KR20120076156A - Method for preparing supported hybrid metallocene catalyst, and supported hybrid metallocene catalyst using the same - Google Patents

Abstract

PURPOSE: A manufacturing method of a hybrid supported metallocene catalyst is provided to maximize catalyst activity at olefin polymerization, and to reduce production cost by using trialkylaluminum which is relatively cheaper than aluminoxane. CONSTITUTION: A manufacturing method of a hybrid supported metallocene catalyst comprises: a step of dipping a first metallocene compound in a carrier; a step of dipping a first cocatalyst containing trialkylaluminum containing a linear or branched C1-10 alkyl in a the carrier; a step of dipping a second metallocene compound in the carrier; and a step of dipping a second cocatalyst comprising borate compound into the carrier. The hybrid supported metallocene catalyst comprises a first metallocene compound, a first cocatalyst which is a trialkylaluminum compound having a linear or a branched C1-10 alkyl group, a second metallocene compound, and a second cocatalyst which is a borate compound in order.

Description

Method for preparing hybrid supported metallocene catalyst, and hybrid supported metallocene catalyst prepared using the same {METHOD FOR PREPARING SUPPORTED HYBRID METALLOCENE CATALYST, AND SUPPORTED HYBRID METALLOCENE CATALYST USING THE SAME}

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

The Ziegler-Natta catalyst widely applied to the 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 of the comonomer is not uniform, thereby limiting the desired physical properties.

Metallocene catalysts, on the other hand, have a narrow molecular weight distribution of the polymer produced by a single active site catalyst having one type of active site and greatly increase the molecular weight, stereoregularity, crystallinity, and especially the reactivity of the comonomer depending on the structure of the catalyst and ligand. There is an advantage that can be adjusted.

The metallocene catalyst system is composed of a combination of a main catalyst composed mainly of a transition metal compound centered on a Group 4 metal and a cocatalyst composed of an organometallic compound composed mainly 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 characteristic of such a catalyst.

The molecular weight and molecular weight distribution of polyolefins are important factors in determining the physical properties of polymers and the flow and mechanical properties that affect their processability. In order to make various polyolefin products, it is important to improve melt processability by controlling molecular weight distribution. In particular, in the case of polyethylene, toughness, strength, environmental stress resistance characteristics, and the like are very important. Therefore, a method of improving the mechanical properties and high processability in the low molecular weight portion of a high molecular weight resin by producing a polyolefin having a bimodal or broad molecular weight distribution has also been proposed.

On the other hand, in the case of producing polyolefin as a supported catalyst through a slurry process, silica is used as a general carrier of the supported catalyst, methyl aluminoxane (MAO) as a cocatalyst on the support and at least one organometallic catalyst (for example, , A supported catalyst prepared by supporting a metallocene catalyst). However, aluminoxanes such as MAO used for activating the supported catalysts are required to be excessive and expensive, which is a major obstacle in terms of cost reduction when used for commercial purposes. In addition, all the MAOs used do not form active species, but also attach to the catalyst to form inactive species. Therefore, efforts are being made to reduce the amount of aluminoxane, such as MAO used generally, or to substitute other promoters.

However, in most of the prior art, when the MAO used for the supported catalyst activation is changed to another catalyst, the catalytic activity is very low, and thus, development of a new catalytically active species is required.

Accordingly, the present invention can replace the MAO generally used as the catalytically active species to maintain a high catalytic activity to produce a polyolefin having a bulk density, high cost that can realize a cost saving by not using an expensive and excessive MAO It is to provide 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 method for producing polyolefin using the hybrid supported metallocene catalyst.

The present invention comprises the steps of supporting the first metallocene compound on the carrier;

Supporting a first promoter comprising a trialkylaluminum compound having a linear or branched alkyl group having 1 to 10 carbon atoms in the carrier;

Supporting a second metallocene compound on the carrier; And

Supporting a second promoter containing a borate compound on the carrier

It provides a method for producing a hybrid supported metallocene catalyst comprising a.

In another aspect, the present invention is prepared by the above method, the first metallocene compound in the carrier; A first cocatalyst which is a trialkylaluminum compound having a linear or branched alkyl group having 1 to 10 carbon atoms; Second metallocene compound; And it provides a hybrid supported metallocene catalyst comprising a second cocatalyst which is a borate compound in sequence.

In another aspect, the present invention provides a method for producing a polyolefin comprising the step of polymerizing at least one or more olefin monomer in the presence of the hybrid supported metallocene catalyst.

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

According to one preferred embodiment of the invention, the step of supporting the first metallocene compound on the carrier; Supporting a first promoter comprising a trialkylaluminum compound on the carrier; Supporting a second metallocene compound on the carrier; And it provides a method for producing a hybrid supported metallocene catalyst comprising the step of supporting a second promoter containing a borate compound on the carrier.

This method of the present invention has the effect of maintaining a very high catalytic activity by using a trialkylaluminum compound as a first cocatalyst for making the active species of the catalyst instead of the conventionally used methylaluminoxane (MAO).

However, when the trialkylaluminum compound alone is used in the preparation of the catalyst, it does not activate the metallocene catalyst and thus does not exhibit activity. Therefore, the present invention is characterized by maximizing its activity by using the trialkylaluminum compound as the first cocatalyst and the borate compound as the second cocatalyst.

Particularly, in the present invention, when preparing a mixed supported metallocene catalyst, the supporting order is not to prepare a catalyst by activating a carrier with a MAO cocatalyst and then contacting the first and second metallocene compounds. In order to support the carrier, the first metallocene compound, the first cocatalyst, the second metallocene compound, and the second cocatalyst are sequentially supported. According to this supporting procedure, the present invention activates the catalyst in the process of alkylating the C1- group of the first metallocene compound and the second metallocene compound by the first promoter, and finally, the second promoter By supporting most surfaces, the effect of increasing the activity of the hybrid supported metallocene catalyst can be given.

Therefore, the invention according to one embodiment of the present invention is synergistically active by using two types of promoters, such as a trialkylaluminum compound-borate compound, and specifying the supporting order to prepare a hybrid supported metallocene catalyst. In addition to showing the effect, it is possible to provide a catalyst which exhibits the effect of MAO-free as a new active species of the supported catalyst, and exhibits excellent activity without using expensive and excessively required MAO.

In the present invention, the weight ratio of the first promoter and the second promoter may be 100: 1 to 10: 1, and preferably 50: 1 to 20: 1. When the weight ratio of the primary and secondary supported promoters meets this range, not only the activity of the finally prepared hybrid supported metallocene catalyst is more excellent, but also the polyolefin prepared using the hybrid supported metallocene catalyst Bulk density can also be maintained at higher levels.

In addition, in the above production method, the supporting amount of the first cocatalyst is preferably 3 to 10 mmol based on 1 g of the carrier, and the supporting amount of the second cocatalyst is 0.01 to 0.5 mmol based on 1 g of the carrier. At this time, if the supported amount of the first cocatalyst is less than 3 mmol, the number of active species of the hybrid supported metallocene catalyst is reduced, so that the activity of the catalyst itself is lowered. Even if it does not increase the activity continuously and may be for the removal of the unsupported excess of the promoter, there is a problem causing the rise of the catalyst price. In addition, if the supported amount of the second cocatalyst is less than 0.01 mmol, there is a problem in that the activity of the supported catalyst is lowered, similarly to the first cocatalyst, and if it exceeds 0.5 mmol, the catalyst price is rapidly increased and the bulk density is increased. There is a problem that the excessively low, causing a decrease in the productivity of the factory.

The supported 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.

In addition, the contact reaction with the carrier for supporting the first metallocene compound, the first promoter including trialkylaluminum, the second metallocene compound, and the second promoter including the borate compound in order May be used or may be reacted without solvent. Solvents 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, acetone, Most organic solvents, such as ethyl acetate, are mentioned, and hexane, heptane, toluene, or dichloromethane is preferable.

Furthermore, in the present invention, when the carrier is sequentially supported on the carrier, the first cocatalyst including the first metallocene compound, the trialkylaluminum, the second cocatalyst including the second metallocene compound and the borate compound are sequentially supported. The conditions are not particularly limited and may be carried out in a range well known to those skilled in the art. For example, the high temperature support and the low temperature support may be appropriately used, and specifically, when the first promoter and the second promoter are supported on the carrier, the temperature conditions may proceed at 25 to 100 ° C. At this time, the supporting time of the first promoter and the supporting time of the second promoter may be appropriately adjusted according to the amount of the promoter to be supported. The reaction temperature between the first and second metallocene compounds and the carrier can be up to -30 ° C to 150 ° C, preferably from room temperature to 100 ° C, more preferably from 30 to 80 ° C. The reacted supported catalyst can be used by filtering or removing the reaction solvent by distillation under reduced pressure, and, if necessary, by using a Soxhlet filter with an aromatic hydrocarbon such as toluene.

In the production method of the present invention, the first cocatalyst is preferably a trialkylaluminum compound having an alkyl group having 1 to 10 carbon atoms in a straight or branched chain, which is used for activation of the first metallocene compound supported on the carrier. That is, the metallocene catalyst is alkylated to serve as a space for coordination polymerization in which a reactant such as ethylene forms a polymer.

Preferred examples of the first cocatalyst include, but are not limited to, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, isoprenyl aluminum, and the like.

In addition, the second cocatalyst means an ionic compound capable of reacting with the first cocatalyst to form a cation complex, and includes an ionic compound in which a common non-coordinating anion and a cation are combined.

For example, the second cocatalyst preferably includes a compound represented by the following Chemical Formula 1-1 or 1-2.

[Formula 1-1]

[LH] ⁺ [Z (A) ₄ ] ^-

[Formula 1-2]

[L] ⁺ [Z (A) ₄ ] ^-

In the above formula, each L is a neutral or cationic Lewis acid, each H is a hydrogen atom, each Z is a Group 13 element, and each A is independently at least one hydrogen is halogen, having 1 to 20 carbon atoms Aryl or alkyl group having 6 to 20 carbon atoms substituted with a hydrocarbyl group, an alkoxy group, a phenoxy group, nitrogen, phosphorus, sulfur or an oxygen atom.

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

By using the second promoter, it is possible to further enhance the activity of the first promoter, thereby producing a hybrid supported metallocene catalyst capable of producing a polyolefin having a high bulk density. In addition, the second cocatalyst may have an effect of forming a coordinating bond between the catalyst having a dialkyl group and the pentafluorophenylborate anion, thereby forming the active species of the 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 is not limited thereto.

In addition, in the method for preparing the hybrid supported metallocene catalyst of the embodiment, the carrier may contain a hydroxyl group on the surface. In other words, the smaller the amount of hydroxyl group (-OH) on the surface of the carrier, the better. However, it is practically difficult to remove all hydroxyl groups. Therefore, the amount of the hydroxy group can be controlled by the preparation method and conditions of the carrier or the drying conditions (temperature, time, drying method, etc.). For example, the amount of hydroxyl groups on the surface of the carrier is preferably 0.1 to 10 mmol / g, more preferably 0.5 to 1 mmol / g. If the amount of the hydroxy group is less than 0.1 mmol / g, the reaction site with the promoter decreases, and if the amount of the hydroxy group exceeds 10 mmol / g, it may be due to moisture other than the hydroxy group present on the surface of the carrier. not.

At this time, in order to reduce side reactions caused by some hydroxy groups remaining after drying, a highly reactive siloxane group participating in the supporting may be used while a carrier chemically removed from the hydroxy group.

In this case, the carrier preferably has a highly reactive hydroxyl group and siloxane group on the surface. Examples of such carriers include silica, silica-alumina, or silica-magnesia, which are dried at high temperatures, which are typically oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , or Mg (NO ₃ ) ₂ . , Carbonate, sulfate or nitrate components.

The carrier is preferably used in a sufficiently dried state before the promoter or the like is supported. 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. When the drying temperature of the carrier is less than 200 ° C., the moisture is too much to react with the surface of the carrier and the promoter reacts. When the carrier temperature is higher than 800 ° C., the surface area decreases as the pores on the surface of the carrier are combined. It is not preferable because it disappears and only siloxane groups remain and the reaction site with the promoter decreases.

In addition, in the above-described method for preparing a hybrid supported metallocene catalyst, the first metallocene compound includes a compound represented by the following Chemical Formula 2, and the second metallocene compound includes a compound represented by the following Chemical Formula 3 It is preferable to:

[Formula 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 as or different from each other, and are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkoxyalkyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 40 carbon atoms, and having 2 carbon atoms. A cyclopentadienyl ligand substituted with one or more selected from alkenyl of 20 to 20, alkylaryl of 7 to 40 carbon atoms, arylalkyl of 7 to 40 carbon atoms, arylalkenyl of 8 to 40 carbon atoms, and hydrocarbyl of 1 to 20 carbon atoms. ego;

Q is a halogen radical,

(3)

In Formula 3,

M is a periodic table Group 4 transition metal;

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 aryl alkyl radical of C _{7 ~ 30} and, Q and Q 'together may form a hydrocarbon ring of C _{1 ~ 20,} and;

B is a C _{1 ~ 4} alkylene radical, dialkyl silicon, germanium, alkyl phosphine, or amine, with two cyclopentadienyl based ligands, or a cyclopentadienyl ligand and JR ⁹ share a series combination _{-y z} A leg tied by;

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 periodic table group 15 element or group 16 element;

z is the oxidation number of the element J;

y is the bond number of the J element;

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

r is an integer from 0 to 2;

Y represents a hetero atom of O, S, N or P;

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

m is an integer of 1-2.

In addition, 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. Can be.

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

[Formula 2-1]

[Formula 2-2]

In addition, the second metallocene compound may be a compound of Formula 3-1, but is not limited thereto.

[Formula 3-1]

On the other hand, in the method for producing a hybrid supported metallocene catalyst of the embodiment described above, the hybrid supported metallocene catalyst is [aluminum metal of the first cocatalyst] / [transition metal of the first and second metallocene compound ] May be included in a molar ratio of 1 to 10,000, preferably in a molar ratio of 1 to 1,000, and more preferably in a molar ratio of 10 to 100. If the molar ratio is less than 1, the aluminum metal content of the first cocatalyst is too low, so that the active species of the catalyst may not be made well, and the activity may be lowered. If the molar ratio exceeds 10,000, the aluminum metal may act as a catalyst poison.

According to the production method of the present invention, a hybrid supported metallocene catalyst capable of producing a polyolefin having a high bulk density as well as showing excellent activity even with a relatively small amount of promoter can be prepared. In particular, the present invention can prepare a catalyst having high catalytic activity without using aluminoxane compounds such as methylaluminoxane (MAO), which is generally required 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 on a carrier; A first cocatalyst which is a trialkylaluminum compound having a linear or branched alkyl group having 1 to 10 carbon atoms; Second metallocene compound; And a second cocatalyst which is a borate compound. The hybrid supported metallocene catalyst of the present invention may have a catalytic activity of 10 to 30.

In addition, according to another embodiment of the present invention, there is provided a method for producing a polyolefin comprising the step of polymerizing at least one or more olefin monomer in the presence of the hybrid supported metallocene catalyst.

In the method for producing a polyolefin, preparing a hybrid supported metallocene catalyst according to the embodiment described above; And under the hybrid supported metallocene catalyst, it is possible to produce a polyolefin having a large bulk density by a method comprising the step of polymerizing an olefinic monomer.

The hybrid supported metallocene catalyst of the present invention may also be used by itself for olefin polymerization, or contacting the metallocene catalyst with an olefinic monomer such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, or the like. It can also be prepared and used as a prepolymerized catalyst.

The olefinic monomers which can be polymerized using the hybrid supported metallocene catalyst of the present invention include ethylene, propylene, alpha olefins, cyclic olefins, etc., and diene olefin monomers or triene olefin monomers having two or more double bonds. Polymerization is also possible. More specifically, examples of the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1- Undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1, 4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, or 3-chloromethylstyrene, and the like. It may be.

In addition, when the metallocene catalyst of the present invention is used without undergoing prepolymerization, an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, isobutane, pentane, hexane, heptane, nonane, decane and their It is also possible to dilute and inject isomers into aromatic hydrocarbon solvents such as toluene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene. The solvent used here is preferably subjected to a small amount of aluminum treatment to remove a small amount of water, air and the like acting as a catalyst poison.

The polymerization reaction may be homopolymerized to one olefin monomer using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor, or solution reactor, or may be copolymerized using two or more monomers.

The polymerization of the polyolefin is preferably carried out by reacting for 1 to 24 hours at a temperature of 25 to 500 ℃ and 1 to 100 kgf / cm2. 25-200 degreeC is more preferable, and, as for the said polymerization temperature, 50-100 degreeC is the most preferable. Further, the reaction pressure is more preferably 1 to 50 kgf / cm 2, most preferably 5 to 40 kgf / cm 2.

The polyolefin prepared by this method may have a weight average molecular weight of 100 to 1,000,000, 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 uses trialkylaluminum as a first cocatalyst and a borate compound as a second cocatalyst when preparing a mixed metallocene supported catalyst, thereby maximizing synergistic effects and thus improving selectivity and activity for a copolymer. There is an effect of providing a novel high activity supported catalyst of MAO-free and a method for producing the same. Accordingly, the present invention exhibits high activity and selectivity to the copolymer while maintaining the advantages of other homogeneous catalysts in the production of polyolefin using the mixed metallocene supported catalyst, thereby producing a high quality polyolefin having excellent productivity with desired physical properties. Can be.

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. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.

The organic reagents and solvents required for catalyst preparation and polymerization were purified by Aldrich's standard method, and ethylene was used by applying high purity products from Applied Gas Technology through water and oxygen filtration devices. It was. The reproducibility of the experiment was enhanced by blocking contact between air and moisture at all stages of catalyst synthesis, loading and olefin polymerization.

To verify the structure of the catalyst, spectra were obtained using 300 MHz NMR (Bruker). 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)

Using 6-chlorohexanol, t-Butyl-O- (CH ₂ ) ₆ -Cl was prepared by the method shown in Tetrahedron Lett. 2951 (1988), and reacted with NaCp. t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was obtained (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 normal butyllithium (n-BuLi) was slowly added, and the temperature was raised to room temperature, followed by reaction for 8 hours. . The solution was then slowly added to a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol) / THF (30 mL) at -78 ° C. and then prepared with a lithium salt solution. The reaction was further performed for 6 hours.

All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of hexane solvent. The filtered solution was dried in vacuo and hexane was added to induce precipitate at low temperature (-20 ° C). The obtained precipitate was filtered at low temperature to give [ ^t Bu-O- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl _{2 as a} white solid. The compound was obtained (yield 92%).

¹ H NMR (300 MHz, CDCl ₃ ): 6.28 (t, J = 2.6 Hz, 2H), 6.19 (t, J = 2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 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)

50 g of Mg (s) was added to a 10 L-reactor at room temperature, followed by 300 mL of THF. After adding 0.5 g of I ₂ , the reactor temperature was maintained at 50 ° C. After the reactor temperature was stabilized, 250 g of 6-t-butoxyhexyl chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. As the 6-t-butoxyhexyl chloride was added, it was observed that the reactor temperature was increased by 4-5 ° C. The stirring was continued for 12 hours while adding 6-t-butoxyhexyl chloride. After 12 hours of reaction, a black reaction solution was obtained. 2 mL of the resulting black solution was taken and water was added to obtain an organic layer. 6-t-butoxyhexane was confirmed by ¹ H-NMR, and the Grignard reaction proceeded well from 6-t-butoxyhexane. Could. Thus 6-t-butoxyhexyl magnesium 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 the synthesized 6-t-butoxyhexyl magnesium chloride was added to the reactor at a rate of 5 mL / min using a feed pump. After supplying the Grignard reagent, the reaction mixture was stirred for 12 hours while slowly raising the temperature of the reactor. After 12 hours, it was confirmed that a white MgCl ₂ salt was produced. Hexane 4L was added to remove the salt through the labdori to obtain a filter solution. After the filter solution was added to the reactor, hexane was removed at 70 ° C. to obtain a pale yellow liquid. The obtained liquid was confirmed to be a desired methyl (6-t-butoxyhexyl) dichlorosilane (methyl (6-t-butoxy hexyl) dichlorosilane) compound through 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)

1.2 mole (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, and the reactor temperature was cooled to -20 ° C. 480 mL of n-BuLi was added to the reactor at a rate of 5 mL / min using a feed pump. After n-BuLi was added, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, an equivalent of methyl (6-t-butoxyhexyl) dichlorosilane (326 g, 350 mL) was added quickly to the reactor. After stirring for 12 hours while slowly raising the temperature of the reactor, the reactor was cooled to 0 ° C., and then 2 equivalents of t-BuNH ₂ was added thereto. Stirring for 12 hours while slowly raising the reactor temperature to room temperature. 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. After adding the filter solution to the reactor again, the hexane was removed at 70 ℃ to obtain a yellow solution. The yellow solution was identified as methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane (methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane) compound by ¹ H-NMR. Could.

-78 synthesized in THF solution from n-BuLi and the ligand methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane (methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane) TiCl ₃ (THF) ₃ (10 mmol) was quickly added to the dilithium salt of the ligand at ° C. The reaction solution was slowly stirred at -78 ° C to room temperature for 12 hours. 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 was obtained. After removing THF from the reaction solution, hexane was added to filter the product. After removing hexane from the filter solution, it was confirmed by ¹ H-NMR that the desired [methyl (6-t-butoxyhexyl) silyl (η5-tetramethylCp) (t-butylamino)) TiCl ₂ compound.

¹ H NMR (300 MHz, CDCl ₃ ): 3.3 (s, 4 H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s , 9H), 0.7 (s, 3H)

< Comparative example  1>

(Carrier drying)

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

(Catalyst manufacture)

100 ml of toluene solution was added to a glass reactor, and 10 g of prepared silica was added thereto, followed by stirring while raising the reactor temperature to 40 ° C. After sufficiently dispersing the silica, 0.116 mmol of the catalyst precursor K1 was dissolved in 50 ml of toluene and introduced into the reactor in solution. The reaction was stirred at 200 rpm for 2 hours. Thereafter, stirring was stopped and the catalyst was allowed to settle, and then the filtrate was removed to remove unsupported impurities. 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. After the temperature was lowered to 40 ° C., the aluminum compound was not reacted by washing with a sufficient amount of toluene. Then, 50 ml of toluene was charged, and 0.059 mmol of the catalyst precursor K2 was dissolved in 50 ml of toluene to make a solution, and then stirred in the reactor for 2 hours. Subsequently, the catalyst was allowed to settle, the toluene layer was separated and removed, and K2 dissolved in advance was added thereto. Subsequently, the toluene remaining was removed by depressurizing at 40 degreeC for about 1 hour, and the supported catalyst for olefin manufacture was manufactured.

< Comparative example  2>

The supported catalyst was prepared in the same manner as in Comparative Example 1, except that only the MAO content was reduced to half by 37.9 ml.

< Comparative example  3>

The supported catalyst was prepared in the same manner as in Comparative Example 2, except that a borate treatment was added in the last step.

That is, in the last step of Comparative Example 2, the catalyst was allowed to settle and the toluene layer was separated and removed, and then 0.174 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (hereinafter referred to as AB) in 50 ml of toluene. After dissolving (1.40g), it was put in a reactor containing a supported catalyst. Further, 50 ml of toluene was further added to the reactor to adjust the total solution amount to about 150 ml, and then stirred at 200 rpm for 1 hour at 80 ° C. Subsequently, the catalyst was allowed to settle, the toluene layer was separated and removed, and the remaining toluene was removed under reduced pressure at 40 ° C. 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 trimethylaluminum (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 only the MAO input step had different conditions. That is, stirring was carried out at 200 rpm for 16 hours while raising only the temperature to 80 ° C. without adding MAO.

< 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 trimethylaluminum (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 triethylaluminum (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>

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

< Example  5>

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

< Example  6>

The supported catalyst was prepared in the same manner as in Example 1, except that the amount of the second cocatalyst (AB) added at last was 0.116 mmol (0.93 g).

< Example  7>

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

Support Method Loading K1
(wt% / g SiO ₂ ) Article 1 promoter
(mmol / g SiO ₂ ) K2
(wt% / g SiO ₂ ) Article 2 promoter
(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) In Table 1, S: silica, K1: first metallocene compound, MAO: methylaluminoxane, TMA: trimethylaluminum, K2: second metallocene compound, B: dimethylanilinium tetrakis (pentafluor Rophenyl) borate

< Experimental Example >

20 mg of the mixed supported metallocene catalyst prepared in Examples 1 to 7 and Comparative Examples 1 to 5 were quantified in a dry box, respectively, placed in a 50 ml glass bottle, sealed with a rubber septum, and taken out of the dry box. Was prepared. The polymerization was carried out in a 2 L metal alloy reactor with temperature control and high pressure, equipped with a mechanical stirrer.

1 liter of hexane and 1-hexene (20 ml) containing 0.5 mmol triethylaluminum were injected into the reactor, and each of the prepared supported catalysts was introduced into the reactor without air contacting, followed by gas ethylene monomer at 80 ° C. Was polymerized for 1 hour with continuous addition at a pressure of 40 Kgf / cm 2. Termination of the polymerization was completed by first stopping stirring and then evacuating and removing ethylene. The polymer obtained therefrom was filtered to remove most of the polymerization solvent and then dried in an oven at 70 ° C. for 4 hours.

Since the activity and the bulk density (Bulk Density), molecular weight for each obtained polymer was measured, the results are shown in Table 2 below.

Support Method 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, when polymethylaluminum is used instead of MAO as the first cocatalyst as in Example 1, and when the supporting order is specified, the preparation of polyolefins having superior bulk activity and high bulk density compared to Comparative Examples 1 to 5 Confirmed that it is possible.

In addition, as in Comparative Example 2, the experiment was conducted to reduce the content of the first promoter, MAO, which occupies the largest cost in the existing process (Comparative Example 1), but it was confirmed that the activity is significantly reduced. As in Comparative Example 4, even when another first promoter was used instead of MAO, no activity was observed.

In addition, although the activity was increased by introducing a second promoter while reducing the MAO content in half in Comparative Example 3, the catalyst cost was doubled because the first promoter and the second promoter were used together. There was no cost advantage. Therefore, there is a problem in supply and demand when applying the factory and there is a limit to commercialization.

Thus, similarly to Example 1, even when the first cocatalyst was used as trimethylaluminum, it was confirmed that the borate compound as the second cocatalyst should be used together to exhibit high activity and stable bulk density. In Examples 2 and 3, as the number of carbon in the alkyl aluminum increases, the effect of increasing the activity is not great, but it can be said that there is an advantage in terms of cost and stability.

In addition, in the case of Examples 4 to 7 it can be seen that more economical than the equivalent level of the effect compared to using the existing MAO.

Claims (16)

Supporting the first metallocene compound on the carrier;
Supporting a first promoter comprising a trialkylaluminum compound having a linear or branched alkyl group having 1 to 10 carbon atoms in the carrier;
Supporting a second metallocene compound on the carrier; And
Supporting a second promoter containing a borate compound on the carrier
Method for producing a hybrid supported metallocene catalyst comprising a. The method of claim 1, wherein the first cocatalyst comprises trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, or isoprenylaluminum. The method of claim 1, wherein the second promoter is trityl tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) A method for producing a hybrid supported metallocene catalyst comprising borate, triethylammonium tetrakis (pentafluorophenyl) borate or tripropylammonium tetrakis (pentafluorophenyl) borate. The method of claim 1, wherein the amount of the first cocatalyst supported is 3 to 10 mmol based on 1 g of the carrier, and the amount of the second cocatalyst is 0.01 to 0.5 mmol based on 1 g of the carrier. . 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 supported metallocene catalyst comprising a compound represented by Formula 3 below. 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 as or different from each other, and are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkoxyalkyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 40 carbon atoms, and having 2 carbon atoms. A cyclopentadienyl ligand substituted with one or more selected from alkenyl of 20 to 20, alkylaryl of 7 to 40 carbon atoms, arylalkyl of 7 to 40 carbon atoms, arylalkenyl of 8 to 40 carbon atoms, and hydrocarbyl of 1 to 20 carbon atoms. ego;
Q is a halogen radical,
(3)

In Chemical Formula 3,
M is a periodic table Group 4 transition metal;
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 aryl alkyl radical of C _{7 ~ 30} and, Q and Q 'together may form a hydrocarbon ring of C _{1 ~ 20,} and;
B is a C _{1 ~ 4} alkylene radical, dialkyl silicon, germanium, alkyl phosphine, or amine, with two cyclopentadienyl based ligands, or a cyclopentadienyl ligand and JR ⁹ share a series combination _{-y z} A leg tied by;
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 periodic table group 15 element or group 16 element;
z is the oxidation number of the element J;
y is the bond number of the J element;
n and n 'are the same as or different from each other, and each independently represent a positive integer of 0 or more;
r is an integer from 0 to 2;
Y represents a hetero atom of O, S, N or P;
A denotes a hydrogen or alkyl radical of C _{1 ~ 10;}
m is an integer of 1-2. According to claim 6, M 'in the compound represented by Formula 2 is selected from the group consisting of titanium, zirconium and hafnium, Q is selected from the group consisting of F, Cl, Br and I as a mixed supported metal Process for preparing a sen catalyst. The method of claim 1, wherein the first metallocene compound comprises a compound of Formula 2-1 or Formula 2-2.
[Formula 2-1]

[Formula 2-2]

The method of claim 1, wherein the carrier has a hydroxyl group and a siloxane group on a surface thereof. The method of claim 1, wherein the carrier comprises any one or more selected from the group consisting of silica, silica-alumina, and silica-magnesia. It is prepared by the method of any one of claims 1 to 10,
A first metallocene compound on the carrier; A first cocatalyst which is a trialkylaluminum compound having a linear or branched alkyl group having 1 to 10 carbon atoms; Second metallocene compound; And a second cocatalyst, which is a borate compound, in sequence. The method of claim 11, wherein the second promoter is trityl tetrakis (pentafluorophenyl) borate, N, N- dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl ) Mixed supported metallocene catalyst comprising borate, triethylammonium tetrakis (pentafluorophenyl) borate or tripropylammonium tetrakis (pentafluorophenyl) borate. The hybrid supported metallocene catalyst of 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 below:
(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 as or different from each other, and are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkoxyalkyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 40 carbon atoms, and having 2 carbon atoms. A cyclopentadienyl ligand substituted with one or more selected from alkenyl of 20 to 20, alkylaryl of 7 to 40 carbon atoms, arylalkyl of 7 to 40 carbon atoms, arylalkenyl of 8 to 40 carbon atoms, and hydrocarbyl of 1 to 20 carbon atoms. ego;
Q is a halogen radical,
(3)

In Chemical Formula 3,
M is a periodic table Group 4 transition metal;
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 aryl alkyl radical of C _{7 ~ 30} and, Q and Q 'together may form a hydrocarbon ring of C _{1 ~ 20,} and;
B is a C _{1 ~ 4} alkylene radical, dialkyl silicon, germanium, alkyl phosphine, or amine, with two cyclopentadienyl based ligands, or a cyclopentadienyl ligand and JR ⁹ share a series combination _{-y z} A leg tied by;
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 periodic table group 15 element or group 16 element;
z is the oxidation number of the element J;
y is the bond number of the J element;
n and n 'are the same as or different from each other, and each independently represent a positive integer of 0 or more;
r is an integer from 0 to 2;
Y represents a hetero atom of O, S, N or P;
A denotes a hydrogen or alkyl radical of C _{1 ~ 10;}
m is an integer of 1-2. The method of claim 11, wherein the hybrid supported metallocene catalyst may include [aluminum metal of the first cocatalyst] / [transition metal of the first and second metallocene compound] in a molar ratio of 1 to 10,000, Preferably, the hybrid supported metallocene catalyst comprising a molar ratio of 1 to 1,000. A process for producing a polyolefin comprising polymerizing at least one or more olefin monomers in the presence of the hybrid supported metallocene catalyst of claim 11. The method of claim 15 wherein the olefin monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-atocene, norbornene, norbonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4- Butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethyl styrene production method of at least one polyolefin selected from the group consisting of.