KR101785705B1 - Catalyst composition and method for preparing polyolefin using the same - Google Patents

Abstract

The present invention relates to a catalyst composition comprising a novel metallocene compound having a high molecular weight and a broad molecular weight distribution and capable of polymerizing a high quality polyolefin having excellent productivity and a process for producing a polyolefin using the same.

Description

Catalyst compositions and methods for preparing polyolefins using the same

The present invention relates to a catalyst composition and a process for producing a polyolefin using the same. More particularly, the present invention relates to a catalyst composition comprising a dinuclear metallocene compound having a novel structure capable of producing a polyolefin having a high molecular weight and a broad molecular weight distribution, and a process for producing a polyolefin using the same.

Ziegler-Natta catalyst widely applied to existing commercial processes is characterized by a wide molecular weight distribution of the produced polymer because it is a multi-site catalyst and the composition distribution of the comonomer is not uniform.

On the other hand, the metallocene catalyst is a single active site catalyst having one kind of active site, and the molecular weight distribution of the produced polymer is narrow and the molecular weight, stereoregularity, crystallinity, and especially reactivity of the comonomer are largely controlled depending on the structure of the catalyst and the ligand There are advantages to be able to. However, the polyolefin polymerized with a metallocene catalyst has a narrow molecular weight distribution, and when applied to a part of products, there is a problem in that it is difficult to apply the polyolefin in a field, for example, productivity is remarkably decreased due to the influence of extrusion load. I have done a lot.

For this, a method using a mononuclear metallocene compound and a dinuclear metallocene compound is known.

For example, U.S. Patent No. 5,032,562 discloses a method for preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. This is a method of producing a bimodal distribution polymer by supporting a Ziegler-Natta catalyst of a titanium (Ti) series which produces a high molecular weight and a zirconium (Zr) based metallocene catalyst which generates a low molecular weight on a support , The supporting process is complicated and the morphology of the polymer is deteriorated due to the co-catalyst.

In addition, studies have been made to change the copolymer selectivity and activity of the catalyst during copolymerization using a dinuclear metallocene compound. In some metallocene catalysts, copolymer incorporation and activity are increased Reported.

For example, Korean Patent Application No. 2003-12308 discloses a method for controlling the molecular weight distribution by carrying a double-nucleated metallocene catalyst and a single nuclear metallocene catalyst together with an activator in a carrier to change the combination of catalysts in the reactor and to polymerize . However, this method has a limitation in simultaneously realizing the characteristics of the individual catalysts, and also disadvantageously causes fouling in the reactor due to liberation of the metallocene catalyst portion in the carrier component of the finished catalyst.

Further, a method for synthesizing a Group 4 metal metallocene catalyst having a biphenylene bridge and the polymerization of ethylene and styrene using this catalyst have been reported (Organometallics, 2005, 24, 3618). According to this method, the activity of the catalyst is higher than that of the mononuclear metallocene catalyst, and the molecular weight of the obtained polymer is high. Another method has been reported to change the bridge structure of the quaternary metallocene catalyst to change the reactivity of the catalyst (Eur. Polym, J. 2007, 43, 1436).

However, when the above methods are used, the Group IV metal metallocene catalyst having a previously reported biphenylene bridge has a problem in the addition of a substituent and a change in its structure. Therefore, a new metallocene catalyst useful for preparing olefins Development is necessary.

In order to solve the above problems, it is an object of the present invention to provide a catalyst composition comprising a nucleophilic metallocene compound having a novel structure.

The present invention also provides a process for producing a polyolefin using the catalyst composition.

In order to solve the above problems, the present invention provides a catalyst composition comprising a dinuclear metallocene compound represented by the following Formula 1:

[Chemical Formula 1]

In Formula 1,

R 1 to R 8 may be the same or different from each other and each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, Or an aryl group having 1 to 20 carbon atoms, and the adjacent two of R1 to R8 may be connected to each other to form at least one aliphatic ring, aromatic ring, or heterocyclic ring, with the proviso that R1 to R8 Are all hydrogen;

R9 and R10 are the same or different from each other and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An aryloxy group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, or an arylalkyl group of 7 to 40 carbon atoms;

X is a halogen atom;

n is an integer of 1 to 10;

The present invention also provides a process for producing a polyolefin comprising polymerizing at least one or more olefin monomers in the presence of the catalyst composition.

The catalyst composition comprising the dinuclear metallocene catalyst according to the present invention can exhibit high activity while maintaining the advantages of other homogeneous catalysts in the production of polyolefins.

Further, the catalyst of the present invention can produce a high quality polyolefin having a high molecular weight and a broad molecular weight distribution and excellent productivity, by freely adjusting the molecular weight and the molecular weight distribution.

The dinuclear metallocene compound of the present invention is a dinuclear metallocene compound having a novel structure, and a catalyst composition comprising such a dinuclear metallocene compound can produce a polyolefin having desired physical properties and molecular weight distribution.

Also, according to the method for producing a polyolefin of the present invention, a polyolefin having a high molecular weight and a broad molecular weight distribution can be polymerized using the catalyst composition comprising the nucleophilic metallocene compound.

Hereinafter, the present invention will be described in detail.

According to an aspect of the present invention, there is provided a catalyst composition comprising a dinuclear metallocene compound represented by the following general formula (1).

The catalyst composition according to one embodiment of the present invention may be a composition comprising a dinuclear metallocene compound represented by the following formula (1) and a cocatalyst.

Alternatively, the catalyst composition according to another embodiment of the present invention may be a composition comprising a mononuclear metallocene compound represented by the following general formula (2) and a linker compound represented by the general formula (3) and a cocatalyst.

[Chemical Formula 1]

In Formula 1,

R 1 to R 8 may be the same or different from each other and each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, Or an aryl group having 1 to 20 carbon atoms, and the adjacent two of R1 to R8 may be connected to each other to form at least one aliphatic ring, aromatic ring, or heterocyclic ring, with the proviso that R1 to R8 Are all hydrogen;

R9 and R10 are the same or different from each other and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An aryloxy group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, or an arylalkyl group of 7 to 40 carbon atoms;

X is a halogen atom;

n is an integer of 1 to 10;

(2)

(3)

In Formula 2, R1 to R10 and X are as defined in Formula 1, and Z in Formula 3 is Cl or Br, and n is 1 to 10.

In the present invention, the term "catalyst composition" means that the three components of the mononuclear metallocene compound, the linker compound and the cocatalyst of the above formula 2, or alternatively the two components of the dinuclear metallocene compound of the above formula Means a state that can be obtained simultaneously with or in any order, in the presence or absence of any suitable solvent, with the composition being added together in the presence or absence of monomers to be active.

That is, the catalyst composition according to the present invention may include a mononuclear metallocene compound of Formula 2, a linker compound of Formula 3, and a cocatalyst, or may include a dinuclear metallocene of Formula 1 and a cocatalyst . Even when the catalyst composition comprises the mononuclear metallocene compound, the linker compound and the cocatalyst, the substantial olefin polymerization reaction is carried out by the dinuclear metallocene compound produced by reacting the mononuclear metallocene compound with the linker compound .

The three or two components of the catalyst composition may be used without being supported on the support, or may be supported on a support as required.

According to one embodiment of the present invention, the dinuclear metallocene compound of the present invention can be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R 1 to R 8 may be the same or different from each other and each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, Or an aryl group having 1 to 20 carbon atoms, and the adjacent two of R1 to R8 may be connected to each other to form at least one aliphatic ring, aromatic ring, or heterocyclic ring, with the proviso that R1 to R8 Are all hydrogen;

R9 and R10 are the same or different from each other and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An aryloxy group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, or an arylalkyl group of 7 to 40 carbon atoms;

X is a halogen atom;

n is an integer of 1 to 10;

The dinuclear metallocene compound of the above formula (1) contains Zr as two central metals in the structure, and the ligand connected to each central metal is a compound having a cyclopentadiene skeleton bonded to a silicon bridge . In addition, the dinuclear metallocene compound of Formula 1 of the present invention can exhibit stable catalytic activity by providing an interval between alkyl chains between the central metals to reduce the interaction between the two central metals.

According to an embodiment of the present invention, in the metallocene compound of Formula 1, each of R1 to R8 independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an amine having 1 to 20 carbon atoms Or adjacent two of R1 to R8 may be connected to each other to form at least one aliphatic ring, aromatic ring or heterocyclic ring. R 9 and R 10 may each independently be hydrogen, alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, X is Cl, and n may be an integer of 2 to 6.

More preferably, the dinuclear metallocene compound of Formula 1 may be represented by one of the following structural formulas (1a) to (1g), but is not limited thereto.

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

According to an embodiment of the present invention, the dinuclear metallocene compound of Formula 1 may be prepared by reacting a compound of Formula 2 and a linker compound of Formula 3 in a molar ratio of 2: And linking the center metal with an alkyl chain.

The reaction for the preparation of the dinuclear metallocene compound of Formula 1 can be carried out by a conventional organic synthesis method well known in the art, and therefore the conditions are not particularly limited and will be described in more detail in the following Examples.

The reaction for the preparation of the mononuclear metallocene compound of formula (2) can be carried out by a conventional organic synthesis method well known in the art. Therefore, the conditions are not particularly limited, do.

The dinuclear metallocene compound represented by the formula (1) produced by this method has a novel structure, and the ligand structure included therein includes a cyclopentadienyl or a derivative skeleton thereof centering on a silicon bridge.

In addition, since the alkyl chain bonded between the central metals of the two metallocene compounds functions as a linker connecting the metal centers of the respective metallocene compounds, it is possible to reduce unnecessary interaction between the metals, It has the characteristics of metallocene and has a characteristic that the ligand structure can be easily deformed.

The promoter that can be included in the catalyst composition of the present invention is an organometallic compound containing a Group 13 metal and is not particularly limited as long as it can be used in the polymerization of olefins under a general metallocene catalyst.

Preferably, the cocatalyst may be at least one selected from the group consisting of compounds represented by the following formulas (4) to (6).

[Chemical Formula 4]

_{- [Al (R 11) -O} ] c-

In the general formula (4), R ₁₁ are the same or different from each other and each independently represents a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, and c is an integer of 2 or more ,

[Chemical Formula 5]

D (R _{12) 3}

In Formula 5,

D is aluminum or boron, R < ₁₂ > is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

[Chemical Formula 6]

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Formula 6,

L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 element, A can be the same or different from each other, and each independently at least one hydrogen atom is replaced by halogen, a hydrocarbon having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with phenoxy.

Examples of the compound represented by Formula 4 include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like.

Examples of the alkyl metal compound represented by Formula 5 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethyl Tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, Dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like can be used.

Examples of the compound represented by Formula 6 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p (O, p-dimethylphenyl) boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, trimethylammoniumtetra (P-trifluoromethylphenyl) boron, tetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p -trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N , N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphine Tetramethylammonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl ) Aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetra Pentafluorophenyl aluminum, diethylammonium tetrapentafluorophenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetra Phenyl aluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenyl aluminum, triphenylcarboniumtetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, etc. have.

The first aspect of the catalyst composition of the present invention comprises: 1) contacting the metallocene compound represented by Formula 1 with the compound represented by Formula 4 or Formula 5 to obtain a mixture; And 2) adding the compound represented by Formula 6 to the mixture.

The catalyst composition according to the present invention can be prepared by a method of contacting the metallocene compound represented by Formula 1 and the compound represented by Formula 4 as a second method.

In the first method of the catalyst composition, the molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 4 or Formula 5 is preferably 1/5000 to 1/2, More preferably from 1/1000 to 1/10, and most preferably from 1/500 to 1/20. When the molar ratio of the metallocene compound represented by the formula (1) / the compound represented by the formula (4) or the formula (5) exceeds 1/2, the amount of the alkylating agent is so small that the alkylation of the metal compound can not proceed completely If the molar ratio is less than 1 / 5,000, alkylation of the metal compound is performed, but there is a problem that activation of the alkylated metal compound can not be completely achieved due to the side reaction between the excess alkylating agent and the activating agent.

The molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 6 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1 / 5 to 1. When the molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 6 is more than 1, the amount of the activator is relatively small, There is a problem that the activity is inferior. When the molar ratio is less than 1/25, the activation of the metal compound is completely performed, but the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is low .

In the second method of preparing the catalyst composition, the molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 4 is preferably 1 / 10,000 to 1/10, 1 / 5,000 to 1/100, and most preferably 1/3 to 1/500. When the molar ratio is more than 1/10, the amount of the activator is relatively small and the activation of the metal compound is not achieved completely. Therefore, there is a problem in that the activity of the catalyst composition is decreased. Although the activation is completely performed, there is a problem that the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is low.

In the preparation of the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane or the like, or an aromatic solvent such as benzene, toluene or the like may be used as a reaction solvent. In addition, the metallocene compound and the co-catalyst compound may be used in the form supported on silica or alumina.

The present invention also provides a method of polymerizing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition.

In the process for producing a polyolefin according to the present invention, specific examples of the olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like.

The polyolefin is more preferably an ethylene / alpha olefin copolymer, but is not limited thereto.

In the case where the polyolefin is an ethylene / alpha olefin copolymer, the content of the alpha-olefin as the comonomer is not particularly limited and may be appropriately selected depending on the use, purpose, etc. of the polyolefin. More specifically from about 1 to about 99 mole%.

The polymerization reaction may be carried out by homopolymerization using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor, or solution reactor, as an olefin monomer, or copolymerization with two or more monomers.

According to one embodiment of the present invention, the polymerization of the polyolefin may be carried out by reacting at a temperature of about 20 to about 110 DEG C and a pressure of about 20 to about 100 bar for about 10 minutes to about 2 hours. Preferably at a temperature of about 80 to about 100 < 0 > C and a pressure of about 30 to about 60 bar.

The polyolefin prepared by the process of the present invention may have a weight average molecular weight of about 5,000 to about 500,000, preferably about 10,000 to about 300,000. The polyolefin may also have a number average molecular weight ranging from about 1,000 to about 200,000, preferably from about 3,000 to about 100,000. Thus, the polyolefin may have a molecular weight distribution (Mw / Mn) of from about 2 to about 15, or from about 3 to about 13, or from about 3 to about 10.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through a specific embodiment of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

< Example >

Nucleus Metallocene  Synthesis of compounds

Produce Example  One

1-1) Preparation of ligand compound

Bu-O- (CH ₂ ) ₆ MgCl ₂ solution as a Grignard reagent from the reaction between tert-Bu-O- (CH ₂ ) ₆ Cl compound and Mg (0) in THF solvent. The prepared Grignard compound was added to a flask containing a MeSiCl ₃ compound (176.1 mL, 1.5 mol) in a state of -30 ° C and THF (2.0 mL), stirred at room temperature for 8 hours or longer, To give tert-Bu-O- (CH ₂ ) ₆ SiMeCl ₂ (yield 92%).

Add fluorene (3.33 g, 20 mmol), hexane (100 mL) and MTBE (methyl tert-butyl ether, 1.2 mL, 10 mmol) to the reactor at -20 ° C and slowly add 8 mL of n-BuLi (2.5 M in Hexane) And the mixture was stirred at room temperature for 6 hours to obtain a fluorenyl lithium solution. After the stirring was completed, the reactor temperature to produce a cooled to -30 ℃, tert-Bu-O- (CH 2) with at -30 ℃ dissolved in hexane _{(100ml) 6 SiMeCl 2 (2.7g} , 10mmol) solution Lt; RTI ID = 0.0 &gt; 1 &lt; / RTI &gt; The mixture was stirred at room temperature for 8 hours or more and then extracted with water and evaporated to obtain tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₁₀ ) ₂ , Yield: 100%).

_{1H NMR (500MHz, CDCl 3)} : -0.35 (MeSi, 3H, s), 0.26 (Si-CH 2, 2H, m), 0.58 (CH 2, 2H, m), 0.95 (CH 2, 4H, m) , 1.17 (tert-BuO, 9H , s), 1.29 (CH 2, 2H, m), 3.21 (tert-BuO-CH 2, 2H, t), 4.10 (Flu-9H, 2H, s), 7.25 (Flu -H, 4H, m), 7.35 (Flu-H, 4H, m), 7.40 (Flu-H, 4H, m), 7.85 (Flu-H, 4H, d).

1-2) Preparation of metallocene compound

To a solution of tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₃ H ₁₀ ) ₂ (3.18 g, 6 mmol) / MTBE (20 mL) prepared in 1-1) Of n-BuLi (2.5M in Hexane) was slowly added and reacted at room temperature for 8 hours or longer to prepare a slurry solution of dilithium salts. The dilithium salt slurry solution prepared above was added slowly to the slurry solution of ZrCl ₄ (THF) ₂ (2.26 g, 6 mmol) / hexane (20 mL) at -20 ° C and further reacted at room temperature for 8 hours. The precipitate was filtered and washed several times with hexane to obtain a red solid (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₉ ) ₂ ZrCl ₂ compound (4.3 g, yield 94.5% ).

1H NMR (500MHz, C6D6): 1.15 (tert-BuO, 9H, s), 1.26 (MeSi, 3H, s), 1.58 (Si-CH 2, 2H, m), 1.66 (CH 2, 4H, m), _{1.91 (CH 2, 4H, m} ), 3.32 (tert-BuO-CH 2, 2H, t), 6.86 (Flu-H, 2H, t), 6.90 (Flu-H, 2H, t), 7.15 (Flu- H, 4H, m), 7.60 (Flu-H, 4H, dd), 7.64

1-3) Preparation of dinuclear metallocene compound

1.68 g (6 mmol, purity 95 wt%) of BrMg- (CH ₂ ) ₄ -MgBr was added to the dried flask and ether was injected into the slurry state. In another dried flask, 6.9 g (10 mmol) of the metallocene compound synthesized in 1-2) above was charged and ether was injected to form a slurry. Then, a BrMg- (CH ₂ ) ₄ -MgBr slurry Was transferred to the slurry of the metallocene compound. The mixture was stirred for one day, filtered, and then the solvent of the filtrate was removed. It was then recrystallized with hexane and then filtered once more to obtain the title dinuclear metallocene compound.

^{1 H NMR (500MHz, C6D6)} : 0.98 (9H, s), 1.12 (3H, s), 1.26 (2H, m), 1.57 (2H, m), 1.4 (4H, m), 1.64 (2H, m) , 1.92 (4H, m), 3.28 (2H, m), 6.84-7.82 (32H, m)

Produce Example  2

2-1) Preparation of ligand compound

0.83 g (5 mmol) of fluorene was added to a dried 250 mL schlenk flask and 30 mL of ether was injected under reduced pressure. After the ether solution was cooled to -78 ° C, the inside of the flask was replaced with argon, and 2.4 mL (6 mmol) of a 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred until the next day. Another 250 mL schlenk flask was filled with 30 mL of ether, and 2.4 mL (20 mmol) of dichlorodimethylsilane was injected. The flask was cooled to -78 ° C and a lithiated solution of 2-hexyl-fluorene was injected through a cannula. The poured mixture was slowly raised to room temperature, stirred for about 5 hours, and then the ether used as a solvent and the excess dichlorodimethylsilane were removed under reduced pressure. Chloro (9H-fluoren-9-yl) dimethylsilane was obtained as a solid, ocher-colored solid in the flask.

0.83 g (5 mmol) of fluorene was injected into a dried 100 mL schlenk flask and dissolved in 30 mL of ether. Then 2.4 mL (6 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise at -78 deg. C and stirred overnight. The previously synthesized chloro (9H-fluoren-9-yl) dimethylsilane was dissolved in 40 mL of ether and the lithiated solution of fluorene was added dropwise at -78 ° C. After overnight reaction, the reaction mixture was quenched by adding 50 mL of water into the flask, and the organic layer was separated and dried with MgSO ₄ . The mixture obtained through filtration was subjected to vacuum depressurization to remove all of the solvent and recrystallized with hexane to obtain a ligand compound.

^{1 H NMR (500 MHz, CDCl} 3): -0.52 (6H, s), 4.26 (2H, s), 7.29 (4H, m), 7.36 (4H, m), 7.53 (4H, m), 7.89 (4H , m)

2-2) Preparation of metallocene compound

1.94 g (5 mmol) of the ligand compound synthesized in 2-1) was dissolved in ether and dissolved in 4.4 mL (11 mmol) of 2.5M nBuLi hexane solution in a dry 250 mL schlenk flask. One day later, 1.88 g (5 mmol) of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL schlenk flask to prepare an ether suspension. Both of the above flasks were cooled to -78 ° C and the lithiated ligand compound was slowly added to the Zr suspension. After the injection, the reaction mixture slowly warmed to room temperature. After the reaction was allowed to proceed for one day, the mixture was filtered in a filter system which did not come in contact with outside air to obtain a metallocene compound.

^{1 H NMR (500MHz, CDCl3)} : 1.46 (6H, s), 6.99 (4H, m), 7.29 (4H, m), 7.68 (4H, m), 7.9 (4H, m)

2-3) Preparation of dinuclear metallocene compound

1.68 g (6 mmol, purity 95 wt%) of BrMg- (CH ₂ ) ₄ -MgBr was added to the dried flask and ether was injected into the slurry state. 5.48 g (10 mmol) of the metallocene compound synthesized in the above 2-2) was added to another dried flask, and ether was injected into the slurry to form a BrMg- (CH ₂ ) ₄ -MgBr slurry Was transferred to the flask where the catalyst was dissolved. After stirring for one day, the solution was filtered and the solvent of filtrate was removed. After recrystallization with hexane, the solution was filtered once more to obtain a dinuclear metallocene compound.

^{1 H NMR (500MHz, CDCl3)} : 1.32 (6H, s), 1.46 (6H, s), 1.3 ~ 1.8 (8H, m), 6.72 ~ 7.9 (32H, m)

Produce Example  3

3-1) Preparation of ligand

0.83 g (5 mmol) of fluorene was added to the dried 250 mL schlenk flask and 50 mL of ether was injected under reduced pressure. After the ether solution was cooled to -78 ° C, the inside of the flask was replaced with argon, and 2.4 mL (6 mmol) of a 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred until the next day. Another 250 mL schlenk flask was filled with 30 mL of ether, and 2.4 mL (20 mmol) of dichlorodimethylsilane was injected. The flask was cooled to -78 ° C and a lithiated solution of 2-hexyl-fluorene was injected through the cannula. The poured mixture was slowly raised to room temperature, stirred for about 5 hours, and then the ether used as a solvent and the excess dichlorodimethylsilane were removed under reduced pressure. Chloro (9H-fluoren-9-yl) dimethylsilane in the form of a deep ocher solid was obtained in the flask.

1.16 g (5 mmol) of 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole was injected into a dried 100 mL schlenk flask and dissolved in 50 mL of ether. 2.4 mL (6 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise at -78 ° C and stirred overnight. The previously synthesized chloro (9H-fluoren-9-yl) dimethylsilane was dissolved in 50 mL of THF and the lithiated solution of fluorene was added dropwise at -78 ° C. After overnight reaction, the flask was quenched by adding 50 mL of water, and the organic layer was separated and dried over MgSO ₄ . The mixture obtained through filtration was subjected to vacuum depressurization to remove all of the solvent and then recrystallized with hexane to obtain a ligand compound.

^{1 H NMR (500 MHz, CDCl} 3): -0.54 (3H, s), -0.49 (3H, s), 2.36 (3H, s), 4.09 (3H, s), 4.17 (1H, s), 4.39 ( 1H, s), 7.24-7.74 (15H, m)

3-2) Preparation of metallocene compound

To a dry 250 mL schlenk flask was added 1.94 g (5 mmol) of the ligand compound synthesized in 3-1), dissolved in 50 mL of toluene and 2 mL of ether, and then 4.4 mL (11 mmol) of 2.5 M nBuLi hexane The solution was subjected to lithiation by adding hexane solution. One day later, 1.88 g (5 mmol) of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL schlenk flask. Toluene was added to the suspension. Both of the above flasks were cooled to -78 ° C and the lithiated ligand compound was slowly added to the Zr suspension. After the injection, the reaction mixture was slowly warmed up to room temperature. The reaction was allowed to proceed for one day. The mixture was filtered through a filter system that did not come in contact with outside air to remove LiCl. After the solvent was completely blown off, The metallocene compound of the title was obtained from the filter cake by re-filtering.

^{1 H NMR (500MHz, CDCl3)} : 1.68 (3H, s), 1.71 (3H, s), 2.56 (3H, s), 3.89 (3H, s), 6.65 ~ 7.86 (15H, m)

3-3) Preparation of dinuclear metallocene compound

1.68 g (6 mmol, purity 95 wt%) of BrMg- (CH ₂ ) ₄ -MgBr was added to the dried flask and ether was injected into the slurry state. In another dried flask, 6.1 g (10 mmol) of the metallocene compound synthesized in the above step 3-2) was added and ether was injected to form a slurry. Then, a BrMg- (CH ₂ ) ₄ -MgBr slurry Was transferred to the slurry in which the metallocene compound was dissolved. After stirring for one day, the filter was filtered and the solvent of the filtrate was removed. After recrystallization with hexane, the solution was filtered once more to obtain a dinuclear metallocene compound.

^{1 H NMR (500MHz, CDCl3)} : 1.17 ~ 1.83 (8H, m), 1.42 (6H, d), 1.61 (6H, d), 2.87 (3H, s), 3.12 (3H, s), 3.89 (3H, s), 3.95 (3H, s), 6.65 ~ 7.86 (30H, m)

Produce Example  4

4-1) Preparation of ligand compound

1.1 g (5 mmol) of 5-methyl-5,10-dihydroindeno [1,2-b] indole (hereinafter referred to as "phenyl indenoindole") was placed in a dried 250 mL schlenk flask, 30 mL of THF was injected. After cooling the THF solution to -78 ° C, the inside of the flask was replaced with argon, and 2.4 mL (6 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred until the next day. Another 250 mL schlenk flask was filled with THF (30 mL) and 2.4 mL (20 mmol) of dichlorodimethylsilane. The flask was cooled to -78 ° C and a lithiated solution of phenylindeneoin stone was injected through the cannula. The poured mixture was slowly warmed to room temperature, stirred for about 5 hours, and then the excess THF and the excess dichlorodimethylsilane used as a solvent were removed under reduced pressure. Brown oil remained in the flask, which was identified by NMR as 10- (chlorodimethylsilyl) -8-methoxy-5-methyl-5,10-dihydroindeno [ (hereinafter referred to as " phenyl indenoindole part ").

^{1 H NMR (500 MHz, CDCl} 3): -0.01 (3H, s), 0.36 (3H, s), 4.09 (3H, s), 4.15 (1H, s), 7.03 ~ 7.96 (8H, m)

After the synthesis of the phenyl indenoindole part was confirmed, 0.83 g (5 mmol) of fluorene was injected into a dried 250 mL schlenk flask and dissolved in 30 mL of THF. Then 2.4 mL (6 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise at -78 ° C and stirred for one day. The previously synthesized phenylindenone moiety was dissolved in 40 mL of THF and the lithiated solution of fluorene was added dropwise at -78 ° C. After overnight reaction, the flask was quenched by adding 50 mL of water, and the organic layer was separated and dried over MgSO ₄ . The mixture obtained through filtration was washed with hexane after removing all of the solvent under reduced pressure to obtain a grayish solid form of a ligand compound.

^{1 H NMR (500 MHz, CDCl} 3): -0.51 (3H, s), -0.48 (3H, s), 4.12 (3H, s), 4.21 (1H, s), 4.38 (1H, s), 7.10 ~ 7.97 (16 H, m)

4-2) Preparation of metallocene compound

To a dry 250 mL schlenk flask, add 0.7 g (1.6 mmol) of the ligand compound synthesized in 4-1) above and dissolve in 30 mL of toluene. Add 2 mL (10 mmol) of MTBE to this solution and add 1.5 mL ) Of 2.5 M nBuLi hexane solution was added to perform lithiation. One day later, 0.6 g (1.6 mmol) of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL schlenk flask, and toluene was added to the suspension. Both of the above flasks were cooled to -78 ° C and the lithiated ligand compound was slowly added to the Zr suspension. After the injection, the reaction mixture was slowly warmed up to room temperature. The reaction was allowed to proceed for one day. The mixture was filtered in a filter system that did not come in contact with outside air to remove LiCl, the solvent was completely blown, The titled metallocene compound was obtained from the cake (filter cake).

¹ H NMR (500 MHz, CDCl ₃ ): 1.68 (3 H, s), 1.71 (3 H, s), 3.92

4-3) Preparation of dinuclear metallocene compound

1.68 g (6 mmol, purity 95 wt%) of BrMg- (CH ₂ ) ₄ -MgBr was added to the dried flask and ether was injected into the slurry state. In another dried flask, 6 g (10 mmol) of the metallocene compound synthesized in 4-2) was added and ether was injected to form a slurry. Then, a BrMg- (CH ₂ ) ₄ -MgBr slurry was prepared under a dry ice / acetone bath The metallocene compound was transferred to the melted slurry. The mixture was stirred for one day, filtered, and then the solvent of the filtrate was removed. After recrystallization with hexane, the solution was filtered once more to obtain a dinuclear metallocene compound.

^{1 H NMR (500MHz, CDCl3)} : 0.92 (4H, m), 1.35 (4H, m), 1.38 (6H, d), 1.42 (6H, d), 3.45 (3H, s), 3.62 (3H, s) , 6.65 ~ 7.86 (30H, m)

Produce Example  5

5-1) Preparation of ligand compound

1.16 g (5 mmol) of 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole was injected into a dried 250 mL schlenk flask and dissolved in 50 mL of THF. After cooling the THF solution to -78 ° C, the inside of the flask was replaced with argon, and 2.4 mL (6 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred until the next day. Another 250 mL schlenk flask was filled with THF (30 mL) and 2.4 mL (20 mmol) of dichlorodimethylsilane. After cooling the flask to -78 ° C, a lithiated solution of 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole was injected through the cannula. The poured mixture was slowly warmed to room temperature, stirred for about 5 hours, and then the excess THF and the excess dichlorodimethylsilane used as a solvent were removed under reduced pressure. A 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole part was obtained in the form of a brown oil in the flask.

After the synthesis of 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole part was confirmed, it was dissolved in 50 mL of THF. Then, 2.5 mL (5 mmol) of 2.0 M NaCp THF solution was injected at -78 ° C using a syringe and stirred overnight. After overnight reaction, the reaction mixture was quenched by adding 50 mL of water to the flask, and the organic layer was separated and dried over MgSO ₄ . The mixture obtained through filtration was washed with hexane after all of the solvent was removed under reduced pressure to obtain a grayish solid form of a ligand compound.

^{1 H NMR (500 MHz, CDCl} 3): -0.42 (3H, s), -0.38 (3H, s), 2.46 (3H, s), 3..41 (1H, s), 4.21 (3H, s) 5.4 ~ 6.8 (5H, m), 7.3 ~ 7.89 (7H, m)

5-2) Preparation of metallocene compound

To a dry 250 mL schlenk flask, add 1.77 g (5 mmol) of the ligand synthesized in 5-1) and dissolve in 50 mL of toluene. Add 2 mL (10 mmol) of MTBE to 4.8 mL (12 mmol) Of 2.5 M nBuLi hexane solution was added to perform lithiation. One day later, 1.88 g (5 mmol) of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL schlenk flask to prepare a suspension of toluene. Both of the above flasks were cooled to -78 ° C and the lithiated ligand compound was slowly added to the Zr suspension. After the injection, the reaction mixture slowly warmed to room temperature. After the reaction was carried out for one day, the mixture was filtered in a filter system that did not come in contact with outside air to remove LiCl, and all of the solvent was blown, followed by recrystallization by pouring hexane and filtering again to obtain a metallocene compound in a filter cake .

^{1 H NMR (500MHz, CDCl3)} : 1.14 (3H, s), 1.25 (3H, s), 2.53 (3H, s), 4.2 (3H, s), 5.46 (1H, s), 5.79 (1H, s) , 6.44 (1H, s), 6.55 (1H, s), 7.1-7.96 (7H, m)

5-3) Preparation of dinuclear metallocene compound

1.68 g (6 mmol, purity 95 wt%) of BrMg- (CH ₂ ) ₄ -MgBr was added to the dried flask and ether was injected into the slurry state. In another dried flask, 5.2 g (10 mmol) of the metallocene compound synthesized in 5-2) was added and ether was injected to form a slurry. Then, a BrMg- (CH ₂ ) ₄ -MgBr slurry Was transferred to the slurry in which the metallocene compound was dissolved. After stirring for one day, filter and remove all of the filtrate solvent. After recrystallization with hexane, the solution was filtered once more to obtain a dinuclear metallocene compound.

^{1 H NMR (500MHz, CDCl3)} : 1.25 (3H, s), 1.42 (4H, m), 1.88 (4H, m), 1.9 (3H, s), 2.02 (3H, s), 2.1 (3H, s) , 2.21 (6H, m), 3.92 (6H, m), 5.82 (8H, m), 6.8-7.9

Polyolefin  polymerization Example

Example  1-1

235 ml of toluene was added to a 500 ml glass reactor, 10 ml of a 10 wt% toluene solution of MAO was added, and 1 mM toluene solution containing the dinuclear metallocene compound of Preparation Example 1 (5 ml, 5 μmol) was added. The polymerization was then started by introducing 50 psig of ethylene into the reactor.

The reaction mixture was stirred for 0.5 hours, and the reaction was poured into an ethanol / hydrochloric acid solution. The mixture was stirred, filtered, washed with ethanol, and then evaporated to obtain an olefin polymer.

Example  1-2

In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 5 ml of 1-hexene was added as a comonomer to a glass reactor to carry out the reaction.

Example  2-1

In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 占 퐉 ol of the dinuclear metallocene compound of Production Example 2 was used.

Example  2-2

In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 占 퐉 ol of the dinuclear metallocene compound of Production Example 2 was used.

Example  3-1

Polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 占 퐉 ol of the dinuclear metallocene compound of Production Example 3 was used in Example 1-1.

Example  3-2

Polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 占 퐉 ol of the dinuclear metallocene compound of Production Example 3 was used in Example 1-2.

Example  4-1

Polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 占 퐉 ol of the dinuclear metallocene compound of Production Example 4 was used in Example 1-1.

Example  4-2

In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 占 퐉 ol of the dinuclear metallocene compound of Production Example 4 was used.

Example  5-1

In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 占 퐉 ol of the dinuclear metallocene compound of Production Example 5 was used.

Example  5-2

In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 占 퐉 ol of the dinuclear metallocene compound of Production Example 5 was used.

Comparative Example  1-1

Polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 占 퐉 ol of the monocyclic metallocene compound obtained in 1-2 of Production Example 1 was used in Example 1-1.

Comparative Example  1-2

Polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 占 퐉 ol of the monocyclic metallocene compound obtained in 1-2 of Production Example 1 was used in Example 1-2.

Comparative Example  2-1

Polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 占 퐉 ol of the monocyclic metallocene compound obtained in 2-2) of Production Example 2 was used in Example 1-1.

Comparative Example  2-2

Polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 占 퐉 ol of the monocyclic metallocene compound obtained in 2-2) of Production Example 2 was used in Example 1-2.

Comparative Example  3-1

In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the monocyclic metallocene compound obtained in 3-2) of Production Example 3 was used.

Comparative Example  3-2

In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the monocyclic metallocene compound obtained in 3-2) of Production Example 3 was used.

Comparative Example  4-1

Polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 占 퐉 ol of the monocyclic metallocene compound obtained in 4-2 of Production Example 4 was used in Example 1-1.

Comparative Example  4-2

Polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 占 퐉 ol of the monocyclic metallocene compound obtained in 4-2 of Production Example 4 was used in Example 1-2.

Comparative Example  5-1

In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the monocyclic metallocene compound obtained in 5-2) of Production Example 5 was used.

Comparative Example  5-2

In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the monocyclic metallocene compound obtained in 5-2) of Production Example 5 was used.

The catalyst activity and the physical properties of the olefin polymer in the comparative examples are shown in Table 1 below.

Comonomer Activity
(Unit: ton / mol hr) Weight average molecular weight (Mw)
(Unit: g / mol) Molecular weight distribution
(PDI) Example 1-1 - 3.9 311,235 6.02 Examples 1-2 1-hexene 5.3 363,998 3.11 Example 2-1 - 3.1 201,000 5.8 Example 2-2 1-hexene 5.9 211,000 5.2 Example 3-1 - 5.5 122,800 6.1 Example 3-2 1-hexene 5.0 197,000 5.7 Example 4-1 - 4.3 267,000 5.5 Example 4-2 1-hexene 3.0 199,000 4.8 Example 5-1 - 7.5 36,000 4.4 Example 5-2 1-hexene 8.5 57,200 3.5 Comparative Example 1-1 - 4.5 277,416 4.98 Comparative Example 1-2 1-hexene 5.5 112,934 2.96 Comparative Example 2-1 - 3.3 151,500 5.6 Comparative Example 2-2 1-hexene 7.0 187,000 2.5 Comparative Example 3-1 - 6.3 46,800 3.4 Comparative Example 3-2 1-hexene 5.0 93,000 2.7 Comparative Example 4-1 - 4.5 203,000 5.2 Comparative Example 4-2 1-hexene 3.0 178,000 3.3 Comparative Example 5-1 - 7.5 24,200 2.7 Comparative Example 5-2 1-hexene 8.7 22,900 3.0

Referring to Table 1, when comparing the examples and the comparative examples, it was found that when the binuclear metallocene catalyst of the present invention is used as compared with the single nucleus metallocene catalyst, the olefin polymer having a high molecular weight and a broad molecular weight distribution Can be obtained. This effect was the same when 1-hexene was used as a comonomer.

Claims (9)

A dinuclear metallocene compound represented by the following formula (1); And
Catalyst composition comprising cocatalyst:
[Chemical Formula 1]

In Formula 1,
R 1 to R 8 may be the same or different from each other and each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, Or an aryl group having 1 to 20 carbon atoms, and the adjacent two of R1 to R8 may be connected to each other to form at least one aliphatic ring, aromatic ring, or heterocyclic ring, with the proviso that R1 to R8 Are all hydrogen;
R9 is a methyl group;
R10 is a tert-butoxyhexyl group;
X is a halogen atom;
n is an integer of 1 to 10;
The compound according to claim 1, wherein each of R1 to R8 independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an amine group having 1 to 20 carbon atoms, And which are linked to form at least one aliphatic ring, aromatic ring or heterocyclic ring.
2. The catalyst composition according to claim 1, wherein X is Cl and n is an integer of 2 to 6 in the formula (1).
The catalyst composition according to claim 1, wherein the dinuclear metallocene compound is represented by one of the following structural formulas (1b) to (1d):
[Chemical Formula 1b]

[Chemical Formula 1c]

&Lt; RTI ID = 0.0 &

The catalyst composition according to claim 1, wherein the cocatalyst is at least one selected from the group consisting of compounds represented by the following formulas (4) to (6):
[Chemical Formula 4]
_{- [Al (R 11) -O} ] c-
In the general formula (4), R ₁₁ are the same or different from each other and each independently represents a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, and c is an integer of 2 or more ,
[Chemical Formula 5]
D (R _{12) 3}
In Formula 5,
D is aluminum or boron, R &lt; ₁₂ &gt; is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
[Chemical Formula 6]
[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-
In Formula 6,
L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 element, A can be the same or different from each other, and each independently at least one hydrogen atom is replaced by halogen, a hydrocarbon having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with phenoxy.
A process for producing a polyolefin comprising polymerizing at least one olefin monomer in the presence of the catalyst composition according to claim 1.
7. The process according to claim 6, wherein the polymerization of the polyolefin is carried out at a temperature of 20 to 110 DEG C and a pressure of 20 to 100 bar.
The method of claim 6, wherein the olefin monomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl- Decene, 1-hexadecene, 1-octadecene, 1-eicosene, and mixtures thereof.
The process for producing a polyolefin according to claim 6, wherein the polyolefin has a molecular weight distribution (Mw / Mn) of 2 to 15.