KR101601935B1 - Dinuclear metallocene compound, catalyst composition and method for preparing polyolefin using the same - Google Patents

Abstract

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

Description

[0001] The present invention relates to a dinuclear metallocene compound, a catalyst composition and a method for preparing the same,

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

Another object of the present invention is to provide a catalyst composition comprising the above-described dinuclear metallocene compound.

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

The present invention provides a binuclear 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;

Q is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 40 carbon atoms, or an arylalkylene group having 7 to 40 carbon atoms;

X is a halogen atom;

n is an integer from 1 to 10;

m is an integer of 0 or 1;

The present invention also provides a catalyst composition comprising the above-described dinuclear metallocene compound.

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 dinuclear metallocene compound according to the present invention is a binuclear metallocene compound having a novel structure and can provide a catalyst capable of polymerizing a polyolefin having a high molecular weight and a broad molecular weight distribution.

In addition, the present invention can exhibit high activity while maintaining the advantages of other homogeneous catalysts in the production of polyolefins by using the catalyst composition comprising the above-mentioned dinuclear metallocene catalyst. 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 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 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;

Q is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 40 carbon atoms, or an arylalkylene group having 7 to 40 carbon atoms;

X is a halogen atom;

n is an integer from 1 to 10;

m is an integer of 0 or 1;

In the present invention, the dinuclear metallocene compound represented by the formula (1) includes Zr as two central metals in the structure, and the ligand connected to the respective central metal has a structure in which two cyclopentadiene skeletons are bonded by a bridge, Or an unbound structure. 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 dinuclear 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 alkenyl group having 1 to 20 carbon atoms Or an 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.

M may be an integer of 0 or 1, and when m is 0, two cyclopentadienyl skeletons are not connected, and when m is 1, the structure connected by -Q (R9R10) .

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

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

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 then connecting the center metal (Zr) with an alkyl chain.

(2)

(3)

In Formula 2, R 1 to R 10, Q, X and m are as defined in Formula 1, and Z is Cl or Br, and n is 1 to 10.

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 cyclopentadienyl or a derivative skeleton thereof.

Further, 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, thereby reducing unnecessary interaction between the metals, And has a characteristic of easy modification of the ligand structure.

According to another embodiment of the present invention, a catalyst composition comprising a dinuclear metallocene compound of Formula 1 and a cocatalyst may be provided. According to another embodiment of the present invention, a catalyst composition comprising a mononuclear metallocene compound of Formula 2 and a linker compound of Formula 3 and a cocatalyst may be provided.

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 and a cocatalyst of Formula 1 . 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.

Such a promoter 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 an olefin 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. Also, 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 5 to about 12.

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

16 mL of 2.5 M n-BuLi (in hexane) was added to a THF solution of indene (6.7 g, 40 mmol) at -20 ° C, and the mixture was stirred at room temperature (RT) overnight. This solution was transferred to 50 mL of xylene dibromide (5.279 g, 20 mmol) in THF under a dry ice / aceton bath. After stirring overnight at room temperature (RT), water was added and the organic layer was extracted with ether. After separating the organic layer, the water remaining with MgSO ₄ was removed and the solvent was vacuum dried to obtain a crude product of light yellow color. This was recrystallized with ether / hexane to obtain a highly pure ligand compound (yield 67%) /

^{1 H NMR (500 MHz, CDCl} 3): 3.24 (4H, s), 3.89 (4H, s), 5.92 (2H, d), 7.18 ~ 7.44 (12H, m)

1-2) Preparation of metallocene compound

11 mmol (2.2 eq.) Of MTBE was added to 50 mL of the toluene solution of 5 mmol of the ligand compound prepared in 1-1), 10 mmol of 2.5 M n-BuLi and 4 mL of the solution were added thereto at -20 ° C and the mixture was stirred overnight at room temperature. ZrCl ₄ (THF) _{2 The} above solution was transferred to a 5.3 mmol toluene slurry under a dry ice / aceton bath and stirred overnight at room temperature. This was filtered to obtain the title yellowish metallocene compound containing LiCl. (Yield 60%)

^{1 H NMR (500 MHz, CDCl} 3): 4.24 (2H, d), 4.37 (2H, d), 5.72 (2H, s), 6.26 (2H, s), 7.15 ~ 7.61 (12H, m)

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, 10 mmol of the metallocene compound synthesized in 1-2) was added and ether was injected to form a slurry. The slurry of BrMg- (CH ₂ ) ₄ -MgBr in a dry ice / aceton bath was introduced into a metallocene The compound was transferred to the slurry in which it was dissolved. After stirring for one day, the solution 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)} : 1.82 (4H, m), 2.03 (4H, m), 3.41 (4H, dd), 3.72 (4H, dd), 5.4 (4H, m), 6.4 (4H, m) , 7.0-7.9 (24H, m)

Produce Example  2

2-1) Preparation of metallocene compound

J. AM. CHEM. SOC. VOL. 126, No. 46, 2004 pp. (1,2,2-ethylene bis (indenyl) ZrCl ₂ ) was synthesized as disclosed in US Pat.

^{1 H NMR (500MHz, C6D6)} : 2.96 (4H, m), 5.75 (2H, d), 6.45 (2H, q), 6.90 ~ 7.28 (8H, m)

2-2) 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, 4.18 g (10 mmol) of the metallocene compound of 2-1) was charged and ether was injected into the slurry form. The slurry of BrMg- (CH ₂ ) ₄ -MgBr Lt; / RTI &gt; slurry. After stirring for one day, the solution was filtered, recrystallized with hexane and further filtered to obtain a dinuclear metallocene compound. (Yield: 34%)

^{1 H NMR (500MHz, C6D6)} : 1.52 (4H, m), 1.85 (4H, m), 2.56 (4H, d), 2.74 (4H, d), 5.54 (4H, d), 6.75 (4H, d) , 6.84 (4H, t), 6.91 (4H, d), 7.09 (4H, t), 7.56

Produce Example  3

3-1) Preparation of metallocene compound

A dried flask was prepared and 8 g (20 mmol) of the metallocene catalyst of Preparation Example 2-1) was prepared. The inside of the flask was replaced with argon, and 800 mL of dry dichloromethane was injected into the slurry state. In a glove box, 580 mg of PtO ₂ was weighed into a flask, and 300 mL of dichloromethane was added to the flask. The slurry was then poured into the metallocene catalyst slurry and agitated for about 5 minutes.

The autoclave pressure vessel was preliminarily washed one day before and dried in an oven. Subsequently, the inside of the pressure vessel was replaced with argon, and then the slurry in which the metallocene catalyst and PtO ₂ were mixed was placed in a pressure vessel using a cannula I moved. All the argon in the pressure vessel was vented, and the reaction was carried out for 20 hours with stirring at 300 rpm while replacing 30 atm of H ₂ . The mixture was filtered in a filter system that did not come in contact with outside air and the solvent of the filtrate was removed to obtain the title metallocene compound.

^{1 H NMR (500MHz, C6D6)} : 1.34 (4H, m), 1.83 (2H, m), 1.85 (2H, m), 2.16 (4H, m), 2.42 (6H, m), 3.14 (2H, m) , 5.25 (2H, d), 6.34 (2H, d)

3-2) Preparation of dinuclear metallocene compound

0.4 g (1.4 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, 1 g (2.3 mmol) of the metallocene compound 3-1) was charged and ether was injected into the slurry form. The slurry of BrMg- (CH ₂ ) ₄ -MgBr Lt; / RTI &gt; slurry. The mixture was stirred for one day and then filtered to obtain a dinuclear metallocene compound. (Yield: 45%)

^{1 H NMR (500MHz, C6D6)} : 1.32 (8H, m), 1.84 (8H, m), 1.94 (8H, m), 2.4 (16H, m), 3.32 (8H, m), 5.24 (4H, d) , 6.56 (4 H, d)

Produce Example  4

4-1) Preparation of metallocene compound

According to a known method, n-BuCp was prepared from n-butylchloride and NaCp, and ZrCl _{4 (} THF) ₂ was reacted with this to prepare a metallocene compound.

¹ H NMR (500 MHz, C6D6): 0.82 (6H, t), 1.20 (4H, m), 1.42 (4H, t), 2.63

4-2) Preparation of dinuclear metallocene compound

2.75 g (5 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, 4.04 g (10 mmol) of the metallocene compound of the above-mentioned 4-1) was added and ether was injected to form a slurry. Then, a slurry of BrMg- (CH ₂ ) ₄ -MgBr Lt; / RTI &gt; compound slurry. The mixture was stirred for one day and then filtered to obtain a dinuclear metallocene compound. (Yield: 85%)

¹ H NMR (500 MHz, C6D6): 0.89 (12H, m), 1.23 (4H, m), 1.28 (8H, m), 1.42 , 5.37-6.20 (12H, m)

Produce Example  5

5-1) Preparation of metallocene compound

1.16 g (10 mmol) of indene was dissolved in THF soltion, and 4.8 ml (12 mmol) of 2.5 M n-BuLi in hexane was added thereto at -78 ° C. and the mixture was stirred overnight at room temperature. The solution was transferred to 50 ml of a THF solution of 1.57 g (5 mmol) of 2,3-bis (bromomethyl) naphthalene under a dryice / aceton bath. After stirring overnight at room temperature, water was added and the organic layer was extracted with ether. The organic layer was separated, the residual water was removed with MgSO _4, and the solvent was vacuum dried to obtain a light yellow crude product. The crude product was recrystallized from ether / hexane to yield a high purity ligand compound (yield 100%).

To the dried 250 mL schlenk flask, 3.8 g (10 mmol) of the ligand compound synthesized above was added and dissolved in 100 mL of toluene. Then, 2 mL (10 mmol) of MTBE was added thereto, and then 8 mL (20 mmol) of 2.5 M nBuLi hexane solution was added for lithiation. One day later, 3.7 g (10 mmol) of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL schlenk flask and prepared with 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, and LiCl was removed. After the solvent was completely blown, hexane was poured into the filter cake to recrystallize the filter cake. ) Yielded a metallocene compound (yield 100%).

(2H, d), 5.71 (4H, brs), 7.15-7.99 (14H, m)

5-2) 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, 5.4 g (10 mmol) of the metallocene compound synthesized in 5-1) 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 solution 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.

(2H, d), 4.2 (2H, d), 4.4 (2H, d), 4.45 (4H, m) 6.1 (8H, m), 6.8 ~ 8.0 (28H, m)

Polyolefin  polymerization Example

Example  One

A 300 mL capacity Andrew bottle was prepared, assembled with the impeller part, and then replaced with argon in a glove box. 180 mL of toluene containing a small amount of trimethylaluminum (TMA) was placed in the Andrew bottle, which was treated in the glove box, and 5 mL of MAO (10 wt% toluene) solution was added. In a separate 100 mL flask, 10 μmol of the dinuclear metallocene compound of Preparation Example 1 was added and dissolved in 20 mL of MAO to prepare a catalyst solution. 5 mL of the catalyst solution was poured into the Andrew bottle and immersed in an oil bath heated to 90 ° C, and the top of the bottle was fixed to a mechanical stirrer. After the inside of the bottle was purged with ethylene gas three times, the ethylene valve was opened and the mechanical stirrer was operated to perform the reaction at 500 rpm for 30 minutes.

After the reaction was completed, the temperature was lowered to room temperature, and the gas inside the container was vented. Approximately 500 mL of ethanol was poured in, stirred for about 1 hour, and the polymer obtained through filtration was dried in an oven at 60 ° C for 20 hours. The mass of the obtained polymer was calculated, and the activity of the catalyst was calculated. From the polymer sample, the molecular weight and the molecular weight distribution (PDI) were confirmed by GPC analysis.

Example  2

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

Example  3

Polyolefin polymerization was carried out in the same manner as in Example 2, except that 5 ml of 1-hexene was further added as a comonomer to proceed the reaction.

Comparative Example  One

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

Comparative Example  2

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

Comparative Example  3

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

The catalyst activity and the physical properties of the olefin polymer in Examples 1 to 3 and Comparative Examples 1 to 3 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 - 6.9 77,316 9.35 Example 2 - 4.5 79,208 9.32 Example 3 1-hexene 10.7 34,698 5.08 Comparative Example 1 - 7.7 49,738 6.00 Comparative Example 2 - 6.9 72,064 6.41 Comparative Example 3 1-hexene 10.0 39,672 3.99

Referring to Table 1, when comparing the examples 1 to 3 and the comparative examples 1 to 3, when the binuclear metallocene catalyst of the present invention is used rather than the single nucleus metallocene catalyst, the high molecular weight and the molecular weight distribution It can be understood that a wide olefin polymer can be obtained. This effect was the same when 1-hexene was used as a comonomer.

Claims (10)

A dinuclear metallocene compound represented by the following formula (1): &lt; EMI ID =
[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;
Q is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 40 carbon atoms, or an arylalkylene group having 7 to 40 carbon atoms;
X is a halogen atom;
n is an integer from 1 to 10;
m is an integer of 1.
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, A heterocyclic metallocene compound linked to form one or more aliphatic, aromatic, or heterocyclic rings.
The method of claim 1, wherein R9 and R10 in Formula 1 are each independently hydrogen, alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, X is Cl, and n is an integer of 2 to 6. compound.
The dinuclear metallocene compound according to claim 1, wherein the dinuclear metallocene compound is represented by one of the following structural formulas (1a) to (1d):
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

&Lt; RTI ID = 0.0 &

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