KR101412118B1 - Method for preparing supported hybrid metallocene catalyst, and supported hybrid metallocene catalyst using the same - Google Patents

Abstract

The present invention is characterized in that trialkyl aluminum is used as the first catalyst in place of the expensive aluminoxane cocatalyst used mainly for the supported catalyst activation, and the borate compound is used as the second catalyst, A method of preparing a hybrid supported metallocene catalyst which shows a cost reduction effect by using trialkyl aluminum as an active species which is relatively less expensive than aluminoxane, and a hybrid supported metallocene catalyst And a method for producing polyolefins using the same.

Description

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

The present invention relates to a process for preparing a hybrid supported metallocene catalyst which can be used in the production of polyolefins, and to a process for producing a polyolefin using the hybrid supported metallocene catalyst and the hybrid supported metallocene catalyst prepared using the same.

Ziegler-Natta catalyst widely applied to existing commercial processes is characterized by a wide molecular weight distribution of the produced polymer because it is a multi-site catalyst and the composition distribution of the comonomer is not uniform.

On the other hand, the metallocene catalyst has a narrow molecular weight distribution of a polymer produced by a single active site catalyst having one kind of active site, and the molecular weight, stereoregularity, crystallinity, especially reactivity of the comonomer, There are advantages that can be adjusted.

The metallocene catalyst system is composed of a combination of a main catalyst mainly composed of a transition metal compound centered on a Group 4 metal and a cocatalyst comprising an organometallic compound mainly composed of a Group 13 metal such as aluminum. Polymers such as polyolefins having a narrow molecular weight distribution can be prepared according to the single active site characteristics of the catalyst.

The molecular weight and molecular weight distribution of polyolefins are important factors in determining the physical properties of the polymer and the flow and mechanical properties affecting the processability of the polymer. In order to produce various polyolefin products, it is important to improve the melt processability by controlling the molecular weight distribution. Particularly, in the case of polyethylene, quality, resistance and resistance to environmental stress are very important. Accordingly, a method of improving the mechanical properties of a high molecular weight resin and the processability in a low molecular weight portion by producing a polyolefin having such a high molecular weight distribution is also proposed.

On the other hand, when the polyolefin is produced through the slurry process, silica is used as a general carrier of the supported catalyst, and methylaluminoxane (MAO) and one or more organometallic catalysts (for example, , A metallocene catalyst) is supported on the supported catalyst. However, since alumoxane such as MAO used for activating the supported catalyst is excessively expensive, it is a big obstacle in terms of cost reduction when it is used for commercial purposes. In addition, all MAOs used do not produce active species, but they also form inert species on the catalyst. Therefore, efforts have been made to reduce the amount of aluminoxane such as MAO, which is generally used, or to replace it with another cocatalyst.

However, in most of the prior arts, when the MAO used for the supported catalyst activation is changed to another catalyst, its catalytic activity is very poor, and it is necessary to develop new catalytic active species.

Accordingly, the present invention relates to a process for producing a polyolefin having a high bulk density by maintaining high catalytic activity in place of MAO used as a catalytically active species, and capable of realizing cost reduction without using an expensive and excessive MAO A method for preparing an active hybrid supported metallocene catalyst and a hybrid supported metallocene catalyst prepared using the same.

The present invention provides a process for producing a polyolefin using the mixed supported metallocene catalyst.

The present invention provides a method for producing a metallocene compound, comprising: supporting a first metallocene compound on a support;

Supporting a first co-catalyst comprising a trialkylaluminum compound having a linear or branched alkyl group having 1 to 10 carbon atoms on the carrier;

Supporting the second metallocene compound on the carrier; And

Supporting a second co-catalyst containing a borate compound on the carrier

Wherein the metallocene catalyst is supported on the catalyst support.

The present invention also relates to a process for preparing a metallocene compound, A first co-catalyst which is a trialkyl aluminum compound having a straight or branched alkyl group having 1 to 10 carbon atoms; A second metallocene compound; And a second co-catalyst, which is a borate compound, in this order.

The present invention also provides a process for producing a polyolefin comprising polymerizing at least one or more olefin monomers in the presence of the mixed supported metallocene catalyst.

Hereinafter, a method for preparing a mixed supported metallocene catalyst and a mixed supported metallocene catalyst according to a specific embodiment of the present invention will be described.

According to a preferred embodiment of the present invention, there is provided a method for preparing a metallocene compound, comprising: supporting a first metallocene compound on a carrier; Supporting a first co-catalyst comprising a trialkyl aluminum compound on the carrier; Supporting the second metallocene compound on the carrier; And carrying a second co-catalyst containing a borate compound on the carrier.

The method of the present invention has an effect of maintaining a very high catalytic activity by using a trialkylaluminum compound instead of methylaluminoxane (MAO) which is generally used as a first catalyst for making active species of the catalyst.

However, when the trialkylaluminum compound is used alone in the preparation of the catalyst, the metallocene catalyst can not be activated, and thus the catalyst does not exhibit activity. Accordingly, the present invention is characterized in that the trialkyl aluminum compound is used as the first promoter and the borate compound is used as the second promoter to maximize its activity.

In particular, the present invention is not directed to the preparation of a catalyst by the catalytic reaction of the first and second metallocene compounds after activating the support with the MAO promoter as in the prior art, The first metallocene compound, the first co-catalyst, the second metallocene compound and the second co-catalyst are successively carried on the carrier in this order. According to this support sequence, the present invention is characterized in that the first co-catalyst activates the catalyst during the alkylation of the C1-group of the first metallocene compound and the second metallocene compound, and finally the second co- It is possible to impart the effect of increasing the activity of the hybrid supported metallocene catalyst by being carried on the surface most.

Therefore, the invention according to an embodiment of the present invention is to provide a method for preparing a mixed supported metallocene catalyst by using two kinds of co-catalysts such as a trialkyl aluminum compound-borate compound, But also a MAO-free effect as a new active species of the supported catalyst, thereby providing a catalyst exhibiting excellent activity without the use of expensive and excessive MAO.

In the present invention, the weight ratio of the first co-catalyst and the second co-catalyst may be 100: 1 to 10: 1, and preferably 50: 1 to 20: 1. When the weight ratio of the first and second supported catalysts satisfies the above range, not only the activity of the finally produced hybrid supported metallocene catalyst is better, but also the performance of the polyolefin prepared using the hybrid supported metallocene catalyst The bulk density can also be maintained at a higher level.

In the above production process, the amount of the first cocatalyst to be supported is preferably 3 to 10 mmol based on 1 g of the carrier, and the amount of the second cocatalyst to be supported is preferably 0.01 to 0.5 mmol based on 1 g of the carrier. If the supported amount of the first co-catalyst is less than 3 mmol, there is a problem that the number of active species of the mixed supported metallocene catalyst is reduced and the activity of the catalyst itself is lowered. If the amount exceeds 10 mmol, the activity may be increased, The activity is not continuously increased, and it is possible to remove excess co-catalyst which is not intermittent, and there is a problem that the catalyst price is increased. If the loading amount of the second co-catalyst is less than 0.01 mmol, there is a problem in that the activity of the supported catalyst is lowered in the same manner as the first co-catalyst. If the loading amount exceeds 0.5 mmol, the catalyst price increases sharply and the bulk density There is a problem that the productivity of the plant is deteriorated.

The loading amount of the first metallocene compound and the second metallocene compound is preferably 0.02 to 1 mmol based on 1 g of the carrier, but is not limited thereto.

The contact reaction of the first metallocene compound, the trialkyl aluminum-containing first cocatalyst, the second metallocene compound, and the second cocatalyst comprising the borate compound in this order with the carrier for carrying is carried out in a solvent May be used, or may be reacted without a solvent. Examples of the solvent that can be used include aliphatic hydrocarbon solvents such as hexane or pentane, aromatic hydrocarbon solvents such as toluene or benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, ether solvents such as diethyl ether or THF, Ethyl acetate and the like, and hexane, heptane, toluene, or dichloromethane is preferred.

Further, in the present invention, when a second co-catalyst containing a first metallocene compound, a first co-catalyst containing trialkyl aluminum, a second metallocene compound and a borate compound is sequentially carried on a carrier, The conditions are not particularly limited and can be performed within a range well known to those skilled in the art. For example, it can be carried out by appropriately using high-temperature loading and low-temperature loading. Specifically, when the first co-catalyst and the second co-catalyst are supported on the carrier, the temperature condition can be carried out at 25 to 100 ° C. At this time, the holding time of the first co-catalyst and the holding time of the second co-catalyst may be appropriately adjusted according to the amount of the co-catalyst to be supported. The reaction temperature of the first and second metallocene compounds and the carrier may be from -30 ° C to 150 ° C, preferably from room temperature to 100 ° C, and more preferably from 30 ° C to 80 ° C. The supported catalyst can be used as it is by filtration of the reaction solvent or by distillation under reduced pressure, and if necessary, it can be used by a Soxhlet filter with aromatic hydrocarbons such as toluene.

In the production method of the present invention, the first co-catalyst is preferably a trialkylaluminum compound having a linear or branched alkyl group having 1 to 10 carbon atoms. This is because the activation of the first metallocene compound supported on the carrier Which catalyzes the metallocene catalyst to provide space for coordination polymerization in which reactants such as ethylene form a polymer.

Preferable examples of the first co-catalyst include, but are not limited to, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, isoprenyl aluminum and the like.

Also, the second co-catalyst means an ionic compound capable of reacting with the first co-catalyst to form a cation complex, and includes an ionic compound in combination with a conventional non-coordinating anion and a cation.

For example, the second catalyst may preferably contain a compound represented by the following general formula (1-1) or (1-2).

[Formula 1-1]

[LH] ⁺ [Z (A) ₄ ] ^-

[Formula 1-2]

[L] ⁺ [Z (A) ₄ ] ^-

Wherein each L is a neutral or cationic Lewis acid, each H is a hydrogen atom, each Z is a Group 13 element, each A is independently selected from the group consisting of halogen, An alkoxy group, a phenoxy group, an aryl or alkyl group having 6 to 20 carbon atoms substituted with nitrogen, phosphorus, sulfur or an oxygen atom.

In Formula 1-1 or Formula 1-2, Z is preferably aluminum or boron.

According to the use of the second co-catalyst, the activity of the first co-catalyst can be further enhanced, and thus a mixed supported metallocene catalyst capable of producing a polyolefin having a high bulk density can be produced. In addition, the second co-catalyst can form coordination bonds between the catalyst having a dialkyl group and an anion of pentafluorophenyl borate to form an active species of polymer polymerization.

Preferable examples of the second cocatalyst include trityl tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) Borate, triethylammonium tetrakis (pentafluorophenyl) borate, or tripropylammonium tetrakis (pentafluorophenyl) borate may be used, but the present invention is not limited thereto.

In the method for producing a hybrid supported metallocene catalyst of one embodiment, the support may contain a hydroxy group on its surface. That is, 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 of the hydroxyl groups. Therefore, the amount of the hydroxy group can be controlled by the preparation method and condition of the carrier or the drying condition (temperature, time, drying method, etc.). For example, the amount of hydroxyl groups on the surface of the support is preferably 0.1 to 10 mmol / g, more preferably 0.5 to 1 mmol / g. If the amount of the hydroxyl group is less than 0.1 mmol / g, the site of reaction with the co-catalyst decreases. If the amount of the hydroxyl group exceeds 10 mmol / g, the hydroxyl group may be present in excess of the hydroxyl group present on the surface of the support. not.

At this time, in order to reduce side reactions caused by some hydroxy groups remaining after drying, it is possible to use a carrier chemically removing the hydroxyl group while preserving siloxane groups having high reactivity to participate in the support.

In this case, it is preferable that the carrier has both a hydroxyl group and a siloxane group having high reactivity on the surface. Examples of such carriers are the dried silica in a high-temperature, silica-alumina, or silica-may be made of magnesia and the like, which typically Na ₂ O, K ₂ CO _3, BaSO _4, or Mg (NO ₃₎ an oxide of a _second, etc. , Carbonate, sulphate or nitrate components.

It is preferable that the carrier is used in a sufficiently dried state before the co-catalyst or the like is carried. At this time, the drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 400 to 600 ° C. If the drying temperature of the carrier is less than 200 ° C, moisture is excessively large and the surface moisture reacts with the cocatalyst. When the temperature exceeds 800 ° C, the pores on the surface of the carrier are combined to reduce the surface area. And only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.

Also, in the above-mentioned method of producing a hybrid supported metallocene catalyst, the first metallocene compound includes a compound represented by the following formula (2), and the second metallocene compound includes a compound represented by the following formula Preferably:

(2)

_{^{(R a) p (R b}} ) M'Q 3 -p

In Formula 2,

p is an integer of 0 or 1;

M 'is a Group 4 transition metal;

R ^a and R ^b may be the same or different from each other and each independently represents hydrogen, alkyl of 1 to 20 carbon atoms, alkoxyalkyl of 2 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 40 carbon atoms, A cyclopentadienyl ligand substituted with at least one member selected from the group consisting of alkenyl having 1 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, and hydrocarbyl having 1 to 20 carbon atoms ego;

Q is a halogen radical,

(3)

In Formula 3,

M is a Group 4 transition metal of the periodic table;

R ¹ is the same or different and each independently represents an aryl radical of C _{1 ~ 20} alkyl radicals, C _{2 ~ 20} alkenyl radicals, C _{3 ~ 30} cycloalkyl radicals, C _{6 ~ 30} of each other, C _{7 ~ 30} alkyl aryl radicals, C _{7 ~ 30} aryl-alkyl radical, or a C _{8 ~ 30} arylalkyl radical;

Q and Q 'are the same or different and are each independently a halogen radical, a C _{1 ~ 20} alkyl radical, an alkylaryl radical of C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} of the Or an arylalkyl radical of C _{7 to 30} , and Q and Q 'together may form a C _{1 to} C ₂₀ hydrocarbon ring;

B is a C _1-4 alkylene radical, a dialkyl silicone, a germanium, an alkylphosphine, or an amine, and two cyclopentadienyl ligands, or cyclopentadienyl ligands and JR ² _zy , It is a bridging bridge;

R ² is a hydrogen radical, an aryl radical of C _{1 ~ 20} alkyl radicals, C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} alkylaryl radicals or C _{7 ~ 30} of the of the a ;

J is a Group 15 element or a Group 16 element of the periodic table;

z is the oxidation number of the element J;

y is the combined number of J elements;

n and n 'are the same as or different from each other, and each independently represents a positive integer of 0 or more;

r is an integer from 0 to 2;

Y represents a heteroatom of O, S, N or P;

A denotes a hydrogen or alkyl radical of C _{1 ~ 10;}

m is an integer of 1 to 2;

In the compound represented by Formula 2, which is an example of the first metallocene compound, M 'is selected from the group consisting of titanium, zirconium and hafnium, and Q is selected from the group consisting of F, Cl, Br and I .

For example, the first metallocene compound may be a compound of the following formula (2-1) or (2-2), but is not limited thereto.

[Formula 2-1]

[Formula 2-2]

The second metallocene compound may be a compound of the following formula (3-1), but is not limited thereto.

[Formula 3-1]

On the other hand, in the above-mentioned method for producing a hybrid supported metallocene catalyst according to one embodiment, the hybrid supported metallocene catalyst comprises [the aluminum metal of the first catalyst] / [the transition metal of the first and second metallocene compounds May be contained in a molar ratio of 1 to 10,000, preferably 1 to 1,000, and more preferably 10 to 100. If the molar ratio is less than 1, the aluminum metal content of the first cocatalyst is too small to produce a catalytically active species and the activity may be lowered. If the molar ratio exceeds 10,000, aluminum metal may act as a catalyst poison.

According to the production method of the present invention, a mixed supported metallocene catalyst which can exhibit excellent activity even at a relatively small amount of the catalyst and enables production of a polyolefin having a high bulk density can be produced. In particular, the present invention can produce a catalyst having high catalytic activity without using an aluminoxane compound such as methyl aluminoxane (MAO), which is generally required to be used for the activation of the metallocene supported catalyst, have.

Therefore, according to another embodiment of the present invention, it is possible to provide a hybrid supported metallocene catalyst prepared by the above method.

Preferably, the hybrid supported metallocene catalyst comprises a first metallocene compound in the support; A first co-catalyst which is a trialkyl aluminum compound having a straight or branched alkyl group having 1 to 10 carbon atoms; A second metallocene compound; And a second co-catalyst which is a borate compound. The hybrid supported metallocene catalyst of the present invention may have a catalytic activity of 10 to 30.

According to another embodiment of the present invention, there is provided a process for producing a polyolefin comprising polymerizing at least one olefin monomer in the presence of the hybrid supported metallocene catalyst.

In this method for producing a polyolefin, there is provided a process for producing a polyolefin comprising the steps of: preparing a mixed supported metallocene catalyst according to one embodiment; And polymerizing the olefin-based monomer under the mixed supported metallocene catalyst to produce a polyolefin having a large bulk density.

The hybrid supported metallocene catalysts of the present invention may be used in olefin polymerization by itself or the metallocene catalyst may be contacted with olefinic monomers such as ethylene, propylene, 1-butene, 1-hexene, To prepare a prepolymerized catalyst.

The polymerizable olefinic monomer using the hybrid supported metallocene catalyst of the present invention is ethylene, propylene, alpha olefin, cyclic olefin, etc., and a diene olefin monomer or triene olefin monomer having two or more double bonds Etc. can also be polymerized. More specifically, examples of the olefinic monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, Dodecene, 1-hexadecene, 1-octadecene, norbornene, norbornene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene or 3-chloromethylstyrene. These two or more monomers may be copolymerized It is possible.

When the metallocene catalyst of the present invention is used without being subjected to the prepolymerization, an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, such as isobutane, pentane, hexane, heptane, An isomer and an aromatic hydrocarbon solvent such as toluene or benzene, or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene. The solvent used here is preferably treated with a small amount of aluminum to remove a small amount of water, air, etc. acting as a catalyst poison.

The polymerization may be carried out homopolymerization using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor or solution reactor as one olefin monomer, or copolymerization using two or more monomers.

The polymerization of the polyolefin is preferably carried out by reacting at a temperature of 25 to 500 ° C and 1 to 100 kgf / cm 2 for 1 to 24 hours. The polymerization temperature is more preferably 25 to 200 占 폚, most preferably 50 to 100 占 폚. The reaction pressure is more preferably 1 to 50 kgf / cm 2, and most preferably 5 to 40 kgf / cm 2.

The polyolefin produced by this method may have a weight average molecular weight of 100 to 1,000,000 and a number average molecular weight range of 100 to 20,000. Therefore, the molecular weight distribution (Mw / Mn) of the polyolefin may be 1 to 50. [

The present invention can maximize the synergistic effect by using the trialkylaluminum as the first catalyst and the borate compound as the second catalyst in the preparation of the mixed metallocene supported catalyst, thereby improving the selectivity and activity for the copolymer Free MAO-free supported catalyst and a process for producing the same. Accordingly, the present invention can provide a high-quality polyolefin having excellent properties and desired physical properties by exhibiting high activity and selectivity for a copolymer while retaining the advantages of other homogeneous catalysts in the production of polyolefins using the mixed metallocene supported catalyst .

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through a specific embodiment of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

Organic reagents and solvents required for catalyst preparation and polymerization were purified by standard methods from Aldrich. Ethylene was passed through Applied Gas Technology's high purity product through water and oxygen filtration equipment Respectively. In all stages of catalyst synthesis, supported and olefin polymerization, the contact between air and water was blocked to improve the reproducibility of the experiment.

Spectra were obtained using 300 MHz NMR (Bruker) to demonstrate the structure of the catalyst. The apparent density was measured by a method specified in DIN 53466 and ISO R 60 using an apparent tester (Apparent Density Tester 1132, manufactured by APT Institute fr Prftechnik).

< Manufacturing example  1>

(Preparation of first metallocene compound: K1)

(CH ₂ ) ₆ -Cl was prepared by the method described in Tetrahedron Lett. 2951 (1988) using 6-chlorohexanol, which was reacted with NaCp t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ (yield 60%, bp 80 ° C / 0.1 mmHg).

Further, t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 ° C, and then normal butyl lithium (n-BuLi) was slowly added thereto. . The solution was again slowly added at -78 ° C to a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol) / THF (30 mL) in a lithium salt solution slowly, Lt; / RTI &gt; for 6 hours.

All volatile materials were vacuum dried, and hexane solvent was added to the obtained oily liquid substance to be filtered. The filtered solution was vacuum dried, and hexane was added thereto to induce a precipitate at a low temperature (-20 ° C). The white solid precipitate was filtered out at a low temperature _{^{[t Bu-O- (CH 2}} ) 6 -C 5 H 4] 2 ZrCl 2 (Yield: 92%).

^{1 H NMR (300 MHz, CDCl} 3): 6.28 (t, J = 2.6 Hz, 2 H), 6.19 (t, J = 2.6 Hz, 2 H), 3.31 (t, 6.6 Hz, 2 H), 2.62 ( t, J = 8 Hz), 1.7-1.3 (m, 8 H), 1.17 (s, 9 H).

_{^{13 C NMR (CDCl 3):}} 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

< Manufacturing example  2>

(Preparation of second metallocene compound: K2)

At room temperature, 50 g of Mg (s) was added to the 10 L reactor and THF 300 mL was added. About 0.5 g of I ₂ was added, and the reactor temperature was maintained at 50 ° C. After the reactor temperature stabilized, 250 g of 6-t-butoxyhexyl chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. The addition of 6-t-butoxyhexyl chloride increased the reactor temperature by 4 ~ 5 ℃. The mixture was stirred for 12 hours while continuously adding 6-t-butoxyhexyl chloride. After 12 hours of reaction, a black reaction solution was obtained. 2 mL of the resulting black solution was added and water was added to obtain an organic layer. 6-t-butoxyhexane was confirmed by ¹ H-NMR, and 6-t-butoxyhexane was confirmed to be a well- I could. Thus, 6-t-butoxyhexylmagnesium chloride was synthesized. 500 g of MeSiCl ₃ and 1 L of THF were added to the reactor and the reactor temperature was cooled to -20 ° C. 560 g of synthesized 6-t-butoxyhexylmagnesium chloride was added to the reactor at a rate of 5 mL / min using a feed pump. After the supply of the Grignard reagent was completed, the temperature of the reactor was slowly elevated to room temperature and stirred for 12 hours. After 12 hours of reaction, it was confirmed that MgCl ₂ salt of white was formed. 4L of hexane was added to remove the salt through labdori to obtain a filter solution. The filter solution was added to the reactor, and hexane was removed at 70 ° C to obtain a pale yellow liquid. The obtained liquid was confirmed to be the desired methyl (6-t-butoxy hexyl) dichlorosilane compound by ¹ H-NMR.

^{1 H NMR (300 MHz, CDCl} 3): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H)

After 1.2 mole (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, the reactor temperature was cooled to -20 占 폚. 480 mL of n-BuLi was added to the reactor at a rate of 5 mL / min using a feed pump. After the addition of n-BuLi, the reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, an equivalent amount of methyl (6-t-butoxyhexyl) dichlorosilane (326 g, 350 mL) was rapidly added to the reactor. After the reactor temperature was slowly raised to room temperature, the mixture was stirred for 12 hours. After the reactor was cooled to 0 ° C, 2 equivalents of t-BuNH ₂ were added. The reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, THF was removed and 4 L of hexane was added to obtain a filter solution from which salt was removed through labdori. The filter solution was added to the reactor again, and hexane was removed at 70 ° C to obtain a yellow solution. The yellow solution was confirmed to be methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane) compound by ¹ H-NMR I could.

Synthesis of -78 (t-butyloxycarbonyl) t-butylamine synthesized from n-BuLi and methyl (6-t-butoxyhexyl) (tetramethyl CpH) t-butylaminosilane TiCl ₃ (THF) ₃ (10 mmol) was added rapidly to the dilithium salt of the ligand. The reaction solution was agitated for 12 hours while slowly raising the temperature to -78 ° C. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution with a blue color was obtained. THF was removed from the resulting reaction solution, and hexane was added to filter the product. After removing the hexane from the filter solution, it was confirmed from the ¹ H-NMR that the desired compound [methyl (6-t-butoxyhexyl) silyl (eta 5-tetramethyl Cp) (t-butylamino)) TiCl ₂ was obtained.

^{1 H NMR (300 MHz, CDCl} 3): 3.3 (s, 4 H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 ~ 0.8 (m), 1.4 (s, 9H), 1.2 (s , &Lt; / RTI &gt; 9H), 0.7 (s, 3H)

< Comparative Example  1>

(Carrier drying)

Silica (SYLOPOL 948, Grace Davison) was dehydrated under vacuum at a temperature of 600 캜 for 12 hours.

(Catalyst preparation)

100 ml of toluene solution was added to the glass reactor, 10 g of the prepared silica was added, and the reactor was stirred while raising the temperature of the reactor to 40 캜. After the silica was sufficiently dispersed, 0.116 mmol of the catalyst precursor K1 was dissolved in 50 ml of toluene, and the solution was charged into the reactor. The reaction was carried out with stirring at 200 rpm for 2 hours. Thereafter, stirring was stopped, the catalyst was settled, and the filtrate was removed to remove impurities that were not supported. 75.8 ml of a 10 wt% methylaluminoxane (MAO) / toluene solution was added, and the mixture was stirred at 200 rpm for 16 hours while raising the temperature to 80 ° C. The temperature was again lowered to 40 ° C and then washed with a sufficient amount of toluene to remove unreacted aluminum compound. Then, 50 ml of toluene was again charged, and 0.059 mmol of the catalyst precursor K2 was dissolved in 50 ml of toluene to prepare a solution, which was then introduced into the reactor and stirred for 2 hours. Then, the catalyst was allowed to settle, and the toluene layer was separated and removed, and then K2 dissolved in advance was added. Subsequently, the remaining toluene was removed by reducing the pressure at 40 캜 for about 1 hour to prepare a supported catalyst for olefin production.

< Comparative Example  2>

A supported catalyst was prepared in the same manner as in Comparative Example 1, except that the amount of MAO was reduced to 37.9 ml in half.

< Comparative Example  3>

A supported catalyst was prepared in the same manner as in Comparative Example 2 except that a borate treatment process was added at the final stage.

That is, in the last step of Comparative Example 2, the catalyst was allowed to settle and the toluene layer was separated and removed. To the 50 ml of toluene was added 0.174 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (1.40 g) was melted and charged into a reactor containing a supported catalyst. Further, about 50 ml of toluene was added to the reactor to adjust the total amount of the solution to about 150 ml, and the mixture was stirred at 80 rpm for 1 hour at 200 rpm. Thereafter, the catalyst was allowed to settle, the toluene layer was separated and removed, and the remaining toluene was removed at 40 ° C under reduced pressure to prepare a supported catalyst for olefin production.

< Comparative Example  4>

A supported catalyst was prepared in the same manner as in Comparative Example 2, except that 50 ml of a hexane solution of 2M trimethyl aluminum (TMA) was added instead of MAO.

< Comparative Example  5>

The supported catalyst was prepared in the same manner as in Comparative Example 3, except that the conditions of the MAO addition step were different. That is, the mixture was stirred at 200 rpm for 16 hours while the temperature was raised to 80 ° C without MAO being added.

< Example  1>

A supported catalyst was prepared in the same manner as in Comparative Example 3, except that 50 ml of a hexane solution of 2M trimethyl aluminum (TMA) was added instead of MAO.

< Example  2>

A supported catalyst was prepared in the same manner as in Comparative Example 3, except that 50 ml of a hexane solution of 2M triethyl aluminum (TEA) was added instead of MAO.

< Example  3>

A supported catalyst was prepared in the same manner as in Comparative Example 3, except that 50 ml of a hexane solution of 2M triisobutylaluminum (TIBA) was added instead of MAO.

< Example  4>

A supported catalyst was prepared in the same manner as in Example 1, except that 0.087 mmol of the 2M first metallocene compound (K1) and 0.044 mmol of the second metallocene compound (K2) were used instead of MAO.

< Example  5>

A supported catalyst was prepared in the same manner as in Example 1, except that 0.058 mmol of the 2M first metallocene compound (K1) and 0.029 mmol of the second metallocene compound (K2) were used instead of MAO.

< Example  6>

A supported catalyst was prepared in the same manner as in Example 1, except that 0.116 mmol (0.93 g) of the second co-catalyst (AB) was added at the end.

< Example  7>

A supported catalyst was prepared in the same manner as in Example 1, except that 0.232 mmol (1.86 g) of the second co-catalyst (AB) was added at the end.

Method of carrying Loading K1
(wt% / g SiO ₂₎ Catalyst 1
(mmol / g SiO ₂₎ K2
(wt% / g SiO ₂₎ Catalyst 2
(mmol / g SiO ₂₎ Comparative Example 1 S / K1 / MAO / K2 7 10 3 0 Comparative Example 2 S / K1 / MAO / K2 7 5 3 0 Comparative Example 3 S / K1 / MAO / K2 / B 7 5 3 0.174 Comparative Example 4 S / K1 / TMA / K2 7 5 3 0 Comparative Example 5 S / K1 / K2 / B 7 0 3 0.174 Example 1 S / K1 / TMA / K2 / B 7 5 3 0.174 Example 2 S / K1 / TEA / K2 / B 7 5 3 0.174 Example 3 S / K1 / TIBA / K2 / B 7 5 3 0.174 Example 4 S / K1 / TMA / K2 / B 5.25 5 2.25 0.174 Example 5 S / K1 / TMA / K2 / B 3.5 5 1.5 0.174 Example 6 S / K1 / TMA / K2 / B 7 5 3 0.116 Example 7 S / K1 / TMA / K2 / B 7 5 3 0.232 Note that in Table 1, S: silica, K1: a first metallocene compound, MAO: methylaluminoxane, TMA: trimethylaluminum, K2: a second metallocene compound, B: dimethylanilinium tetrakis Phenyl) borate

< Experimental Example >

20 mg of the hybrid supported metallocene catalysts prepared in Examples 1 to 7 and Comparative Examples 1 to 5 were quantitatively measured in a dry box and packed in a 50 ml glass bottle, sealed with a rubber septum, taken out from a dry box, Were prepared. The polymerization was carried out in a 2 liter metal alloy reactor equipped with a mechanical stirrer, temperature controllable and used at high pressure.

1 liter of hexane containing 0.5 mmol of triethylaluminum and 20 ml of 1-hexene were charged into the reactor. The prepared supported catalysts were introduced into the reactor without air contact, and then the gaseous ethylene monomer Was continuously polymerized at a pressure of 40 Kgf / cm &lt; 2 &gt; for 1 hour. The termination of the polymerization was completed by first stopping the stirring and then removing ethylene by evacuation. The resulting polymer was filtered to remove most of the polymerization solvent, and then dried in an oven at 70 ° C for 4 hours.

The activity, bulk density and molecular weight of each polymer thus obtained were measured, and the results are shown in Table 2 below.

Method of carrying activation
(kgPE / gCat) BD
(g / ml) Comparative Example 1 S / K1 / MAO / K2 15.5 0.393 Comparative Example 2 S / K1 / MAO / K2 5.8 0.397 Comparative Example 3 S / K1 / MAO / K2 / B 25.7 0.396 Comparative Example 4 S / K1 / TMA / K2 0 - Comparative Example 5 S / K1 / K2 / B 4.4 0.373 Example 1 S / K1 / TMA / K2 / B 20.5 0.402 Example 2 S / K1 / TEA / K2 / B 10.4 0.412 Example 3 S / K1 / TIBA / K2 / B 6.8 0.431 Example 4 S / K1 / TMA / K2 / B 20.0 0.354 Example 5 S / K1 / TMA / K2 / B 14.5 0.350 Example 6 S / K1 / TMA / K2 / B 19.7 0.416 Example 7 S / K1 / TMA / K2 / B 27.1 0.386

Referring to Table 2 above, when trimethylaluminum was used instead of MAO as the first co-catalyst and the order of carrying was specified, the production of a polyolefin having an excellent activity and a high bulk density as compared with Comparative Examples 1 to 5 .

In addition, as in Comparative Example 2, the experiment was conducted to reduce the content of MAO, which is the largest catalyst in the conventional process (Comparative Example 1), but the activity was markedly decreased. As in Comparative Example 4, no activity was observed at all when using a different first cocatalyst instead of MAO.

Further, in Comparative Example 3, the activity of the second catalyst was further increased by halving the content of MAO. However, since the first catalyst to be used and the second catalyst were used together, the catalyst cost doubled , There was no advantage in terms of cost. Therefore, there is a problem in supply and demand when applying the factory, and there is a limit to commercialization.

Thus, when the first co-catalyst was used as the trimethylaluminum in the same manner as in Example 1, it was confirmed that the borate compound as the second co-catalyst had to be used together to exhibit high activity and to exhibit a stable bulk density. As in Examples 2 and 3, the activity increase effect was not so great as the number of carbons in the alkyl aluminum was increased, but the improvement in cost and stability is considered to be possible.

In addition, in Examples 4 to 7, it is more economical than that using existing MAO because it exhibits an effect equal to or higher than that of the conventional MAO.

Claims (16)

Supporting the first metallocene compound on the carrier;
Supporting a first co-catalyst comprising a trialkylaluminum compound having a linear or branched alkyl group having 1 to 10 carbon atoms on the carrier;
Supporting the second metallocene compound on the carrier; And
Supporting a second co-catalyst containing a borate compound on the carrier,
Wherein the first co-catalyst comprises trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum or isoprenyl aluminum. delete The method of claim 1, wherein the second cocatalyst is selected from the group consisting of trityl tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) ) Borate, triethylammonium tetrakis (pentafluorophenyl) borate, or tripropylammonium tetrakis (pentafluorophenyl) borate. The method for producing a hybrid supported metallocene catalyst according to claim 1, wherein the supported amount of the first co-catalyst is 3 to 10 mmol based on 1 g of the support and the supported amount of the second co-catalyst is 0.01 to 0.5 mmol based on 1 g of the support . The method of claim 1, wherein the supported amount of the first metallocene compound and the second metallocene compound is 0.02 to 1 mmol based on 1 g of the carrier, respectively. The method of claim 1, wherein the first metallocene compound comprises a compound represented by Formula 2 and the second metallocene compound comprises a compound represented by Formula 3: Way:
(2)
(R ^a ) _p (R ^b ) M'Q _3-p
In Formula 2,
p is an integer of 0 or 1;
M 'is a Group 4 transition metal;
R ^a and R ^b may be the same or different from each other and each independently represents hydrogen, alkyl of 1 to 20 carbon atoms, alkoxyalkyl of 2 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 40 carbon atoms, A cyclopentadienyl ligand substituted with at least one member selected from the group consisting of alkenyl having 1 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, and hydrocarbyl having 1 to 20 carbon atoms ego;
Q is a halogen radical,
(3)

In Formula 3,
M is a Group 4 transition metal of the periodic table;
R ¹ is the same or different and each independently represents an aryl radical of C _{1 ~ 20} alkyl radicals, C _{2 ~ 20} alkenyl radicals, C _{3 ~ 30} cycloalkyl radicals, C _{6 ~ 30} of each other, C _{7 ~ 30} alkyl aryl radicals, C _{7 ~ 30} aryl-alkyl radical, or a C _{8 ~ 30} arylalkyl radical;
Q and Q 'are the same or different and are each independently a halogen radical, a C _{1 ~ 20} alkyl radical, an alkylaryl radical of C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} of the Or an arylalkyl radical of C _{7 to 30} , and Q and Q 'together may form a C _{1 to} C ₂₀ hydrocarbon ring;
B is a C _1-4 alkylene radical, a dialkyl silicone, a germanium, an alkylphosphine, or an amine, and two cyclopentadienyl ligands, or cyclopentadienyl ligands and JR ² _zy , It is a bridging bridge;
R ² is a hydrogen radical, an aryl radical of C _{1 ~ 20} alkyl radicals, C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} alkylaryl radicals or C _{7 ~ 30} of the of the a ;
J is a Group 15 element or a Group 16 element of the periodic table;
z is the oxidation number of the element J;
y is the combined number of J elements;
n and n 'are the same as or different from each other, and each independently represents a positive integer of 0 or more;
r is an integer from 0 to 2;
Y represents a heteroatom of O, S, N or P;
A denotes a hydrogen or alkyl radical of C _{1 ~ 10;}
m is an integer of 1 to 2; The compound according to claim 6, wherein M 'is selected from the group consisting of titanium, zirconium and hafnium, and Q is selected from the group consisting of F, Cl, Br and I, Lt; / RTI &gt; The method for producing a hybrid supported metallocene catalyst according to claim 1, wherein the first metallocene compound comprises a compound represented by the following general formula (2-1) or (2-2).
[Formula 2-1]

[Formula 2-2]

The method of producing a hybrid supported metallocene catalyst according to claim 1, wherein the carrier has a hydroxyl group and a siloxane group on its surface. The method of producing a hybrid supported metallocene catalyst according to claim 1, wherein the carrier comprises at least one selected from the group consisting of silica, silica-alumina, and silica-magnesia. 10. A process for the preparation of a compound according to any one of claims 1 to 9,
A first metallocene compound in the carrier; A first co-catalyst which is a trialkyl aluminum compound having a straight or branched alkyl group having 1 to 10 carbon atoms; A second metallocene compound; And a second co-catalyst, which is a borate compound, in this order. 12. The process of claim 11, wherein the second cocatalyst is selected from the group consisting of trityl tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) ) Borate, triethylammonium tetrakis (pentafluorophenyl) borate, or tripropylammonium tetrakis (pentafluorophenyl) borate. The hybrid metallocene catalyst according to claim 11, wherein the first metallocene compound comprises a compound represented by Formula 2 and the second metallocene compound comprises a compound represented by Formula 3:
(2)
(R ^a ) _p (R ^b ) M'Q _3-p
In Formula 2,
p is an integer of 0 or 1;
M 'is a Group 4 transition metal;
R ^a and R ^b may be the same or different from each other and each independently represents hydrogen, alkyl of 1 to 20 carbon atoms, alkoxyalkyl of 2 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 40 carbon atoms, A cyclopentadienyl ligand substituted with at least one member selected from the group consisting of alkenyl having 1 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, and hydrocarbyl having 1 to 20 carbon atoms ego;
Q is a halogen radical,
(3)

In Formula 3,
M is a Group 4 transition metal of the periodic table;
R ¹ is the same or different and each independently represents an aryl radical of C _{1 ~ 20} alkyl radicals, C _{2 ~ 20} alkenyl radicals, C _{3 ~ 30} cycloalkyl radicals, C _{6 ~ 30} of each other, C _{7 ~ 30} alkyl aryl radicals, C _{7 ~ 30} aryl-alkyl radical, or a C _{8 ~ 30} arylalkyl radical;
Q and Q 'are the same or different and are each independently a halogen radical, a C _{1 ~ 20} alkyl radical, an alkylaryl radical of C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} of the Or an arylalkyl radical of C _{7 to 30} , and Q and Q 'together may form a C _{1 to} C ₂₀ hydrocarbon ring;
B is a C _1-4 alkylene radical, a dialkyl silicone, a germanium, an alkylphosphine, or an amine, and two cyclopentadienyl ligands, or cyclopentadienyl ligands and JR ² _zy , It is a bridging bridge;
R ² is a hydrogen radical, an aryl radical of C _{1 ~ 20} alkyl radicals, C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} alkylaryl radicals or C _{7 ~ 30} of the of the a ;
J is a Group 15 element or a Group 16 element of the periodic table;
z is the oxidation number of the element J;
y is the combined number of J elements;
n and n 'are the same as or different from each other, and each independently represents a positive integer of 0 or more;
r is an integer from 0 to 2;
Y represents a heteroatom of O, S, N or P;
A denotes a hydrogen or alkyl radical of C _{1 ~ 10;}
m is an integer of 1 to 2; 12. The method of claim 11, wherein the mixed supported metallocene catalyst comprises [a first catalyst aluminum metal] / [a transition metal of the first and second metallocene compounds] in a molar ratio of 1 to 10,000. Supported metallocene catalysts. 12. A process for producing a polyolefin comprising polymerizing at least one olefin monomer in the presence of the hybrid supported metallocene catalyst of claim 11. 16. The process of claim 15 wherein said olefin monomer is 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- Wherein the polyolefin is at least one selected from the group consisting of butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.