KR101901016B1 - Catalyst composition for olefin polymerization and process for preparing polyolefin copolymer - Google Patents

Abstract

The present invention relates to a process for preparing a polyolefin copolymer comprising polymerizing at least one olefinic monomer in the presence of a catalyst composition comprising a specific compound and a metallocene compound and a polyolefin copolymer prepared therefrom.

Description

TECHNICAL FIELD [0001] The present invention relates to a catalyst composition for olefin polymerization and a process for producing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a catalyst composition for olefin polymerization and a process for producing a polyolefin copolymer.

As a method for industrially producing polyolefins by polymerizing olefins, a liquid phase polymerization process, a slurry phase polymerization process, a gas phase polymerization process and the like are known. The liquid phase polymerization process is a process in which polymerization is performed in a state in which a polymer is melted in a liquid phase. The slurry phase polymerization process is a process in which a polymer produced in a liquid phase polymerization medium is dispersed in a solid state to perform polymerization. Is dispersed in a fluidized state to polymerize the polymer. In this polymerization process, depending on the polymerization conditions, a fouling phenomenon occurs in which olefins or polyolefins adhere to the inner wall of the reactor, the heat exchanger, and the cooler in the process, and agglomeration phenomenon occurs in which the resultant polyolefin coagulates near the softening point . When the fouling and aggregation phenomenon occurs, the olefin does not diffuse evenly, which makes it difficult to control the polymerization reaction or to transfer and remove heat in the reactor, resulting in the formation of polyolefin having uneven particle size and density. This problem may occur more severely when a polyolefin is produced using a metallocene catalyst having a higher activity per metal than a Ziegler-Natta catalyst.

Various attempts have been made to minimize the fouling and aggregation phenomena occurring in the production of polyolefins. For example, U.S. Patent No. 4,650,841 discloses a method for preventing fouling by reducing the catalytic activity using an inactivating agent, and U.S. Patent No. 5,733,988 discloses a method for adding alcohols, ethers, ammonia, etc. as a fouling inhibitor And the like. However, since these methods lower the activity of the catalyst, the activity of the polymerization reaction is lowered and the production efficiency is inevitably lowered. In addition, U.S. Patent No. 5,270,407 discloses a method for preventing fouling by adding a polysiloxane to a catalyst system, and U.S. Patent No. 3,956,257 discloses a fouling prevention method using hydrocarbyl aluminum alkoxide. However, these methods also have a limitation in that the overall catalytic activity is reduced.

Therefore, there is still a demand for a technique for maintaining the catalytic activity while reducing the fouling and aggregation phenomena occurring in the production of the polyolefin copolymer.

An object of the present invention is to provide a catalyst composition for olefin polymerization which can maintain the catalytic activity while reducing the occurrence of fouling and bunching phenomena.

Another object of the present invention is to provide a process for producing a polyolefin copolymer which is less prone to fouling and aggregation by using a specific catalyst.

In order to achieve the above object, the present invention provides a compound represented by the following general formula (1) or (2): And a catalyst composition for olefin polymerization comprising a metallocene compound.

[Chemical Formula 1]

(In the formula 1,

m is an integer of 1 to 20,

And a plurality of R ^1-1 are the same or different, each independently represent a (C ₁ -C ₃₀₎ alkyl or hydroxy.)

(2)

(In the formula (2)

n is an integer of 1 to 20,

A plurality of R < ^1-2 > are the same or different and are each independently (C ₁ -C ₃₀ ) alkyl)

The present invention also relates to a compound represented by the above formula (1) or (2); And polymerizing one or more olefinic monomers in the presence of a catalyst comprising a metallocene compound.

In addition, the present invention provides a polyolefin copolymer produced by the above production method.

According to the present invention, by producing a polyolefin copolymer using a specific catalyst composition, it is possible to minimize the fouling and aggregation while maintaining the intrinsic activity of the catalyst, thereby achieving a more stable polymerization process.

In the polymerization process for producing a polyolefin copolymer, fouling and aggregation occur depending on the polymerization conditions, and when the metallocene catalyst is used as compared with the Ziegler-Natta catalyst, the above phenomena occur more seriously. This phenomenon hinders uniform diffusion of olefins, making it difficult to control the polymerization reaction and heat transfer and heat removal in the reactor, resulting in the formation of polyolefins having uneven particle size and density.

Accordingly, in the present invention, in order to minimize fouling and aggregation while maintaining the activity of the metallocene catalyst used in the production of the polyolefin copolymer, it is preferred that the compound of formula 1 and the metallocene compound be contained, And a metallocene compound are used as catalysts for olefin polymerization. When such a catalyst composition is used, the polyolefin copolymer can be stably prepared by preventing the occurrence of fouling and aggregation without changing the catalytic activity.

≪ Catalyst composition for olefin polymerization >

As an example according to the present invention, the catalyst composition for olefin polymerization comprises the compound represented by the above formula (1) or (2); And a metallocene compound, which will be described in detail as follows.

The compound represented by Formula 1 includes alkyloxy, or includes alkyloxy and hydroxy. In Formula 1, it is preferable that at least one of the plurality of R < ^1-1 > is hydroxy. The compound represented by the formula (1) is not particularly limited, and a non-limiting example thereof may be dipentaerythritol and the like.

The compound represented by Formula 2 includes two hydroxides. In formula (2), the plurality of R ^{1-2 s} may be the same as or different from each other, and are each independently (C ₁ -C ₁₀ ) alkyl. The compound represented by the formula (2) is not particularly limited, and a non-limiting example thereof is [(hydroxymethyl) (triethylsilyl) amino] methanol] or the like.

The compound represented by the formula (1) or (2) is a compound used as a donor in olefin polymerization using a conventional Ziegler-Natta catalyst, and is known to have no effect on fouling and aggregation. However, the present inventors have found that when the olefin is polymerized using the metallocene compound as a catalyst, the compound represented by the above formula (1) or (2) can suppress the generation of static electricity by the fine particles. Therefore, the compound represented by Formula 1 or 2 can be used as a new antistatic agent.

The metallocene compound represented by the following Chemical Formula 3 is a main catalyst compound containing a transition metal.

(3)

In Formula 3, M is selected from the group consisting of Group 4 elements on the periodic table and is preferably selected from the group consisting of titanium (Ti), zirconium (Zr), and hafnium (Hf).

Q ¹ and Q ² are the same or different and each independently halogen, (C ₁ -C ₂₀₎ alkyl, (C ₂ -C ₂₀₎ alkenyl, (C ₂ -C ₂₀₎ alkynyl each other, (C ₆ - C ₂₀₎ aryl, alkyl amido (C ₁ -C ₂₀₎ alkyl (C ₆ -C ₂₀₎ aryl, (C ₆ -C ₂₀₎ aryl (C ₁ -C ₂₀₎ alkyl, (C ₁ -C ₂₀₎ degrees, (C ₆ -C ₂₀ ) arylamido and (C ₁ -C ₂₀ ) alkylidene. Preferably, Q ¹ and Q ² are halogen or (C ₁ -C ₂₀ ) alkyl, more preferably methyl or chlorine.

R ² to R ¹¹ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; And (C ₁ -C ₂₀ ) silyl, with or without an acetal, ketal or ether group, wherein R ² and R ³ or R ⁴ and R ⁵ may be linked together to form a ring, , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ^10, or two or more of R ¹⁰ and R ¹¹ may be connected to each other to form a ring. It is preferable that R ² to R ⁶ are hydrogen or methyl, and it is preferable that R ⁷ to R ¹¹ are all hydrogen.

R ¹² to R ¹⁴ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; (C ₁ -C ₂₀ ) silyl with or without an acetal, ketal or ether group; (C ₁ -C ₂₀₎ alkoxy; And (C ₆ -C ₂₀ ) aryloxy, wherein R ¹² and R ¹³ or R ¹³ and R ¹⁴ may be connected to each other to form a ring. It is preferable that all of R ¹² to R ¹⁴ are hydrogen.

The metallocene compound represented by the general formula (3) is effective for controlling the electronic and stereoscopic environment around the metal containing the substituent.

In the above catalyst composition, the amount of the compound represented by the general formula (1) or (2) and the metallocene compound is not particularly limited. Considering the catalytic activity and the manufacturing cost, the amount of the compound represented by the above formula (1) or (2) is determined based on the solution of the compound represented by the above formula (1) or (2) diluted with the solvent in the presence of a metallocene catalyst, To 1,000 ppm, preferably from 3,000 ppm to 7,000 ppm, and more preferably from 4,000 ppm to 6,000 ppm, based on the compound of the free flowing powder form.

The catalyst composition may further include at least one catalyst compound selected from the group consisting of the compounds represented by the general formulas (1) and (2) and the metallocene compounds as well as the compounds represented by the following general formulas (4) to (8) The promoter compounds represented by the formulas (4) to (8) serve to activate the metallocene compound.

[Chemical Formula 4]

- [Al (R ^2-1 ) -O] a-

In Formula 4, R ^2-1 is independently selected from the group consisting of a halogen radical, a (C ₁ -C ₂₀ ) hydrocarbyl radical and a (C ₁ -C ₂₀ ) hydrocarbyl radical substituted with halogen, a is an integer of 2 or more.

In consideration of the activity of the metallocene compound, in the promoter compound represented by Formula 4, R ^2-1 is preferably selected from the group consisting of methyl, ethyl, n-butyl and isobutyl.

The promoter compound represented by the above formula (4) is not particularly limited and is preferably alkyl aluminoxane. Nonlimiting examples are methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, decylaluminoxane, and the like.

[Chemical Formula 5]

- [(Me) AlO] n-

In Formula 5, n is an integer of 10 to 50.

The n may be polymethylaluminoxane having a number within a range (n is a certain integer) or polymethylaluminoxane having a plurality of units (n different integers).

[Chemical Formula 6]

D (R ^3-1 ) ₃

In Formula 6, D is aluminum or boron.

R ^3-1 are each independently selected from the group consisting of a halogen radical, a (C ₁ -C ₂₀ ) hydrocarbyl radical and a (C ₁ -C ₂₀ ) hydrocarbyl radical substituted with a halogen.

In consideration of catalytic activity of the metallocene compound, it is preferable that D is aluminum and R ^3-1 is methyl or isobutyl in the promoter compound represented by Formula 6. Or D is boron, and R < ^3-1 > is preferably pentafluorophenyl.

The promoter compound represented by Formula 6 is not particularly limited, and examples thereof include, but not limited to, trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, Trialkylaluminum such as trioctylaluminum and tridecylaluminum; Dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum methoxide, dibutylaluminum methoxide and the like; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, and dibutylaluminum chloride; Alkylaluminum dialkoxides such as methylaluminum dimethoxide, ethylaluminum dimethoxide and butylaluminum dimethoxide; alkylaluminum dialkoxides such as methylaluminum dimethoxide, ethylaluminum dimethoxide and butylaluminum dimethoxide; Alkylaluminum dihalide such as methylaluminum dichloride, ethylaluminum dichloride, and butylaluminum dichloride; Trialkylboron such as trimethylboron, triethylboron, triisobutylboron, tripropylboron and tributylboron; Tripentafluorophenylboron, and the like.

(7)

[LH] ⁺ [Z (A) ₄ ] ^-

[Chemical Formula 8]

[L] ⁺ [Z (A) ₄ ] ^-

In the above formulas (7) and (8), L is a neutral or cationic Lewis acid.

Z is selected from the group consisting of Group 13 elements on the periodic table.

A are the same or different, each independently represent at least one hydrogen atom is halogen, (C ₁ -C ₂₀₎ hydrocarbyl, (C ₁ -C ₂₀₎ alkoxy (C ₆ -C ₂₀₎ aryl, (C substituted with ₁ -C ₂₀₎ alkoxy substituted with (C ₁ -C ₂₀₎ alkyl radical, (C ₆ -C ₂₀₎ aryloxy radicals substituted with a (C ₆ -C ₂₀₎ aryl and (C ₆ -C ₂₀₎ aryloxy (C ₁ -C ₂₀ ) alkyl radical substituted with a radical.

Considering the metallocene compound of the active to the metal, in the co-catalyst compound represented by the above formula (7) wherein [LH] ⁺ is dimethylanilinium cation dimethyl, wherein [Z (A) _4] ^- is [B (C ₆ F ₅ ) ₄ ] ^- .

The promoter compound represented by the general formula (7) is not particularly limited and examples thereof include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluoro (Pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) Anilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate ) N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) 5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t-triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) (N, N-dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) borate), N, N-dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetra N, N-dimethyl-2,4,6-pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (2,3,5,6-tetrafluorophenyl) ) 2,3,4,6-tetrafluorophenyl) borate, N, N-diethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate (triethylammonium tetrakis , 4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophcnyl) borate, tri (n, Butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6- (2,3,4,6-tetrafluorophenyl) borate, ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate (N, N-dimethylanilin iodine tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) , 3,4,6-tetrafluorophenyl) borate, N, N-dimethyl 2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) 2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate) and the like.

[L] ⁺ is [(C ₆ H ₅ ) ₃ C] ⁺ , and the [Z (A)] is the same as that of the metallocene compound. ₄ ] ^- is preferably [B (C ₆ F ₅ ) ₄ ] ^- .

The cosurfactant compound represented by Formula 8 is not particularly limited and examples thereof include di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate (di- (i-propyl) ammonium tetrakis dialkylammoniums such as dicyclohexylammonium tetrakis (pentafluorophenyl) borate, etc .; and dialkylammoniums such as dicyclohexylammonium tetrakis (pentafluorophenyl) borate; Triphenylphosphonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolylphosphonium tetrakis (pentafluorophenyl) Trialkylphosphoniums such as tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (2,6-dimethylphenyl) phosphonium tetrakis Di (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate, , Dialkyloxonium such as di (2,6-dimethylphenyloxonium tetrakis (pentafluorophenyl) borate), diphenylsulfonium tetrakis (penta Fluorophenyl) borane (Pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis Dialkylsulfonium such as bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate), tropylium tetrakis (pentafluorophenyl) borate (pentafluorophenyl) borate, triphenylmethylcarbenium tetrakis (pentafluorophenyl) borate, benzene (diazonium) tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate) and the like.

The amount of the promoter compound represented by the general formulas (4) to (8) is not particularly limited, and the molar ratio of the metallocene compound to the promoter compound is 1: 1 to 100,000, preferably 1: 1 To 10,000, and more preferably from 1: 1 to 5,000.

The compound represented by the formula (1) or (2) and the metallocene compound may be used without any treatment or may be used in a state in which the compound is supported on the carrier. At this time, one or more cocatalyst compounds selected from the group consisting of the compounds represented by Chemical Formulas 4 to 8 may be further supported. The carrier as can be used for the porous carrier when using the known catalysts, inorganic or organic materials used in the art, without limitation, Non-limiting examples include SiO _2, Al ₂ O _3, MgO, MgCl _2, CaCl _2, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , SiO ₂ -Al ₂ O ₃ , SiO ₂ -MgO, SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, borax, zeolite, starch, and cyclodextrine. The carrier is one or more selected from the group consisting of silica (SiO ₂ ), silica-alumina (SiO ₂ -Al ₂ O ₃ ) and silica-magnesia (SiO ₂ -MgO) desirable.

In order to support the compound represented by the general formula (1) or (2) and the metallocene compound on the support, the metallocene compound and / or the promoter compound may be supported on the support and then the compound represented by the general formula have. As a method of supporting the metallocene compound and / or the promoter compound on the support, a method of directly supporting the metallocene compound on a dehydrated support; A method in which a carrier is pretreated with a promoter compound and then a metallocene compound is supported; A method in which a metallocene compound is supported on a support and then the support is treated with a co-catalyst compound; A method in which a metallocene compound is reacted with a cocatalyst compound, and then a carrier is added to cause a reaction; and the like. The support carrying the metallocene compound and / or the promoter compound may further contain the compound represented by the above formula (1) or (2) and may be used as a final catalyst composition.

Examples of the solvent that can be used in the above carrying method include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc. An aliphatic hydrocarbon-based solvent; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; and aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; Halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane, and trichloroethane; Or a mixture thereof.

The above carrying method is advantageous from the viewpoint of efficiency of the carrying process and is carried out at a temperature of from -70 to 200 캜, preferably from -50 to 150 캜, more preferably from 0 to 100 캜, for 10 to 60 minutes, It is advantageous in terms of the efficiency of the deposition process to be performed for 20 to 40 minutes.

Such a catalyst composition for olefin polymerization contains a specific compound and a metallocene compound. With the above specific compound, static electricity generated in the olefin polymerization process can be suppressed, and fouling and aggregation phenomenon can be minimized to produce polyolefin have.

≪ Process for producing polyolefin polymer &

According to one embodiment of the present invention, a method for producing a polyolefin copolymer comprises: reacting a compound represented by Formula 1 or 2; And polymerizing the at least one olefinic monomer in the presence of a catalyst comprising a metallocene compound.

The catalyst containing the compound represented by Formula 1 or 2 and the metallocene compound is as described in the catalyst composition for olefin polymerization.

The olefin-based monomer may be at least one member selected from the group consisting of (C ₂ -C ₂₀ ) α-olefins. The olefinic monomer may be, for example, ethylene, propylene, 1-butene, isobutene, pentene, 1-hexene, heptene, 1-octene,

The polymerization of the olefin monomer may be carried out in a slurry phase, a solution phase, a gas phase, or a bulk phase. When the polymerization reaction is carried out in a liquid phase or a slurry, the solvent or the olefin-based monomer itself can be used as a medium. The solvent which can be used in the polymerization reaction may be selected from the group consisting of butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, Aliphatic hydrocarbon solvents such as undecane, dodecane, cyclopentane, methylcyclopentane, and cyclohexane; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene and chlorobenzene; aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene and chlorobenzene; Halogenated aliphatic hydrocarbons such as dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, and 1,2-dichloroethane, menstruum; Or a mixture thereof.

At this time, the amount of the catalyst to be used may be determined within a range in which the polymerization reaction of the monomers can sufficiently take place in the slurry, liquid phase, gas phase or massive process, and is not particularly limited. However, considering the catalytic activity, the addition amount of the catalyst is preferably from 10 ^-8 to 1 mol (L) based on the concentration of the central metal (M) of the metallocene compound contained in the catalyst per unit volume (L) of the olefin- / L, preferably from 10 ^-7 to ¹⁰ may be a ^{2 mol / L - 1 mol /} L, more preferably from 10 ^-7 to 10.

The polymerization reaction may be carried out in a batch type, semi-continuous type, or continuous type reaction.

The polymerization temperature and pressure conditions are not particularly limited and can be determined in consideration of the efficiency of the polymerization reaction depending on the kind of the reaction to be applied and the type of the reactor. The polymerization temperature may be -50 to 500 占 폚, preferably 0 to 400 占 폚, more preferably 0 to 300 占 폚, and the polymerization pressure is 1 to 3,000 atm, preferably 1 to 1,000 atm, May be between 1 and 500 atmospheres.

The process for producing such a polyolefin copolymer includes a step of polymerizing one or more olefin monomers in the presence of a specific catalyst, so that fouling and aggregation do not occur during polymerization while maintaining the activity of the catalyst, Coalescence can be produced.

However, the present invention is not limited only to the steps of the above-described production method, and the steps of each step may be modified or optionally mixed as necessary.

<Polyolefin Copolymer>

The polyolefin copolymer is provided by the above production method according to an example of the present invention.

The polyolefin copolymer may have a weight average molecular weight (Mw) of 10,000 to 2,000,000, preferably 30,000 to 1,000,000, and more preferably 50,000 to 80,000.

The polyolefin copolymer may have a molecular weight distribution (Mw / Mn) of 1 to 10, preferably 1.5 to 8, more preferably 1.5 to 6.

EXAMPLES The present invention will now be described in detail with reference to the following examples, but it should be understood that the present invention is not construed as being limited thereto.

[ Preparation Example  1] Preparation of Catalyst

The synthesis reaction for preparing the catalyst was carried out in an inert atmosphere such as nitrogen or argon, and the standard Schlenk technique and the glove box technique were used.

Toluene, normal henxane, used in the preparation of the catalyst was purchased from Sigma-Aldrich as an anhydrous grade and activated molecular sieve (4A) or activated alumina (Alumina) layer Which was further dried and then used. Methylaluminoxane (MAO) was purchased from Albemarle and a 10% toluene solution (HS-MAO-10%) in which methylaluminoxane was dissolved was used. Silica was purchased from Grace and used without further treatment. Bis (1-butyl-3-methylcyclopentadienyl) zirconium dichloride used as a metallocene compound was purchased from S-PCI and used without purification. Amtmer 163 is a conventional antistatic agent to prevent fouling, and was purchased from Croda.

<Step 1>

In a glove box, 0.049 g of the metallocene compound and 1.0 g of silica were added to two round bottom flasks (250 mL), and each flask was taken out of the glove box. To the flask containing the metallocene compound, 10 mL of toluene was added, and the metallocene compound was completely dissolved. 5.25 mL of methylaluminoxane was slowly added at room temperature, and the mixture was stirred for 1 hour. 10 mL of toluene was added to the flask containing the silica, the temperature of the slurry silica was lowered to 0 ° C, and the mixed solution of the metallocene compound and methylaluminoxane was slowly added. The mixture was stirred for 1 hour, then heated to 70 DEG C and reacted for 3 hours. After the completion of the reaction, the stirring was stopped, and the toluene layer was separated and removed. The reaction product was washed with n-hexane and then vacuumed to remove any remaining toluene to obtain a pale brown free flowing powder. there was.

<Step 2>

To the compound of the free flowing powder obtained in <Step 1>, dipentaerythritol diluted with n-hexane, 10,000 ppm, stirred for 30 minutes, filtered, and dried to prepare a catalyst.

The structure of dipentaerythritol is as follows.

[ Preparation Example  2] Preparation of Catalyst

The same procedure as in Preparation Example 1 was carried out except that [(hydroxymethyl) (triethylsilyl) amino] methanol was used instead of dipentaerythritol used in <Step 2> To prepare a catalyst.

The structure of the [(hydroxymethyl) (triethylsilyl) amino] methanol is as follows.

[ Preparation Example  3] Preparation of Catalyst

A catalyst was prepared in the same manner as in Preparation Example 1 except that Atmer 163 was used instead of dipentaerythritol used in < Step 2 >.

[ Example  1] Production of polyolefin copolymer

The polymerization reaction for preparing the polyolefin copolymer was carried out by introducing ethylene at a constant pressure after injection of a required amount of solvent, catalyst, alpha-olefin comonomer, etc. in a reactor completely blocked with outside air (autoclave).

Solvents such as toluene and n-hexane used in the polymerization reaction were purchased from Sigma-Aldrich in an anhydrous grade and passed through an activated molecular sieve (Molecular Sieve, 4A) or an activated alumina layer Dried and used. Triethylaluminium (TEAL) was purchased from Albemarle. 1-Hexene was purchased from Sigma-Aldrich.

First, the inside of a high-pressure reactor (internal capacity: 2 L, stainless steel) was replaced with nitrogen and then 1 L of normal hexane was charged at room temperature. Then, 1 mmol of triethylaluminum and 20 mL of 1-hexene were charged, Were injected in sequence.

Thereafter, when the temperature of the reactor was raised to 80 ° C, ethylene gas was introduced into the reactor at a pressure of 8 bar, and polymerization was carried out for 1 hour while maintaining the temperature at 80 ° C. At the completion of the polymerization reaction, the ethylene supply was stopped, and the reactor temperature was cooled to 20 DEG C, and unreacted ethylene was discharged outside the reactor. To deactivate the remaining catalyst in the reactor, 20 mL of acidified ethanol was added to the reactor. Thereafter, the reaction product was separated by filtration into a solid component, and then dried at 80 DEG C in a vacuum oven to prepare an olefin copolymer.

[ Example  2] Preparation of polyolefin copolymer

A polyethylene copolymer was prepared in the same manner as in Example 1, except that the catalyst prepared in Preparation Example 2 was used in place of the catalyst prepared in Preparation Example 1.

[ Comparative Example  1] Process for producing a polyolefin copolymer

A polyethylene copolymer was prepared in the same manner as in Example 1, except that the compound prepared in <Step 1> of Preparation Example 1 was used instead of the catalyst prepared in Preparation Example 1.

[ Comparative Example  2] Process for producing polyolefin copolymer

A polyethylene copolymer was prepared in the same manner as in Example 1 except that the catalyst prepared in Preparation Example 3 was used in place of the catalyst prepared in Preparation Example 1. [

[ Experimental Example  1] Measurement of physical properties

The properties of the polyethylene copolymers prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured, and the results are shown in Table 1 below.

The polymerization activity of the catalyst in the preparation of the copolymer was calculated by the following equation.

Polymerization activity (kg / mmol · hr) = (yield) / [(mmol of catalyst) * {(60) / (polymerization time)}]

Antistatic agent Bulk density
(g / ml) Polymerization activity
(kg.PE / g.cat) Example 1 Dipentaerythritol 0.41 1.6 Example 2 [(Hydroxymethyl) (triethylsilyl) amino] methanol 0.42 1.5 Comparative Example 1 - 0.34 1.7 Comparative Example 2 Atmer163 0.34 1.2

As shown in Table 1, the polyolefin copolymers prepared in Examples 1 and 2 had a higher bulk density than the polyolefin copolymers prepared in Comparative Example 1, and had a higher polymerization activity than the polyolefin copolymers prepared in Comparative Example 2 Was reduced by a small amount.

Claims (14)

A compound represented by the following formula (1) or (2); And a metallocene compound.
[Chemical Formula 1]

(In the formula 1,
m is an integer of 1 to 20,
And a plurality of R ^1-1 are the same or different, each independently represent a (C ₁ -C ₃₀₎ alkyl or hydroxy.)
(2)

(In the formula (2)
n is an integer of 1 to 20,
A plurality of R &lt; ^1-2 &gt; are the same or different and are each independently (C ₁ -C ₃₀ ) alkyl) The method according to claim 1,
The compound represented by Formula 1 is dipentaerythritol and the compound represented by Formula 2 is [(hydroxymethyl) (triethylsilyl) amino] methanol ([(Hydroxymethyl) (triethylsilyl) amino] methanol ). &Lt; / RTI &gt; The method according to claim 1,
Wherein the compound represented by Formula 1 or 2 is an antistatic agent. The method according to claim 1,
Wherein the metallocene compound is represented by the following general formula (3).
(3)

(3)
M is selected from the group consisting of Group 4 elements on the periodic table,
Q ¹ and Q ² are the same or different and each independently halogen, (C ₁ -C ₂₀₎ alkyl, (C ₂ -C ₂₀₎ alkenyl, (C ₂ -C ₂₀₎ alkynyl each other, (C ₆ - C ₂₀₎ aryl, alkyl amido (C ₁ -C ₂₀₎ alkyl (C ₆ -C ₂₀₎ aryl, (C ₆ -C ₂₀₎ aryl (C ₁ -C ₂₀₎ alkyl, (C ₁ -C ₂₀₎ degrees, (C ₆ -C ₂₀ ) arylamido and (C ₆ -C ₂₀ ) arylamido,
R ² to R ¹¹ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; And (C ₁ -C ₂₀ ) silyl, with or without an acetal, ketal or ether group, wherein R ² and R ³ or R ⁴ and R ⁵ may be linked together to form a ring, , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ^10, or at least two of R ¹⁰ and R ¹¹ may be linked together to form a ring,
R ¹² to R ¹⁴ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; (C ₁ -C ₂₀ ) silyl with or without an acetal, ketal or ether group; (C ₁ -C ₂₀₎ alkoxy; And (C ₆ -C ₂₀ ) aryloxy, wherein R ¹² and R ^13, or R ¹³ and R ¹⁴ may be linked together to form a ring. delete The method according to claim 1,
And at least one promoter compound selected from the group consisting of compounds represented by the following formulas (4) to (8).
[Chemical Formula 4]
- [Al (R ^2-1 ) -O] a-
(In the formula 4,
R ^2-1 are each independently selected from the group consisting of a halogen radical, a (C ₁ -C ₂₀ ) hydrocarbyl radical and a (C ₁ -C ₂₀ ) hydrocarbyl radical substituted with a halogen,
a is an integer of 2 or more.
[Chemical Formula 5]
- [(Me) AlO] n-
(In the above formula (5)
and n is an integer of 10 to 50.)
[Chemical Formula 6]
D (R ^3-1 ) ₃
(6)
D is aluminum or boron,
R ^3-1 are each independently selected from the group consisting of halogen radicals, (C ₁ -C ₂₀₎ hydrocarbyl radical and a (C ₁ -C ₂₀₎ substituted by halogen, hydrocarbyl radical.)
(7)
[LH] ⁺ [Z (A) ₄ ] ^-
[Chemical Formula 8]
[L] ⁺ [Z (A) ₄ ] ^-
(In the above formulas (7) and (8)
L is a neutral or cationic Lewis acid,
Z is selected from the group consisting of Group 13 elements on the periodic table,
A are the same or different, each independently represent at least one hydrogen atom is halogen, (C ₁ -C ₂₀₎ hydrocarbyl, (C ₁ -C ₂₀₎ alkoxy (C ₆ -C ₂₀₎ aryl, (C substituted with ₁ -C ₂₀₎ alkoxy substituted with (C ₁ -C ₂₀₎ alkyl radical, (C ₆ -C ₂₀₎ aryloxy radicals substituted with a (C ₆ -C ₂₀₎ aryl and (C ₆ -C ₂₀₎ aryloxy (C ₁ -C ₂₀ ) alkyl radical substituted with a radical selected from the group consisting of The method according to claim 1,
A catalyst composition for olefin polymerization, which further comprises a compound represented by the above formula (1) or (2) and a carrier that supports the metallocene compound. 8. The method of claim 7,
The support is _{SiO 2, Al 2 O 3,} MgO, MgCl 2, CaCl 2, ZrO 2, TiO 2, B 2 O 3, CaO, ZnO, BaO, ThO 2, SiO 2 -Al 2 O 3, SiO 2 - At least one selected from the group consisting of MgO, SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, bauxite, zeolite, starch and cyclodextrin Catalyst composition for olefin polymerization. A compound represented by the following formula (1) or (2); And polymerizing at least one olefinic monomer in the presence of a catalyst comprising a metallocene compound.
[Chemical Formula 1]

(In the formula 1,
m is an integer of 1 to 20,
And a plurality of R ^1-1 are the same or different, each independently represent a (C ₁ -C ₃₀₎ alkyl or hydroxy.)
(2)

(In the formula (2)
n is an integer of 1 to 20,
A plurality of R ^1-2 are the same or different, each independently represent a (C ₁ -C ₃₀₎ alkyl or hydroxy.) 10. The method of claim 9,
Wherein the metallocene compound is represented by the following general formula (3).
(3)

(3)
M is selected from the group consisting of Group 4 elements on the periodic table,
Q ¹ and Q ² are the same or different and each independently halogen, (C ₁ -C ₂₀₎ alkyl, (C ₂ -C ₂₀₎ alkenyl, (C ₂ -C ₂₀₎ alkynyl each other, (C ₆ - C ₂₀₎ aryl, alkyl amido (C ₁ -C ₂₀₎ alkyl (C ₆ -C ₂₀₎ aryl, (C ₆ -C ₂₀₎ aryl (C ₁ -C ₂₀₎ alkyl, (C ₁ -C _20), and Fig. (C ₆ -C ₂₀ ) arylamido,
R ² to R ¹¹ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; And (C ₁ -C ₂₀ ) silyl, with or without an acetal, ketal or ether group, wherein R ² and R ³ or R ⁴ and R ⁵ may be linked together to form a ring, , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ^10, or at least two of R ¹⁰ and R ¹¹ may be linked together to form a ring,
R ¹² to R ¹⁴ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; (C ₁ -C ₂₀ ) silyl with or without an acetal, ketal or ether group; (C ₁ -C ₂₀₎ alkoxy; And (C ₆ -C ₂₀ ) aryloxy, wherein R ¹² and R ^13, or R ¹³ and R ¹⁴ may be linked together to form a ring. 10. The method of claim 9,
Wherein the catalyst further comprises at least one promoter compound selected from the group consisting of compounds represented by the following general formulas (4) to (8).
[Chemical Formula 4]
- [Al (R ^2-1 ) -O] a-
(In the formula 4,
R ^2-1 are each independently selected from the group consisting of a halogen radical, a (C ₁ -C ₂₀ ) hydrocarbyl radical and a (C ₁ -C ₂₀ ) hydrocarbyl radical substituted with a halogen,
a is an integer of 2 or more.
[Chemical Formula 5]
- [(Me) AlO] n-
(In the above formula (5)
and n is an integer of 10 to 50.)
[Chemical Formula 6]
D (R ^3-1 ) ₃
(6)
D is aluminum or boron,
R ^3-1 are each independently selected from the group consisting of halogen radicals, (C ₁ -C ₂₀₎ hydrocarbyl radical and a (C ₁ -C ₂₀₎ substituted by halogen, hydrocarbyl radical.)
(7)
[LH] ⁺ [Z (A) ₄ ] ^-
[Chemical Formula 8]
[L] ⁺ [Z (A) ₄ ] ^-
(In the above formulas (7) and (8)
L is a neutral or cationic Lewis acid,
Z is selected from the group consisting of Group 13 elements on the periodic table,
A are the same or different, each independently represent at least one hydrogen atom is halogen, (C ₁ -C ₂₀₎ hydrocarbyl, (C ₁ -C ₂₀₎ alkoxy (C ₆ -C ₂₀₎ aryl, (C substituted with ₁ -C ₂₀₎ alkoxy substituted with (C ₁ -C ₂₀₎ alkyl radical, (C ₆ -C ₂₀₎ aryloxy radicals substituted with a (C ₆ -C ₂₀₎ aryl and (C ₆ -C ₂₀₎ aryloxy (C ₁ -C ₂₀ ) alkyl radical substituted with a radical selected from the group consisting of 10. The method of claim 9,
Wherein the olefinic monomer is selected from the group consisting of (C ₂ -C ₂₀ ) alpha-olefins. A polyolefin copolymer produced by the method of any one of claims 9 to 12. 14. The method of claim 13,
A weight average molecular weight (Mw) of 10,000 to 2,000,000 and a molecular weight distribution (Mw / Mn) of 1 to 10.