KR101727701B1 - Dinuclear metallocene compound, and method for preparing the same - Google Patents

Abstract

The present invention relates to a novel structure of a dinuclear metallocene compound capable of producing a polyolefin having a high molecular weight distribution and a high molecular weight, and a process for producing the same. The dinuclear metallocene compound according to the present invention is a binuclear metallocene compound having a novel structure and unlike a single active site catalyst, it has a high accessibility to a substrate and can provide a catalyst having multiple active sites exhibiting high activity, When such a compound is used as a catalyst, the molecular weight of the polymer can be increased.

Description

A dinuclear metallocene compound and a method for preparing same,

The present invention relates to binuclear metallocene compounds, and processes for their preparation. More specifically, the present invention relates to a novel structure of a dinuclear metallocene compound capable of producing a high molecular weight polyolefin, and a process for producing 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.

As such a metallocene catalyst, WO 2008/084931 discloses a transition metal compound in which a monocyclopentadienyl ligand having an amido group is coordinated. However, this method is problematic in that the polyolefin polymerized with the mononuclear metallocene catalyst has a problem in that it is difficult to be applied on the spot because the molecular weight distribution is narrow and the productivity is remarkably decreased due to the influence of the extrusion load when applied to some products. I have done a lot of effort to adjust. A polymer having a narrow molecular weight distribution has a low melt flowability and melt tension, low moldability, and low stiffness.

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, there is a problem in the addition of a substituent group and a change of structure in the case of a Group 4 metal metallocene catalyst having a previously reported biphenylene bridge.

Therefore, it is necessary to develop a new metallocene catalyst having multiple active sites useful for the production of olefins, exhibiting high activity and having a wide molecular weight distribution.

Disclosed is a novel heterophasic metallocene compound capable of producing a highly active, high molecular weight polyolefin, and a process for producing the same.

It is another object of the present invention to provide a novel heterophasic catalyst composition using the above-mentioned dinuclear metallocene compound.

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

According to one aspect of the present invention, there is provided a nucleophilic metallocene compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₄ and R ₈ to R ₁₂ may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; Silyl radical; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; Or an arylalkyl radical having 7 to 20 carbon atoms; Two or more adjacent ones of R ₁ to R ₄ may be connected to each other to form an aliphatic ring or an aromatic ring;

R ₅ to R ₇ may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical; Two or more adjacent ones of R ₅ to R ₇ may be connected to each other to form an aliphatic ring or aromatic ring;

CY is an aliphatic or aromatic ring containing nitrogen and may be substituted or unsubstituted with halogen, an alkyl or aryl radical having 1 to 20 carbon atoms, and when the number of substituents is plural, two or more substituents in the substituent are connected to each other An aliphatic or aromatic ring;

M ₁ and M ₂ may be the same or different from each other and are each independently a Group 4 transition metal;

X ₁ and X ₂ may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms;

R ₁₃ is a substituent comprising a group 15 or group 16 heteroatom bonded to an imine carbon atom, each substituent independently selected from the group consisting of hydrogen, a halogen radical, a straight or branched alkyl radical having from 1 to 20 carbon atoms, an alkyl radical having from 2 to 20 carbon atoms An alkenyl radical, a silyl radical, an aryl radical having 6 to 20 carbon atoms, an alkylaryl radical having 7 to 20 carbon atoms, or an arylalkyl radical having 7 to 20 carbon atoms;

Each R ₁₄ is independently an aryl radical having 6 to 20 carbon atoms, which is substituted with hydrogen, halogen or an alkyl group having 1 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or a cycloalkyl radical having 3 to 20 carbon atoms;

n is an integer of 0 to 10;

In a second aspect of the present invention, there is provided a process for preparing the dinuclear metallocene compound, which comprises reacting a compound represented by the following formula (2) with a compound represented by the following formula (3).

[Chemical Formula 1]

(2)

(3)

Wherein R ₁ to R ₁₄ , CY, M ₁ , M ₂ , X ₁ , X ₂ , and n are as defined above, and M is Li or Mg.

The third aspect of the present invention also relates to the above-described dinuclear metallocene compound; And an alkyl aluminum compound in a molar ratio of 1: 10 to 1: 5.

The dinuclear metallocene compound according to the present invention is a dinuclear metallocene compound having a novel structure and unlike a single active site catalyst, since it has two active sites, it has high accessibility to a substrate and thus has multiple active sites Catalyst can be provided.

Also, when the catalyst of the present invention is used, high comonomer incorporation can be expected due to high accessibility of the comonomer, high molecular weight distribution with high activity according to multiple active sites, and high molecular weight polyolefin can be produced.

In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

Moreover, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

Also in the present invention, when referring to each layer or element being "on" or "on" each layer or element, it is meant that each layer or element is formed directly on each layer or element, Layer or element may be additionally formed between each layer, the object, and the substrate.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the present invention will be described in detail.

According to one embodiment of the present invention, there is provided a binuclear metallocene compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₄ and R ₈ to R ₁₂ may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; Silyl radical; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; Or an arylalkyl radical having 7 to 20 carbon atoms; Two or more adjacent ones of R ₁ to R ₄ may be connected to each other to form an aliphatic ring or an aromatic ring;

R ₅ to R ₇ may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical; Two or more adjacent ones of R ₅ to R ₇ may be connected to each other to form an aliphatic ring or aromatic ring;

CY is an aliphatic or aromatic ring containing nitrogen and may be substituted or unsubstituted with halogen, an alkyl or aryl radical having 1 to 20 carbon atoms, and when the number of substituents is plural, two or more substituents in the substituent are connected to each other An aliphatic or aromatic ring;

M ₁ and M ₂ may be the same or different from each other and are each independently a Group 4 transition metal;

X ₁ and X ₂ may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms;

R ₁₃ is a substituent comprising a group 15 or group 16 heteroatom bonded to an imine carbon atom, each substituent independently selected from the group consisting of hydrogen, a halogen radical, a straight or branched alkyl radical having from 1 to 20 carbon atoms, an alkyl radical having from 2 to 20 carbon atoms An alkenyl radical, a silyl radical, an aryl radical having 6 to 20 carbon atoms, an alkylaryl radical having 7 to 20 carbon atoms, or an arylalkyl radical having 7 to 20 carbon atoms;

Each R ₁₄ is independently an aryl radical having 6 to 20 carbon atoms, which is substituted with hydrogen, halogen or an alkyl group having 1 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or a cycloalkyl radical having 3 to 20 carbon atoms;

n is an integer of 0 to 10;

The present invention relates to a process for preparing a heterogeneous dinuclear transition metal catalyst having two active sites, unlike a conventional single catalyst, as a polymerization catalyst for olefin polymerization.

In the case of the dinuclear catalyst, when a heterogeneous cationic species is formed, the accessibility of the comonomer is increased, so that a high comonomer incorporation can be expected. In addition, since there are multiple active sites, accessibility, Can exhibit high activity. Therefore, the nucleophilic metallocene compound of formula (1) of the present invention can secure multiple active sites and exhibits high activity compared to the conventional ones, and thus can produce a polyolefin having a high molecular weight when used as a catalyst.

According to an embodiment of the present invention, in the dinuclear metallocene compound of Formula 1, each of R ₁ to R ₁₂ is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, Two adjacent ones of R ₁ to R _{7 may} be connected with each other to form at least one aliphatic ring or aromatic ring, but the present invention is not limited thereto.

The CY may be a pentagonal or hexagonal aliphatic or aromatic ring including an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, but the present invention is not limited thereto.

M ₁ and M ₂ may each independently be titanium (Ti), zirconium (Zr), or hafnium (Hf), and X ₁ and X ₂ are each independently halogen or an alkyl group having 1 to 20 carbon atoms However, the present invention is not limited thereto.

In the dinuclear metallocene compound of Formula 1, R ₁₃ is a substituent containing a hetero atom of Group 15 or Group 16, and R ₁₄ may be bonded to the imine carbon atom through the 15 or 16 group hetero atom. In Formula 1, R ₁₄ is a substituent containing a group 14 atom, and R ₁₃ is bonded to the imine carbon atom through the group 14 atom.

Preferably, in the above formula (1), the substituent comprising the R ₁₃ to 15 group or 16 group heteroatom includes, independently of each other, a Group 15 or Group 16 atom substituted with a straight or branched alkyl radical having 1 to 20 carbon atoms And R ₁₄ each independently represents hydrogen or an aryl radical having 6 to 20 carbon atoms substituted with halogen, but the present invention is not limited thereto.

The dinuclear metallocene compound of formula (1) of the present invention is a transition metal compound in which a dinuclear ligand in which a monocyclopentadienyl ligand having a quinolone group or an indolin group amido group introduced therein is crosslinked with an amide group is coordinated to a Group 4 transition metal Lt; / RTI >

That is, the dinuclear metallocene compound represented by the above-mentioned formula (1) can be produced by reacting a single metallocene compound in which a phenylene group having a cyclic amido group is bridged and an amidine-containing cyclopentadienyl ligand in the presence of an alkylenedioxy (-O- CH ₂ ) n O-). Therefore, in the case of the present invention, two metal centers are connected by a diether chain serving as a linker to reduce unnecessary interaction between metals, thereby having stable catalytic activity and being easy to deform the structure do. Therefore, the dinuclear metallocene compound of the present invention has multiple active sites unlike a single active site catalyst, so that the accessibility and the opportunity for the substrate and the active site to meet can be high, indicating high activity. Accordingly, when the above-described dinuclear metallocene compound is used as a catalyst in polyolefin polymerization or copolymerization, a polyolefin having a high molecular weight and a broad molecular weight distribution can be produced with high activity. Also, various substituents can be introduced into a cyclic amido ring such as cyclopentadienyl and quinoline or indolin, which ultimately makes it possible to easily control the electronic and stereoscopic environment around the metal. That is, by using a compound having such a structure as a catalyst, it is easy to control the structure and physical properties of the olefin polymer produced.

Examples of the binuclear metallocene compound represented by the formula (1) include, but are not limited to, the following compounds.

According to another aspect of the present invention, there is provided a process for preparing a dinuclear metallocene compound represented by the following formula (1), which comprises reacting a compound represented by the following formula (2) and a compound represented by the following formula do.

[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,

R ₁ to R ₄ and R ₈ to R ₁₂ may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; Silyl radical; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; Or an arylalkyl radical having 7 to 20 carbon atoms; Two or more adjacent ones of R1 to R4 may be connected to each other to form an aliphatic ring or an aromatic ring;

R ₅ to R ₇ may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical; Two or more adjacent ones of R5 to R7 may be connected to each other to form an aliphatic ring or an aromatic ring;

CY is an aliphatic or aromatic ring containing nitrogen and may be substituted or unsubstituted with halogen, an alkyl or aryl radical having 1 to 20 carbon atoms, and when the number of substituents is plural, two or more substituents in the substituent are connected to each other An aliphatic or aromatic ring;

M is Li or Mg;

M ₁ and M ₂ may be the same or different from each other and are each independently a Group 4 transition metal;

X ₁ and X ₂ may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms;

R ₁₃ is a substituent comprising a group 15 or group 16 heteroatom bonded to an imine carbon atom, each substituent independently selected from the group consisting of hydrogen, a halogen radical, a straight or branched alkyl radical having from 1 to 20 carbon atoms, an alkyl radical having from 2 to 20 carbon atoms An alkenyl radical, a silyl radical, an aryl radical having 6 to 20 carbon atoms, an alkylaryl radical having 7 to 20 carbon atoms, or an arylalkyl radical having 7 to 20 carbon atoms;

Each R ₁₄ is independently an aryl radical having 6 to 20 carbon atoms, which is substituted with hydrogen, halogen or an alkyl group having 1 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or a cycloalkyl radical having 3 to 20 carbon atoms;

n is an integer of 0 to 10;

The method for producing the dinuclear metallocene compound of the present invention comprises mixing the single nucleated metallocene compound represented by Formula 2 and the amidine-containing compound represented by Formula 3, stirring the mixture for a predetermined time, .

This reaction can also be carried out at low temperature and under a solvent. Preferably, the step of reacting the compound represented by Formula 2 with the compound represented by Formula 3 may be performed by stirring at -70 ° C to -30 ° C in a THF solvent. In the present invention, as the reaction proceeds at a low temperature, the selectivity of the reaction can be increased.

The diol compound represented by the formula (2) may be reacted with 1.0 equivalent of the equivalent of the single nucleated metallocene compound represented by the formula (3).

The compound represented by Formula 2 is reacted in an organic solvent in the presence of a base represented by the following Formula 4 with RM represented by RM (wherein R is an alkyl group having 1 to 10 carbon atoms and M is Li or Mg) , And then reacting the compound represented by the following formula (5).

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (4) and (5)

R ₁ to R ₄ may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; Silyl radical; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; Or an arylalkyl radical having 7 to 20 carbon atoms; Two or more adjacent ones of R ₁ to R ₄ may be connected to each other to form an aliphatic ring or an aromatic ring;

R ₅ to R ₇ may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical; Two or more adjacent ones of R ₅ to R ₇ may be connected to each other to form an aliphatic ring or aromatic ring;

CY is an aliphatic or aromatic ring containing nitrogen and may be substituted or unsubstituted with halogen, an alkyl or aryl radical having 1 to 20 carbon atoms, and when the number of substituents is plural, two or more substituents in the substituent are connected to each other An aliphatic or aromatic ring;

M ₁ is a Group 4 transition metal;

X ₁ and X ₂ may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms;

n is an integer of 0 to 10;

The compounds represented by RM include n-BuLi and the like, but the present invention is not limited thereto. The method for producing the single nuclear metallocene compound represented by the above-mentioned formula (5) can be produced according to a method known in the technical field of the present invention, and is not particularly limited.

Meanwhile, the reaction for preparing the compound represented by the formula (2) can be carried out by stirring at -70 ° C to -20 ° C in an organic solvent, preferably a THF solvent.

Further, in the above method, the stirring time of each reaction can be performed by stirring for 12 hours or more, for example, about 12 hours to about 36 hours, but the present invention is not limited thereto. Further, the stirring may be performed in an organic solvent such as MTBE (methyl tertiary-butyl ether) or toluene, and may be obtained in the form of a dinuclear metallocene compound by extraction with n-hexane, but the production method of the present invention is not limited thereto .

The process for preparing the dinuclear metallocene compound represented by the above formula (1) will be described in more detail in the following Examples.

According to the production process of the present invention, the dinuclear metallocene compound represented by the formula (1) can be prepared by a simple process under relatively mild conditions, and the distance of the dinuclear active point can be controlled according to the alkyl chain length of the diol compound, The activity can be easily controlled while reducing the action. In addition, it has a stable catalytic activity and is easy to deform the structure. Unlike a single-site catalyst, it has high activity because it has high accessibility to a substrate.

The dinuclear metallocene compound represented by the above formula (1) can be used alone or in combination with a cocatalyst to prepare a polyolefin polymer as a catalyst composition, and particularly a polyolefin having a high molecular weight can be produced with high activity. For example, an olefin homopolymer or an olefin copolymer can be provided by carrying out a polymerization process by bringing the catalyst composition containing the dinuclear metallocene compound represented by Formula 1 into contact with a monomer.

Therefore, according to another embodiment of the present invention, the above-mentioned dinuclear metallocene compound; And an alkyl aluminum compound in a molar ratio of 1:10 to 10: 1.

That is, in the present invention, when the alkylaluminum compound: the transition metal compound of Formula 1 is contacted with the borate promoter at a specific molar ratio of the above-described ratio, preferably 5: 1, to produce a polymer having a high molecular weight distribution and a high molecular weight There is a characteristic that an improved catalyst composition can be provided.

The alkylaluminum compound may be a trialkylaluminum compound having a straight or branched alkyl group having 1 to 20 carbon atoms, but is not limited thereto. Examples of the trialkylaluminum may include at least one member selected from the group consisting of trimethylaluminum, triethylaluminum, and triisobutylaluminum.

In addition, the present invention may further include a cocatalyst in the catalyst composition, if necessary, and the kind thereof is not particularly limited. The catalyst composition may further comprise a reaction solvent, and examples of the reaction solvent include hydrocarbon solvents such as pentane, hexane or heptane; Aromatic solvents such as benzene or toluene, but are not limited thereto.

The present invention also provides a process for producing a polyolefin comprising copolymerizing at least one olefin monomer under the catalyst composition. As the olefin monomer, materials well known in the art can be used, and the kind thereof is not particularly limited. The polyolefin produced by this method has a broad molecular weight distribution and can exhibit a high molecular weight as compared with the conventional polyolefin.

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 >

The organic reagents and solvents used in the following examples were purchased from Aldrich and purified by standard methods. At every stage of the synthesis, the contact between air and water is blocked to improve the reproducibility of the experiment.

Nucleus Metallocene  Synthesis of compounds

Manufacturing example  One

(Preparation of compound of formula (2)

[Reaction Scheme 1]

1,6-hexanediol (1.0 g, 8.46 mmol) of Formula 4 was dissolved in 70 mL of THF at -40 ° C and n-BuLi (3.4 mL, 8.46 mmol) was slowly added dropwise thereto to obtain lithium 6-hydroxyhexan- (lithium 6-hydroxyhexane-1-olate, white powder) (Compound A).

Then, a solution of the compound of Formula 5 (8.46 mmol) in 40 mL of THF was added dropwise to a solution of lithium 6-hydroxyhexane-1-olate (8.46 mmol, in THF 40 mL slurry). After slowly dropping at low temperature, the temperature was gradually raised for about 1 hour, and then stirred at room temperature for 12 hours. Yellow powder was obtained through extraction with toluene.

_{^{1 H NMR (CDCl 3):}} δ 0.06 (s, 3H, Ti-CH 3), 1.35 (s, 4H, (CH 2) 2), 1.89 ~ 1.87 (m, 4H, (CH 2) 2), 1.77 (s, 3H, Cp-CH 3), 1.91 (m, 6H, Cp-CH 3), 1.97 (s, 3H, Cp-CH 3), 2.11 ~ 2.10 (m, 5H, Cp-CH 3 and quonoline- _{CH 2), 2.62 ~ 2.60 (} m, 2H, quinoline-CH 2), 3.75 (m, 2H, OCH 2), 4.19 ~ 4.09 (m, 2H, quinoline-NCH 2), 4.22 ~ 4.20 (m, 2H, O-CH ₂ ), 6.72 (m, 1H, aromatic), 6.96 (m, 2H, aromatic) ppm

Manufacturing example  2

(Preparation of Compound 3)

Compound No. 3 was synthesized with reference to WO 2005 / 090418A1.

Example  One

(Preparation of compound 1)

[Reaction Scheme 2]

A solution of Compound (3) (100 mg, 0.2 mmol) of Preparation Example 2 in 10 mL of THF was added to a slurry obtained by dissolving Compound (2) (89 mg, 0.2 mmol) of Preparation Example 1 in 10 mL of THF at -20 ° C And gradually dropped. When the dropwise addition was completed, the temperature was gradually raised, and the mixture was stirred at room temperature for 12 hours. The solvent was then dried and extracted with toluene to obtain an orange oil compound (1).

_{^{1 H NMR (CDCl 3):}} δ 0.16 ~ 0.20 (m, 3H, Cp-CH 3), 1.93 (s, 15H, Cp *). 1.27 (m, 6H, CH ( CH 3) 2), 1.30 ~ 1.34 (m, 4H, (CH 2) 2), 1.43 (m, 12H, CP (CH3) 4), 1.58 ~ 1.55 (m, 4H, _{(CH 2) 2), 1.59} (m, 6H, CH (CH 3) 2), 3.76 (m, 2H, N-CH 2), 3.41 ~ 3.74 (m, 2H, N-CH), 4.36 ~ 4.15 ( _{m, 6H, O- (CH 2} ) 2, N-CH 2), 6.89 ~ 6.91 (3H, PhH), 6.98 (1H, PhH), 7.27 ~ 7.28 (2H, PhH) ppm

Comparative Example  One

Compounds of the above formula were prepared according to the methods described in Examples 1 and 2 of WO 2008/08431 A1.

Preparation of olefin copolymer

Experimental Example  One

A hexane solvent (1.0 L) and 210 mL of 1-octene were added to a 2 L autoclave reactor, and then the temperature of the reactor was preheated to 120 ° C. (1.0 mu mol) of the compound of Example 1 treated with triisobutylaluminum compound (2.5 mu mol) and a dimethylanilinium tetrakis (pentafluorophenyl) borate co-catalyst (20 mu mol) were sequentially added to a 25 mL catalyst storage tank (Al: Ti molar ratio = 10: 1). In addition, trioctyl aluminum was used as a scavenger. Ethylene pressure (35 bar) was then charged into the autoclave reactor, and the catalyst composition was injected into the reactor using argon gas at a high pressure to conduct the copolymerization reaction for 8 minutes. Next, the remaining ethylene gas was removed and the polymer solution was added to excess ethanol to induce precipitation. The precipitated polymer was washed with ethanol and acetone two to three times, respectively, and then dried in a vacuum oven at 80 캜 for 12 hours or more, and then the physical properties thereof were measured.

compare Experimental Example  One

In the same manner as in Experimental Example 1, except that triisobutylaluminum compound (10 占 퐉 ol) and 1.0 占 퐉 ol of the compound of Comparative Example 1 were used instead of the compound of Example 1 in Experimental Example 1, an ethylene-1-octene copolymer .

That is, a hexane solvent (1.0 L) and 210 mL of 1-octene were added to a 2 L autoclave reactor, and then the temperature of the reactor was preheated to 120 ° C. (1.0 mu mol) of the compound of Comparative Example 1 treated with a triisobutylaluminum compound (2.5 mu mol) and a dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (20 mu mol) were sequentially added to a 25 mL catalyst storage tank (Al: Ti molar ratio = 10: 1). Ethylene pressure (35 bar) was then charged into the autoclave reactor, and the catalyst composition was injected into the reactor using argon gas at a high pressure to proceed the copolymerization reaction for 8 minutes. Next, the remaining ethylene gas was removed and the polymer solution was added to excess ethanol to induce precipitation. The precipitated polymer was washed with ethanol and acetone two to three times, respectively, and then dried in a vacuum oven at 80 캜 for 12 hours or more, and then the physical properties thereof were measured.

Experimental Example 1 Comparative Experimental Example 1 Catalyst compound Example 1 Comparative Example 1 Reaction temperature (unit: ℃) 120 120 Catalyst compound (unit: μmol) 1.0 2.0 Al (cocatalyst): Ti (catalyst compound) mole ratio 10 10 1-octene dosage
(Unit: mL) 210 210 Activity
(Unit: kgPOE / mmol Ti hr) 70 91 Melt Index I ₂
(Unit: g / 10 min) 0.47 1.27 density
(Unit: g / ml) 0.8654 0.8657 Tm (unit: ° C) 51.3, 99.9 53.4 Mw (g / gmol) 172.838 133,959 Mn (g / gmol) 77,213 59,273 PDI (g / gmol) 2.24 2.26

Referring to Table 1, the dinuclear metallocene compound of the present invention has multiple active sites as a structure connected by a diether chain, compared to a single metallocene compound, and thus has high accessibility to a substrate. That is, when the dinuclear metallocene compound of Example 1 was used, dicationic species were formed to improve the accessibility of the comonomer, thereby inducing a high comonomer bond and exhibiting multiple active sites. Thus, unnecessary interaction between the metals is minimized, so that stable catalytic activity is obtained. Thus, a portion having high crystallinity and a portion having low crystallinity are simultaneously present from the dinuclear active sites having different comonomer reactivity, It was possible to produce a polyolefin having a higher molecular weight than that of a rossen catalyst.

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 ₁₂ are each independently hydrogen or an alkyl radical having 1 to 20 carbon atoms;
CY is a hexagonal aliphatic ring containing nitrogen substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms;
M ₁ and M ₂ are each independently titanium (Ti), zirconium (Zr), or hafnium (Hf);
X ₁ and X ₂ may be the same or different from each other and are each independently a halogen radical; Or an alkyl radical having 1 to 20 carbon atoms;
R &lt; ₁₃ &gt; is a substituent comprising a heteroatom of group 15 bonded to an imine carbon atom, said substituent being each independently hydrogen, or substituted with a straight or branched alkyl radical having from 1 to 20 carbon atoms;
Each R &lt; ₁₄ &gt; is independently an aryl radical having 6 to 20 carbon atoms, which is substituted with hydrogen, halogen or an alkyl group having 1 to 20 carbon atoms;
n is an integer of 0 to 3;
delete delete The dinuclear metallocene compound according to claim 1, wherein the compound represented by the formula (1) is represented by the following structural formula:

A process for producing a dinuclear metallocene compound represented by the following formula (1), comprising reacting a compound represented by the following formula (2) and a compound represented by the following formula (3)
[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,
R ₁ to R ₁₂ are each independently hydrogen or an alkyl radical having 1 to 20 carbon atoms;
CY is a hexagonal aliphatic ring containing nitrogen substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms;
M ₁ and M ₂ are each independently titanium (Ti), zirconium (Zr), or hafnium (Hf);
X ₁ and X ₂ may be the same or different from each other and are each independently a halogen radical; Or an alkyl radical having 1 to 20 carbon atoms;
R &lt; ₁₃ &gt; is a substituent comprising a heteroatom of group 15 bonded to an imine carbon atom, said substituent being each independently hydrogen, or substituted with a straight or branched alkyl radical having from 1 to 20 carbon atoms;
Each R &lt; ₁₄ &gt; is independently an aryl radical having 6 to 20 carbon atoms, which is substituted with hydrogen, halogen or an alkyl group having 1 to 20 carbon atoms;
n is an integer of 0 to 3;
The process according to claim 5, wherein the step of reacting the compound represented by the formula (2) and the compound represented by the formula (3) is carried out by stirring at -70 ° C to -20 ° C in a THF solvent, Gt;
6. The compound according to claim 5, wherein the compound represented by the formula (2)
Reacting a diol compound represented by the following formula (4) with an organic solvent in the presence of a base represented by RM (wherein R is an alkyl group having 1 to 10 carbon atoms and M is Li or Mg), and then reacting the compound &Lt; / RTI &gt; in the presence of a metal catalyst.
[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (4) and (5)
R ₁ to R ₇ are each independently hydrogen or an alkyl radical having 1 to 20 carbon atoms;
CY is a hexagonal aliphatic ring containing nitrogen substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms;
M ₁ is each independently titanium (Ti), zirconium (Zr), or hafnium (Hf);
X ₁ and X ₂ may be the same or different from each other and are each independently a halogen radical; Or an alkyl radical having 1 to 20 carbon atoms;
n is an integer of 0 to 3;
A dinuclear metallocene compound according to claim 1; And an alkyl aluminum compound in a molar ratio of 1:10 to 10: 1.
The catalyst composition of claim 8, wherein the molar ratio is 5: 1.
The catalyst composition according to claim 9, wherein the alkyl aluminum compound is a trialkyl aluminum compound having a straight or branched alkyl group having 1 to 20 carbon atoms.