KR102204960B1 - Method for preparing of supported hybrid metallocene catalyst, the supported hybrid metallocene catalyst prepared by the same method, and method for preparing polyolefin using the same - Google Patents

Abstract

The present invention relates to a method for preparing a mixed supported metallocene catalyst, a mixed supported metallocene catalyst prepared by the above method, and a method for producing a polyolefin using the same. According to the method for preparing a hybrid supported metallocene catalyst of the present invention, an alkyl aluminum and a borate compound are used as cocatalysts instead of expensive aluminoxane, which is mainly used for activating the supported metallocene catalyst, and the loading order is specified, thereby making aluminoxane. It is possible to maximize catalytic activity during olefin polymerization without using it, and to obtain a high molecular weight polyolefin.

Description

A method of preparing a mixed supported metallocene catalyst, a mixed supported metallocene catalyst prepared by the above production method, and a method of producing a polyolefin using the same TECHNICAL FIELD , AND METHOD FOR PREPARING POLYOLEFIN USING THE SAME}

The present invention relates to a method for preparing a mixed supported metallocene catalyst, a mixed supported metallocene catalyst prepared by the above method, and a method for producing a polyolefin using the same.

Since the Ziegler-Natta catalyst widely applied to the existing commercial process is a multi-active point catalyst, it is characterized by a wide molecular weight distribution of the resulting polymer, and the composition distribution of comonomers is not uniform, so there is a limit to securing desired physical properties.

On the other hand, metallocene catalysts have a narrow molecular weight distribution of polymers produced as single active point catalysts with one kind of active point, and greatly increase molecular weight, stereoregularity, crystallinity, and especially the reactivity of comonomers depending on the structure of the catalyst and ligand. It has the advantage of being adjustable.

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 composed of an organometallic compound mainly composed of a Group 13 metal such as aluminum. Polymers such as polyolefins having a narrow molecular weight distribution may be prepared according to the characteristics of the single active point of the catalyst.

The molecular weight and molecular weight distribution of the polyolefin are important factors in determining the flow and mechanical properties that affect the physical properties of the polymer and the processability of the polymer. In order to make various polyolefin products, it is an important factor to improve the melt processability by controlling the molecular weight distribution. In particular, in the case of polyethylene, toughness, strength, and resistance to environmental stress are very important. Accordingly, a method of improving the mechanical properties of a high molecular weight resin and workability in a low molecular weight portion by preparing a polyolefin having a bimodal or broad molecular weight distribution is also proposed.

Meanwhile, 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, and methylaluminoxane (MAO) as a cocatalyst and at least one organometallic catalyst (for example, , A supported catalyst prepared by supporting a metallocene catalyst) is used. However, MAO used for activation of the supported catalyst is expensive and requires an excessive amount compared to the metallocene catalyst, which accounts for a significant portion of the catalyst cost, which is a big factor that degrades the price competitiveness of the metallocene-produced polyolefin in a commercial aspect.

Accordingly, efforts are being made to reduce the amount of aluminoxane, such as MAO, which is generally used, or to replace it with another cocatalyst. However, in most prior art, MAO used for activating the supported catalyst is changed to another catalyst and used. If so, the catalytic activity is very poor, and thus a method for producing a supported catalyst is required.

In order to solve the problems of the prior art, thus, the present invention exhibits high catalytic activity despite not using MAO, which is generally used as a catalytically active species, and a hybrid supported metallocene capable of producing a high molecular weight polyolefin. An object of the present invention is to provide a method for preparing a catalyst, a mixed supported metallocene catalyst prepared by the above method, and a method for preparing a polyolefin using the same.

Accordingly, according to the production method of the present invention, high-quality and high-molecular-weight polyolefins can be produced with high activity without using MAO, which is expensive and must be used in excess, thereby realizing reduction in production costs.

Accordingly, according to an aspect of the present invention,

Supporting the alkyl aluminum on the carrier;

Supporting a first metallocene compound represented by the following formula (1) and a second metallocene compound represented by the following formula (2) on the carrier on which the alkyl aluminum is supported; And

It provides a method for producing a hybrid supported metallocene catalyst comprising the step of supporting a borate compound on a carrier on which the alkyl aluminum, the first metallocene compound, and the second metallocene compound are supported.

[Formula 1]

In Formula 1,

M ₁ is a Group 4 transition metal;

Cp ₁ is any one cyclic compound selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl, and at least one hydrogen of the cyclic compound is Each independently substituted with one of C1 to 20 alkyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl. Can;

Z ₁ And Z ₂ is the same as or different from each other, and each independently halogen, C1 to C20 alkyl, C2 to C10 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl;

B is carbon, silicon, or germanium;

R ₁ to R ₃ are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C2 to C20 alkenyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 To C20 alkylaryl, or C7 to C20 arylalkyl;

[Formula 2]

In Chemical Formula 2,

M ₂ is a Group 4 transition metal;

Cp ₂ and Cp ₃ are the same as or different from each other, each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl Is a cyclic compound, and at least one hydrogen of the cyclic compound is each independently C1 to 20 alkyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to May be substituted with any one of C20 arylalkyl;

Z ₃ And Z ₄ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl, C2 to C10 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl.

In addition, according to another aspect of the present invention, there is provided a mixed supported metallocene catalyst prepared according to the above production method.

In addition, according to another aspect of the present invention, in the presence of a mixed supported metallocene catalyst, there is provided a method for producing a polyolefin comprising the step of polymerizing an olefin monomer.

In the present invention, when preparing a hybrid supported metallocene catalyst, the first and second metallocene compounds are supported on a carrier pre-supported with alkyl aluminum, not MAO, as a first cocatalyst compound, and a borate compound as a second cocatalyst compound Then, a mixed supported metallocene catalyst was prepared by supporting. The hybrid supported metallocene catalyst of the present invention prepared as described above can produce high-molecular-weight polyolefins with high activity without using expensive MAO.

Hereinafter, a method for preparing a mixed supported metallocene catalyst according to a specific embodiment of the present invention, a mixed supported metallocene catalyst prepared by the above method, and a method for preparing a polyolefin using the same will be described.

A method for preparing a hybrid supported metallocene catalyst according to an embodiment of the present invention,

Supporting the alkyl aluminum on the carrier;

Supporting a first metallocene compound represented by the following formula (1) and a second metallocene compound represented by the following formula (2) on the carrier on which the alkyl aluminum is supported; And

And supporting a borate compound on a carrier on which the alkyl aluminum, the first metallocene compound, and the second metallocene compound are supported.

[Formula 1]

In Formula 1,

M ₁ is a Group 4 transition metal;

Cp ₁ is any one cyclic compound selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl, and at least one hydrogen of the cyclic compound is Each independently substituted with one of C1 to 20 alkyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl. Can;

Z ₁ And Z ₂ is the same as or different from each other, and each independently halogen, C1 to C20 alkyl, C2 to C10 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl;

B is carbon, silicon, or germanium;

R ₁ to R ₃ are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C2 to C20 alkenyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 To C20 alkylaryl, or C7 to C20 arylalkyl;

[Formula 2]

In Chemical Formula 2,

M ₂ is a Group 4 transition metal;

Cp ₂ and Cp ₃ are the same as or different from each other, each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl Is a cyclic compound, and at least one hydrogen of the cyclic compound is each independently C1 to 20 alkyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to May be substituted with any one of C20 arylalkyl;

Z ₃ And Z ₄ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl, C2 to C10 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl.

In the method for preparing a hybrid supported metallocene catalyst according to the present invention, the substituents of the above formula will be described in more detail as follows.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

C1 to C20 alkyl may be straight chain, branched chain or cyclic alkyl. Specifically, the C1 to C20 alkyl is a straight chain alkyl having 1 to 20 carbon atoms; Straight chain alkyl having 1 to 10 carbon atoms; Straight chain alkyl having 1 to 5 carbon atoms; Branched or cyclic alkyl having 3 to 20 carbon atoms; Branched or cyclic alkyl having 3 to 15 carbon atoms; Or it may be a branched chain or cyclic alkyl having 3 to 10 carbon atoms. More specifically, alkyl having 1 to 20 carbon atoms is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, or It may be a cyclohexyl group or the like.

The C2 to C20 alkenyl may be a straight chain, branched chain or cyclic alkenyl. Specifically, the C2 to C20 alkenyl is a straight chain alkenyl having 2 to 20 carbon atoms, a straight chain alkenyl having 2 to 10 carbon atoms, a straight chain alkenyl having 2 to 5 carbon atoms, a branched alkenyl having 3 to 20 carbon atoms, and 3 carbon atoms. It may be a branched chain alkenyl having 3 to 15 carbon atoms, a branched chain alkenyl having 3 to 10 carbon atoms, a cyclic alkenyl having 5 to 20 carbon atoms, or a cyclic alkenyl having 5 to 10 carbon atoms. More specifically, the alkenyl having 2 to 20 carbon atoms may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl.

C1 to C20 alkoxy may be a straight chain, branched chain or cyclic alkoxy group. Specifically, the C1 to C20 alkoxy is a straight chain alkoxy group having 1 to 20 carbon atoms; Straight chain alkoxy having 1 to 10 carbon atoms; A straight chain alkoxy group having 1 to 5 carbon atoms; Branched or cyclic alkoxy having 3 to 20 carbon atoms; Branched or cyclic alkoxy having 3 to 15 carbon atoms; Or it may be a branched chain or cyclic alkoxy having 3 to 10 carbon atoms. More specifically, the alkoxy having 1 to 20 carbon atoms is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentoxy group, iso -It may be a pentoxy group, a neo-pentoxy group, or a cyclohectoxy group.

C2 to C20 alkoxyalkyl is a structure including -Ra-O-Rb, and may be a substituent in which one or more hydrogens of alkyl (-Ra) are substituted with alkoxy (-O-Rb). Specifically, the C2 to C20 alkoxyalkyl is a methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, iso-propoxyethyl group, iso-propoxyhexel group, tert-butoxymethyl group, tert -Butoxyethyl group or tert-butoxyhexyl group.

C6 to C20 aryl may mean monocyclic, bicyclic or tricyclic aromatic hydrocarbons. Specifically, the C6 to C20 aryl may be a phenyl group, a naphthyl group, or an anthracenyl group.

C7 to C20 alkylaryl may mean a substituent in which at least one hydrogen of the aryl is substituted by alkyl. Specifically, the C7 to C20 alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, or cyclohexylphenyl.

C7 to C0 arylalkyl may mean a substituent in which one or more hydrogens of alkyl are substituted by aryl. Specifically, the C7 to C0 arylalkyl may be a benzyl group, phenylpropyl, or phenylhexyl.

Examples of the Group 4 transition metal include titanium, zirconium, and hafnium.

The method for preparing a hybrid supported metallocene catalyst according to the present invention is a first cocatalyst that uses an alkyl aluminum compound instead of methylaluminoxane (MAO), which is generally used as a cocatalyst compound for a metallocene supported catalyst, to make the active species of the catalyst. The present invention was completed on the basis of the fact that it is used as a compound and has the effect of maintaining a very high catalytic activity by first being supported on a carrier before supporting the metallocene compound.

That is, in the present invention, when the hybrid supported metallocene catalyst is prepared, the loading sequence is not to prepare a catalyst by contacting the first and second metallocene compounds after activating the carrier with the MAO cocatalyst as in the prior art. First, an alkylaluminum compound is supported as a first cocatalyst compound on the prepared carrier. Next, the first metallocene compound and the second metallocene compound are supported on the carrier on which the first cocatalyst compound is supported. In this case, the order of loading between the first and second metallocene compounds is not limited, and the first metallocene compound may be supported first, or the second metallocene compound may be supported first. Next, a borate compound is finally supported as a second cocatalyst compound on a carrier on which the first cocatalyst compound, the first metallocene compound, and the second metallocene compound are all supported.

As described above, by sequentially supporting the first cocatalyst compound, the first and second metallocene compounds, and the second cocatalyst compound, the present invention provides the first cocatalyst compound as the first metallocene compound and the second metal. The catalyst is activated in the process of alkylation of the sen compound, and finally, the second cocatalyst compound is supported on the most surface of the carrier, thereby increasing the activity of the hybrid supported metallocene catalyst.

In addition, the present invention is characterized by maximizing its activity by using the alkylaluminum compound as the first cocatalyst compound and the borate compound as the second cocatalyst compound.

Therefore, the present invention according to an embodiment of the present invention uses two types of cocatalyst compounds of an alkylaluminum compound and a borate compound, and by specifying the supporting order to prepare a hybrid supported metallocene catalyst, a synergistic effect on activity In addition to showing the effect of MAO-free as a new active species of the supported catalyst, it is possible to provide a catalyst exhibiting excellent activity without the use of expensive and excessive amounts of MAO.

In addition, the hybrid supported metallocene catalyst prepared by the above production method can prepare a high molecular weight polyolefin having a weight average molecular weight of about 500,000 g/mol, and the polyolefin thus prepared can be mainly used for film applications. .

In the prior art for the MAO-free supported catalyst, there was also an example of using alkyl aluminum, but in order to exhibit sufficient activity, the amount of alkyl aluminum used was 3 mmol or more per 1 g of the carrier, and a large amount of aluminum compound should still be used, and low molecular weight polyolefins were used. There is a disadvantage that it is limited to the production use and is not suitable for producing high molecular weight polyolefins.

Meanwhile, according to an embodiment of the present invention, the weight ratio of the first cocatalyst compound and the second cocatalyst compound may be 100:1 to 10:1, and preferably 50:1 to 20:1. have. When the weight ratio of the first and secondly supported cocatalysts satisfies this range, not only the activity of the finally prepared hybrid supported metallocene catalyst is more excellent, but also the polyolefin prepared using the mixed supported metallocene catalyst The weight average molecular weight can be maintained at a higher level.

In addition, in the preparation method, the amount of the first cocatalyst compound supported is from about 0.1 to less than about 3 mmol, preferably from about 0.5 to less than about 3 mmol, more preferably from about 0.5 to less than about 1 g of the carrier. It may be 2 mmol or less, and the supported amount of the second cocatalyst compound may be about 0.01 to about 0.5 mmol, preferably about 0.01 or more to about 0.3 mmol, based on 1 g of the carrier. If the supported amount of the first cocatalyst compound is less than 0.1 mmol, the number of active species of the mixed supported metallocene catalyst is reduced, resulting in a problem of lowering the activity of the catalyst itself.If it is 3 mmol or more, the activity may increase, but excessive prescription Even if it does not increase the activity continuously, it can be used to remove the excess cocatalyst that is not supported, and there is a problem that causes an increase in catalyst price. In addition, when the amount of the second cocatalyst compound supported is less than 0.01 mmol, there is a problem that the activity of the supported catalyst is lowered, and when it exceeds 0.5 mmol, the catalyst price is rapidly increased, and the productivity of the plant is reduced. .

According to an exemplary embodiment of the present invention, the loading amount of the first metallocene compound and the second metallocene compound may each independently be about 0.02 to about 1 mmol based on 1 g of the carrier, but is not limited thereto.

In addition, in the contact reaction with a carrier for carrying the first cocatalyst compound containing alkyl aluminum, the first metallocene compound, the second metallocene compound, and the second cocatalyst compound containing a borate compound in the order A solvent may be used, and it may be reacted without a 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.

In addition, in the production method of the present invention, the first cocatalyst compound including alkyl aluminum, the first metallocene compound, the second metallocene compound, and the second cocatalyst compound including a borate compound may be sequentially supported on the carrier. In this case, the loading 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 support and low-temperature support, and specifically, when the first cocatalyst compound and the second cocatalyst compound are supported on the carrier, the temperature condition may be performed at 25 to 100°C. In this case, the loading time of the first cocatalyst compound and the loading time of the second cocatalyst compound may be appropriately adjusted according to the amount of the cocatalyst compound to be supported.

Further, the reaction temperature between the first and second metallocene compounds and the carrier may be -30°C to 150°C, preferably room temperature to 100°C, and more preferably 30 to 80°C. The reacted supported catalyst can be used as it is by filtration of the reaction solvent or distillation under reduced pressure, and if necessary, it can be used after filtering with an aromatic hydrocarbon such as toluene.

In the production method of the present invention, the first cocatalyst compound is preferably an alkylaluminum compound having a linear or branched alkyl group having 1 to 10 carbon atoms, which contributes to the activation of the metallocene compound, that is, the metal By alkylating the rosene catalyst, it serves to provide a space for coordination polymerization in which reactants such as ethylene form a polymer.

Examples of the first cocatalyst compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-propylaluminum, trin-butylaluminum, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentyl Aluminum, trin-pentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, isoprenyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, and the like, but are not limited thereto.

In addition, the second cocatalyst compound refers to an ionic compound capable of forming a cationic complex by reacting with the first cocatalyst compound, and includes an ionic compound in which a conventional non-coordinating anion and a cation are combined.

Depending on the use of the second cocatalyst compound, the activity of the first cocatalyst compound can be further enhanced, and accordingly, a hybrid supported metallocene catalyst capable of producing a polyolefin having a high weight average molecular weight can be prepared. . In addition, the second cocatalyst compound may have an effect of forming an active species of polymer polymerization by forming a coordination bond between a catalyst having a dialkyl group and a pentafluorophenylborate anion.

Examples of the second cocatalyst compound 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 addition, in the method for preparing the hybrid supported metallocene catalyst of the embodiment, the carrier may contain a hydroxyl group on its surface. That is, the smaller the amount of hydroxy groups (-OH) on the surface of the support is possible, the better, but it is practically difficult to remove all hydroxy groups. Therefore, the amount of the hydroxy group can be adjusted by the method and conditions for preparing the carrier or drying conditions (temperature, time, drying method, etc.). For example, the amount of hydroxy 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 cocatalyst decreases, and if it exceeds 10 mmol/g, it is not preferable because it may be caused by 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 remaining hydroxy groups after drying, a carrier having a high reactive siloxane group participating in the support may be preserved while chemically removing this hydroxy group may be used.

In this case, the carrier preferably has a highly reactive hydroxyl group and a siloxane group together on the surface. Examples of such a carrier include silica dried at high temperature, silica-alumina, or silica-magnesia, and these are usually 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 cocatalyst or the like is supported. In this case, 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, there is too much moisture so that the moisture on the surface and the cocatalyst react, and when it exceeds 800°C, the pores on the surface of the carrier are combined and the surface area decreases, and there are many hydroxyl groups on the surface. It is not preferable because it disappears and only siloxane groups remain, and the reaction site with the cocatalyst decreases.

In the above-described method for preparing a hybrid supported metallocene catalyst, the first metallocene compound includes a compound represented by the following Formula 1, and the second metallocene compound includes a compound represented by the following Formula 2 desirable:

[Formula 1]

In Formula 1,

M ₁ is a Group 4 transition metal;

Cp ₁ is any one cyclic compound selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl, and at least one hydrogen of the cyclic compound is Each independently substituted with one of C1 to 20 alkyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl. Can;

Z ₁ And Z ₂ is the same as or different from each other, and each independently halogen, C1 to C20 alkyl, C2 to C10 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl;

B is carbon, silicon, or germanium;

R ₁ to R ₃ are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C2 to C20 alkenyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 To C20 alkylaryl, or C7 to C20 arylalkyl;

[Formula 2]

In Chemical Formula 2,

M ₂ is a Group 4 transition metal;

Cp ₂ and Cp ₃ are the same as or different from each other, each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl Is a cyclic compound, and at least one hydrogen of the cyclic compound is each independently C1 to 20 alkyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to May be substituted with any one of C20 arylalkyl;

Z ₃ And Z ₄ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl, C2 to C10 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl.

The first metallocene compound represented by Formula 1 may be, for example, a compound represented by the following structural formula, but the present invention is not limited thereto.

In addition, the compound represented by Formula 2 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

According to another embodiment of the present invention, a hybrid supported metallocene catalyst prepared according to the above production method is provided.

The hybrid supported metallocene catalyst includes at least one of the first metallocene compound represented by Formula 1 and at least one of the second metallocene compound represented by Formula 2 above. It is mixedly supported on a carrier together with a cocatalyst compound.

The first metallocene compound represented by Chemical Formula 1 of the mixed supported metallocene catalyst mainly contributes to making a high molecular weight copolymer, and the second metallocene compound represented by Chemical Formula 2 mainly contains a low molecular weight copolymer. You can contribute to making it.

Therefore, in the hybrid supported betalocene catalyst obtained according to the production method of the present invention, different kinds of the catalyst including the first metallocene compound represented by Formula 1 and the second metallocene compound represented by Formula 2 By including at least two metallocene compounds, a high molecular weight polyolefin having a weight average molecular weight of about 500,000 g/mol can be prepared.

Meanwhile, in the manufacturing method of the hybrid supported metallocene catalyst of the embodiment described above, the hybrid supported metallocene catalyst is an aluminum metal included in the first cocatalyst compound/transition metal of the first and second metallocene compounds. May be included in a molar ratio of 1 to 10,000, preferably 1 to 1,000, 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 compound is too small, so that catalytically active species are not well made, so that the activity may be lowered. If the molar ratio exceeds 10,000, the aluminum metal may rather act as a catalyst poison.

According to the manufacturing method of the present invention, a hybrid supported metallocene catalyst that not only exhibits excellent activity even with a relatively small amount of cocatalyst, but also enables the production of high molecular weight polyolefins can be prepared. In particular, the present invention is to prepare a catalyst having high catalytic activity without the use of an aluminoxane compound such as methylaluminoxane (MAO), which is expensive and requires an excessive amount, which should be generally used for activation of a metallocene supported catalyst. I can.

In the method for preparing a hybrid supported metallocene catalyst according to the present invention, the mass ratio of the total transition metal contained in the first metallocene compound and the second metallocene compound to the carrier may be 1: 10 to 1: 1,000. . When the carrier and the metallocene compound are included in the mass ratio, the optimum shape may be exhibited.

In addition, the mass ratio of the cocatalyst compound to the carrier may be 1:1 to 1:100. In addition, the mass ratio of the first metallocene compound to the second metallocene compound is 10:1 to 1:10, preferably 5:1 to 1:5 Can be When the cocatalyst and the metallocene compound are included in the mass ratio, the activity and the polymer microstructure can be optimized.

The hybrid supported metallocene catalyst obtained according to the production method of the present invention can itself be used for polymerization of olefinic monomers. In addition, the mixed supported metallocene catalyst according to the present invention may be prepared and used as a prepolymerized catalyst by contact reaction with an olefinic monomer. For example, the catalyst may be separately used as ethylene, propylene, 1-butene, 1-hexene, and 1-octene. It may also be prepared and used as a prepolymerized catalyst by contacting with an olefin-based monomer such as.

In the method for preparing a hybrid supported metallocene catalyst according to the present invention, the loading order of the first metallocene compound and the second metallocene compound may be changed as necessary. That is, the first metallocene compound is first supported on a carrier, and then the second metallocene compound is additionally supported to prepare a hybrid supported metallocene catalyst, or the second metallocene compound is added to the carrier. After first supporting, a hybrid supported metallocene catalyst may be prepared by additionally supporting the first metallocene compound.

In the preparation of the hybrid supported metallocene catalyst as described above, the temperature may be about 0 to about 100° C., and the pressure may be performed under normal pressure, but is not limited thereto. Polyolefin can be prepared by polymerizing the olefin-based monomer in the presence of the mixed supported metallocene catalyst obtained according to the production method of the present invention as described above.

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

As a specific example of the olefinic monomer, 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-eicosene, norbornene, norbornadiene, ethylidene nobornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene , 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like, and two or more of these monomers may be mixed and copolymerized.

The polymerization reaction may be performed by homopolymerization with one olefinic monomer or copolymerization with two or more monomers using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor, or solution reactor.

The hybrid supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane, chlorobenzene, and It can be dissolved or diluted in a hydrocarbon solvent substituted with the same chlorine atom and injected. The solvent used here is preferably used after removing a small amount of water or air acting as a catalyst poison by treating a small amount of alkyl aluminum, and it is also possible to further use a cocatalyst.

When a polyolefin is prepared using the hybrid supported metallocene catalyst obtained according to the production method of the present invention, a polyolefin having a high molecular weight and a broad molecular weight distribution can be prepared. The polyolefin has not only excellent physical properties, but also excellent processability.

For example, the polyolefin prepared using the hybrid supported metallocene catalyst obtained according to the production method of the present invention has a high weight of about 400,000 to about 800,000 g/mol or about 450,000 to about 600,000 g/mol. Average molecular weight (Mw) Can be indicated.

Hereinafter, the present invention will be described in detail through examples of the present invention. However, the embodiments of the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited by the embodiments described below.

< Example >

Preparation Example 1: Preparation Example of the First Metallocene Compound

(tBu-O-(CH ₂ ) ₆ )(CH ₃ )Si(C ₅ (CH ₃ ) ₄ )(tBu-N)TiCl ₂ Manufacture of

After 50 g of Mg(s) was added to a 10 L reactor at room temperature, 300 mL of THF was added. After about 0.5 g of I ₂ was added, the temperature of the reactor 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 6-t-butoxyhexyl chloride was added, it was observed that the temperature of the reactor was increased by about 4 to 5°C. 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. After taking 2 mL of the resulting black solution, water was added to obtain an organic layer, and 6-t-butoxyhexane was confirmed through 1H-NMR. It can be seen that the Grignard reaction proceeded well from the 6-t-butoxyhexane. Thus, 6-t-butoxyhexyl magnesium chloride was synthesized.

After adding 500 g of MeSiCl ₃ and 1 L of THF to the reactor, the temperature of the reactor 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 feeding pump. After completion of the feeding of the Grignard reagent, the reactor was stirred for 12 hours while slowly raising the temperature to room temperature. It was confirmed that a white MgCl ₂ salt was formed after 12 hours of reaction. 4 L of hexane was added to remove the salt through labdori to obtain a filter solution. After the obtained 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 the desired methyl(6-t-butoxy hexyl)dichlorosilane {Methyl(6-t-butoxy hexyl)dichlorosilane} compound through 1H-NMR.

1H-NMR (CDCl3): 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 adding 1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF to the reactor, the reactor temperature was cooled to -20°C. It was added to the reactor at a rate of 5 mL/min using an n-BuLi 480 mL feeding pump. After n-BuLi was added, the reactor was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, an equivalent amount of methyl (6-t-butoxy hexyl) dichlorosilane (326 g, 350 mL) was rapidly added to the reactor. After stirring for 12 hours while slowly raising the reactor temperature to room temperature, the reactor temperature was cooled to 0° C. and 2 equivalents of t-BuNH2 were added. The reactor was stirred for 12 hours while slowly raising the 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 salts were removed through Labdori. After the filter solution was added to the reactor again, hexane was removed at 70° C. to obtain a yellow solution. The obtained yellow solution was confirmed to be a methyl(6-t-butoxyhexyl)(tetramethylCpH)t-butylaminosilane (Methyl(6-t-buthoxyhexyl)(tetramethylCpH)t-Butylaminosilane) compound through 1H-NMR. .

TiCl ₃ (THF) ₃ (10 mmol) in the dilithium salt of the ligand at -78°C synthesized in THF solution from n-BuLi and the ligand dimethyl(tetramethylCpH)t-butylaminesilane (Dimethyl(tetramethylCpH)t-Butylaminosilane) ) Was added rapidly. The reaction solution was stirred for 12 hours while slowly raising from -78°C to room temperature. After stirring for 12 hours, an equivalent 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 blue-colored dark black solution was obtained. After removing THF from the resulting reaction solution, hexane was added to filter the product. After removing hexane from the filter solution to be obtained, the desired ([methyl(6-t-buthoxyhexyl)silyl(η5-tetramethylCp)(t-Butylamido)]TiCl ₂ ) is (tBu-O-(CH ₂ ) ₆ from 1H-NMR. )(CH ₃ )Si(C ₅ (CH ₃ ) ₄ )(tBu-N)TiCl ₂ .

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

Preparation Example 2: Preparation Example of the Second Metallocene Compound

[tBu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ Manufacture of

Using 6-chlorohexanol, t-Butyl-O-(CH ₂ ) ₆ -Cl was prepared by the method suggested in the literature (Tetrahedron Lett. 2951 (1988)), and NaCp was reacted thereto. t-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80°C / 0.1 mmHg).

In addition, t-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78°C, and normal butyl lithium (n-BuLi) was slowly added, the temperature was raised to room temperature, and then reacted for 8 hours. . The previously synthesized lithium salt solution was slowly added to the suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol)/THF (30 mL) at -78°C again at room temperature. It was further reacted for 6 hours.

All volatile substances were vacuum-dried, and hexane solvent was added to the obtained oily liquid substance to filter it out. After vacuum drying the filtered solution, hexane was added to induce a precipitate at low temperature (-20°C). The obtained precipitate was filtered at low temperature to obtain a white solid [tBu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound (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, 8H), 1.17 (s, 9H).

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.

<Preparation Example of Hybrid Supported Catalyst>

Example One

1-1 Drying of carrier

Silica (SYLOPOL 948 manufactured by Grace Davison) was dehydrated while applying vacuum at a temperature of 600°C for 12 hours.

1-2 Preparation of supported catalyst

After adding 100 mL of a toluene solution to a glass reactor, 10 g of prepared silica was added, and the mixture was stirred while raising the reactor temperature to 40°C. After sufficiently dispersing silica, 14 mL of a 25 wt% triisobutyl aluminum (hereinafter referred to as TIBA)/toluene solution was added, and the mixture was stirred at 200 rpm for 16 hours while raising the temperature to 60°C. After lowering the temperature to 40° C. again, unreacted aluminum compounds were removed by washing with a sufficient amount of toluene. 50 mL of toluene was added again, and 0.706 mmol of the first metallocene compound (K2 catalyst) of Preparation Example 1 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Thereafter, 0.413 mmol of the second metallocene compound (K1 catalyst) of Preparation Example 2 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Then, 1.12 mmol (0.90g) of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (hereinafter referred to as AB) was dissolved in 50 mL of toluene. It was introduced into a reactor containing a supported catalyst, and stirred at 40° C. for 2 hours at 200 rpm. Then, the catalyst was settled, the toluene layer was separated and removed, and then replaced with hexane. The catalyst was settled again, the hexane layer was separated and removed, and the pressure was reduced at 40°C to remove the remaining hexane to prepare a hybrid supported catalyst.

Example 2

After adding 100 mL of a toluene solution to a glass reactor, 10 g of silica of Example 1-1 was added, the mixture was stirred while raising the reactor temperature to 40°C. After sufficiently dispersing the silica, 14 mL of a 25 wt% TIBA/toluene solution was added, and the mixture was stirred at 200 rpm for 16 hours while raising the temperature to 95°C. After lowering the temperature to 80° C. again, unreacted aluminum compounds were removed by washing with a sufficient amount of toluene. 50 mL of toluene was added again, and 0.706 mmol of the first metallocene compound (K2 catalyst) of Preparation Example 1 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Thereafter, 0.413 mmol of the second metallocene compound (K1 catalyst) of Preparation Example 2 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Then, AB 1.12 mmol (0.90g) was dissolved in 50 mL of toluene, and then added to a reactor including a supported catalyst, followed by stirring at 80° C. for 2 hours at 200 rpm. Then, the catalyst was settled, the toluene layer was separated and removed, and then replaced with hexane. The catalyst was settled again, the hexane layer was separated and removed, and the pressure was reduced at 40°C to remove the remaining hexane to prepare a hybrid supported catalyst.

Example 3

After adding 100 mL of a toluene solution to a glass reactor, 10 g of silica of Example 1-1 was added, the mixture was stirred while raising the reactor temperature to 40°C. After sufficiently dispersing silica, 7 mL of a 25 wt% TIBA/toluene solution was added, and the mixture was stirred at 200 rpm for 16 hours while raising the temperature to 95°C. After lowering the temperature to 80° C. again, unreacted aluminum compounds were removed by washing with a sufficient amount of toluene. 50 mL of toluene was added again, and 0.706 mmol of the first metallocene compound (K2 catalyst) of Preparation Example 1 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Thereafter, 0.413 mmol of the second metallocene compound (K1 catalyst) of Preparation Example 2 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Then, AB 1.12 mmol (0.90g) was dissolved in 50 mL of toluene, and then added to a reactor including a supported catalyst, followed by stirring at 40° C. for 2 hours at 200 rpm. Then, the catalyst was settled, the toluene layer was separated and removed, and then replaced with hexane. The catalyst was settled again, the hexane layer was separated and removed, and the pressure was reduced at 40°C to remove the remaining hexane to prepare a hybrid supported catalyst.

Comparative Example 1

After adding 100 mL of a toluene solution to a glass reactor, 10 g of silica of Example 1-1 was added, the mixture was stirred while raising the reactor temperature to 40°C. After sufficiently dispersing silica, 57 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 60°C. After lowering the temperature to 40° C. again, unreacted aluminum compounds were removed by washing with a sufficient amount of toluene. 50 mL of toluene was added again, and 0.706 mmol of the first metallocene compound (K2 catalyst) of Preparation Example 1 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Thereafter, 0.413 mmol of the second metallocene compound (K1 catalyst) of Preparation Example 2 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Then, the catalyst was settled, the toluene layer was separated and removed, and then replaced with hexane. The catalyst was settled again, the hexane layer was separated and removed, and the pressure was reduced at 40°C to remove the remaining hexane to prepare a hybrid supported catalyst.

Comparative Example 2

After adding 100 mL of a toluene solution to a glass reactor, 10 g of silica of Example 1-1 was added, the mixture was stirred while raising the reactor temperature to 40°C. After sufficiently dispersing silica, 57 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 95°C. After lowering the temperature to 80° C. again, unreacted aluminum compounds were removed by washing with a sufficient amount of toluene. 50 mL of toluene was added again, and 0.706 mmol of the first metallocene compound (K2 catalyst) of Preparation Example 1 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Thereafter, 0.413 mmol of the second metallocene compound (K1 catalyst) of Preparation Example 2 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Then, the catalyst was settled, the toluene layer was separated and removed, and then replaced with hexane. The catalyst was settled again, the hexane layer was separated and removed, and the pressure was reduced at 40°C to remove the remaining hexane to prepare a hybrid supported catalyst.

Comparative Example 3

After adding 100 mL of a toluene solution to a glass reactor, 10 g of silica of Example 1-1 was added, the mixture was stirred while raising the reactor temperature to 40°C. After sufficiently dispersing the silica, 28.5 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 60°C. After lowering the temperature to 40° C. again, unreacted aluminum compounds were removed by washing with a sufficient amount of toluene. 50 mL of toluene was added again, and 0.706 mmol of the first metallocene compound (K2 catalyst) of Preparation Example 1 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Thereafter, 0.413 mmol of the second metallocene compound (K1 catalyst) of Preparation Example 2 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Then, the catalyst was settled, the toluene layer was separated and removed, and then replaced with hexane. The catalyst was settled again, the hexane layer was separated and removed, and the pressure was reduced at 40°C to remove the remaining hexane to prepare a hybrid supported catalyst.

Comparative Example 4

After adding 100 mL of a toluene solution to a glass reactor, 10 g of silica of Example 1-1 was added, the mixture was stirred while raising the reactor temperature to 40°C. After sufficiently dispersing silica, 57 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 60°C. After lowering the temperature to 40° C. again, unreacted aluminum compounds were removed by washing with a sufficient amount of toluene. 50 mL of toluene was added again, and 0.706 mmol of the first metallocene compound (K2 catalyst) of Preparation Example 1 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Thereafter, 0.413 mmol of the second metallocene compound (K1 catalyst) of Preparation Example 2 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Then, AB 1.12 mmol (0.90g) was dissolved in 50 mL of toluene, and then added to a reactor including a supported catalyst, followed by stirring at 80° C. for 2 hours at 200 rpm. Then, the catalyst was settled, the toluene layer was separated and removed, and then replaced with hexane. The catalyst was settled again, the hexane layer was separated and removed, and the pressure was reduced at 40°C to remove the remaining hexane to prepare a hybrid supported catalyst.

Comparative Example 5

A supported catalyst was prepared according to the method of Example 3 of Korean Publication No. 2012-0076156.

More specifically, 100 mL of a toluene solution was added to a glass reactor, and 10 g of silica of Example 1-1 was added, followed by stirring while raising the reactor temperature to 40°C. After sufficiently dispersing the silica, 1.16 mmol of the second metallocene compound (K1 catalyst) of Preparation Example 2 was dissolved in 50 mL of toluene, added to the reactor in a solution state, and reacted with stirring at 200 rpm for 2 hours. Thereafter, the stirring was stopped and the catalyst was settled, and the filtrate was removed to remove impurities that were not supported. 25 mL of a 2M TIBA/hexane solution was added, and the mixture was stirred at 200 rpm for 16 hours while raising the temperature to 80°C. After lowering the temperature to 40° C. again, unreacted aluminum compounds were removed by washing with a sufficient amount of toluene. 50 mL of toluene was again filled, and 0.605 mmol of the first metallocene compound (K2 catalyst) of Preparation Example 1 was dissolved in 50 mL of toluene to make a solution, and the mixture was added to the reactor and stirred for 2 hours. Thereafter, the catalyst was settled, the toluene layer was separated and removed, and AB 1.74 mmol (1.40 g) in 50 mL of toluene was added to the reactor containing the supported catalyst. In addition, about 50 mL of toluene was added to the reactor to adjust the total amount of the solution to about 150 mL, and then stirred at 80° C. for 1 hour at 200 rpm. Thereafter, the catalyst was settled, the toluene layer was separated and removed, and the pressure was reduced at 40°C to remove the remaining toluene, thereby preparing a supported catalyst for olefin production.

The supported catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 5 are summarized and shown in Table 1 below.

Loading order Loading MAO
(mmol/g SiO ₂ ) TIBA
(mmol/g SiO ₂ ) AB
(mmol/g SiO ₂ ) K2 (wt%/g SiO ₂ ) K1
(wt%/g SiO ₂ ) Example 1 S/TIBA/K2/K1/AB 0 1.5 0.112 3.5 2.5 Example 2 S/TIBA//K2/K1/AB 0 1.5 0.112 3.5 2.5 Example 3 S/TIBA//K2/K1/AB 0 0.75 0.112 3.5 2.5 Comparative Example 1 S/MAO/K2/K1 7.5 0 0 3.5 2.5 Comparative Example 2 S/MAO/K2/K1 7.5 0 0 3.5 2.5 Comparative Example 3 S/MAO/K2/K1 3.75 0 0 3.5 2.5 Comparative Example 4 S/MAO/K2/K1/AB 7.5 0 0.112 3.5 2.5 Comparative Example 5 S/K1/TIBA/K2/AB 0 5 0.174 3 7

In Table 1, S: silica, K2: Preparation Example 1 catalyst, K1: Preparation Example 2 catalyst, MAO: methylaluminoxane, TIBA: triisobutylaluminum, AB: N,N-dimethylanilinium tetrakis (pentafluoro Lophenyl) borate.

<Experimental Example>

Ethylene-1-hexene copolymerization

20 mg of each of the supported catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 5 was quantified in a dry box, placed in a 50 mL glass bottle, sealed with a rubber septum, and removed from the dry box to prepare a catalyst to be injected. I did. The polymerization was carried out in a 2L metal alloy reactor equipped with a mechanical stirrer and capable of controlling temperature and used at high pressure.

1 L of hexane containing 0.5 mmol triethylaluminum and 1-hexene (10 mL) were injected into this reactor, and each supported catalyst prepared above was introduced into the reactor without air contact, and then gaseous ethylene monomer at 80°C. The polymerization was carried out for 1 hour while continuously applying the pressure at 40 gf/cm ² . The polymerization was terminated by first stopping the stirring and then evacuating and removing ethylene.

The polymer obtained therefrom was dried in a vacuum oven at 70° C. for 4 hours after most of the polymerization solvent was filtered off.

The polymerization activity for each of the catalysts prepared above, the molecular weight and molecular weight distribution of the obtained polymer are shown in Table 2 below.

division Polymerization activity
(kg-PE/g-Cat.) Weight average molecular weight
(g/mol) Molecular weight distribution
(MWD) Example 1 7.0 656,000 2.9 Example 2 10.2 677,000 2.8 Example 3 8.1 572,000 3.0 Comparative Example 1 5.0 403,000 3.8 Comparative Example 2 6.9 424,000 2.9 Comparative Example 3 3.0 353,000 3.1 Comparative Example 4 7.9 258,000 2.8 Comparative Example 5 6.8 198,000 2.6

Referring to Table 2, as in Examples 1 to 3, alkyl aluminum (TIBA) is supported on the carrier, the first and second metallocenes are supported, and finally, when the borate compound is used as a cocatalyst, the same amount of It was confirmed that a polyolefin having a high molecular weight could be prepared with high activity compared to Comparative Example 1 in which the metallocene compound was supported under the same supporting conditions.

In Comparative Example 2, the catalyst activity could be increased by increasing the supporting temperature of the metallocene precursor, but there was little effect of increasing the molecular weight of the polyolefin. In addition, both the catalytic activity and the molecular weight of the polyolefin were significantly lower than that of the supported catalyst of Example 2 prepared under the same conditions (the amount of the metallocene compound supported and the temperature supported).

In addition, as in Comparative Example 3, when the content of MAO was reduced, it was confirmed that the catalytic activity was remarkably reduced, resulting in poor productivity.

In Comparative Example 4, it was confirmed that a polyolefin was formed similarly to the supported catalyst of Comparative Example 1, but AB was additionally supported in the last order, but the catalytic activity was increased but the molecular weight was significantly reduced. It can be seen that this is because the K1 catalyst, which is a low molecular weight polyolefin-generated metallocene compound, was more activated by the AB cocatalyst supported at the end.

Comparative Example 5 did not use MAO, but was a catalyst supported in the order of a second metallocene catalyst, an alkyl aluminum, a first metallocene catalyst, and a borate compound different from the supported order of the present application, and the weight average molecular weight was significantly low. Polyolefin was produced.

As described above, according to Examples 1 to 3, the alkylaluminum and borate are appropriately combined without the use of MAO, and the activity is improved by using a supported catalyst with a specific support order, thereby showing high activity with only a small amount of cocatalyst, thereby reducing catalyst cost. I could have contributed greatly. In addition, it was confirmed that high molecular weight polyolefin polymerization was possible to facilitate process operation.

Claims (12)

Supporting the alkyl aluminum on the carrier;
Supporting a first metallocene compound represented by the following formula (1) and a second metallocene compound represented by the following formula (2) on the carrier on which the alkyl aluminum is supported; And
Comprising the step of supporting a borate compound on a carrier on which the alkyl aluminum, the first metallocene compound, and the second metallocene compound are supported,
The supported amount of the alkyl aluminum is 0.1 to less than 3 mmol based on 1 g of the carrier, and the supported amount of the borate compound is 0.01 to 0.5 mmol based on 1 g of the carrier,
Method for producing a mixed supported metallocene catalyst:
[Formula 1]

In Formula 1,
M ₁ is a Group 4 transition metal;
Cp ₁ is any one cyclic compound selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl, and at least one hydrogen of the cyclic compound is Each independently substituted with one of C1 to 20 alkyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl. Can;
Z ₁ And Z ₂ is the same as or different from each other, and each independently halogen, C1 to C20 alkyl, C2 to C10 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl;
B is carbon, silicon, or germanium;
R ₁ to R ₃ are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C2 to C20 alkenyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 To C20 alkylaryl, or C7 to C20 arylalkyl;
[Formula 2]

In Formula 2,
M ₂ is a Group 4 transition metal;
Cp ₂ and Cp ₃ are the same as or different from each other, each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl Is a cyclic compound, and at least one hydrogen of the cyclic compound is each independently C1 to 20 alkyl, C1 to C20 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to May be substituted with any one of C20 arylalkyl;
Z ₃ And Z ₄ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl, C2 to C10 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, or C7 to C20 arylalkyl.
According to claim 1, wherein the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum and isoprenyl aluminum containing any one or more selected from the group consisting of, hybrid supported metal Method for producing a rosene catalyst.
The method of claim 1, wherein the borate compound is trityl tetrakis (pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate , Triethylammonium tetrakis (pentafluorophenyl) borate and tripropylammonium tetrakis (pentafluorophenyl) borate comprising any one or more selected from the group consisting of, a method for producing a hybrid supported metallocene catalyst.
delete The method of claim 1, wherein the supported amounts of the first metallocene compound and the second metallocene compound are the same or different, and each independently, is 0.02 to 1 mmol based on 1 g of the carrier. Manufacturing method.
The method of claim 1, wherein the first metallocene compound represented by Formula 1 is one of the following structural formulas:

The method of claim 1, wherein the second metallocene compound represented by Formula 2 is one of the following structural formulas:

The method of claim 1, wherein silica, alumina, magnesia, or a mixture thereof is used as the support.
The method of claim 1, wherein the first metallocene compound and the second metallocene compound are sequentially supported.
A hybrid supported metallocene catalyst prepared according to the manufacturing method of any one of claims 1 to 3 and 5 to 9.
A method for producing a polyolefin comprising polymerizing an olefin monomer in the presence of the hybrid supported metallocene catalyst of claim 10.
The method of claim 11, 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-eicosene, norbornene, norbornadiene, ethylidene nobornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4- Butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and a method for producing a polyolefin comprising at least one selected from the group consisting of 3-chloromethylstyrene.