KR20140121771A - Metallocene catalyst system comprising antistatic agents and method for preparing polyolefin using the same - Google Patents

Abstract

The present invention relates to a metallocene catalyst system comprising an antistatic agent and a method for preparing a polyolefin using the same. According to the present invention, a metallocene catalyst system can operate the process more stably by minimizing fouling and agglomeration while maintaining the specific activity of the catalyst when a polyolefin is prepared through gas-phase polymerization.

Description

TECHNICAL FIELD [0001] The present invention relates to a metallocene catalyst system comprising an antistatic agent and a polyolefin,

The present invention relates to a metallocene catalyst system comprising an antistatic agent and a process for producing a polyolefin using the same.

This application claims the benefit of Korean Patent Application No. 10-2013-0038151, filed on April 8, 2013, filed with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

As a method for industrially producing polyolefins from olefins, a solution polymerization process, a slurry polymerization process, and a gas phase polymerization process are known. Among them, the solution polymerization process is a process in which a polymer is melted in a liquid phase, and a slurry polymerization process is a process in which a polymer produced in a liquid phase polymerization medium is dispersed in a solid state and a gas phase polymerization process is carried out in a gas phase polymerization medium The resulting polymer is dispersed in a fluidized state.

In general, the gas phase polymerization process is carried out at a temperature lower than the melting point of the polymer to be formed. If the temperature is raised above the critical temperature for several reasons, the polymer particles are softened and aggregated or stick to the reaction apparatus. Therefore, in the gas phase polymerization step, fouling occurs in which the polymer adheres to the inner wall surface of the circulation gas line, the heat exchanger, the inner wall of the cooler, and the agglomeration of the produced polyolefin near the softening point. This phenomenon may be influenced by the polymerization medium, molecular weight, concentration of comonomer, and the like. This phenomenon can also be exacerbated as the concentration of the polymer particles is higher and the size of the polymer particles is smaller.

When the fouling and aggregation phenomenon becomes severe in the gas phase polymerization process, heat transfer and heat removal in the reactor become difficult, and normal polyolefin transfer is hindered. As a result, smooth control of the polymerization reaction and long- do.

Accordingly, 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 of preventing fouling by reducing the catalytic activity by using an inactivating agent, and U.S. Patent No. 5,733,988 discloses a method of adding alcohol, ether, ammonia, . However, since these methods lower the activity of the catalyst, the activity of the reaction is lowered and the production efficiency is inevitably lowered. U.S. Patent No. 5,270,407 discloses a method of preventing fouling by adding a polysiloxane to a catalyst system, and U.S. Patent No. 3,956,257 discloses a method of preventing fouling using hydrocarbyl aluminum alkoxide. However, these methods also have a limitation in that the overall catalytic activity is reduced.

Accordingly, the present invention provides a metallocene catalyst system capable of maintaining the intrinsic activity of a catalyst during the production of a polyolefin through gas phase polymerization, while minimizing fouling and aggregation to enable more stable process operation.

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

According to the present invention,

Metallocene compounds;

At least one metal salt selected from the group consisting of an alkali metal salt and an alkaline earth metal salt; And

But are not limited to, metallic stearates, stearic acid, alkyl stearates having 3 to 40 carbon atoms, glycerol, sorbitan monooleate, and ethoxylated amines) and at least one antistatic agent selected from the group consisting of

A metallocene catalyst system for olefin polymerization is provided.

Here, the metallocene compound may be a compound represented by the following formula (1)

[Chemical Formula 1]

In Formula 1,

M is a Group 4 transition metal;

Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with at least one hydrocarbon group having 1 to 20 carbon atoms;

R ¹ and R ² are the same as or different from each other and each independently represents hydrogen, alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 10 carbon atoms, alkoxyalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, Aryloxy having 2 to 20 carbon atoms, alkylaryl having 7 to 40 carbon atoms, arylalkyl having 7 to 40 carbon atoms, arylalkenyl having 8 to 40 carbon atoms, or alkynyl having 2 to 10 carbon atoms;

R ³ is a divalent hydrocarbon group which crosslinks (Cp ¹ R ¹ ) and (Cp ² R ² ) by a covalent bond and contains an element selected from the group consisting of silicon, germanium, phosphorus, nitrogen, boron and aluminum ;

m is 0 or 1;

The metal salt may be at least one compound selected from the group consisting of lithium chloride, sodium chloride, and calcium chloride.

The metal salt may include 1: 0.001 to 1: 100 based on the molar ratio of the metal contained in the metal salt to 1 mole of the transition metal contained in the metallocene compound.

Meanwhile, the metallic stearates may be at least one compound selected from the group consisting of Al-stearate, Zn-stearate, and Mg-stearate. Lt; / RTI >

And, the ethoxylated amine may be a compound represented by the following formula (2): < EMI ID =

(2)

In Formula 2,

R ^a is an alkyl group having 6 to 20 carbon atoms,

R ^b is independently an alkenyl group having 1 to 3 carbon atoms,

n are each independently an integer of 1 to 20;

The antistatic agent may be included in an amount of 0.001 to 5% by weight based on the total weight of the catalyst system.

Further, the metallocene catalyst system for olefin polymerization may further contain a cocatalyst compound.

The metallocene catalyst system for olefin polymerization may further include an inert carrier on which the metallocene compound, the metal salt, and the antistatic agent are supported.

On the other hand, according to the present invention, there is provided a process for producing a polyolefin comprising the step of vapor-phase-polymerizing at least one olefin-based monomer in the presence of the above-mentioned metallocene catalyst system.

Here, the olefin monomer may be at least one compound selected from the group consisting of an alpha-olefin having 2 to 20 carbon atoms, a diolefin having 1 to 20 carbon atoms, a cycloolefin having 3 to 20 carbon atoms, and a cycloolefin having 3 to 20 carbon atoms Lt; / RTI >

The metallocene catalyst system according to the present invention can maintain the intrinsic activity of the catalyst during the production of the polyolefin through gas phase polymerization, while minimizing the fouling and agglomeration phenomenon, thereby enabling a more stable process operation.

Hereinafter, a metallocene catalyst system according to embodiments of the present invention and a method for producing a polyolefin using the same will be described.

Prior to that, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. And, the singular forms used herein include plural forms unless the phrases expressly have the opposite meaning. Also, as used herein, the meaning of "comprising" or "containing" embodies certain features, areas, integers, steps, acts, elements or components, But does not exclude the addition of components.

On the other hand, the inventors of the present invention have found that when a metallocene catalyst system comprising an alkali metal salt, an alkaline earth metal salt or a mixture thereof is used in a process of repeatedly studying a production method of a polyolefin, It is confirmed that fouling and aggregation phenomenon are minimized and a more stable and efficient process operation is possible.

According to this embodiment of the present invention,

Metallocene compounds;

At least one metal salt selected from the group consisting of an alkali metal salt and an alkaline earth metal salt; And

But are not limited to, metallic stearates, stearic acid, alkyl stearates having 3 to 40 carbon atoms, glycerol, sorbitan monooleate, and ethoxylated amines) and at least one antistatic agent selected from the group consisting of

A metallocene catalyst system for olefin polymerization is provided.

That is, the metallocene catalyst system according to one embodiment of the present invention can improve the friction between the polymer particles during the production of the polyolefin by gas phase polymerization or the friction between the polymer particles and the inner wall of the reactor, The static electricity generated by the catalyst can be minimized while the intrinsic activity of the catalyst can be stably maintained. This is because the above metallocene catalyst system is formed by forming the particle size and the bulk density of the polymer present in the reactor within a range in which the generation of static electricity due to friction can be minimized. Particularly, in the synergistic action by the metal salt and the antistatic agent .

Meanwhile, the metallocene catalyst system according to the present invention may include a conventional metallocene compound, and the constitution thereof is not particularly limited.

However, according to one embodiment of the present invention, the metallocene compound may be a compound represented by the following formula (1)

[Chemical Formula 1]

In Formula 1,

M is a Group 4 transition metal;

Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with at least one hydrocarbon group having 1 to 20 carbon atoms;

R ¹ and R ² are the same as or different from each other and each independently represents hydrogen, alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 10 carbon atoms, alkoxyalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, Aryloxy having 2 to 20 carbon atoms, alkylaryl having 7 to 40 carbon atoms, arylalkyl having 7 to 40 carbon atoms, arylalkenyl having 8 to 40 carbon atoms, or alkynyl having 2 to 10 carbon atoms;

R ³ is a divalent hydrocarbon group which crosslinks (Cp ¹ R ¹ ) and (Cp ² R ² ) by a covalent bond and contains an element selected from the group consisting of silicon, germanium, phosphorus, nitrogen, boron and aluminum ;

m is 0 or 1;

According to the present invention, in the above formula (1), M may be an element such as Ti, Zr or Hf which is a transition metal of Group 4.

When m is 1 in the above formula ( ¹ ), it means that (Cp ¹ R ¹ ) and (Cp ² R ² ) are bridged structures bridged by R ^{3. When} m is 0, Compound structure "

By way of non-limiting example, the metallocene compound may be selected from the group consisting of BisIndenylZrCl ₂ , BisIndenylHfCl ₂ , Bis (1-butyl-3-methylcyclopentadienyl) ZrCl ₂ , Bis (cyclopentadienyl) ZrCl ₂ , ) ZrCl ₂ , rac-Dimethylsilylene-bis (1-indenyl) ZrCl ₂ , (Cyclopentadienyl) IndenylZrCl ₂ , and [Dimethylsilyl (η ⁵ -tetramethylcyclopentadienyl) (t-butylamido)] TiCl ₂ .

Meanwhile, the metallocene catalyst system for olefin polymerization according to the present invention includes a metal salt.

Wherein the metal salt is at least one compound selected from the group consisting of an alkali metal salt and an alkaline earth metal salt; Specifically, it may be a compound containing at least one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, calcium, strontium, barium and radium. In particular, it is preferable that the metal salt is at least one compound selected from the group consisting of lithium chloride, sodium chloride and calcium chloride, since it can exhibit sufficient antistatic effect while minimizing catalyst deactivation, have.

The metal salt may be used in a ratio of 1: 0.001 to 1: 100, or 1: 0.01 to 1: 100, or 1: 100, based on the molar ratio of the metal contained in the metal salt to 1 mol of the transition metal contained in the metallocene compound. : 0.1 to 1: 100. That is, in order to sufficiently exhibit the antistatic effect required in the present invention, the metal salt is preferably used in an amount of from 1: 1 to 1: 1 based on the molar ratio of the metal contained in the metal salt to one mole of the transition metal contained in the metallocene compound. 0.001 or more. However, if the metal salt is included in an excess amount, the degree of improvement of the antistatic effect relative to the addition amount may be lowered, and the activity of the catalyst may be reduced through reaction with the catalyst. Accordingly, it may be advantageous that the metal salt is included in an amount of 1: 100 or less based on the molar ratio of the metal contained in the metal salt to 1 mole of the transition metal contained in the metallocene compound. In other words, the metal salt may be contained in an amount of approximately 0.1 to 5 wt% relative to the metallocene compound.

Meanwhile, the metallocene catalyst system for olefin polymerization according to the present invention includes an antistatic agent.

As the antistatic agent, compounds common in the art to which the present invention belongs can be used without any particular limitation. However, according to one embodiment, the antistatic agent is selected from the group consisting of metallic stearates, stearic acid (C ₁₇ H ₃₅ COOH), alkyl stearate having 3 to 40 carbon atoms, glycerol, At least one compound selected from the group consisting of sorbitan monooleate, and ethoxylated amines may be preferred.

Non-limiting examples, the metallic stearates (metallic stearates) an aluminum-stearate (Al-stearate, for example _{Al (C 17 H 35 COO)} 3), zinc-stearate (Zn-stearate), and magnesium- And stearate (Mg-stearate).

And, the ethoxylated amine may be a compound represented by the following formula (2): < EMI ID =

(2)

In Formula 2,

R ^a is an alkyl group having 6 to 20 carbon atoms,

R ^b is independently an alkenyl group having 1 to 3 carbon atoms,

n are each independently an integer of 1 to 20;

As non-limiting examples, the ethoxylated amines include C ₁₂ H ₂₅ N (CH ₂ CH ₂ OH) ₂ , C ₁₈ H ₃₇ N (CH ₂ CH ₂ OH) ₂ , and the like.

Such an antistatic agent may be contained in an amount of 0.001 to 5 wt%, or 0.01 to 3 wt%, or 0.1 to 1 wt% based on the total weight of the catalyst system. That is, in order to sufficiently exhibit the antistatic effect required in the present invention, it is advantageous that the antistatic agent is contained in an amount of 0.001% by weight or more based on the total weight of the catalyst system. However, when the antistatic agent is contained in an excess amount, the degree of improvement of the antistatic effect relative to the addition amount may be lowered, and the activity of the catalyst may be reduced through reaction with the catalyst. Accordingly, it may be advantageous that the antistatic agent is included in an amount of 5% by weight or less based on the total weight of the catalyst system.

Meanwhile, the metallocene catalyst system according to the present invention may further include a cocatalyst compound.

The promoter compound may be a conventional compound capable of activating the metallocene compound, and may preferably be at least one compound selected from the group consisting of compounds represented by the following formulas (3), (4) and (5) :

(3)

R ³² - [Al (R ³¹ ) -O] _a -R ³³

In Formula 3,

R ³¹ , R ³² and R ³³ are each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

a is an integer of 2 or more;

[Chemical Formula 4]

D (R < ^{41 >} ) ₃

In Formula 4,

D is aluminum or boron;

R ⁴¹ is each independently halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen;

[Chemical Formula 5]

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

In Formula 5,

L is a neutral or cationic Lewis base;

[LH] ⁺ or [L] ⁺ is a Bronsted acid;

H is a hydrogen atom;

Z is a Group 13 element;

A is independently at each occurrence one or more hydrogen atoms independently selected from the group consisting of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted with an alkoxy or phenoxy radical having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.

Here, in order to allow the promoter compound to exhibit a better activation effect, R ³¹ in Formula 3 is methyl, ethyl, n-butyl or isobutyl; D in the formula 4 is aluminum, R ⁴¹ is methyl or isobutyl; Or D is boron and R < ⁴¹ > is pentafluorophenyl; And [LH] ⁺ is dimethylanilinium cation dimethyl In Formula _{5, [Z (A) 4} ] - is _{[B (C 6 F 5)} 4] - a, [L] ⁺ is [(C ₆ H _{5) 3} C] ⁺ .

In the above Chemical Formulas 3 and 4, "hydrocarbyl" is a monovalent functional group in which hydrogen atoms are removed from a hydrocarbon, and may include ethyl, phenyl, and the like.

As a non-limiting example, the compound represented by Formula 3 may be methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, or the like.

In addition, as a non-limiting example, the compound represented by the above-mentioned general formula (4) may be used in combination with one or more compounds selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, Tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum Ethoxide and the like.

In addition, as a non-limiting example, the compound represented by Formula 5 may be a compound selected from the group consisting of trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) Tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (triisopropylsilyl) , 5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxy tris (pentafluorophenyl) borate, N, N-dimethyl- 2,4,6- trimethylanilinium tetrakis (Pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, hexadecyldimethylammonium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecyl anil (Pentafluorophenyl) borate, methyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate, and the like.

Wherein the co-catalyst compound is present in an amount of from 1: 1 to 1: 10,000, or from 1: 1 to 1: 1,000, based on the molar ratio of the metal contained in the co-catalyst compound to one mole of the transition metal contained in the metallocene compound, Or from 1: 1 to 1: 100.

The metallocene catalyst system according to the present invention may further include an inert carrier on which the metallocene compound, the metal salt, and the antistatic agent are supported.

As the inert carrier, inorganic or organic carriers customary in the technical field of the present invention can be used without particular limitation; Preferably, _{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 -CrO 2 O 3, may be a SiO ₂ -TiO ₂ -MgO, bauxite, zeolite.

As a non-limiting example, the supported catalyst according to the above embodiment may be prepared by suspending a silica gel, stirring the mixture while slowly adding a co-catalyst compound (such as methylaluminoxane), adding an antistatic agent and a metallocene compound thereto, Washing and drying processes.

According to another embodiment of the present invention, there is provided a process for producing a polyolefin comprising the step of vapor-phase-polymerizing at least one olefin-based monomer in the presence of a metallocene catalyst system.

The olefin monomer may be at least one compound selected from the group consisting of an alpha-olefin having 2 to 20 carbon atoms, a diolefin having 1 to 20 carbon atoms, a cycloolefin having 3 to 20 carbon atoms, and a cycloolefin having 3 to 20 carbon atoms Lt; / RTI >

As a non-limiting example, the olefinic monomer may have a number of carbon atoms including ethylene, propylene, 1-butene, 1-pentene and 1-hexene. 2 to 20 alpha-olefins; But are not limited to those containing 1,3-butadiene, 1,4-pentadiene and 2-methyl-1,3-butadiene. A diolefin having 1 to 20 carbon atoms; The number of carbons including 3 carbon atoms, including cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbonene and methyl-2-norbonene, Cyclo-olefin or cyclo-diolefin of from 1 to 20 carbon atoms; Substituted styrene in which an alkyl group, an alkoxy group, a halogen group, an amine group, a silyl group, a haloalkyl group or the like is bonded to a phenyl ring of styrene or styrene; Or a mixture thereof.

Further, according to the present invention, the production method of the polyolefin can exhibit higher efficiency than in gas phase polymerization.

Hereinafter, preferred embodiments of the present invention will be described in detail. It should be understood, however, that these examples are for illustrative purposes only and are not to be construed as limiting the scope of the present invention.

Example  One

2 g of silica gel (XPO2402, Grace Davision) was placed in a 100 ml round-bottomed flask, suspended in 10 ml of toluene under a nitrogen atmosphere, and 11 ml of methylaluminoxane (10% by weight of toluene solution) was slowly added. Subsequently, the mixture was stirred at 70 DEG C for 2 hours, washed with 10 mL of toluene three times, and then vacuum-dried at 40 DEG C to obtain a cocatalyst-supported silica.

1 g of the above-cocatalyst-supported silica was suspended in 10 ml of toluene. In another flask, a solution of 20 mg of bis (indenyl) zirconium (IV) dichloride (BisIndenylZrCl ₂ ) dissolved in 5 ml of toluene was prepared. Thereafter, a bis (indenyl) zirconium (IV) dichloride solution was added to the silica suspension solution using a cannula, and the mixture was stirred at 70 ° C for 2 hours. This was washed three times with 10 ml of toluene, and then vacuum-dried at 40 DEG C to obtain a catalyst carrying a promoter and a metallocene compound.

Then, 1 g of the above supported catalyst, 10 mg of lithium chloride and 10 ml of ethoxylated amine (C ₁₈ H ₃₇ N (C ₂ H ₄ OH) ₂ , trade name: Kemamine AS-990) were suspended in 10 ml of toluene And stirred at 70 [deg.] C for 2 hours. Then, this was washed three times with 10 ml of toluene, and then dried under vacuum at 40 ° C to obtain a supported catalyst system.

Example  2

2 g of silica gel (XPO2402, Grace Davision) was placed in a 100 ml round-bottomed flask, suspended in 10 ml of toluene under a nitrogen atmosphere, and 11 ml of methylaluminoxane (10% by weight of toluene solution) was slowly added. Subsequently, the mixture was stirred at 70 DEG C for 2 hours, washed with 10 mL of toluene three times, and then vacuum-dried at 40 DEG C to obtain a cocatalyst-supported silica.

1 g of the above-cocatalyst-supported silica was suspended in 10 ml of toluene. In another flask, a solution of 20 mg of bis (indenyl) zirconium (IV) dichloride (BisIndenylZrCl ₂ ) dissolved in 5 ml of toluene was prepared. Thereafter, a bis (indenyl) zirconium (IV) dichloride solution was added to the silica suspension solution using a cannula, and the mixture was stirred at 70 ° C for 2 hours. This was washed three times with 10 ml of toluene, and then vacuum-dried at 40 DEG C to obtain a catalyst carrying a promoter and a metallocene compound.

Subsequently, 1 g of the above supported catalyst, 10 mg of lithium chloride and 10 ml of ethoxylated amine (trade name: Atmer 163) were suspended in 10 ml of toluene, and the mixture was stirred at 70 ° C for 2 hours. Then, this was washed three times with 10 ml of toluene, and then dried under vacuum at 40 ° C to obtain a supported catalyst system.

Comparative Example  One

2 g of silica gel (XPO2402, Grace Davision) was placed in a 100 ml round-bottomed flask, suspended in 10 ml of toluene under a nitrogen atmosphere, and 11 ml of methylaluminoxane (10% by weight of toluene solution) was slowly added. Subsequently, the mixture was stirred at 70 DEG C for 2 hours, washed with 10 mL of toluene three times, and then vacuum-dried at 40 DEG C to obtain a cocatalyst-supported silica.

1 g of the above-cocatalyst-supported silica was suspended in 10 ml of toluene. In another flask, a solution of 20 mg of bis (indenyl) zirconium (IV) dichloride (BisIndenylZrCl ₂ ) dissolved in 5 ml of toluene was prepared. Thereafter, a bis (indenyl) zirconium (IV) dichloride solution was added to the silica suspension solution using a cannula, and the mixture was stirred at 70 ° C for 2 hours. This was washed three times with 10 ml of toluene, and then vacuum-dried at 40 DEG C to obtain a catalyst carrying a promoter and a metallocene compound.

Comparative Example  2

A supported catalyst system was obtained in the same manner as in Example 1 except that no ethoxylated amine (C ₁₈ H ₃₇ N (C ₂ H ₄ OH) ₂ , trade name: Kemamine AS-990) was added.

Test Example : Manufacture of polyethylene

A 2 L high-pressure reactor was kept under vacuum at 80 ° C for 1 hour, after which 1 L of purified hexane was added. 0.6 ml of triisobutylaluminum (1M hexane solution) was added to remove water, and 50 mg of the supported catalyst according to Example 1, Example 2, Comparative Example 1 or Comparative Example 2 was suspended in hexane and connected to the reactor It was injected through a container.

Then, the reactor was heated to 80 ° C, nitrogen was introduced, the pressure was adjusted to 1 bar, ethylene was injected, and 100 mL of 1-butene was injected using a syringe pump while keeping the internal pressure constant at 15 bar. After one hour, the residual ethylene was discharged to terminate the polymerization. The residual suspension was filtered and dried naturally to give polyethylene with free flowing properties.

The average polymerization activity (gPE / gCAT), average particle size (APS, ㎛), bulk density (g / cc) and occurrence of fouling phenomenon of each catalyst were confirmed. Respectively.

In this case, when the fouling phenomenon occurs, O is generated, and when not generated, X is not generated.

catalyst Polymerization activity
(gPE / gCAT) APS (占 퐉) BD
(g / cc) Fouling Example 1 3400 810 0.40 Not Detected (O) Example 2 3100 785 0.40 Not Detected (O) Comparative Example 1 3700 843 0.44 Fouling (X) Comparative Example 2 3600 840 0.42 Not Detected (△)

As can be seen from Table 1, the catalyst systems of Examples 1 and 2 were found to contain no metal salt and antistatic agent at the same time, so that the fouling phenomenon did not appear even though the activity of the catalyst was not greatly decreased.

Claims (15)

Metallocene compounds;
At least one metal salt selected from the group consisting of an alkali metal salt and an alkaline earth metal salt; And
But are not limited to, metallic stearates, stearic acid, alkyl stearates having 3 to 40 carbon atoms, glycerol, sorbitan monooleate, and ethoxylated amines) and at least one antistatic agent selected from the group consisting of
≪ / RTI >
The method according to claim 1,
Wherein the metallocene compound is a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

In Formula 1,
M is a Group 4 transition metal;
Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with at least one hydrocarbon group having 1 to 20 carbon atoms;
R ¹ and R ² are the same as or different from each other and each independently represents hydrogen, alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 10 carbon atoms, alkoxyalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, Aryloxy having 2 to 20 carbon atoms, alkylaryl having 7 to 40 carbon atoms, arylalkyl having 7 to 40 carbon atoms, arylalkenyl having 8 to 40 carbon atoms, or alkynyl having 2 to 10 carbon atoms;
R ³ is a divalent hydrocarbon group which crosslinks (Cp ¹ R ¹ ) and (Cp ² R ² ) by a covalent bond and contains an element selected from the group consisting of silicon, germanium, phosphorus, nitrogen, boron and aluminum ;
m is 0 or 1;
The method according to claim 1,
Wherein the metal salt is a compound comprising at least one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, calcium, strontium, barium and radium.
The method according to claim 1,
Wherein the metal salt is at least one compound selected from the group consisting of lithium chloride, sodium chloride and calcium chloride.
The method according to claim 1,
Wherein the metal salt comprises 1: 0.001 to 1: 100 based on the molar ratio of the metal contained in the metal salt to 1 mole of the transition metal contained in the metallocene compound.
The method according to claim 1,
Wherein the metallic stearates are at least one compound selected from the group consisting of Al-stearate, Zn-stearate, and Mg-stearate. Metallocene catalyst systems for olefin polymerization.
The method according to claim 1,
Wherein the ethoxylated amine is a compound represented by the following formula (2): < EMI ID =
(2)

In Formula 2,
R ^a is an alkyl group having 6 to 20 carbon atoms,
R ^b is independently an alkenyl group having 1 to 3 carbon atoms,
n are each independently an integer of 1 to 20;
The method according to claim 1,
Wherein the ethoxylated amine is C ₁₂ H ₂₅ N (CH ₂ CH ₂ OH) ₂ or C ₁₈ H ₃₇ N (CH ₂ CH ₂ OH) ₂ .
The method according to claim 1,
Wherein the antistatic agent is contained in an amount of 0.001 to 5 wt% based on the total weight of the catalyst system.
The method according to claim 1,
A metallocene catalyst system for olefin polymerization, further comprising at least one cocatalyst compound selected from the group consisting of compounds represented by the following formulas (3), (4) and (5)
(3)
R ³² - [Al (R ³¹ ) -O] _a -R ³³
In Formula 3,
R ³¹ , R ³² and R ³³ are each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
a is an integer of 2 or more;
[Chemical Formula 4]
D (R < ^{41 >} ) ₃
In Formula 4,
D is aluminum or boron;
R ⁴¹ is each independently halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen;
[Chemical Formula 5]
^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -
In Formula 5,
L is a neutral or cationic Lewis base;
[LH] ⁺ or [L] ⁺ is a Bronsted acid;
H is a hydrogen atom;
Z is a Group 13 element;
A is independently at each occurrence one or more hydrogen atoms independently selected from the group consisting of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted with an alkoxy or phenoxy radical having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.
11. The method of claim 10,
R ³¹ in Formula 3 is methyl, ethyl, n-butyl or isobutyl;
D in the formula 4 is aluminum, R ⁴¹ is methyl or isobutyl; Or D is boron and R < ⁴¹ > is pentafluorophenyl;
And [LH] ⁺ is dimethylanilinium cation dimethyl In Formula _{5, [Z (A) 4} ] - is _{[B (C 6 F 5)} 4] - a, [L] ⁺ is [(C ₆ H _{5) 3} C] ⁺ , metallocene catalyst system for olefin polymerization.
11. The method of claim 10,
Wherein the promoter compound is present in a ratio of 1: 1 to 1: 10,000, based on the molar ratio of the metal contained in the cocatalyst compound to one mole of the transition metal contained in the metallocene compound, in the metallocene catalyst system for olefin polymerization .
The method according to claim 1,
The metallocene compound, the metal salt, and the inert carrier on which the antistatic agent is supported.
A process for producing a polyolefin comprising the step of gas-phase polymerization of at least one olefin-based monomer in the presence of the metallocene catalyst system according to claim 1.
15. The method of claim 14,
Wherein the olefinic monomer is at least one compound selected from the group consisting of an alpha-olefin having 2 to 20 carbon atoms, a diolefin having 1 to 20 carbon atoms, a cycloolefin having 3 to 20 carbon atoms, and a cycloolefin having 3 to 20 carbon atoms. A method for producing a polyolefin.