KR101637026B1 - Metallocene supported catalyst and method for preparing polyolefin using the same - Google Patents

Abstract

The present invention relates to a novel metallocene supported catalyst and a process for producing a polyolefin using the metallocene supported catalyst. The metallocene supported catalyst according to the present invention can be used in the production of polyolefins, has excellent activity, is excellent in reactivity with comonomers, and can effectively produce olefin polymers having high molecular weight and low molecular weight.

Description

METALLOCENE SUPPORTED CATALYST AND METHOD FOR PREPARING POLYOLEFIN USING THE SAME Technical Field [1] The present invention relates to a metallocene supported catalyst,

The present invention relates to a novel metallocene supported catalyst and a process for producing a polyolefin using the metallocene supported catalyst.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to conventional commercial processes since the invention of the 50's. However, since the Ziegler-Natta catalyst is a multi-site catalyst containing a plurality of active sites, the molecular weight distribution of the polymer is broad, There is a problem that the desired physical properties can not be secured.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst, . The polymer has a narrow molecular weight distribution according to the single active site property and a homogeneous composition distribution of the comonomer is obtained. According to the modification of the ligand structure and the polymerization conditions of the catalyst, the stereoregularity of the polymer, Crystallinity and so on.

U.S. Patent No. 5,032,562 discloses a method of 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.

U.S. Patent No. 5,525,678 discloses a method of using an olefin polymerization catalyst system capable of simultaneously polymerizing a high molecular weight polymer and a low molecular weight polymer by supporting a metallocene compound and a non-metallocene compound on a carrier simultaneously. This is a disadvantage in that the metallocene compound and the non-metallocene compound must be supported separately and the carrier must be pretreated with various compounds for the supporting reaction.

U.S. Patent No. 5,914,289 discloses a method of controlling the molecular weight and molecular weight distribution of a polymer by using a metallocene catalyst supported on each support. However, the amount of the solvent used for preparing the supported catalyst and the preparation time are long , And the metallocene catalyst used had to be carried on the carrier, respectively.

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 activating agent in a carrier to change and polymerize the combination of catalysts in the reactor have. 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.

Therefore, there is a continuing need for a method for producing a polyolefin having desired physical properties by preparing a hybrid supported metallocene catalyst having excellent activity in order to solve the above-mentioned disadvantages.

In order to solve the problems of the prior art, the present invention provides a metallocene supported catalyst capable of producing a highly active and high molecular weight polyolefin, a process for producing the same, and a polyolefin produced using the same.

In particular, the present invention relates to a metallocene compound capable of polymerizing a polyolefin having a high molecular weight and a low molecular weight, exhibiting a high polymerization activity even when supported on a carrier, excellent in reactivity with comonomer, a supported catalyst containing the metallocene compound, To provide a polyolefin produced by using the polyolefin.

The present invention relates to at least one metallocene compound represented by the following general formula (1): A cocatalyst compound; And a metallocene supported catalyst comprising a carrier.

[Chemical Formula 1]

In Formula 1,

M is a Group 4 transition metal;

B is carbon, silicon or germanium;

Q ₁ and Q ₂ are the same or different and are each independently selected from the group consisting of hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, A C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

X ₁ and X ₂ are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

C ₁ and C ₂ are the same or different from each other, and each independently represents one of the following formulas (2a), (2b), (2c), or (2d), provided that at least one of C ₁ and C ₂ is represented by formula (2a);

(2a)

(2b)

[Chemical Formula 2c]

(2d)

In the above formulas (2a), (2b), (2c) and (2d)

R ₁ to R ₂₈ are the same or different from each other and each independently represents hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, A C1 to C20 silyl ether group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, ,

R ' ₁ to R' ₃ are the same or different from each other and each independently represent hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group,

Two or more adjacent R ₁ to R ₂₈ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

The present invention also provides a process for producing a polyolefin comprising polymerizing an olefin monomer in the presence of the catalyst.

Further, the present invention provides a polyolefin produced by the above-mentioned production method.

The metallocene supported catalyst according to the present invention can be used in the production of polyolefins, has excellent activity, is excellent in reactivity with comonomer, and can produce polyolefins having high molecular weight and low molecular weight.

In particular, the metallocene catalyst compound of the present invention exhibits high polymerization activity even when supported on a carrier, and can polymerize polyolefins having a high molecular weight and a low molecular weight.

In addition, since the lifetime of the catalyst is long, the activity can be maintained even in a long residence time in the reactor.

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, integers, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

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 more detail.

The metallocene supported catalyst according to the present invention comprises at least one metallocene compound represented by the following general formula (1): A cocatalyst compound; And a carrier.

[Chemical Formula 1]

In Formula 1,

M is a Group 4 transition metal;

B is carbon, silicon or germanium;

Q ₁ and Q ₂ are the same or different and are each independently selected from the group consisting of hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, A C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

X ₁ and X ₂ are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

C ₁ and C ₂ are the same or different from each other, and each independently represents one of the following formulas (2a), (2b), (2c), or (2d), provided that at least one of C ₁ and C ₂ is represented by formula (2a);

(2a)

(2b)

[Chemical Formula 2c]

(2d)

In the above formulas (2a), (2b), (2c) and (2d)

R ₁ to R ₂₈ are the same or different from each other and each independently represents hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, A C1 to C20 silyl ether group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, ,

R ' ₁ to R' ₃ are the same or different from each other and each independently represent hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group,

Two or more adjacent R ₁ to R ₂₈ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

The present invention can produce a highly active polyolefin as well as maintain excellent copolymerization by using the structural formula (2a) having a specific substituent in at least one of C ₁ and C ₂ of the above formula (1).

In the metallocene supported catalyst according to the present invention, the substituents of the above formula (1) will be more specifically described below.

Examples of the C1 to C20 alkyl group include a linear or branched alkyl group and specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, An octyl group, and the like, but are not limited thereto.

The C2 to C20 alkenyl group includes a straight chain or branched alkenyl group, and specific examples include, but are not limited to, an allyl group, an ethenyl group, a propenyl group, a butenyl group, and a pentenyl group.

The C6 to C20 aryl group includes an aryl group of a monocyclic or condensed ring, and specifically includes, but is not limited to, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group and a fluorenyl group.

The C5 to C20 heteroaryl group includes a heteroaryl group of a monocyclic or condensed ring and includes a carbazolyl group, a pyridyl group, a quinolinyl group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, , Triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.

Examples of the C1 to C20 alkoxy groups include, but are not limited to, a methoxy group, an ethoxy group, a phenyloxy group, a cyclohexyloxy group, and a tert-butoxyhexyl group.

Examples of the C1 to C20 alkylsilyl group include methylsilyl group, dimethylsilyl group, trimethylsilyl group and the like, but are not limited thereto.

A silyl group of the C1 to C20 is a silyl group, dimethylsilyl group _{(-CH 2 -Si (CH 3)} 2 H), trimethyl silyl methyl group _{(-CH 2 -Si (CH 3)} 3) , and the like. However, But is not limited thereto.

Examples of the Group 4 transition metal include titanium (Ti), zirconium (Zr), hafnium (Hf), and the like.

In the metallocene supported catalyst according to the present invention, R ₁ to R ₂₈ in the above formulas (2a), (2b), (2c) and (2d) are each independently selected from the group consisting of hydrogen, halogen, a methyl group, an ethyl group, a propyl group, A halogen atom, an ether group, a trimethylsilyl group, a trimethylsilyl group, a trimethylsilyl group, a trimethylsilyl group, a trimethylsilyl group, a trimethylsilyl group, a trimethylsilyl group, , A tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, a dimethyl ether group, a tert-butyldimethylsilyl ether group, a methoxy group, an ethoxy group or a tert-butoxyhexyl group , But is not limited thereto.

Q ₁ and Q ₂ in the general formula (1) are each independently selected from the group consisting of hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxymethyl group, -Methyl-1-methoxyethyl group, a tert-butoxyhexyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group, but is not limited thereto.

In addition, B in the above formula (1) is preferably silicon, but it is not limited thereto.

The metallocene compound of Formula 1 is characterized in that at least one C1 to C20 silylalkyl group such as trimethylsilyl methyl is included in the substituent of Formula 2a.

More specifically, the indene derivative of the above formula (2a) has a relatively low electron density compared to the indanediol derivative or the fluorenyl derivative, and the silylalkyl group having a large steric hindrance has a similar steric hindrance effect and electron density factor An olefin polymer having a relatively low molecular weight as compared with the metallocene compound having a structure can be polymerized with high activity.

The indenoindole derivative represented by Formula 2b, the fluorenyl derivative which may be represented by Formula 2c, the indene compound represented by Formula 2d, The derivative forms a structure bridged by a bridge and exhibits a high polymerization activity by having a nonspecific electron pair capable of acting as a Lewis base in the ligand structure.

According to an embodiment of the present invention, specific examples of the functional group represented by the formula (2a) include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

Specific examples of the functional group represented by Formula 2b include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

Specific examples of the functional group represented by Formula 2c include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

Specific examples of the functional group represented by the formula (2d) include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

In addition, specific examples of the metallocene compound represented by Formula 1 include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

The metallocene compound of formula (1) can polymerize olefin polymers having high activity, excellent activity, and high molecular weight and low molecular weight.

In addition, at the same time, when the polymerization reaction including hydrogen is carried out in order to produce an olefin polymer having a broad molecular weight distribution, the metallocene compound according to the present invention exhibits low hydrogen reactivity, Polymerization of an olefinic polymer having a molecular weight is possible. Therefore, even when used in combination with a catalyst having other properties, it is possible to produce an olefin polymer satisfying the characteristics of a high molecular weight and a low molecular weight without lowering the activity, and it is possible to produce olefin polymers containing high molecular weight and low molecular weight olefin polymers An olefin polymer having a molecular weight distribution can be easily produced.

According to an embodiment of the present invention, the metallocene compound of Formula 1 may be prepared by ligating an indene derivative and a cyclopentadiene derivative with a bridge compound to prepare a ligand compound, and then adding a metal precursor compound to perform metallation. , But is not limited thereto.

More specifically, for example, a lithium salt is prepared by reacting an indene derivative with an organolithium compound such as n-BuLi, and a halogenated compound of the bridging compound is mixed and then reacted to prepare a ligand compound. The ligand compound or a lithium salt thereof and a metal precursor compound are mixed and reacted for about 12 hours to about 24 hours until the reaction is completed. The reaction product is then filtered and dried under reduced pressure to obtain the metallocene compound represented by Formula 1 . The method for preparing the metallocene compound of the formula (1) will be described in the following examples.

The metallocene supported catalyst of the present invention may further include at least one of the promoter compounds represented by the following formulas (3), (4) or (5) in addition to the metallocene compound.

(3)

_{- [Al (R 30) -O} ] m -

In Formula 3,

R ₃₀ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

m is an integer of 2 or more;

[Chemical Formula 4]

J ( _R31 ) ₃

In Formula 4,

R ₃₁ is as defined in Formula 3 above;

J is aluminum or boron;

[Chemical Formula 5]

[EH] ⁺ [ZA ₄ ] ^- or [E] ⁺ [ZA ₄ ] ^-

In Formula 5,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a Group 13 element;

A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .

Examples of the compound represented by the general formula (3) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.

Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N , N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra (p- Phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.

Preferably, alumoxane can be used, more preferably methylalumoxane (MAO), which is alkylalumoxane.

The metallocene supported catalyst according to the present invention is characterized in that it comprises, as a first method, 1) contacting a metallocene compound represented by the formula 1 with a compound represented by the formula 3 or 4 to obtain a mixture; And 2) adding the compound represented by Formula 5 to the mixture.

The metallocene supported catalyst 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 3 as a second method.

In the first method of the supported catalyst production method, the molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 3 or Formula 4 is preferably 1 / 5,000 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 (3) or the formula (4) is more than 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 1/5000, the alkylation of the metal compound is performed, but the alkylated metal compound is not fully activated 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 5 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 5 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 price of the supported catalyst is insufficient due to the excess activating agent remaining or the purity of the produced polymer is low .

In the second method of the above-mentioned supported catalyst production method, the molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 3 is preferably 1 / 10,000 to 1/10, 1 / 5,000 to 1/100, and most preferably 1/3000 to 1/500. When the molar ratio exceeds 1/10, the amount of the activating agent is relatively small and the activation of the metal compound can not be completely performed, resulting in a decrease in activity of the supported catalyst. When the molar ratio is less than 1 / 10,000, The activation is completely carried out, but there is a problem that the unit price of the supported catalyst is insufficient due to the remaining excess of the activating agent, or the purity of the produced polymer is lowered.

In the production of the supported catalyst, hydrocarbon solvents such as pentane, hexane, heptane and the like or aromatic solvents such as benzene, toluene and the like can be used as a reaction solvent.

In addition, the supported catalyst may include the metallocene compound and the co-catalyst compound in the form of being supported on a carrier.

When the metallocene compound and the cocatalyst compound are used in a carrier-supported form, about 0.5 to about 20 parts by weight of the metallocene compound and about 1 to about 1,000 parts by weight of the cocatalyst are used per 100 parts by weight of the carrier . Preferably, from about 1 to about 15 parts by weight of the metallocene compound and from about 10 to about 500 parts by weight of the cocatalyst may be included per 100 parts by weight of the support, and most preferably about 100 parts by weight of the support About 1 to about 100 parts by weight of the metallocene compound and about 40 to about 150 parts by weight of the cocatalyst.

In the metallocene supported catalyst of the present invention, the mass ratio of the total transition metal to the carrier contained in the metallocene compound may be 1:10 to 1: 1,000. When the carrier and the metallocene compound are contained in the above mass ratio, they can exhibit an optimum shape. In addition, the mass ratio of the cocatalyst compound to the carrier may be from 1: 1 to 1: 100. When the cocatalyst and the metallocene compound are contained in the mass ratio, the activity and the polymer microstructure can be optimized.

On the other hand, in this case, the carrier is not limited in its constitution as long as it is usually a metal, a metal salt or a metal oxide used for a supported catalyst. Specifically, it may be in a form containing any one of the carrier selected from the group consisting of silica, silica-alumina and silica-magnesia. The carrier may be dried at elevated temperatures and these may typically comprise oxides, carbonates, sulfates or nitrate components of metals such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ and Mg (NO ₃ ) ₂ and the like.

The amount of the hydroxyl group (-OH) on the surface of the support is preferably as small as possible, but it is practically difficult to remove all the hydroxy groups. The amount of the hydroxy group can be controlled by the method of preparing the carrier, the preparation conditions and the drying conditions (temperature, time, drying method, etc.), preferably 0.1 to 10 mmol / g, more preferably 0.1 to 1 mmol / , More preferably 0.1 to 0.5 mmol / g. In order to reduce side reactions caused by some of the hydroxyl groups remaining after drying, it is also possible to use a carrier chemically removing the hydroxyl group while preserving a highly reactive siloxane group participating in the loading.

The metallocene supported catalyst according to the present invention may itself be used for the polymerization of olefinic monomers. The metallocene supported catalyst according to the present invention may be prepared by reacting with an olefin-based monomer to prepare a prepolymerized catalyst. For example, the catalyst may be separately used in combination with ethylene, propylene, 1-butene, 1-hexene, Or may be prepared by contacting with the same olefin-based monomer to prepare a prepolymerized catalyst.

The metallocene supported catalyst according to the present invention can be produced, for example, by supporting a promoter compound on a support, and supporting the metallocene compound represented by the above formula (1) on the support. Between each of these carrying steps, a washing step using a solvent may be further carried out.

The metallocene supported catalyst may be prepared at a temperature of about 0 ° C to about 100 ° C and a pressure of atmospheric pressure, but is not limited thereto.

Meanwhile, the present invention provides a process for producing a polyolefin which polymerizes an olefin monomer in the presence of the metallocene supported catalyst and a polyolefin produced from the process.

The olefinic monomer may be ethylene, alpha-olefin, cyclic olefin, diene olefin having 2 or more double bonds, or triene olefin.

Specific examples of the olefin-based monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Dodecene, 1-tetradecene, 1-hexadecene, 1-icocene, norbornene, norbornene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene , 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene. These two or more monomers may be mixed and copolymerized.

The polymerization reaction may be carried out by a solution polymerization process, a slurry process or a gas phase process using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor, and the like. Further, homopolymerization with one olefin monomer or copolymerization with two or more kinds of monomers can be carried out.

The metallocene supported catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane and chlorobenzene A chlorine atom-substituted hydrocarbon solvent, or the like. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

The polymerization of the olefinic monomer can be carried out by reacting at a temperature of from about 25 to about 500 DEG C and from about 1 to about 100 kgf / cm < ² > for about 1 to about 24 hours. In particular, the polymerization of the olefinic monomer may be carried out at a temperature of from about 25 ° C to about 500 ° C, preferably from about 25 ° C to about 200 ° C, more preferably from about 50 ° C to about 100 ° C. The reaction pressure can also be carried out at from about 1 to about 100 kgf / cm ² , preferably from about 1 to about 50 kgf / cm ² , and more preferably from about 5 to about 40 kgf / cm ² .

The metallocene supported catalyst of the present invention can effectively polymerize the olefin-based monomer with excellent activity. In particular, the activity of the metallocene supported catalyst is not less than 2.0 kg / gCat · hr, calculated as the ratio of the weight (kg) of the produced polymer per unit weight (g) Or 2.0 to 30 kg / gCat · hr, preferably 2.5 kg / gCat · hr or more, and more preferably 2.8 kg / gCat · hr or more.

The polyolefin prepared according to the present invention may be a polyethylene polymer, 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, it may be more than 0 and 99 mol% or less.

The polyolefin prepared above can exhibit high molecular weight and low molecular weight through relatively high activity and excellent comonomer reactivity as compared with the polyolefin prepared using a similar organometallic compound as a catalyst.

According to one embodiment of the present invention, the weight average molecular weight (Mw) of the olefin-based polymer may be about 10,000 to about 1,000,000 g / mol. In particular, when the metallocene compound supported on the supported catalyst comprises a deneoin derivative or a fluorenyl derivative, it is preferred that the molar ratio of at least about 350,000 g / mol, such as from about 350,000 to about 1,000,000 g / mol, g / mol or higher can be produced. In addition, when the metallocene compound comprises an indene derivative, a low molecular weight polyolefin having a molecular weight of about 150,000 g / mol or less, such as about 10,000 to about 150,000 g / mol, or about 100,000 g / mol or less, Lt; / RTI > Here, the olefinic polymer may have a molecular weight distribution (Mw / Mn) of about 1 to about 10, preferably about 3 to about 6.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

<Examples>

&Lt; Preparation Example of Metallocene Compound >

Example 1

Preparation of 1-1 ligand compounds

The dried 250 mL Schlenk flask was filled with 2.3 g (20 mmol) of indene and dissolved in 40 mL of diethylether under argon gas. After cooling the solution to 0 ° C, 9.6 mL (24 mmol) of 2.5 M n-BuLi (hexane solution) dissolved in hexane was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 hours. To this mixture was added dropwise dimethyldichlorosilicone in an amount of 0.5 equivalent based on indene, and the mixture was stirred for one day. 50 mL of water was added thereto, and the organic layer was extracted three times with 50 mL of ether. An appropriate amount of MgSO ₄ was added to the collected organic layer, stirred for a while, filtered, and the solvent was dried under reduced pressure.

The resultant was dried well in a Schlenk flask, and 40 mL of distilled THF was added under argon gas and cooled to -78 ° C. To the solution, 2.1 equivalents of iodomethyl trimethylsilane was added to indene, and the temperature was slowly raised to room temperature, followed by stirring for 24 hours. 50 mL of water was added thereto, and the organic layer was extracted three times with 50 mL of ether. An appropriate amount of MgSO ₄ was added to the collected organic layer, stirred for a while, filtered, and the solvent was dried under reduced pressure to obtain 4.2 g (molecular weight: 460.87, 9.2 mmol) of a dark brown oily ligand compound. The obtained ligand compound was used for the preparation of the metallocene compound without separate separation process.

^{1 H NMR (500 MHz, CDCl} 3): -0.47, -0.34. (2H, s), 3.52 (1H, s), 3.55 (1H, s), 5.97 (2H, m), 7.36 (3H, m), 7.44 (1H, m)

Preparation of 1-2 metallocene compounds

The ligand compound synthesized in 1-1 was added to a 250 mL Schlenk flask dried in an oven, dissolved in 4 equivalents of methyl tert-butyl ether and 50 mL of toluene, and 2 equivalents of n-BuLi hexane solution Was lithiated. After one day, all of the solvent in the flask was removed under vacuum and dissolved in the same amount of toluene. In the glove box, one equivalent of ZrCl ₄ (THF) ₂ was taken in a 250 mL Schlenk flask and toluene was added to prepare a suspension. Both of the above flasks were cooled to -78 ° C. and the lithiated ligand compound was slowly added to the toluene suspension of ZrCl ₄ (THF) ₂ . After the completion of the pouring, the reaction mixture was slowly warmed to room temperature and stirred for one day to conduct the reaction. Toluene in the mixture was removed through vacuum decompression to about 1/5 volume, recrystallized by adding hexane of about 5 times the amount of toluene remaining . The mixture was filtered to avoid contact with the outside air to obtain a metallocene compound. The filter cake was washed on the top of the filter using a little hexane and then weighed in a glove box, , And purity.

2.68 g (4.32 mmol) of an orange solid (filtrate) dominated by the Meso compound and 1.89 g (3.04 mmol) of an orange solid (filter cake) dominated by racemic compounds were identified. The ratio of racemic to meso was found to be 13.08: 86.92 when the Meso compound was dominant, and the ratio of racemic to meso was 90.32: 9.68 when the racemic compound was dominant.

^{1 H NMR (500 MHz, CDCl} 3): -0.12 (18H, m), 0.82, 1.07, 1.36 (6H, t), 2.31 (4H, s), 5.23 (2H, s), 6.83 (2H, m) , 7.10 (2H, m), 7.30 (2H, d), 7.48 (2H, d).

Example 2

2-1 Preparation of ligand compound

4.05 g (20 mmol) of ((1H-inden-3-yl) methyl) trimethylsilane was charged into a dried 250 mL Schlenk flask and dissolved in 40 mL of diethylether under argon gas. After cooling the solution to 0 ° C, 1.2 equivalents of 2.5 M n-BuLi (hexane solution) dissolved in hexane was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 hours. A solution of 2.713 g (10 mmol) of silicone tether in 30 mL of hexane was prepared in another 250 mL Schlenk flask, cooled to -78 ° C., and the above prepared mixture was slowly added dropwise thereto. After the dropwise addition, the mixture was slowly warmed to room temperature and stirred for 24 hours. 50 mL of water was added thereto, and the organic layer was extracted three times with 50 mL of ether. An appropriate amount of MgSO ₄ was added to the collected organic layer, stirred for a while, filtered and the solvent was dried under reduced pressure to obtain 6.1 g (molecular weight: 603.11, 10.05 mmol, 100.5% yield) of a yellow oil-like ligand compound. The obtained ligand compound was used for the preparation of the metallocene compound without separate separation process.

¹ H NMR (500 MHz, CDCl ₃ ): 0.02 (18 H, m), 0.82 (3 H, m), 1.15 (1H, m), 2.02 (2H, m), 3.21 (2H, m), 3.31 (1H, s), 5.86 ) 7.32 (3 H, m).

2-2 Preparation of metallocene compound

The ligand compound synthesized in 2-1 was added to a 250 mL Schlenk flask dried in an oven, dissolved in 4 equivalents of methyl tert-butyl ether and 60 mL of toluene, and 2 equivalents of n-BuLi hexane solution Was lithiated. After one day, all of the solvent in the flask was removed under vacuum and dissolved in the same amount of toluene. In the glove box, one equivalent of ZrCl ₄ (THF) ₂ was taken in a 250 mL Schlenk flask and toluene was added to prepare a suspension. Both of the above flasks were cooled to -78 ° C. and the lithiated ligand compound was slowly added to the toluene suspension of ZrCl ₄ (THF) ₂ . After the completion of the pouring, the reaction mixture was slowly warmed to room temperature and stirred for one day to conduct the reaction. Toluene in the mixture was removed through vacuum decompression to about 1/5 volume, recrystallized by adding hexane of about 5 times the amount of toluene remaining . The mixture was filtered to avoid contact with the outside air to obtain a metallocene compound. The filter cake was washed on the top of the filter using a little hexane and then weighed in a glove box, , And purity.

7.3 g (9.56 mmol, 95.6%) of a purple oil were obtained from 6.1 g (10 mmol) of the ligand compound and stored in toluene solution. (Purity: 100%, molecular weight: 763.23)

¹ H NMR (500 MHz, CDCl ₃ ): 0.03 (18H, m), 0.98, 1.28 (3H, d), 1.40 (9H, m), 1.45 (1H, m), 6.98 (1H, m), 6.94 (1H, m) , 7.36 (2H, m), 7.43 (1H, m), 7.57 (1H, m)

Example 3

3-1 Preparation of a ligand compound

The dried 250 mL Schlenk flask was filled with 1.66 g (10 mmol) of fluorene and placed in an argon atmosphere. 50 mL of ether was then added under reduced pressure. ether solution was cooled to 0 ° C, the inside of the flask was replaced with argon, and 4.8 mL (12 mmol) of 2.5 M n-BuLi hexane solution was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for one day. Another 250 mL Schlenk flask was filled with 40 mL of hexane and then 2.713 g (10 mmol) of silicone tether was injected. After the injection, the mixture was cooled to -78 deg. C, and the mixture prepared above was slowly added dropwise thereto. After the injection, the temperature was slowly raised to room temperature and stirred for 12 hours.

To another dried 250 mL Schlenk flask, 2.02 g (10 mmol) of ((1H-inden-3-yl) methyl) trimethylsilane was added and dissolved in 50 mL of THF. The solution was cooled to 0 ° C, and 4.8 mL (12 mmol) of 2.5 M n-BuLi (hexane solution) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 12 hours.

The fluorene mixture prepared above was cooled to -78 ° C, lithiated ((1H-inden-3-yl) methyl) trimethylsilane was added dropwise thereto, the temperature was slowly raised to room temperature, and the mixture was stirred for 24 hours. 50 mL of water was added thereto, and the organic layer was extracted three times with 50 mL of ether. An appropriate amount of MgSO ₄ was added to the collected organic layer, stirred for a while, filtered and the solvent was dried under reduced pressure to obtain 5.8 g (molecular weight 566.96, 10.3 mmol, yield: 103%) of a yellow oil-like ligand compound. The obtained ligand compound was used for the preparation of the metallocene compound without separate separation process.

¹ H NMR (500 MHz, CDCl ₃ ): 0.00, 0.26 (3H, d), 0.46 (9H, m), 0.67 (1H, m), 0.83 (2H, m), 1.42 (2H, m), 1.49 (2H, m), 1.60 (1H, s), 4.52 (1H, m), 6.01, 6.26, 6.37 (1H, s), 7.50 (1H, m), 7.59-7.80 , &lt; / RTI &gt; d), 8.29 (2H, m).

3-2 Preparation of metallocene compound

The ligand compound synthesized in 3-1 was added to a 250 mL Schlenk flask dried in an oven, dissolved in 4 equivalents of methyl tert-butyl ether and 60 mL of toluene, and 2 equivalents of n-BuLi hexane solution Was lithiated. After one day, all of the solvent in the flask was removed under vacuum and dissolved in the same amount of toluene. In the glove box, one equivalent of ZrCl ₄ (THF) ₂ was taken in a 250 mL Schlenk flask and toluene was added to prepare a suspension. Both of the above flasks were cooled to -78 ° C. and the lithiated ligand compound was slowly added to the toluene suspension of ZrCl ₄ (THF) ₂ . After the completion of the pouring, the reaction mixture was slowly warmed to room temperature and stirred for one day to conduct the reaction. Toluene in the mixture was removed through vacuum decompression to about 1/5 volume, recrystallized by adding hexane of about 5 times the amount of toluene remaining . The mixture was filtered to avoid contact with the outside air to obtain a metallocene compound. The filter cake was washed on the top of the filter using a little hexane and then weighed in a glove box, , And purity.

4.05 g (5.56 mmol, 55.6%) of an orange solid was obtained (purity: 100%, molecular weight: 727.08).

¹ H NMR (500 MHz, CDCl ₃ ): -0.13 (9H, m), -0.13 (3H, m), 0.53 (2H, m), 7.18 (2H, m), 1.50 (2H, s), 1.64 , 7.38 (1H, m), 7.46-7.56 (4H, m), 7.72

Example 4

4-1 Preparation of ligand compounds

The dried 250 mL Schlenk flask was filled with 2.33 g (10 mmol) of indenoindole and placed in an argon atmosphere. 50 mL of ether was then added under reduced pressure. The ether solution was cooled to 0 ° C, the inside of the flask was replaced with argon, and 4.8 mL (12 mmol) of 2.5 M n-BuLi hexane solution was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for one day. Another 250 mL Schlenk flask was filled with 40 mL of hexane and then 2.713 g (10 mmol) of silicone tether was injected. After the injection, the mixture was cooled to -78 deg. C, and the mixture prepared above was slowly added dropwise thereto. After the injection, the temperature was slowly raised to room temperature and stirred for 12 hours.

After confirming the synthesis of indenoindole compound, 2.02 g (10 mmol) ((1H-inden-3-yl) methyl) trimethylsilane was added to another dried 250 mL Schlenk flask and dissolved in 50 mL of THF. The solution was cooled to 0 ° C, and 4.8 mL (12 mmol) of 2.5 M n-BuLi (hexane solution) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 12 hours.

The indenoindole mixture prepared above was cooled to -78 ° C., lithiated ((1H-inden-3-yl) methyl) trimethylsilane was added dropwise thereto, the temperature was slowly raised to room temperature, and the mixture was stirred for 24 hours. 50 mL of water was added thereto, and the organic layer was extracted three times with 50 mL of ether. An appropriate amount of MgSO ₄ was added to the collected organic layer, stirred for a while, filtered, and the solvent was dried under reduced pressure to give 6.5 g (molecular weight 634.05, 10.3 mmol, yield: 103%) of a yellow oil-like ligand compound. The obtained ligand compound was used for the preparation of the metallocene compound without separate separation process.

¹ H NMR (500 MHz, CDCl ₃ ): -0.40, -0.37 (3H, d), 0.017 (9H, m), 1.10 3.41 (3H, s), 5.62, 5.95, 5.95, 6.11, (1H, s), 7.04 -7.32 (9 H, m), 7.54 (1 H, m), 7.75 (1 H, m).

4-2 Preparation of metallocene compound

The ligand compound synthesized in 4-1 was added to a 250 mL Schlenk flask dried in an oven, dissolved in 4 equivalents of methyl tert-butyl ether and 60 mL of toluene, and 2 equivalents of n-BuLi hexane solution Was lithiated. After one day, all of the solvent in the flask was removed under vacuum and dissolved in the same amount of toluene. In the glove box, one equivalent of ZrCl ₄ (THF) ₂ was taken in a 250 mL Schlenk flask and toluene was added to prepare a suspension. Both of the above flasks were cooled to -78 ° C. and the lithiated ligand compound was slowly added to the toluene suspension of ZrCl ₄ (THF) ₂ . After the completion of the pouring, the reaction mixture was slowly warmed to room temperature and stirred for one day to conduct the reaction. Toluene in the mixture was removed through vacuum decompression to about 1/5 volume, recrystallized by adding hexane of about 5 times the amount of toluene remaining . The mixture was filtered to avoid contact with the outside air to obtain a metallocene compound. The filter cake was washed on the top of the filter using a little hexane and then weighed in a glove box, , And purity.

Ether was used as the solvent of the metallation, and 6.08 g (7.65 mmol, 76.5%) of a red solid was obtained from 6.4 g (10 mmol) of the ligand (purity: 100%, molecular weight: 794.17).

¹ H NMR (500 MHz, CDCl ₃ ): -0.23, -0.16 (9H, d), 0.81 (3H, m), 1.17 (9H, m), 1.20-1.24 ), 1.62-1.74 (5H, m), 1.99-2.11 (2H, m), 2.55 (3H, d), 3.33 m), 7.29 (1H, m), 7.36 (1H, m), 7.44 (1H, m), 7.84 (1H, m).

Comparative Example 1

5-1 Preparation of ligand compounds

11.54 g (40 mmol) of indene was placed in a dried 250 mL schlenk flask and 200 mL of methyl tertiary-butyl ether (MTBE) was introduced under argon. The MTBE solution was cooled to 0 ° C and 48 mL (120 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 to give lithiated indene (15.4 g, 51 mmol). In another 250 mL schlenk flask, 3.8 mL (10 mmol) of Lithiated indene was charged with 40 mL of THF and the flask was cooled to -78 ° C. To this was added 5.1 mL of chloro trimethylsilane (4 eq. To 4 eq. Of indene). The mixture was stirred at room temperature for one day. After stirring for one day, 50 mL of water was added to the flask and quenched. The organic layer was separated and dried with MgSO ₄ . As a result, 4.0 g (9.2 mmol, 91.5%) of a brown oil was obtained .

^{1 H NMR (500 MHz, CDCl} 3): -0.09 (18H, s), 0.60 (6H, s), 3.62 (2H, s), 6.92 (2H, m), 7.16 (4H, m), 7.46 (2H , &lt; / RTI &gt; m), 7.52 (2H, m).

5-2 Preparation of metallocene compound

The ligand synthesized in 5-1 was added to a 250 mL schlenk flask dried in an oven, dissolved in 4 equivalents of MTBE and 60 mL of toluene, and then 2.1 equivalents of n-BuLi solution was added and lithiated until the next day. 2.1 equivalents of ZrCl ₄ (THF) ₂ in a glove box was placed in a 250 mL schlenk flask and toluene-loaded suspension was prepared. Both flasks were cooled to -78 ° C and ligand anion was slowly added to the Zr suspension. After the injection, the reaction mixture was slowly warmed to room temperature. After stirring for one day, toluene in the mixture was removed by vacuum decompression to about 1/5 volume and hexane of volume about 5 times that of the remaining solvent was added. The reason for adding hexane at this time is that the synthesized catalyst precursor accelerates crystallization because the solubility of hexane is lowered. The hexane slurry was filtered under argon, filtered, and both the filtered solid and the filtrate were evaporated under reduced pressure. The remaining filter cake and filtrate were confirmed by NMR, respectively, and the yield and purity were checked by weighing and sampling in the glove box. 3.9 g (9.2 mmol) of the ligand yielded 3.09 g (2.9 mmol) of a yellow filter cake predominantly of the Meso compound and 2.66 g (4.48 mmol) of an ocher-colored solid (Filtrate) predominating with racemic compounds. In the predominant case of Meso compounds, the ratio of racemic to meso was 5.1: 94.9% and in case of Racemic predominant compound, it was present in the ratio of 83.3: 16.7%.

¹ H NMR purity (wt%) = 70.5% (Meso dominant), 100% (Racemic dominant). Mw = 592.93.

^{1 H NMR (500 MHz, CDCl} 3): 0.34 (18H, s), 0982 (3H, s), 1.33 (3H, s), 6.13 (2H, s), 6.84 (2H, m), 7.12 (2H, m), 7.48 (2 H, d), 7.70 (2 H, d).

Comparative Example 2

6-1 Preparation of ligand compounds

1.96 g (8.4 mmol) of Indenoindole was placed in a 250 mL schlenk flask and dissolved in 50 mL of ether under reduced pressure. After cooling the solution to 0 ° C, 4.0 mL (10 mmol) of 2.5 M n-BuLi hexane solution was dropwise added dropwise, and the mixture was stirred at room temperature for one day. The dried 250 mL schlenk flask was filled with 40 mL of hexane and then injected with 2.53 g (8.4 mmol) of silicone tether. After the flask was cooled to -78 ° C, Indenoindole Lithiated solution was injected dropwise into the cannula. After the injection, the temperature was raised to room temperature and stirring was continued for 12 hours. After confirming the synthesis of the indenoindole part, 1.56 g (8.4 mmol) of (1H-inden-3-yl) trimethylsilane was added to the dried 250 mL schlenk flask and dissolved by injecting 50 mL of ether. After cooling the solution to 0 ° C, 4.0 mL (10 mmol) of 2.5 M n-BuLi hexane solution was dropwise added dropwise, and the mixture was stirred at room temperature for 12 hours. The previously synthesized Indenoindole part was cooled to -78 ° C, and a lithiated (1H-inden-3-yl) trimethylsilane solution was added dropwise thereto with a cannula. The mixture was heated to room temperature and stirred overnight. Then, about 50 mL of water was added to the flask to quench the organic layer. The organic layer was separated, dried over MgSO ₄ and filtrated to obtain a pure organic solution. The solution was evaporated under reduced pressure to obtain 5.6 g (8.9 mmol, 106.6%) of a brown oil.

¹ H NMR purity (wt%) = 100%. Mw = 620.03.

¹ H NMR (500 MHz, CDCl 3): -0.06 (3H, s), 0.12, 0.23, 0.33 (9H, m), 0.86 (1H, m), 1.28 (1H, m), 2.41, 2.45, 2.48 (3H, s), 3.25 (2H, m), 4.02-4.09 (3H, s), 6.64, 6.91 ), 7.32-7.57 (5H, m), 7.78 (1H, m).

6-2 Preparation of metallocene compound

The ligand synthesized in 6-1 was added to a 250 mL schlenk flask dried in an oven, dissolved in 4 equivalents of MTBE and 60 mL of toluene, and then 2.1 equivalents of nBuLi solution was added and lithiated until the next day. 2.1 equivalents of ZrCl ₄ (THF) ₂ in a glove box was placed in a 250 mL schlenk flask and a suspension containing ether was prepared. Both flasks were cooled to -78 ° C and ligand anion was slowly added to the Zr suspension. After the injection, the reaction mixture was slowly warmed to room temperature. When the metallation of the ligand containing the indenoindole derivative was successfully proceeded, it was confirmed that the color of the catalyst precursor specific index purple appeared. After stirring for one day, the ethers in the mixture were removed by vacuum depressurization to about 1/5 volume and hexane of volume about 5 times that of the remaining solvent was added. The reason for adding hexane at this time is that the synthesized catalyst precursor accelerates crystallization because the solubility of hexane is lowered. The hexane slurry was filtered under argon, filtered, and both the filtered solid and the filtrate were evaporated under reduced pressure. The remaining filter cake and filtrate were confirmed by NMR, respectively, and the yield and purity were checked by weighing and sampling in the glove box. 4.3 g (65.6%) of red catalyst precursor from 5.56 g (8.4 mmol) of ligand was obtained from Filtrate and stored in toluene solution (1.8695 g / mmol).

NMR standard purity (wt%) = 100%. Mw = 780.14.

¹ H NMR (500 MHz, CDCl ₃ ): -0.11, -0.07 (3H, s), 0.23, 0.29, 0.38 (9H, s), 0.87 (1H, m), 1.21 (3H, m), 2.56 (3H, m), 3.32 (2H, m), 3.87, 3.94, 4.02, 4.12 - 7.03 (2H, m), 7.13-7.17 (2H, m), 7.25 (2H, m), 7.41 (1H, m), 7.54-7.63 (2H, m), 7.79 (2H, m).

&Lt; Preparation Example of Supported Catalyst >

Catalyst Preparation Examples 1 to 4 and Comparative Catalyst Preparation Examples 1 to 2

100 mL of toluene was placed in a 300 mL BSR (Bench Scale Reactor) reactor and 10 g of silica (Grace Davison, SP952X burned at 200 캜) was added at 40 캜 and stirred for 30 minutes (500 rpm). 10 wt% MAO 8 mmol / g-SiO ₂ was added, the temperature was raised to 60 ° C, and the reaction was carried out with stirring (500 rpm) for 16 hours. The temperature of the reactor was lowered to 40 ° C, stirring was stopped, and the mixture was settled for 10 minutes and then decantrated. The toluene was filled up to 100 mL of the reactor and stirred for 10 minutes, settling for 10 minutes, and decantation. After toluene was filled to 100 mL, 0.1 mmol / g-SiO ² of catalyst precursors (Examples 1 to 4 and Comparative Examples 1 and 2) was added to the reactor and reacted for 1.5 hours with stirring (500 rpm). After the reactor temperature was lowered to room temperature, stirring was stopped, and the mixture was settled for 10 minutes before decantation. The toluene was filled up to 100 mL of the reactor and stirred for 10 minutes, settling for 10 minutes, and decantation. The reactor was charged with hexane up to 100 mL, and stirred for 10 minutes, settling for 10 minutes, and decantation. Hexane was added to 100 mL and ASA (Atmer 163) 2 wt% / g-SiO ₂ was added. After stirring for 10 minutes, the slurry was transferred to a flask and dried under reduced pressure for 3 hours.

&Lt; Embodiment of polyethylene polymerization >

Polymerization Production Examples 1 to 4 and Polymerization Comparative Production Examples 1 to 2: Production of polyolefin

Ethylene polymerization

2 mL of an autoclave reactor was charged with 2 mL of TEAL and 0.5 mL of ASA, and 0.6 kg of hexane was added thereto. Then, the mixture was heated to 80 DEG C with stirring at 500 rpm. 20 to 30 mg of the supported catalyst (Catalyst Preparation Examples 1 to 4 and Comparative Catalyst Preparation Examples 1 and 2) and hexane were charged in a vial. When the temperature reached 80 ° C, the catalyst and hexane contained in the vial were charged into the reactor, kg. When hexane was added, the temperature was lowered. Therefore, the mixture was stirred at 100 rpm until the temperature reached 80 ° C. When the temperature reached 80 ° C, ethylene was injected under a pressure of 40 bar and reacted for 1 hour while stirring at 500 rpm. After the completion of the reaction, the obtained polymer was firstly removed with hexane through a filter and then dried in an oven at 80 ° C for 3 hours.

The reaction conditions and the results of Polymerization Examples 1 to 4 and Polymerization Comparative Preparation Examples 1 to 2 are summarized in the following Table 1.

catalyst
Precursor Recipe activation
(kgPE / gCat.) M _W
(× 10 ⁴ ) MAO (60 DEG C) Met (40 DEG C) mmol / g-SiO ₂ mmol / g-SiO ₂ Production Example 1 Example 1 8 0.1 8.4 8.0 Production Example 2 Example 2 8 0.1 11.6 8.4 Production Example 3 Example 3 8 0.1 3.0 40.0 Production Example 4 Example 4 8 0.1 4.6 47.6 Comparative Preparation Example 1 Comparative Example 1 8 0.1 1.0 - Comparative Production Example 2 Comparative Example 2 8 0.1 0.5 - Polymerization conditions: ethylene pressure 40 bar, temperature 80 캜, reaction time 60 min.

Claims (15)

At least one metallocene compound represented by the following formula (1);
A cocatalyst compound; And
At least one carrier selected from the group consisting of silica, silica-alumina and silica-magnesia,
Wherein the metallocene compound has a mass ratio of transition metal to support of from 1: 10 to 1: 1,000 and a mass ratio of the promoter to the support of from 1: 1 to 1: 100.
[Chemical Formula 1]

In Formula 1,
M is a Group 4 transition metal;
B is silicon;
Q ₁ and Q ₂ are the same or different and are each independently hydrogen, a C 1 to C 20 alkyl group, a C 2 to C 20 alkoxyalkyl group;
X ₁ and X ₂ are the same or different from each other and are each independently halogen or a C1 to C20 alkyl group;
C ₁ and C ₂ are the same or different and each independently represents one of the following structural formulas (2a), (2b), (2c) or (2d) with the proviso that at least one of C ₁ and C ₂ is represented by the formula (2a);
(2a)

(2b)

[Chemical Formula 2c]

(2d)

In the above formulas (2a), (2b), (2c) and (2d)
Halogen, a C1 to C20 alkyl group, a C1 to C20 silylalkyl group, and a C6 to C20 aryl group, and R &_lt; ₁ &gt; to R &_lt; ₂₈ &_gt;, which are the same or different from each other,
R ' ₁ to R' ₃ are the same or different from each other and are each independently a C1 to C20 alkyl group,
Two or more adjacent R ₁ to R ₂₈ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.
The method according to claim 1,
R ₁ to R ₂₈ in formulas (2a), (2b), (2c) and (2d) are each independently selected from the group consisting of hydrogen, halogen, methyl, ethyl, propyl, isopropyl, , A heptyl group, an octyl group, or a trimethylsilylmethyl group.
The method according to claim 1,
Q ₁ and Q ₂ in Formula 1 are each independently selected from the group consisting of hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxymethyl group, Methylene-1-methoxyethyl group, or tert-butoxyhexyl group.
The method according to claim 1,
The compound represented by Formula 1 is a metallocene supported catalyst having one of the following structural formulas:

The method according to claim 1,
The metallocene supported catalyst comprising at least one of the compounds represented by the following general formula (4), (5), or (6)
[Chemical Formula 4]
- [Al (R ₂₃ ) -O] _n -
In Formula 4,
R ₂₃ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
n is an integer of 2 or more;
[Chemical Formula 5]
J (R ₂₃ ) ₃
In Formula 5,
R ₂₃ is as defined in Formula 4 above;
J is aluminum or boron;
[Chemical Formula 6]
_{^{[EH] + [ZA '4}} ] - or _{^{[E] + [ZA' 4}} ] -
In Formula 6,
E is a neutral or cationic Lewis acid;
H is a hydrogen atom;
Z is a Group 13 element;
A 'may be the same as or different from each other, and independently at least one hydrogen atom is replaced by halogen, an aryl group having 6 to 20 carbon atoms, to be.
The method according to claim 1,
Wherein the functional group represented by Formula 2a is one of the following structural formulas.

.
The method according to claim 1,
Wherein the functional group represented by Formula 2b is one of the following structural formulas.

The method according to claim 1,
Wherein the functional group represented by Formula 2c is one of the following structural formulas.

A process for producing a polyolefin comprising polymerizing an olefin monomer in the presence of a metallocene catalyst according to claim 1.
10. The method of claim 9,
Wherein the polymerization is carried out by a solution polymerization process, a slurry process or a gas phase process.
10. The method of claim 9,
The olefin-based monomer may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, Norbornene, norbornene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-hexadiene, 1-hexadecene, - at least one monomer selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.
10. The method of claim 9,
Wherein the catalyst activity is 2.0 kg / gCat · hr or more calculated on the basis of the weight (kg) of the polymer produced per unit weight (g) of the catalyst unit used as a reference based on the unit time (h).
10. A polyolefin produced by the process according to claim 9.
14. The method of claim 13,
A polyolefin having a weight average molecular weight of 10,000 to 1,000,000 g / mol. The method according to claim 1,
Wherein the functional group represented by Formula 2d is one of the following structural formulas.