KR20090063799A - Supported hybrid metallocene catalyst, method for preparing the same, and the method for preparing polyolefin using the supported hybrid metallocene catalyst - Google Patents

Abstract

A supported hybrid metallocene catalyst is provided to polymerize polyolefin with excellent workability and property by being applied to a single polymerization reactor. A supported hybrid metallocene catalyst comprises (a) a first metallocene compound represented by chemical formula 1, (b) a second metallocene compound represented by chemical formula 2, (c) cocatalyst and (d) carrier. A method of manufacturing the supported hybrid metallocene catalyst comprises the steps of: dipping the first metallocene compound in the carrier to prepare a first supported catalyst; contacting the first supported catalyst with the cocatalyst to prepare a second supported catalyst; and dipping the second metallocene compound in the second supported catalyst to prepare the supported catalyst for polyolefin polymerization where the first metallocene compound and the second metallocene compound are dipped in the carrier.

Description

Hybrid supported metallocene catalyst, preparation method thereof and preparation method of polyolefin using hybrid supported metallocene catalyst

The present invention relates to a hybrid supported metallocene catalyst, a method for preparing the same, and a method for producing a polyolefin using the hybrid supported metallocene catalyst.

The metallocene catalyst system comprises a combination of a main catalyst composed mainly of a transition metal compound centered on a Group 4 metal and a cocatalyst composed of an organometallic compound composed mainly of aluminum. A polymer having a narrow molecular weight distribution can be prepared according to the single active site characteristic of such a catalyst.

The molecular weight and molecular weight distribution of polyolefins are important factors in determining the physical properties of polymers and the flow and mechanical properties that affect their processability. In order to make various polyolefin products, it is important to improve melt processability by controlling molecular weight distribution (C.A. Sperat, W. A. Franta, H. W. Starkweather Jr., J. Am. Chem. Soc., 75, 1953, 6127). Especially in the case of polyethylene, enhanced toughness, strength, environmental stress cracking resistance (ESCR) are very important. Therefore, a method of improving the mechanical properties and high processability in the low molecular weight portion of a high molecular weight resin by preparing a polyolefin having bimodal or broad molecular weight distribution has been proposed.

Polyolefins having bimodal and broad molecular weight distributions are polymers containing both average molecular weights of low molecular weight and high molecular weight. In the past, many attempts have been made to synthesize a polymer having such a molecular weight distribution.

In the first example, a method of preparing polyolefins having different molecular weights through post-reaction or melt mixing has been devised (US Pat. No. 4,461,873). However, such physical mixing is not only expensive to produce additional production costs, but also contains a large amount of gel due to the compatibility of the two polymers to be mixed, it is impossible to use for applications such as film and container.

In the second example, two or more multistage reactors are introduced to change the reaction conditions such as hydrogen and comonomer injection amount in each reactor to induce different molecular weights to produce polyethylene having a broad molecular weight distribution or bimodal molecular weight distribution as desired. (CA Sperat, WA Franta, HW Starkweather Jr., J. Am. Chem. Soc., 75, 1953 6127, N. Kurod a, Y. Miyazaki, K. Matsumura, K. Jubo, M. Miyashi and T. Horie, 1979 Ger. 28,856,548). Such a method can solve problems such as gel generation as described above, but it is not preferable in terms of economics because of difficulty in operation and high operation cost.

The third example is a more useful strategy than the two examples above, in which two different catalysts are mixed in a single reactor or two or more catalysts are introduced into one carrier to polymerize.

Conventional methods for controlling the molecular weight distribution of polymers generally form complexes of multiple metals using two or more different metals when preparing a catalyst, and the molecular weight distribution is controlled by manipulating the active site of each metal catalyst component. To improve. Most patents and documents refer to the hybrid support of a metallocene compound and a Ziegler-Natta series of titanium metal compounds in one carrier (US Pat. No. 6,444,605 B1, US Pat. No. 6,399,531 B1, US Pat. No. 6,417,129). B2, US Pat. No. 6,399,723 B1, US Pat. No. 5,614,456, Korean Unexamined Patent Publication No. 1988-045993, Korean Unexamined Patent Publication No. 1998-045994, Korean Unexamined Patent Publication No. 1999-022334 2000-0042620).

The polyolefin prepared by this method has a limitation in the physical properties of the polymer due to the specific polymerization characteristics of Ziegler-Natta and metallocene catalyst. For example, metallocene catalysts have various modifications to the stereoregularity, copolymerization properties, molecular weight, crystallinity, etc. of the resulting polymer by modifying the ligand structure of the catalyst or controlling the polymerization conditions compared to the Ziegler-Natta catalyst. It has the characteristics to make it possible.

Therefore, it is possible to produce a polyolefin having desired properties such as molecular weight distribution, stereoregularity, copolymerization properties by using a mixture of metallocene catalysts having specific properties with each other.

As described above, the production of polyolefins having bimodal or broad molecular weight distributions using metallocene catalysts is generally proposed using two different metallocene catalyst systems having different growth rates and polymerization stop rate constants. JA Ewen, Stud., Surf.Sci.amp; Catal. Vol. 1986 25, US Pat. No. 6,384,161 B1).

In addition, the Kaminsky group of professors in Germany carried out ethylene polymerization under two different homogeneous metallocene catalysts, including the Cp ₂ ZrCl ₂ -Cp ₂ HfCl ₂ -MAO catalyst system, resulting in a uniform molecular weight distribution (Mw / Mn). It has been reported to be 4.1 to 10.0 wider than the 1.9 to 2.3 of the system (A. Ahlers, W. Kaminsky, Makromol. Chem., Rapid Commun., 9, 1988 457).

Meanwhile, commercial processes for producing polyolefins may be classified into high pressure processes, solution processes, slurry processes, and gas phase processes. With the development of metallocene catalysts, efforts are being made to produce new products using these processes as they are and changing only catalysts. Processes most commonly applied to metallocene catalysts to date include solution processes, gas phase processes, slurry processes, and the like. In the gas phase process or slurry process, the apparent density of the polymer must be controlled to increase the yield per unit volume of the reactor, and the problem of fouling caused by the polymer being entangled on the wall of the reactor for continuous operation is to be solved. Is holding. The most widely used method for increasing the apparent density and solving the fouling problem is to immobilize a homogeneous metallocene catalyst on a solid carrier such as silica, alumina and the like.

In the case of silica, which is most used among these carriers, drying at a high temperature removes the hydroxyl groups on the surface with water to produce siloxane groups as shown in Scheme 1 below. When the drying temperature is 200 to 500 ° C, hydroxyl group (-OH) which can be easily removed is reversibly removed with water to form a less reactive siloxane group, but when the drying temperature is above 600 ° C, the hydroxyl group is difficult to remove. It has been reported that until the removal to the water by force, the ring strain is large and highly reactive siloxane groups (IS. Chuang and GE Maciel, Journal of American Chemical Society, 118, 1996, 401). As such, highly reactive siloxane groups formed by drying at 600 ° C. or higher have been reported to react with alkoxy silane groups as in Scheme 1 (J. Blmel, Journal of American Chemical Society, 117, 1995, 2112; LH Dubois, Journal of American Chemical Society, 115, 1993, 1190).

(Scheme 1)

In the reaction scheme, the left side is general silica, the center is silica having a highly reactive siloxane group formed by drying at 600 ° C. or higher, and the right side is silica to which an alkoxy silane group is reacted and connected.

However, in the above documents and patents, only polymerization by hybridization of two catalysts is proposed, and only mention of organometallic compounds selection and homogeneous catalyst system for controlling molecular weight distribution, polymer properties, etc. There is no specificity in the production of the supported catalyst applicable to the slurry process.

The present invention is a hybrid supported metallocene catalyst prepared by sequentially adding two different metallocene compounds, a preparation method thereof, and a polyolefin having improved processability and physical properties by applying the hybrid supported metallocene catalyst to a single polymerization reactor. Its purpose is to provide a manufacturing method that can be made.

The present invention provides a hybrid supported metallocene catalyst comprising (a) a first metallocene compound, (b) a second metallocene compound, (c) a promoter and (d) a carrier.

In addition, the present invention comprises the steps of (A) supporting the first metallocene compound on the carrier to prepare a first supported catalyst; (B) contacting the cocatalyst to the first supported catalyst of step (A) to prepare an activated first supported catalyst; And (C) supporting a second metallocene compound on the activated first supported catalyst of step B) to prepare a supported catalyst for polyolefin polymerization in which the first metallocene compound and the second metallocene compound are supported on a carrier. It provides a method for producing a hybrid supported metallocene catalyst comprising the step of.

In addition, the present invention provides a polymerization method of a polyolefin comprising the step of polymerizing an olefin monomer using the hybrid supported metallocene catalyst.

The hybrid supported metallocene catalyst according to the present invention may be prepared by adding two different metallocene compounds sequentially and then applying a single polymerization reactor to polymerize a polyolefin having improved processability and physical properties for each application.

The hybrid supported metallocene catalyst according to the present invention includes (a) a first metallocene compound represented by the following Chemical Formula 1, (b) a second metallocene compound represented by the following Chemical Formula 2, (c) a cocatalyst and ( d) comprising a carrier:

In Chemical Formula 1,

M is a Group 4 transition metal;

(C ₅ R ^a ) and (C ₅ R ^b ) may be the same as or different from each other, and each independently selected from hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl and hydrocarbyl Cyclopentadienyl ligand, which is a metalloid of a group 14 metal substituted with one or more, or a cyclopentadienyl ligand, in which two adjacent carbon atoms of C ₅ are connected by hydrocarbyl to form one or more rings having 4 to 16 carbon atoms;

Q is selected from halogen, alkyl, alkenyl, aryl, alkylaryl, arylalkyl and alkylidene;

p is 0 or 1;

In Chemical Formula 2,

R1 to R7 may be the same or different from each other, and each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl or arylalkyl having 7 to 20 carbon atoms And a metalloid radical of a Group 14 metal substituted with at least one selected from hydrocarbyl, an alkoxy radical having 1 to 20 carbon atoms, an aryloxy radical having 6 to 20 carbon atoms, a silyl radical and an amino radical;

Two or more of them may be connected to each other by alkylidene including alkyl having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms to form an aliphatic or aromatic ring;

CY1 is a substituted or unsubstituted aliphatic or aromatic ring;

The substituent substituted at CY1 is selected from the group consisting of hydrogen, a halogen radical, an alkyl radical having 1 to 20 carbon atoms and an aryl radical having 6 to 20 carbon atoms, and when there are a plurality of substituents, at least two substituents from each other are substituted with each other. Can be joined to form an aliphatic or aromatic ring;

M is a Group 4 transition metal;

N is nitrogen;

Q1 and Q2 are the same as or different from each other, and are independently a halogen radical, an alkyl amido radical having 1 to 20 carbon atoms, an aryl amido radical having 6 to 20 carbon atoms, an alkyl radical having 1 to 20 carbon atoms, and an alkenyl having 2 to 20 carbon atoms. Radical, an aryl radical having 6 to 20 carbon atoms, an alkylaryl or arylalkyl radical having 7 to 20 carbon atoms, and an alkylidene radical having 1 to 20 carbon atoms.

In this case, at least one hydrogen present in R ^a and R ^b of the first metallocene compound represented by Chemical Formula 1 may be substituted with any one or more of radicals represented by Chemical Formula a, Chemical Formula b, and Chemical Formula c. have:

[Formula a]

In Chemical Formula a,

Z is oxygen or sulfur;

R and R ′ may be the same or different from each other, and each independently selected from hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl and arylalkenyl, and two R ′ are linked to each other to form a ring Can form;

G is alkoxy, aryloxy, alkylthio, arylthio, phenyl and substituted phenyl and can be linked to R 'to form a ring;

If Z is sulfur, G is necessarily alkoxy or aryloxy;

If G is alkylthio, arylthio, phenyl, or substituted phenyl, Z is necessarily oxygen;

[Formula b]

In Chemical Formula b,

Z is oxygen or sulfur and at least one of the two Z is an oxygen atom;

R and R '' may be the same or different from each other, and are each independently hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl;

R may be linked to R ″ to form a ring;

Two R ″ may be linked to each other to form a ring unless they are a hydrogen radical;

[Formula c]

In Chemical Formula c,

R and R '' ', which may be the same or different from each other, are each independently hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl;

Two adjacent R ′'s may be linked to each other to form a ring;

If at least one of R is a hydrogen radical, then R '' 'are not all hydrogen, and if at least one of R' '' is hydrogen, then R is not all hydrogen.

Specifically, the second metallocene compound represented by Formula 2 includes a compound represented by Formula 3 below:

In Chemical Formula 3,

R1 to R13 is the same as the definition of R1 to R7 of Formula 1,

M, N, Q1 and Q2 are the same as defined in Chemical Formula 1.

Specifically, the second metallocene compound represented by Chemical Formula 2 includes the following structures.

In the above formulas,

R1 to R14 and Q1 and Q2 are as defined in the formula (1).

In the second metallocene compound of Chemical Formula 2, the metal site is connected by a cyclopentadienyl ligand in which an amido group is linked to a phenylene bridge in a ring form, thereby structurally having a narrow Cp-MN angle, and a monomer. The Q1-M-Q2 angle approaching is characterized by keeping wide. In addition, unlike the CGC structure connected by the silicon bridge, in the compound structure represented by Formula 2, Cp, phenylene bridge, and nitrogen are more stable and rigid five-membered ring structure together with metal sites by ring-shaped bonds. consist of. That is, the nitrogen atom of the amido group is connected to the phenylene bridge by two bonds in the form of a ring to have a more complex complex structure.

Therefore, when the second metallocene compound is activated by reacting with a promoter such as methylaluminoxane and then applied to olefin polymerization, a polyolefin having characteristics such as high activity, high molecular weight and high copolymerization even at high polymerization temperature is produced. It is possible to. In particular, due to the structural characteristics of the catalyst, it is possible to prepare ultra low density polyolefin copolymers having a density of less than 0.910 g / cc because not only unsupported linear low density polyethylene having a density of 0.910 to 0.930 g / cc but also a large amount of alpha-olefin can be introduced. Can be.

In addition, various substituents may be introduced into the cyclopentadienyl ring and the quinoline ring, which ultimately control the structure and physical properties of the polyolefin produced by easily controlling the electronic and three-dimensional environment around the metal. The compound of Formula 2 is preferably used to prepare a catalyst for polymerization of olefin monomers, but is not limited thereto. In addition, the compound of Formula 2 may be applied to any field in which the transition metal compound may be used.

The (c) promoter included in the hybrid supported metallocene catalyst according to the present invention preferably includes a metal compound containing a Group 13 metal, for example, Al, Ga, In, Tl, etc. in the periodic table. More preferably, the compound represented by the formula (4) is included. As the cocatalyst (c), a cocatalyst used when polymerizing an olefin under a general metallocene catalyst may be used. When the promoter is supported on the carrier, a bond is generated between the hydroxyl group on the carrier and the Group 13 metal.

-[Al (R15) -O] a-

In Chemical Formula 4,

R 15 may be the same as or different from each other, and each independently represent a halogen or a hydrocarbyl having 1 to 20 carbon atoms unsubstituted or substituted with halogen, and a is an integer of 2 or more.

Specifically, the compound represented by Chemical Formula 4 includes methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane.

The carrier (d) included in the hybrid supported metallocene catalyst according to the present invention contains a hydroxyl group on the surface, and the amount of the hydroxyl group on the surface of the carrier (d) is preferably 0.1 to 10 mmol / g, and 0.5 to More preferred is 1 mmol / g. The amount of the hydroxyl group on the surface of the (d) carrier may be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxy group is less than 0.1 mmol / g, the reaction site with the promoter decreases, and if the amount of the hydroxy group exceeds 10 mmol / g, it may be due to moisture other than the hydroxy group present on the surface of the silica particles. Not.

In addition, the d) carrier preferably contains a highly reactive hydroxyl group and siloxane group on the surface. For example, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used as the carrier, and these are usually oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Carbonate, sulfate, and nitrate components.

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. When the drying temperature of the carrier is less than 200 ° C., the moisture is too much to react with the surface of the carrier and the promoter reacts. When the carrier temperature exceeds 800 ° C., the pores on the surface of the carrier are combined to reduce the surface area, and more hydroxyl groups are present on the surface. It is not preferable because it disappears and only siloxane groups remain and the reaction site with the promoter decreases.

In addition, the hybrid supported metallocene catalyst of the present invention preferably contains [group 13 metal] / [transition metal] in a molar ratio of 1 to 10,000, more preferably 1 to 1,000, and most preferably 10 to 100. Do. If the molar ratio is less than 1, the content of the Group 13 metal is too small, so that almost no catalytically active species is made, and the activity is very low. If the molar ratio exceeds 10,000, the Group 13 metal may act as a catalyst poison.

The method for preparing a mixed supported metallocene catalyst according to the present invention includes the steps of (A) supporting a first metallocene compound on a carrier to prepare a first supported catalyst; (B) preparing a second supported catalyst by contacting a cocatalyst to the first supported catalyst of step (A); And (C) supporting a second metallocene compound on the second supported catalyst of step (B) to prepare a supported catalyst for polyolefin polymerization in which the first metallocene compound and the second metallocene compound are supported on a carrier. Characterized in that it comprises a step.

A solvent may be used as the contact reaction between the first metallocene compound and the carrier, or may be reacted without a solvent. Solvents that can be used include aliphatic hydrocarbon solvents such as hexane and pentane, aromatic hydrocarbon solvents such as toluene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, ether solvents such as diethyl ether and THF, acetone and ethyl Mostly organic solvents such as acetate, and hexane, heptane, toluene, or dichloromethane are preferred.

The reaction temperature is possible up to -30 to 150 ℃, preferably from room temperature to 100 ℃, more preferably 70 to 90 ℃. The reacted supported catalyst can be used by filtering or removing the reaction solvent by distillation under reduced pressure, and, if necessary, by using a Soxhlet filter with an aromatic hydrocarbon such as toluene.

The first supported catalyst of the present invention is a supported catalyst which can be used as it is when polymerizing olefins. The hybrid supported metallocene catalyst of the present invention further supports a second metallocene compound, which is an organometallic compound which can be derived from a high molecular weight olefin, on the first supported catalyst.

The method of preparing the hybrid supported metallocene catalyst by supporting the second metallocene compound on the first supported catalyst can be divided into two methods.

The first method is to prepare a second supported catalyst by activating the first supported catalyst as a cocatalyst, and then contacting the second supported catalyst with the second metallocene compound in a solvent to carry out the second supported metallocene compound. It is supported on the catalyst.

In the second method, the activated second metallocene compound is prepared by activating the second metallocene compound with a cocatalyst, and then the activated second metallocene compound and the first supported catalyst are brought into contact with each other under a solvent. The metallocene compound is supported on the first supported catalyst.

Polymerization method of the polyolefin according to the invention is characterized in that it comprises the step of polymerizing the olefin monomer using the hybrid supported metallocene catalyst.

As another exemplary embodiment of the present invention, a method for preparing a polyolefin may include preparing a hybrid supported metallocene catalyst according to the present invention; And polymerizing an olefinic monomer under the hybrid supported metallocene catalyst.

In the method for producing a polyolefin according to the present invention, the hybrid supported metallocene catalyst used for the polymerization of the olefinic monomer may be used as the olefinic monomer polymerization. In addition, the catalyst may be prepared by using a prepolymerized catalyst by contact reaction with the olefinic monomer. For example, the catalyst may be separately contacted with an olefinic monomer such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, and the like. It can also be prepared and used as a catalyst.

The olefinic monomer polymerizable using the hybrid supported metallocene catalyst may be ethylene, alpha-olefin, cyclic olefin, diene olefin or triene olefin having two or more double bonds.

Specific examples of the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, norbonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene And 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like, and these monomers may be mixed and copolymerized.

Under the hybrid supported metallocene catalyst, in the step of polymerizing the olefinic monomer, it is preferable to polymerize the olefinic monomer at a temperature of 50 to 150 ° C.

The olefin polymerization process using the supported catalyst for olefin polymerization can use all of a slurry, a gas phase process, and a mixing process of a slurry and a gas phase, and a slurry or a gas phase process is preferable.

In the method for preparing polyolefin according to the present invention, the hybrid supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof, such as toluene and benzene. It may be dissolved or diluted in an aromatic hydrocarbon solvent, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, or chlorobenzene. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter.

Hereinafter, the present invention will be described in detail through embodiments of the present invention. However, embodiments of the present invention may be modified in various forms, the scope of the present invention should not be construed in a way that is limited by the embodiments described below. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

Preparation Example 1 Preparation of First Metallocene Catalyst-Synthesis of [tBu-O- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ )

Using 6-chlorohexanol, tBu-O- (CH ₂ ) ₆ -Cl was prepared by the method shown in Tetrahedron Lett. 2951 (1988), and NaCp was reacted to tBu- O- (CH ₂ ) ₆ -C ₅ H _{5 was} obtained (yield 60%, bp 80 ° C./0.1 mmHg). Zirconium was added in the same manner to the above to obtain tBu-O- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ (yield 92%).

1 H NMR (300 MHz, CDCl ₃ ): 6.28 (t, J = 2.6 Hz, 2H), 6.19 (t, J = 2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J = 8 Hz), 1.7-1.3 (m, 8H), 1.17 (s, 9H);

13 C NMR (CDCl ₃ ): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

Preparation Example 2 Preparation of Second Metallocene Catalyst-[(6-methyl-1,2,3,4-tetrahydroquinolin-8-yl) trimethylcyclopentadienyl--η ⁵ , κ-N] titanium dichloride compound

A solution of 6-methyl-1,2,3,4-tetrahydroquinoline (1.16 g, 7.90 mmol) in carbon tetrachloride (4 mL) was cooled to -20 ° C. N-bromosuccinimide (1.41 g, 7.90 mml) solid was slowly added thereto, and the reaction temperature was raised to room temperature for 5 hours. The resulting compound was separated by column chromatography using MC and hexane (v: v = 1: 1) solvent to obtain a pale yellow oil, 8-bromo-1,2,3,4-tetrahydro-6-methyl. Quinoline was obtained (0.71 g, 40%).

2,3-dimethyl-5-oxocyclopent-1-enylboronic acid (1.27 g, 8.26 mmol), Na ₂ CO ₃ (1.25 g, 11.8 mmol), Pd (PPh ₃ ) ₄ (0.182 g, 0.157 mmol) And degassed DME (dimethylether) (21 mL) and distilled water in a mixture of the above-described synthesized 8-bromo-1,2,3,4-tetrahydro-6-methylquinoline (7.87 mmol). water) (7 mL) was added and the solution obtained was heated at 95 ° C. overnight. The reaction solution was cooled to room temperature and extracted twice with ethyl acetate solvent (50 mL). The obtained compound was separated by column chromatography using hexane and ethyl acetate (2: 1) solvent to give a pale yellow solid, 5- (3,4-dimethyl-2-cyclopenten-l-one) -7-methyl-. 1,2,3,4-tetrahydroquinoline was obtained. (90%).

Anhydrous La (OTf) ₃ (21.4 mmol) and TFH (24 mL) solutions were cooled to −78 ° C., followed by addition of MeLi (13.4 mL, 21.4 mmol) for 1 hour. To the synthesized 5- (3,4-dimethyl-2-cyclopenten-l-one) -7-methyl-1,2,3,4-tetrahydroquinoline (7.13 mmol) compound was added thereto at -78 deg. The reaction was carried out for 2 hours, and extracted with water and an acetate solvent. The organic layer obtained was shaken with HCl (2 N, 20 mL) for 2 minutes, neutralized with aqueous NaHCO ₃ solution (20 mL) and dried over MgSO ₄ . The obtained compound was separated by column chromatography using hexane and ethyl acetate solvent (10: 1) to give pale yellow solid 1,2,3,4-tetrahydro-6-methyl-8- (2,3,5 -Trimethylcyclopenta-1,3-dienyl) quinoline ligand (40%).

1,2,3,4-tetrahydro-6-methyl-8- (2,3,5-trimethylcyclopenta-1,3-dienyl) quinoline ligand (0.696 mmol) and Ti (NMe ₂ ) _{4 obtained above} The compound (0.156 g, 0.696 mmol) was dissolved in toluene (2 mL), and the reaction solution was reacted at 80 ° C. for 2 days, and all the solvents were removed to obtain a red solid compound. (100%)

Toluene (2 mL) was added to the red solid compound obtained above, Me ₂ SiCl ₂ (0.269 g, 2.09 mmol) was added at room temperature, and the reaction solution was reacted for about 4 hours. The obtained compound was recrystallized at -30 ° C under hexanes to give a pure red solid (0.183 g, 66%).

¹ H NMR (C ₆ D ₆ ): δ 1.36-1.44 (m, 2H, CH ₂ CH ₂ CH ₂ ), 1.76 (s, 3H, CH ₃ ), 1.85 (s, 3H, CH ₃ ), 2.07 (s , 3H, CH ₃ ), 2.18 (s, 3H, CH ₃ ), 2.12 (t, J = 4 Hz, 2H, CH ₂ ), 4.50-4.70 (m, 2H, N-CH ₂ ), 6.02 (s, 1H , Cp-H), 6.59 (s, 1H, C ₆ H ₂ ), 6.78 (s, 1H, C ₆ H ₂ ) ppm.

¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 12.76, 14.87, 15.06, 21.14, 22.39, 26.32, 54.18, 117.49, 120.40, 126.98, 129.53, 130.96, 131.05, 133.19, 143.22, 143.60, 160.82 ppm. Anal. Calc. (C ₁₈ H ₂₁ Cl ₂ NTi): C, 58.41; H, 5.72; N, 3.78%. Found: C, 58.19; H, 5.93; N, 3.89%.

Comparative Preparation Example 1 Preparation of Second Metallocene Catalyst-(Synthesis of tBu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) ZrCl ₂ )

Solution of tBu-O- (CH ₂ ) ₆ MgCl (Grignard) reagent (0.14 mol) from reaction between tBu-O- (CH ₂ ) ₆ Cl compound and Mg (0) in diethyl ether (Et ₂ O) solvent ) To this was added MeSiCl ₃ compound (24.7 mL, 0.21 mol) at -100 ° C, and stirred at room temperature for 3 hours or more, and the filtered solution was dried in vacuo to give a compound of tBu-O- (CH ₂ ) ₆ SiMeCl ₂ . Was obtained (yield 84%). Fluorenyllithium (4.82 g, 0.028 mol) / hexane (150 in a solution of tBu-O- (CH ₂ ) ₆ SiMeCl ₂ (7.7 g, 0.028 mol) dissolved in hexane (50 mL) at -78 ° C. Ml) solution was added slowly over 2 hours. The white precipitate (LiCl) was filtered off and the desired product was extracted with hexane to vacuum dry all volatiles to give (tBu-O- (CH ₂ ) ₆ ) SiMe (9-C ₁₃ H ₁₀ ) as a pale yellow oil. Obtained (yield 99%).

THF solvent (50 mL) was added thereto, and reacted with a C ₅ H ₅ Li (2.0 g, 0.028 mol) / THF (50 mL) solution at room temperature for 3 hours or more, and all volatiles were vacuum dried and extracted with hexane. (TBu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₅ ) (9-C ₁₃ H ₁₀ ) compound was obtained as a final ligand (yield 95%). The structure of the ligand was confirmed by 1 H NMR.

1 H NMR (400 MHz, CDCl ₃ ): 1.17, 1.15 (t-BuO, 9H, s), -0.15, -0.36 (MeSi, 3H, s), 0.35, 0.27 (CH ₂ , 2H, m), 0.60, 0.70 (CH ₂ , 2H, m), 1.40, 1.26 (CH ₂ , 4H, m), 1.16, 1.12 (CH ₂ , 2H, m), 3.26 (tBuOCH ₂ , 2H, t, 3JH-H = 7 Hz), 2.68 (methyleneCpH, 2H, brs), 6.60, 6.52, 6.10 (CpH, 3H, brs), 4.10, 4.00 (FluH, 1H, s), 7.86 (FluH, 2H, m), 7.78 (FluH, 1H, m), 7.53 (FluH, 1H, m), 7.43-7.22 (FluH, 4H, m)

In addition, the solution was added to a solution of (tBu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₅ ) (9-C ₁₃ H ₁₀ ) (12 g, 0.028 mol) / THF (100 mol) at -78 ° C. Add 2 equivalents of n-BuLi and react for at least 4 hours while raising to room temperature to form (tBu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₅ Li) (9-C ₁₃ H) in the form of an orange solid. ₁₀ Li) was obtained (yield 81%). In addition, a dilithium salt (2.0 g, 4.5 mmol) / ether was added to a suspension solution of ZrCl ₄ (1.05 g, 4.50 mmol) / ether (30 mL) at -78 ° C. , 30 ml) was added slowly and further reacted at room temperature for 3 hours. All volatiles were dried in vacuo and filtered off by adding dichloromethane solvent to the oily liquid material obtained. The filtered solution was dried in vacuo and hexane was added to induce a precipitate. The obtained precipitate was washed several times with hexane to give racemic- (tBu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) ZrCl ₂ compound as a red solid. Obtained (yield 54%).

1 H NMR (400 MHz, CDCl ₃ ): 1.19 (t-BuO, 9H, s), 1.13 (MeSi, 3H, s), 1.79 (CH ₂ , 4H, m), 1.60 (CH ₂ , 4H, m), 1.48 (CH ₂ , 2H, m), 3.35 (tBuOCH ₂ , 2H, t, 3JH-H = 7 Hz), 6.61 (CpH, 2H, t, 3JH-H = 3 Hz), 5.76 (CpH, 2H, d, 3JH- H = 3 Hz), 8.13 (FluH, 1H, m), 7.83 (FluH, 1H, m), 7.78 (FluH, 1H, m), 7.65 (FluH, 1H, m), 7.54 (FluH, 1H, m), 7.30 (FluH, 2H, m), 7.06 (FluH, 1H, m)

13 C NMR (400 MHz, CDCl ₃ ): 27.5 (Me ₃ CO, q, 1 JC-H = 124 Hz), -3.3 (MeSi, q, 1 JC-H = 121 Hz), 64.6, 66.7, 72.4, 103.3, 127.6, 128.4, 129.0 (7C, s), 61.4 (Me ₃ COCH 2, t, 1JC-H = 135 Hz), 14.5 (ipsoSiCH ₂ , t, 1JC-H = 122 Hz), 33.1, 30.4, 25.9, 22.7 (4C, t, 1JC -H = 119 Hz), 110.7, 111.4, 125.0, 125.1, 128.8, 128.1, 126.5, 125.9, 125.3, 125.1, 125.0, 123.8 (FluC and CpC, 12C, d, 1JC-H = 171 Hz, 3JC-H = 10 Hz)

Examples 1 to 6 Preparation of Hybrid Supported Catalysts

(Carrier manufacturing)

Silica (SYLOPOL 948 from Grace Davison) was dehydrated under vacuum at a temperature of 800 ° C. for 15 hours.

(Production of the First Supported Catalyst)

1.0 g of the prepared silica was put in a glass reactor, 10 ml of toluene was added thereto, and 10 ml of a hexane solution in which the first metallocene compound synthesized in Preparation Example 1 was dissolved in the amount shown in Table 1 below was added thereto. The reaction was stirred at 90 ° C. for 2 hours. After the reaction was completed, the stirring was stopped, the toluene was separated and removed, and then washed three times with 20 ml of toluene solution, and then the pressure was removed to remove the toluene to obtain a first supported catalyst as a solid powder.

(Preparation of Second Supported Catalyst-Activation of First Supported Catalyst)

A methylaluminoxane (MAO) solution containing 12 mmol aluminum in a toluene solution was added to each of the first supported catalysts on which the first metallocene compound was loaded, stirred at 40 ° C., and reacted slowly to a sufficient amount of toluene. After washing to remove the unreacted aluminum compound, toluene was removed under reduced pressure at 50 ℃ to prepare a second supported catalyst as a solid. The solid thus prepared may be used as a catalyst for olefin polymerization without further treatment.

(Production of Hybrid Supported Metallocene Catalyst)

In order to prepare a hybrid supported metallocene catalyst, the amount of the second metallocene compound prepared in Preparation Example 2 in the second supported catalyst on which the first metallocene compound and the promoter are supported is shown in Table 1 below. Toluene solution dissolved in was added thereto, stirred at 40 ° C. for reaction, washed with a sufficient amount of toluene, dried under vacuum, and a mixed supported metallocene catalyst as a solid powder was obtained.

The hybrid supported metallocene catalyst prepared as described above may be used as a final catalyst. Alternatively, 30 psig of ethylene may be added for 2 minutes and prepolymerized at room temperature for 1 hour before use. In order to show a more effective supported catalyst, this prepolymerization was not performed in this embodiment.

<Comparative Examples 1 and 2>

1.0 g of the prepared silica was put in a glass reactor, 10 ml of toluene was added thereto, and 10 ml of a hexane solution in which the first metallocene compound synthesized in Preparation Example 1 was dissolved in the amount shown in Table 1 below was added thereto. The reaction was stirred at 90 ° C. for 2 hours. After the reaction was completed, the stirring was stopped, the toluene was separated by layers, and then washed three times with 20 ml of toluene solution, and then the pressure was removed to remove the toluene, thereby obtaining a catalyst as a solid powder.

<Comparative Examples 3 and 4>

1.0 g of the prepared silica was added to a glass reactor, to which a methylaluminoxane (MAO) solution containing 12 mmol aluminum was added to the toluene solution, and stirred at 40 ° C. for a slow reaction, followed by washing with a sufficient amount of toluene to react. After removing the aluminum compound, the toluene was removed under reduced pressure at 50 ° C. to prepare a supported catalyst as a solid.

Toluene solution in which the second metallocene compound prepared in Preparation Example 2 was dissolved in the amount shown in Table 1 was added to the supported catalyst, stirred at 40 ° C. for reaction, washed with a sufficient amount of toluene, and dried in vacuo. A catalyst which is a solid powder was obtained.

<Comparative Examples 5 to 10>

A hybrid supported catalyst was prepared by the same method as the method for preparing the hybrid supported catalyst of Examples 1 to 6, except that the catalyst prepared in Comparative Preparation Example 1 was used instead of the second metallocene catalyst.

Experimental Example 1 Semi-Batch Ethylene Polymerization

50 mg of each of the supported catalysts prepared in Examples 1 to 6 and Comparative Examples 1 to 6 were quantified in a dry box, respectively, placed in a 50 ml glass bottle, sealed with a rubber diaphragm, and taken out from the dry box. The catalyst was prepared. The polymerization was carried out in a 2 L metal alloy reactor with temperature control and a high pressure equipped with a mechanical stirrer.

1 liter of hexane and 1-hexene (20 ml) containing 1.0 mmol triethylaluminum were introduced into the reactor, and each of the supported catalysts was introduced into the reactor without air contacting, and then at 80 ° C. The gas ethylene monomer was polymerized for 1 hour with continuous addition of pressure at 9 Kgf / cm 2. Termination of the polymerization was completed by first stopping stirring and then evacuating and removing ethylene.

The polymer obtained therefrom was filtered to remove most of the polymerization solvent and then dried in an 80 ° C. vacuum oven for 4 hours.

Ethylene polymerization activity, melt index, apparent density, molecular weight and molecular weight distribution of each of the catalysts prepared above are shown in Table 2 below.

division First metallocene catalyst Promoter Second metallocene catalyst 1/2 metallocene loading (g / g in g-SiO ₂ ) Example 1 Preparation Example 1 MAO Preparation Example 2 0.05 / 0.05 Example 2 Preparation Example 1 MAO Preparation Example 2 0.05 / 0.1 Example 3 Preparation Example 1 MAO Preparation Example 2 0.05 / 0.2 Example 4 Preparation Example 1 MAO Preparation Example 2 0.1 / 0.05 Example 5 Preparation Example 1 MAO Preparation Example 2 0.1 / 0.1 Example 6 Preparation Example 1 MAO Preparation Example 2 0.1 / 0.2 Comparative Example 1 Preparation Example 1 MAO - 0.05 / 0.00 Comparative Example 2 Preparation Example 1 MAO - 0.1 / 0.00 Comparative Example 3 - MAO Preparation Example 2 0.0 / 0.05 Comparative Example 4 - MAO Preparation Example 2 0.0 / 0.1 Comparative Example 5 Preparation Example 1 MAO Comparative Production Example 1 0.05 / 0.05 Comparative Example 6 Preparation Example 1 MAO Comparative Production Example 1 0.05 / 0.1 Comparative Example 7 Preparation Example 1 MAO Comparative Production Example 1 0.05 / 0.2 Comparative Example 8 Preparation Example 1 MAO Comparative Production Example 1 0.1 / 0.05 Comparative Example 9 Preparation Example 1 MAO Comparative Production Example 1 0.1 / 0.1 Comparative Example 10 Preparation Example 1 MAO Comparative Production Example 1 0.1 / 0.2

division Active (g) Apparent density (g / cc) I ₂₁ (g / 10min) Mw (ⅹ10 ³ ) PDI Example 1 2089 0.40 2.7 278 5.2 Example 2 2242 0.41 2.1 320 5.5 Example 3 2368 0.41 1.5 371 5.8 Example 4 4021 0.42 3.4 174 5.7 Example 5 4177 0.40 3.0 192 5.8 Example 6 4300 0.41 2.7 249 6.2 Comparative Example 1 1753 0.34 6.7 112 5.6 Comparative Example 2 3220 0.31 7.6 90 7.0 Comparative Example 3 872 0.37 0.7 451 3.2 Comparative Example 4 1346 0.36 1.0 406 3.6 Comparative Example 5 1735 0.42 3.2 210 5.8 Comparative Example 6 1858 0.41 3.0 236 5.3 Comparative Example 7 1847 0.42 2.8 258 5.8 Comparative Example 8 3343 0.40 4.7 148 6.9 Comparative Example 9 3577 0.41 4.4 175 6.9 Comparative Example 10 3707 0.42 3.5 194 7.5

When ethylene polymerization was carried out using the respective supported catalysts prepared according to the present embodiment as described above, there was no fouling phenomenon in which the reactor wall or polymer particles were entangled with each other, and the apparent density was excellent from 0.40 to 0.41 g / cc. Do. In addition, the weight average molecular weight (Mw) can be adjusted to 150,000 to 400,000, the molecular weight distribution (PDI) can also maintain a five point range. In Comparative Examples 1 to 4, only one of each of the first metallocene catalyst and the second metallocene catalyst system used in the examples was supported, and as shown above, when only each catalyst was used, the activity was high. Due to the low molecular weight, the physical properties are weak, or the molecular weight is high and the physical properties are strong, but the activity is low, so commercial value is low.

However, when two catalysts, the first metallocene catalyst and the second metallocene catalyst, are supported by using the hybrid supported catalyst technology proposed in the present invention, the desired molecular weight and physical properties can be maximized while maintaining the unique characteristics of the catalyst. Can be maintained. In addition, the different types of chains produced by the first metallocene catalyst and the second metallocene catalyst are entangled so that the apparent density of the resulting polymers is much higher than when each polymerized.

The second metallocene catalyst used in the above embodiment has a characteristic of making PE having high activity and low molecular weight, which is higher than that of the conventionally known catalyst system (Comparative Preparation Example 1). Therefore, in the case of the polymerization examples 1 to 6 using the hybrid supported catalyst made using the same, polymers having higher activity and lower density and higher molecular weight can be obtained than those of the comparative examples 5 to 10. In addition, by adjusting the ratio of the first metallocene catalyst and the second metallocene catalyst, it is possible to produce a PE of various physical properties in the medium-low density (0.910 ~ 0.940) region than the conventional comparative examples.

Claims (14)

(a) a first metallocene compound represented by Formula 1, (b) a second metallocene compound represented by the following formula (2), (c) a promoter and (d) a hybrid supported metallocene catalyst comprising a carrier: [Formula 1]

In Chemical Formula 1, M is a Group 4 transition metal; (C ₅ R ^a ) and (C ₅ R ^b ) may be the same as or different from each other, and each independently selected from hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl and hydrocarbyl Cyclopentadienyl ligand, which is a metalloid of a group 14 metal substituted with one or more, or a cyclopentadienyl ligand, in which two adjacent carbon atoms of C ₅ are connected by hydrocarbyl to form one or more rings having 4 to 16 carbon atoms; Q is selected from halogen, alkyl, alkenyl, aryl, alkylaryl, arylalkyl and alkylidene; p is 0 or 1; [Formula 2]

In Chemical Formula 2, R1 to R7 may be the same or different from each other, and each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl or arylalkyl having 7 to 20 carbon atoms And a metalloid radical of a Group 14 metal substituted with at least one selected from hydrocarbyl, an alkoxy radical having 1 to 20 carbon atoms, an aryloxy radical having 6 to 20 carbon atoms, a silyl radical and an amino radical; Two or more of them may be connected to each other by alkylidene including alkyl having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms to form an aliphatic or aromatic ring; CY1 is a substituted or unsubstituted aliphatic or aromatic ring; The substituent substituted at CY1 is selected from the group consisting of hydrogen, a halogen radical, an alkyl radical having 1 to 20 carbon atoms and an aryl radical having 6 to 20 carbon atoms, and when there are a plurality of substituents, at least two substituents from each other are substituted with each other. Can be joined to form an aliphatic or aromatic ring; M is a Group 4 transition metal; N is nitrogen; Q1 and Q2 are the same as or different from each other, and are independently a halogen radical, an alkyl amido radical having 1 to 20 carbon atoms, an aryl amido radical having 6 to 20 carbon atoms, an alkyl radical having 1 to 20 carbon atoms, and an alkenyl having 2 to 20 carbon atoms. Radical, an aryl radical having 6 to 20 carbon atoms, an alkylaryl or arylalkyl radical having 7 to 20 carbon atoms, and an alkylidene radical having 1 to 20 carbon atoms. The method of claim 1, wherein at least one hydrogen present in R ^a and R ^b of the first metallocene compound represented by Chemical Formula 1 is any one or more of radicals represented by the following Chemical Formulas a, b and c. Hybrid supported metallocene catalyst that is substituted: [Formula a]

In Chemical Formula a, Z is oxygen or sulfur; R and R ′ may be the same or different from each other, and each independently selected from hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl and arylalkenyl, and two R ′ are linked to each other to form a ring Can form; G is alkoxy, aryloxy, alkylthio, arylthio, phenyl and substituted phenyl and can be linked to R 'to form a ring; If Z is sulfur, G is necessarily alkoxy or aryloxy; If G is alkylthio, arylthio, phenyl, or substituted phenyl, Z is necessarily oxygen; [Formula b]

In Chemical Formula b, Z is oxygen or sulfur and at least one of the two Z is an oxygen atom; R and R '' may be the same or different from each other, and each independently selected from hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl and arylalkenyl; R may be linked to R ″ to form a ring; Two R ″ may be linked to each other to form a ring unless they are a hydrogen radical; [Formula c]

In Chemical Formula c, R and R '' 'may be the same or different from each other, and each independently selected from hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl and arylalkenyl; Two adjacent R ′'s may be linked to each other to form a ring; If at least one of R is a hydrogen radical, then R '' 'are not all hydrogen, and if at least one of R' '' is hydrogen, then R is not all hydrogen. The hybrid supported metallocene catalyst of claim 1, wherein the second metallocene compound represented by Chemical Formula 2 comprises a compound represented by the following Chemical Formula 3: [Formula 3]

In Chemical Formula 3, R1 to R13 is the same as the definition of R1 to R7 of Formula 1, M, N, Q1 and Q2 are the same as defined in Chemical Formula 1. The hybrid supported metallocene catalyst of claim 1, wherein the second metallocene compound represented by Chemical Formula 2 includes the following structures:

In the above formulas, R1 to R14 is the same as the definition of R1 to R7 of Formula 1, Q1 and Q2 are as defined in the formula (1). The hybrid supported metallocene catalyst according to claim 1, wherein the (c) promoter comprises a metal compound including a Group 13 metal in the periodic table. The hybrid supported metallocene catalyst of claim 1, wherein the (c) promoter comprises a compound represented by the following Chemical Formula 4: [Formula 4] -[Al (R15) -O] a- In Formula 4, R 15 may be the same as or different from each other, each independently represent a halogen or a hydrocarbyl having 1 to 20 carbon atoms unsubstituted or substituted with halogen, and a is an integer of 2 or more. The hybrid supported metallocene catalyst of claim 6, wherein the compound represented by Chemical Formula 4 includes methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane. The hybrid supported metallocene catalyst according to claim 1, wherein the (d) carrier contains a hydroxyl group and a siloxane group on the surface. The hybrid supported metallocene catalyst according to claim 8, wherein the carrier (d) comprises 0.1 to 10 mmol / g of hydroxyl group on the surface. The hybrid supported metallocene catalyst of claim 1, wherein the (d) carrier is dried at 200 to 800 ° C. The hybrid supported metallocene catalyst of claim 1, wherein the (d) carrier is made of at least one selected from silica, silica-alumina, and silica-magnesia. The hybrid supported metallocene catalyst of claim 5, wherein the mixed supported metallocene catalyst contains [group 13 metal] / [transition metal] in a molar ratio of 1 to 10,000. (A) supporting a first metallocene compound on a carrier to prepare a first supported catalyst; (B) preparing a second supported catalyst by contacting a cocatalyst to the first supported catalyst of step (A); And (C) preparing a supported catalyst for polyolefin polymerization in which the first metallocene compound and the second metallocene compound are supported on the carrier by supporting the second metallocene compound in the second supported catalyst of step (B). Method for producing a hybrid supported metallocene catalyst comprising a. A method of polymerizing a polyolefin comprising polymerizing an olefinic monomer using the hybrid supported metallocene catalyst according to any one of claims 1 to 12.