0.55 part by weight with respect to 100 parts by weight of the base compound. Within the content range, the amount of the first metallocene compound And a composition of the second metallocene compound can be prepared.

The hydrogenation reaction is a reaction in which hydrogen is added to a carbon-carbon multiple bond (double bond, triple bond), a nitro group, or a carbonyl group. Due to the high flammability and explosiveness of hydrogen, Lt; / RTI >

Transition metals (Ti, Zr, Cr, Mo, Co, Fe, etc.), which have strong adsorption strengths of hydrogen, are not suitable for hydrogenation catalysts because hydrogen activated on the catalyst surface is difficult to transfer to reactants. Conversely, transition metals (Mg, Zn, Ag, Si, Pb, etc.) whose hydrogen adsorption strength is too weak are not sufficiently activated by hydrogen, resulting in low hydrogenation activity. Therefore, ruthenium (Ru), rhodium (Rh), palladium (Pd), and platinum (Pt) which are suitable for the hydrogen adsorption strength and easy to move the activated hydrogen are preferable as the hydrogenation catalyst.

In addition to noble metal catalysts such as ruthenium (Ru), rhodium (Rh), palladium (Pd) and platinum (Pt), nickel (Ni) can be used as a hydrogenation catalyst. However, nickel (Ni) has a low catalytic activity, so a high-temperature and high-pressure process is required relative to a noble metal catalyst in order to obtain a high yield.

In order to utilize the expensive noble metal catalyst in the catalytic reaction as much as possible, it is possible to use at least one noble metal such as platinum (Pt), ruthenium (Ru), rhodium (Rh) or palladium (Pd) The carrier may be, for example, carbon, silica, alumina, zeolite, and the like, but is not limited thereto. Preferably, a hydrogenation catalyst (Pd / C) in which palladium (Pd) is supported on a carbon carrier may be used. Pd / C can provide a composition of the first metallocene compound and the second metallocene compound at a higher yield than PtO ₂ .

Pd / C can be selected from the group consisting of benzene, toluene, xylene, o-xylene, m-xylene, p-xylene, mesitylene, tetralin, anisole, cumene, Can be dispersed in an aromatic solvent such as 1,4-diethylbenzene, 1-ethyl-2-methylbenzene, 1-ethyl-3-methylbenzene and 1-ethyl-4-methylbenzene.

For example, in Formula 1, Formula 2 and Formula B, X may be halogen, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ^7, wherein R ^8, wherein R ^9, wherein R ^10, wherein R ¹¹ and wherein R ¹² may be one of hydrogen, C _1-20 alkyl, C _6-14 aryl group, each independently, the R ¹³ and Each of R ¹⁴ may independently be a C _1-10 alkyl group or a C _6-14 aryl group. The C _1-20 alkyl group and the C _1-15 mono or multicyclic compound may have one or more carbon atoms selected from the group consisting of a nitrogen element (N), an oxygen element (O) or a sulfur element (S).

In this case, the base compound may be one of compounds represented by the following Formulas B-1 to B-20, and the first metallocene compound may be represented by the following Formulas 1-1 to 1-20 And the second metallocene compound may be one of the compounds represented by the following general formulas (2-1) to (2-20).

(B-1)

(Formula B-2)

(Formula B-3)

(Formula B-4)

(B-5)

(B-6)

(B-7)

(Formula B-8)

(B-9)

(B-10)

(B-11)

(B-12)

(B-13)

(B-14)

(Formula B-15)

(B-16)

(B-17)

(Formula B-18)

(Formula B-19)

(Formula B-20)

(1-1)

(1-2)

(1-3)

(Formula 1-4)

(Formula 1-5)

(Formula 1-6)

(Formula 1-7)

(Formula 1-8)

(Formula 1-9)

(1-10)

(Formula 1-11)

(Formula 1-12)

(Formula 1-13)

(Formula 1-14)

(Formula 1-15)

(Formula 1-16)

(Formula 1-17)

(1-18)

(Formula 1-19)

(1-20)

(Formula 2-1)

(2-2)

(Formula 2-3)

(2-4)

(Formula 2-5)

(Formula 2-6)

(Formula 2-7)

(Formula 2-8)

(Formula 2-9)

(Formula 2-10)

(2-11)

(2-12)

(Formula 2-13)

(2-14)

(Formula 2-15)

(2-16)

(2-17)

(2-18)

(2-19)

(Formula 2-20)

Hereinafter, a method of polymerizing an olefin polymer using the metallocene supported catalyst as a polymerization catalyst and the olefin polymer produced therefrom will be described in detail.

The process for preparing an olefin polymer according to the invention comprises polymerizing the olefin monomers in the presence of the metallocene supported catalyst. The olefin monomers can be selected from the group consisting of, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-dodecene, 1-tetradecene, 1-hexadecene, and the like, and the olefin polymer may be a homopolymer or a copolymer.

The olefin polymer can be produced, for example, by gas phase polymerization, solution polymerization, slurry polymerization or the like. When the olefin polymer is prepared by the solution polymerization method or the slurry polymerization method, examples of the solvent to be used 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.

[Example 1]

Rac - dimethylsilyl (indenyl) ( tetrahydroindenyl ) zirconium dichloride and Rac-dimethylsilyl bis (tetrahydroindenyl) zirconium dichloride Synthesis at 1: 1 ratio

In a glove box, 502 mg (1 eq.) Of Rac-dimethylsilylene bis (indenyl) zirconium dichloride and Pd / C solution were placed in a 100 mL autoclave. The Pd / C solution was prepared by dispersing 11 mg (0.5 mol%) of 5 wt% Pd / C in 25 mL of toluene. After injecting 30 bar of hydrogen into the autoclave, the mixture was stirred at 70 캜 for 14 hours. After completion of the reaction, the solution in the autoclave was filtered, and the resulting transition metal compound crystals were dissolved by using 25 mL of toluene, followed by filtration. The filtered solution was collected and the solvent was removed in vacuo to obtain a mixture of Rac-dimethylsilyl (indenyl) (tetrahydroindenyl) zirconium dichloride and Rac-dimethylsilyl bis (tetrahydroindenyl) zirconium dichloride in 90% yield.

Rac - dimethylsilyl ( indenyl ) ( tetrahydroindenyl ) zirconium dichloride

1H NMR (CDCl3, 300 MHz) 7.71 (d, IH), 7.46 (d, IH), 7.40 (t, , 6.04 (d, IH), 5.66 (d, IH), 3.01-1.45 (8H), 1.01 (s, 3H), 0.89 (s, 3H).

Rac - dimethylsilyl bis (tetrahydroindenyl) Zirconium Dichloride

(M, 2H), 2.76-2.50 (m, 2H), 2.76-2.50 (m, 2H) 2.04-1.88 (m, 2H), 1.86-1.70 (m, 2H), 1.64-1.42 (m, 4H), 0.76 (s, 6H).

The carrier used was Grace silica (SP2410). Add 5 ml of toluene solution to the glass reactor and add 1 g of silica. After the silica was sufficiently dispersed, a mixed solution of the metallocene compound and methyl aluminum ox (MAO) was added. Followed by stirring at 90 占 폚 for 3 hours. The temperature was lowered to room temperature and then washed with a sufficient amount of toluene to remove the unreacted aluminum compound to prepare a supported metallocene supported catalyst.

1 L of hexane containing 0.5 mmol of triisobutylaluminum (TIBAL) and 1-hexene (50 mL) were introduced into the polymerization reactor, and 30 mg of the metallocene supported catalyst prepared in Example 1 was introduced. Ethylene was continuously added at 80 ° C to maintain gaseous ethylene at 14 atm and hydrogen was polymerized at 3 cc / min for 1 hour. The termination of the polymerization was first stopped by stopping the stirring and then the ethylene was removed by evacuation. The polymerization solvent was filtered to remove most of the solvent and dried in a vacuum oven at 60 캜 for 2 hours to obtain a polyolefin.

[Example 2]

Rac - dimethylsilyl ( indenyl ) ( tetrahydroindenyl ) zirconium dichloride and Rac-dimethylsilyl bis (tetrahydroindenyl) zirconium dichloride Synthesis at 1: 2 ratio

In a glove box, 502 mg (1 eq.) Of Rac-dimethylsilylene bis (indenyl) zirconium dichloride and Pd / C solution were placed in a 100 mL autoclave. The Pd / C solution was prepared by dispersing 11 mg (0.5 mol%) of 5 wt% Pd / C in 25 mL of toluene. After injecting 30 bar of hydrogen into the autoclave, the mixture was stirred at 70 ° C for 15 hours. After completion of the reaction, the solution in the autoclave was filtered, and the resulting transition metal compound crystals were dissolved by using 25 mL of toluene, followed by filtration. The filtered solution was collected and the solvent was removed in vacuo to obtain a mixture of Rac-dimethylsilyl (indenyl) (tetrahydroindenyl) zirconium dichloride and Rac-dimethylsilyl bis (tetrahydroindenyl) zirconium dichloride in 90% yield.

Then, a metallocene supported catalyst and a polyolefin were prepared according to the method of Example 1.

[Example 3]

Rac - dimethylsilyl ( indenyl ) ( tetrahydroindenyl ) zirconium dichloride and Rac-dimethylsilyl bis (tetrahydroindenyl) zirconium dichloride Synthesis at 1: 3 ratio

In a glove box, 502 mg (1 eq.) Of Rac-dimethylsilylene bis (indenyl) zirconium dichloride and Pd / C solution were placed in a 100 mL autoclave. The Pd / C solution was prepared by dispersing 11 mg (0.5 mol%) of 5 wt% Pd / C in 25 mL of toluene. After injecting 30 bar of hydrogen into the autoclave, the mixture was stirred at 70 DEG C for 16 hours. After completion of the reaction, the solution in the autoclave was filtered, and the resulting transition metal compound crystals were dissolved by using 25 mL of toluene, followed by filtration. The filtered solution was collected and the solvent was removed in vacuo to obtain a mixture of Rac-dimethylsilyl (indenyl) (tetrahydroindenyl) zirconium dichloride and Rac-dimethylsilyl bis (tetrahydroindenyl) zirconium dichloride in 90% yield.

[Comparative Example 1]

Rac - dimethylsilyl bis (tetrahydroindenyl) Synthesis of zirconium dichloride

In a glove box, 502 mg (1 eq.) Of Rac-dimethylsilylene bis (indenyl) zirconium dichloride and Pd / C solution were placed in a 100 mL autoclave. The Pd / C solution was prepared by dispersing 59.5 mg (2.5 mol%) of 5 wt% Pd / C in 25 mL of toluene. After injecting 30 bar of hydrogen into the autoclave, the mixture was stirred at 70 캜 for 5 hours. After completion of the reaction, the solution in the autoclave was filtered, and the resulting transition metal compound crystals were dissolved by using 25 mL of toluene, followed by filtration. The filtered solution was collected and the solvent was removed in vacuo to give 0.91 g (90%) of pale green solid compound Rac-dimethylsilyl bis (tetrahydroindenyl) zirconium dichloride. A supported metallocene catalyst was prepared in the same manner as in the above examples except for the metallocene compound.

[Experimental Example]

(MFR), the number average molecular weight (Mn), the weight average molecular weight (Mw), the molecular weight distribution, the number of long chain branches per 10000 total carbon atoms in the polyolefins obtained in Examples 1 to 3 and Comparative Example 1 (LCB / 10 ⁴ C), the number of short chain branches (SCB) / 1000 total carbon atoms per 1000 carbon atoms in total, and the melt strength.

The weight average molecular weight, the molecular weight distribution, and the SCB were measured using GPC-IR. Wherein the MFR is a value obtained by dividing a melt flow index (MFI) by a melt index (MI), the melt flow index being an extrusion amount at a load of 21.6 kg for 10 minutes, the melt index being 10 minutes , Which was measured using a Melt Indexer manufactured by Toyoseki Corporation. The molecular weight distribution is a ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight. The melt strength was measured at a temperature of 190 DEG C and an extrusion rate of 0.32 mm / s using GOTTFERT RG-25.

The number of long chain branches per 10000 total carbon atoms (LCB / 10 ⁴ C) was measured using a Advanced Rheometric Expansion System (ARES) manufactured by TA INSTRUMENT under the conditions of a strain of 10%, a temperature of 190 DEG C, a frequency of 0.1 to 500 rad / sec. < / RTI > Calculation methods are described in the literature ([1] Wood Adams, Paula M., Dealy, John M. Journal of Rheology. 40, (1996); 761-778, [2] Wood Adams, Paula M., Dealy, Macromolecules, 33, (2000), 7481-7488).

First, the complex viscosity (? *) Data obtained at 0.1 to 500 rad / sec was fitted to the Carreau-Yasuda viscosity model of the following equation (1) to determine the zero shear viscosity (? ₀ ).

(Equation 1)

In Equation (1)

η * (ω) is the complex viscosity at frequency ω, and η ₀ The C is the viscous relaxation time, a is the width variable, b is 1-n, and n is an index representing the power law slope.

The data obtained by frequency sweep of η ₀ and atmospheric relaxation and electric field sensor (ARES) are fitted to the Vinogradov fluidity model of the following equation 2 to calculate η * at a frequency of more than 500 rad / sec Respectively.

(Equation 2)

? * is the complex viscosity,? ₀ The Where N is the number of terms, A is the empirical constants obtained through data fitting, i is the tolerance, v is the logarithmic viscosity curve in the power law region, The logarithmic viscosity curve is a slope of the logarithmic viscosity curve. The N and the A are empirical constants for different polymers, and can be obtained by fitting data obtained through ARES.

The value of? * According to the frequency was converted into a molecular weight distribution using the following formula 3, and this was defined as a molecular weight distribution based on the viscosity value (hereinafter referred to as a viscosity MWD).

(Equation 3)

? * is the complex viscosity,? ₀ The M is the reduced molecular weight,? Is an exponent associated with the dependence of the Young's modulus on the weight-average molecular weight, and? In the power law region, Is the slope of the logarithmic viscosity curve, and is the frequency.

The ratio of the M value corresponding to the maximum value of the molecular weight distribution (GPC MWD) obtained from the GPC-IR divided by the M value corresponding to the maximum value of the viscosity MWD has a relationship expressed by the following formula 4, ⁴ C was calculated.

(Equation 4)

The equation (4) when the ratio obtained by dividing the M value corresponding to the maximum of the molecular weight distribution (referred to as GPC MWD) obtained from the GPC-IR with the M value corresponding to the maximum value of the viscosity MWD less than 1, the LCB / 10 ⁴ C If zero, or more IR-GPC molecular weight distribution (MWD GPC ") the value M corresponding to the maximum viscosity ratio LCB / 10 divided by the value M corresponding to the maximum value of the MWD of the resulting C ⁴ from a 1 GPC- Means that the logarithm of the ratio of the M value corresponding to the maximum value of the molecular weight distribution (GPC MWD) obtained from IR divided by the M value corresponding to the maximum value of the viscosity MWD is multiplied by 1.125.

MFR Mn Mw Polydispersity index (PDI) SCB LCB
/ 10 ⁴ C The melt strength (cN) Example 1 76 29,279 191,547 6.542 10.6 0.42 15.833 Example 2 77 27,785 180,480 6.496 11.3 0.51 13.011 Example 3 63 26,826 170,316 6.349 9.5 0.58 10.817 Comparative Example 1 47 27,220 141,684 5.205 9.9 0.58 8

From the results shown in Table 1 and FIG. 1, it can be seen that Examples 1 to 3 produced polyolefins having a broad molecular weight distribution as compared with Comparative Example 1. From the results of Table 1, FIG. 2 and FIG. 3, it can be seen that in Examples, the melt strength of the polymer region was increased and the melt flow index, that is, workability, was improved as compared with Comparative Example. 2, when Rac-dimethylsilyl (4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dichloride is present, the melt strength is high and Rac-dimethylsilyl (4,5,6,7-tetrahydroindenyl) ) zirconium dichloride, the melt strength was increased.

4, the LCB / 10 ⁴ C of Examples 1 to 3 and the melt strength satisfy the following formula (5).

(Equation 5)

^{-31.3 × (LCB / 10 4 C} ) +28 < melt strength (190 ℃) <-31.3 × ( LCB / 10 4 C) +30

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims

carrier;
At least one first metallocene compound among the compounds represented by the following general formula (1) carried on the carrier;
At least one second metallocene compound among compounds represented by the following general formula (2) carried on the carrier; And
A promoter compound carried on the carrier;
The metallocene supported catalyst according to claim 1,

(Formula 1)

(2)
In the above Chemical Formulas 1 and 2,
M is any one of titanium (Ti), zirconium (Zr), and hafnium (Hf);
Q is any one of carbon (C), silicon (Si), germanium (Ge), or tin (Sn);
X is each independently any one of halogen, C _1-10 alkyl group, and C _2-10 alkenyl group;
^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11 and R ¹² are each independently hydrogen, C _1-20 alkyl, C _{3- A} cycloalkyl group, a C _6-14 aryl group, or two adjacent R ⁿ and R ⁿ ⁺¹ (n is 1 to 11) out of R ^m (m is 1 to 12) a C _1-4 alkyl group if forms a substituted or unsubstituted C _1-15 membered ring, two adjacent R to the C _1-4 alkyl group form a substituted or unsubstituted C _1-15 membered ring and ⁿ R ^m other than R ^{n + 1} are each independently selected from hydrogen, a C _1-20 alkyl group, a C _3-6 cycloalkyl group, and a C _6-14 aryl group;
R ¹³ and R ¹⁴ are each independently a C _1-10 alkyl group or a C _6-14 aryl group.

The method according to claim 1,
X is halogen;
Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are independently Is hydrogen, a C _1-20 alkyl group, or a C _6-14 aryl group;
And R ¹³ and R ¹⁴ are each independently a C _1-10 alkyl group or a C _6-14 aryl group.

10. The method of claim 9,
_Wherein the C _1-20 alkyl group and the C _1-15 mono or multicyclic compound are each substituted with one of a nitrogen element (N), an oxygen element (O), or a sulfur element (S).

The method according to claim 1,
Wherein the promoter compound is at least one of a first co-catalyst compound of at least one of the compounds represented by the following formula (3), at least one second co-catalyst compound of the compounds represented by the following formula (4) And a mixture of the second co-catalyst compound. The metallocene supported catalyst according to claim 1,

(Formula 3)

(Formula 4)
In the above Formulas 3 and 4,
Ra is halogen, a C _1-20 alkyl group substituted with halogen, a C _3-6 cycloalkyl group, a C _6-14 aryl group;
n is an integer of 2 or more;
D is aluminum or boron;
Rb to Rd are the same or different from each other and each independently represents a C _1-20 alkyl group, a C _3-6 cycloalkyl group, or a C _6-14 aryl group substituted or unsubstituted with hydrogen, halogen, or halogen.

The method according to claim 1,
The total amount of the supported amount of the first metallocene compound and the supported amount of the second metallocene compound is 0.01 mmol to 1 mmol based on 1 g of the carrier and the supported amount of the promoter compound is 2 mmol to 15 mmol Characterized in that the metallocene supported catalyst.

A process for preparing an olefin polymer characterized by polymerizing olefin monomers in the presence of the metallocene supported catalyst according to any of claims 1 to 5.

The method according to claim 6,
Wherein the monomer of the olefin polymer is at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene and 1-octene.