KR101492571B1 - Hybride supported metallocene catalysts and method for preparing the same - Google Patents

Abstract

The present invention relates to a hybrid supported metallocene catalyst, a process for producing the metallocene catalyst, and a process for producing a polyolefin using the same. More specifically, in a process for producing a polyolefin copolymer resin using an olefin monomer, a mixed carrier metallocene catalyst in which two different specific metallocene compounds are carried on one carrier is contained at a certain ratio, There is provided a method for obtaining a polymer having a broad molecular weight distribution in a single reactor without blending of the polymer.

Description

Hybrid supported metallocene catalysts and methods for preparing same

The present invention relates to a hybrid supported metallocene catalyst, a process for producing the metallocene catalyst, and a process for producing a polyolefin using the same.

The metallocene catalyst is advantageous in that the molecular weight distribution of the polymer produced as a single active site catalyst is narrow and the molecular weight, stereoregularity, crystallinity, and particularly reactivity of the comonomer can be greatly controlled according to the structure of the catalyst and the ligand.

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

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

On the other hand, typical methods for producing polyolefins having a wide molecular weight distribution include a method using two reactors and a method using blending.

Among these, the method using two reactors is a method using two reactors in which the amount of hydrogen is changed by using the fact that the molecular weight is reduced as hydrogen is charged into the reactor. However, this method has a disadvantage that the process becomes complicated, and there is a problem that two reactors are required.

In addition, the method using blending is to polymerize the polyolefins and then blend them. In this case, additional cost is incurred in blending, which makes it difficult to obtain an uneconomical and uniform blend.

It is known that it is difficult to produce a polyolefin having a wide molecular weight distribution by using a single-site catalyst, a metallocene catalyst.

In order to solve the problems of the prior art as described above, the present invention is to provide a hybrid supported metallocene catalyst in which two different metallocene compounds are supported on one carrier and a method for producing the same.

Another object of the present invention is to provide a process for producing a polyolefin having a broad molecular weight distribution economically without blending by using one reactor and without using a method of using two reactors or blending as in the prior art by using the hybrid supported metallocene catalyst And a method for producing the same.

According to an aspect of the present invention,

Carrier, and

There is provided a hybrid supported metallocene catalyst comprising a first metallocene compound of Formula 1 and a second metallocene compound of Formula 2 supported on the support:

[Chemical Formula 1]

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

In Formula 1,

p is an integer of 0 or 1;

M 'is a Group 4 transition metal;

R ^a and R ^b may be the same or different from each other and each independently represents hydrogen, alkyl of 1 to 20 carbon atoms, alkoxyalkyl of 2 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 40 carbon atoms, A cyclopentadienyl ligand substituted with at least one member selected from the group consisting of alkenyl having 1 to 20 carbon atoms, alkylaryl having 7 to 40 carbon atoms, arylalkyl having 7 to 40 carbon atoms, arylalkenyl having 8 to 40 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms ego;

Q is a halogen radical,

(2)

In Formula 2,

R ¹ to R ¹⁷ are the same or different from each other and each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms; Or R ¹ to R ¹⁷ are bonded to each other to form a cycloalkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms; ^At least one of R ¹ to R ¹⁷ is a substituent other than hydrogen and halogen in the substituent,

L is a straight or branched alkylene group having 1 to 10 carbon atoms,

D is -O-, -S-, -N (R ¹⁸ ) - or -Si (R ¹⁹ ) (R ²⁰ ) -, wherein R ¹⁸ to R ²⁰ are the same or different and each independently hydrogen, halogen , An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

A represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, An alkoxy group of 2 to 20 carbon atoms, a heterocycloalkyl group of 2 to 20 carbon atoms, a heteroaryl group of 5 to 20 carbon atoms,

M is a transition metal of Group 4,

X ¹ and X ² are the same or different from each other and each independently represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a nitro group, an amido group, An alkylsilyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or a sulfonate group of 1 to 20 carbon atoms.

The metallocene catalyst of the present invention may further comprise a cocatalyst, and the cocatalyst may include at least one selected from compounds represented by the following general formulas (3), (4) and (5)

(3)

^{- [Al (R 18) -O} ] a -

[Chemical Formula 4]

D ¹ (R ¹⁹ ) ₃

[Chemical Formula 5]

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

(Wherein,

R ¹⁸ may be the same or different and each independently represents a halogen or a substituted or unsubstituted hydrocarbyl of 1 to 20 carbon atoms substituted with halogen, a is an integer of 2 or more,

R < ¹⁹ > may be the same or different from each other and are each independently halogen; A hydrocarbon having 1 to 20 carbon atoms or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen,

D ¹ is aluminum or boron,

L is independently a neutral Lewis base, [LH] + or [L] ⁺ is a Bronsted acid, H is a hydrogen atom,

Z are each independently a Group 13 element,

E is independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, and the aryl group or the alkyl group is an aryl group or an alkyl group in which at least one hydrogen atom is substituted with a halogen, a hydrocarbon having 1 to 20 carbon atoms, an alkoxy or phenoxy, will be)

According to another embodiment of the present invention, there is also provided a method for producing a metallocene compound,

Supporting the promoter on the carrier, and

Supporting the second metallocene compound on the carrier

The present invention provides a method for producing the above-described hybrid supported metallocene catalyst.

The present invention also provides a process for producing a polyolefin comprising copolymerizing at least one olefin monomer under the above-mentioned hybrid supported metallocene catalyst in one polymerization reactor equipped with a stirrer and a device capable of temperature control.

The polyolefin having a high density and a broad molecular weight distribution can be produced by using the hybrid supported metallocene catalyst of the present invention. In particular, the hybrid supported metallocene catalyst of the present invention is free from the phenomenon of entanglement of the polymers during polymerization or sticking to the wall of the reactor, excellent bulk density and excellent particle shape, so that it can be directly applied to existing slurry process or vapor phase process can do. Therefore, the present invention can economically produce polyolefins without blending using one reactor, and such polyolefins can be applied to various fields such as pipes, high-strength fibers, and containers.

1 shows a GPC graph for Example 3 and Comparative Example 2 of the present invention.

Hereinafter, the method of producing the polyolefin resin of the present invention will be described in detail.

The present invention relates to a hybrid supported metallocene catalyst capable of synthesizing a polyolefin having a wide molecular weight distribution even by using one reactor without blending and a method for producing the same.

According to one embodiment of the invention there is provided a hybrid supported metallocene catalyst comprising a support and a first metallocene compound of the formula 1 and a second metallocene compound of the formula 2 supported on the support:

[Chemical Formula 1]

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

In Formula 1,

p is an integer of 0 or 1;

M 'is a Group 4 transition metal;

R ^a and R ^b may be the same or different from each other and each independently represents hydrogen, alkyl of 1 to 20 carbon atoms, alkoxyalkyl of 2 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 40 carbon atoms, A cyclopentadienyl ligand substituted with at least one member selected from the group consisting of alkenyl having 1 to 20 carbon atoms, alkylaryl having 7 to 40 carbon atoms, arylalkyl having 7 to 40 carbon atoms, arylalkenyl having 8 to 40 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms ego;

Q is a halogen radical,

(2)

In Formula 2,

R ¹ to R ¹⁷ are the same or different from each other and each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms; Or R ¹ to R ¹⁷ are bonded to each other to form a cycloalkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms; ^At least one of R ¹ to R ¹⁷ is a substituent other than hydrogen and halogen in the substituent,

L is a straight or branched alkylene group having 1 to 10 carbon atoms,

D is -O-, -S-, -N (R ¹⁸ ) - or -Si (R ¹⁹ ) (R ²⁰ ) -, wherein R ¹⁸ to R ²⁰ are the same or different and each independently hydrogen, halogen , An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

A represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, An alkoxy group of 2 to 20 carbon atoms, a heterocycloalkyl group of 2 to 20 carbon atoms, a heteroaryl group of 5 to 20 carbon atoms,

M is a transition metal of Group 4,

X ¹ and X ² are the same or different from each other and each independently represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a nitro group, an amido group, An alkylsilyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or a sulfonate group of 1 to 20 carbon atoms.

The present invention provides a hybrid supported metallocene catalyst capable of producing a polyolefin having a broad molecular weight distribution economically by a simple process by selecting a suitable metallocene catalyst and controlling the loading ratio, and a method for producing the same.

The hybrid metallocene catalyst of the present invention can be produced by using the compound of the formula 1 as the first metallocene compound and the compound of the formula 2 by using the second metallocene compound, It is possible to broaden the molecular weight distribution by carrying out polymerization of the olefin monomer in one reactor without using a method of using two reactors or blending the polyolefin separately.

Further, in the present invention, by controlling the loading ratio of the first metallocene compound and the second metallocene compound to be specifically controlled, it is possible to produce a polyolefin having better impact strength and pressure resistance characteristics than conventional ones.

Preferably, in the mixed metallocene catalyst, the loading ratio of the first metallocene compound and the second metallocene compound to 1 g of the carrier may be 100: 1 to 1: 100. In this case, the ratio means the molar ratio of the first metallocene to the second metallocene. If the supported ratio is less than 100: 1, the first metallocene only plays a dominant role. Therefore, there is a problem that sufficient impact strength and pressure resistance characteristics can not be exhibited. If the supported ratio is more than 1: 100, only the second metallocene There is a problem that it is difficult to show activity. In the mixed metallocene catalyst, the ratio of the sum of the first metallocene and the second metallocene to the weight of the carrier may be in the range of 0.005 to 0.30 (i.e., 0.5 to 30%). If the ratio is less than 0.005, there is a problem that the catalyst does not exhibit sufficient activity. If the ratio is more than 0.30, the ratio of metallocene to carrier is high, so that not all metallocene is supported.

In the first metallocene compound, M 'is selected from the group consisting of titanium, zirconium and hafnium, and Q may be selected from the group consisting of F, Cl, Br and I.

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

[Formula 1-1]

[Formula 1-2]

In the metallocene compound according to the present invention, specific substituents of the above-mentioned formula (2) are as follows.

The C ₁ -C ₂₀ alkyl group includes a linear or branched alkyl group and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, , Octyl group and the like.

Examples of the C ₂ -C ₂₀ alkenyl group include a linear or branched alkenyl group, and specific examples thereof include an allyl group, an ethynyl group, a propenyl group, a butenyl group, and a pentenyl group.

The C ₆ to C ₂₀ aryl group includes an aryl group of a monocyclic or condensed ring, and specifically includes a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, and a fluorenyl group.

The C ₅ -C ₂₀ heteroaryl group includes a heteroaryl group of a monocyclic or condensed ring and includes a carbazolyl group, a pyridyl group, a quinoline group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, A thiol group, a thiol group, a thiol group, a tetrahydrofuranyl group, and a tetrahydrofuranyl group.

The alkoxy group of C ₁ ~ C ₂₀ may include a methoxy group, an ethoxy group, a phenyl-oxy group, cyclohexyloxy group.

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

R 1 to R 17 in Formula 2 are each independently selected from the group consisting of hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, .

The L in Formula 2 is more preferably a C ₄ to C ₈ linear or branched alkylene group, but is not limited thereto. The alkylene group may be substituted or unsubstituted with a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, or a C ₆ to C ₂₀ aryl group.

Wherein A in Formula 2 is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert- butyl group, a methoxymethyl group, a tert- - methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group.

Examples of the metallocene compound of the formula (2) of the present invention include compounds represented by the following formula (2-1), but the present invention is not limited thereto.

[Formula 2-1]

In the mixed supported metallocene catalyst of the present invention, the carrier for supporting the first metallocene compound and the second metallocene compound may contain a hydroxy group on the surface thereof. That is, the amount of the hydroxyl group (-OH) on the surface of the support is preferably as small as possible, but it is practically difficult to remove all of the hydroxyl groups. Therefore, the amount of the hydroxy group can be controlled by the preparation method and condition of the carrier or the drying condition (temperature, time, drying method, etc.). For example, the amount of hydroxyl groups on the surface of the support is preferably 0.1 to 10 mmol / g, more preferably 0.5 to 1 mmol / g. If the amount of the hydroxyl group is less than 0.1 mmol / g, the site of reaction with the co-catalyst decreases. If the amount of the hydroxyl group exceeds 10 mmol / g, the hydroxyl group may be present in excess of the hydroxyl group present on the surface of the support. not.

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

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

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

The hybrid metallocene catalyst of the present invention may further comprise a cocatalyst for producing active species of the catalyst. The use of the above promoter can maintain the catalytic activity.

The cocatalyst can be used as long as it is a cocatalyst which is used when polymerizing olefin under a general metallocene catalyst. This cocatalyst causes a bond between the hydroxy group and the Group 13 transition metal in the support. Also, the presence of the promoter on the surface of the carrier can contribute to securing the intrinsic properties of the present specific catalyst composition without the fouling phenomenon that the polymer particles are entangled with each other on the wall surface of the reactor.

The promoter may include at least one selected from the group consisting of compounds represented by the following formulas (3), (4) and (5).

(3)

^{- [Al (R 18) -O} ] a -

[Chemical Formula 4]

D ¹ (R ¹⁹ ) ₃

[Chemical Formula 5]

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

In this formula,

R ¹⁸ may be the same or different and each independently represents a halogen or a substituted or unsubstituted hydrocarbyl of 1 to 20 carbon atoms substituted with halogen, a is an integer of 2 or more,

R < ¹⁹ > may be the same or different from each other and are each independently halogen; A hydrocarbon having 1 to 20 carbon atoms or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen,

D ¹ is aluminum or boron,

L is independently a neutral Lewis base, [LH] + or [L] ⁺ is a Bronsted acid, H is a hydrogen atom,

Z are each independently a Group 13 element,

E is independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, and the aryl group or the alkyl group is an aryl group or an alkyl group in which at least one hydrogen atom is substituted with a halogen, a hydrocarbon having 1 to 20 carbon atoms, an alkoxy or phenoxy, will be.

Examples of the compound represented by the general formula (3) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.

Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium tributylammonium (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N , N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra (p- Phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.

In the present invention, the molar ratio of the cocatalyst to the first metallocene compound may be in a molar ratio of 1: 1 to 10,000, preferably 1: 1,000, more preferably 10: 100 in terms of molar ratio.

The molar ratio of the cocatalyst to the second metallocene compound may be in a molar ratio of 1: 1 to 10,000, preferably in a molar ratio of 1 to 1,000, more preferably in a range of 10 to 100 Molar ratio.

At this time, if the molar ratio is less than 1, the metal content of the first cocatalyst is too small, so that the catalytic activity species can not be made well and the activity may be lowered. If the molar ratio exceeds 10,000, the metal of the cocatalyst may act as a catalyst poison have.

The supported amount of the cocatalyst may be 1 to 25 mmol based on 1 g of the carrier.

According to another embodiment of the present invention, there is provided a process for producing a metallocene compound, comprising the steps of: supporting a first metallocene compound on a support; supporting the promoter on the support; and supporting the second metallocene compound on the support There is provided a process for producing the above-mentioned hybrid supported metallocene catalyst.

That is, in the process for producing the hybrid supported metallocene catalyst of the present invention, it is preferable that the process of carrying the carrier, the first metallocene compound, the cocatalyst and the second metallocene compound in the order of excellent impact strength and pressure resistance characteristics And is preferable for giving high activity.

According to the method of the present invention, when a carrier is used and a supported metallocene catalyst is prepared by specifying the loading ratio of the first metallocene compound and the second metallocene compound described above, A polyolefin can be provided.

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

The method for preparing the hybrid supported metallocene catalyst in the present invention can be carried out under a solvent or without solvent. When a solvent is used, usable solvents 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, ethers such as diethyl ether or THF Most organic solvents such as a solvent, acetone, ethyl acetate and the like can be mentioned, and hexane, heptane, toluene or dichloromethane is preferable.

Meanwhile, according to another embodiment of the present invention, there is provided a process for producing a copolymer comprising copolymerizing at least one olefin monomer under the above-mentioned hybrid supported metallocene catalyst in one polymerization reactor equipped with a stirrer and a device capable of temperature control A process for producing a polyolefin is provided.

The present invention provides a process for producing a polyolefin which can be reacted in a single reactor without blending by using a mixed supported metallocene catalyst in which two different metallocene compounds are supported on one carrier.

Therefore, the present invention can produce a polymer having a molecular weight distribution broader than that of conventional polymers. Such a polyolefin having a broad molecular weight distribution according to the present invention can exhibit a wide range of molecular weights from a low molecular weight to a high molecular weight. Therefore, according to the present invention, the low molecular weight portion of the polyolefin improves the processability, and the high molecular weight portion of the polyolefin improves the physical properties.

In the present invention, the apparatus configuration for producing a polyolefin resin includes one polymerization reactor equipped with a mechanical stirrer and a temperature controllable apparatus.

In addition, the polymerization reaction of the present invention can be homopolymerized with one olefin monomer or two or more kinds of monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

In addition, the polymerization reactor may include a copolymerization reaction tank in which a feedstock feedstock for feeding the respective raw materials is connected. In addition, the polymerization reactor may be connected to one or more gas-liquid separators, a distillation column, and a heat exchanger through a transfer line to purify the polymerized material.

In addition, the hybrid supported metallocene catalyst of the present invention may be used for olefin polymerization by itself, and may optionally be contacted with olefinic monomers such as ethylene, propylene, 1-butene, 1-hexene, prepolymerization catalyst may be used.

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

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

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

The polyolefin prepared by this method may have a weight average molecular weight of 1,000 to 5,000,000 and a number average molecular weight of 100 to 50,000. In the present invention, the polyolefin-based molecular weight distribution (Mw / Mn) is preferably 2 or more, more preferably 2.5 or more, and most preferably 3 to 8, but is not limited thereto. In particular, the polyolefin of the present invention may have a degree of dispersion (PDI) of 5 to 8 and a bulk density (BD) of 0.35 to 0.45.

Hereinafter, the present invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

≪ Preparation Example 1 &

1st Metallocene  Preparation of compound (1-1)

[Formula 1-1]

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

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

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

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

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

≪ Preparation Example 2 &

Second Metallocene  Preparation of compound (Formula 2-1)

[Formula 2-1]

1) Preparation of ligand compound

Bu-O- (CH ₂ ) ₆ MgCl ₂ solution as a Grignard reagent was obtained from the reaction between tert-Bu-O- (CH ₂ ) ₆ Cl compound and Mg (0) in THF solvent. The obtained Grignard compound was added to a flask containing MeSiCl ₃ compound (176.1 mL, 1.5 mol) and THF (2.0 mL) at -30 ° C, stirred at room temperature for 8 hours or longer, dried _{tert-Bu-O- (CH 2} ) 6 to obtain a compound of SiMeCl ₂ (92% yield).

(3.33 g, 20 mmol), hexane (100 mL) and MTBE (1.2 mL, 10 mmol) were added to the reactor at -20 ° C and 8 mL of n-BuLi (2.5 M in Hexane ) Was added slowly, and the mixture was stirred at room temperature for 6 hours. After stirring was completed, the reactor temperature was cooled to -30 ° C and a solution of tert-Bu-O- (CH ₂ ) ₆ SiMeCl ₂ (2.7 g, 10 mmol) in hexane (100 mL) The prepared fluorenyl lithium solution was slowly added over 1 hour. The mixture was stirred at room temperature for 8 hours or more and then extracted with water and evaporated to obtain tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₉ ) ₂ , Yield: 100%). The structure of the ligand was confirmed by ¹ H-NMR.

_{^{1 H NMR (500MHz, CDCl 3}} ): -0.35 (MeSi, 3H, s), 0.26 (Si-CH 2, 2H, m), 0.58 (CH 2, 2H, m), 0.95 (CH 2, 4H, m ), 1.17 (tert-BuO, 9H, s), 1.29 (CH 2, 2H, m), 3.21 (tert-BuO-CH 2, 2H, t), 4.10 (Flu-9H, 2H, s), 7.25 ( (Flu-H, 4H, m), 7.35 (Flu-H, 4H, m), 7.40 (Flu-H, 4H, m), 7.85 (Flu-H, 4H, d).

2) Preparation of metallocene compound of formula (2-1)

To a solution of (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₉ ) ₂ (3.18 g, 6 mmol) / MTBE (20 mL) at -20 ° C. was added 4.8 mL of n-BuLi in Hexane was slowly added and the reaction was carried out for 8 hours or more while raising the temperature to room temperature. Then, the dilithium salts slurry solution prepared above was reacted with ZrCl ₄ (THF) ₂ (2.26 g, 6 mmol) / hexane 20 mL) slurry solution, and further reacted at room temperature for 8 hours. The precipitate was filtered and washed several times with hexane to obtain a red solid (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₈ ) ₂ ZrCl ₂ compound (4.3 g, yield 94.5% ).

¹ H NMR (500 MHz, C6D6): 1.15 (tert-BuO, 9H, s), 1.26 (MeSi, 3H, s), 1.58 (Flu-H, 2H, t), 1.91 (CH2, 4H, m), 3.32 (tert- 4H, m), 7.60 (Flu-H, 4H, dd), 7.64

≪ Examples 1-3 >

A mixed supported metallocene catalyst was prepared using the metallocene compound of Formula 1-1 and the metallocene compound of Formula 2-1, and silica as a carrier. At this time, the two different metallocene compounds were carried on the carrier so that the molar ratio was as follows. The weight ratio of the two metallocenes was adjusted to 10% of the weight of the silica.

* Example 1: Formula 1-1 / Formula 2-1 = 4/7

* Example 2: Formula 1-1 / Formula 2-1 = 3/8

* Example 3: Formula 1-1 / Formula 2-1 = 2/8

This carrier was used by calcining Grace silica (product name: SP952X_1836) at 500 占 폚.

Specifically, 100 ml of a toluene solution was added to a glass reactor, and 10 g of the prepared silica was added thereto, followed by stirring while raising the reactor temperature to 60 ° C. After sufficiently dispersing the silica, the metallocene catalyst of Formula 1-1 was added thereto and stirred for 2 hours. Stirring was stopped, and 53.1 ml of a 10 wt% methylaluminoxane (MAO) / toluene solution was added thereto, followed by stirring at 80 ° C and 200 rpm for 16 hours. Thereafter, the temperature was lowered again to 40 ° C and then washed with a sufficient amount of toluene to remove unreacted aluminum compound.

Subsequently, 100 ml of toluene was charged, the metallocene catalyst of the above formula (2-1) was added, and the mixture was stirred for 2 hours. In this case, the amounts of the metallocene catalysts of the formulas 1-1 and 2-1 were as described above, and they were respectively dissolved in 20 ml of toluene and then added in a solution state.

Then, the mixed solution was stirred for 2 hours to react. After completion of the reaction, stirring was stopped, the toluene layer was separated and removed, and the remaining toluene was removed at 40 ° C under reduced pressure to prepare a mixed metallocene supported catalyst.

≪ Comparative Example 1 &

The procedure of Example 1 was repeated except that the metallocene compound of Formula 1-1 and the metallocene compound of Formula 6, which was a conventional metallocene catalyst, were supported on a carrier in a molar ratio of 3.5: 7, Supported metallocene catalysts.

[Chemical Formula 6]

<Example 4>

Olefin polymerization

Ethylene was polymerized using the hybrid supported metallocene catalysts prepared in Examples 1 to 3 and Comparative Example 1 under the conditions shown in Table 1 to prepare polyethylene.

Specifically, 20 mg of each of the hybrid supported metallocene catalysts was quantified in a dry box, each was packed in a 50 ml glass bottle, sealed with a rubber septum, and taken out from a dry box to prepare a catalyst to be injected. The olefin polymerization was carried out in a 2 L metal alloy reactor equipped with a thermostatable device equipped with a mechanical stirrer and used at high pressure.

1 liter of hexane containing 0.5 mmol of triethylaluminum and 20 ml of 1-hexene were charged into the reactor, and the prepared supported catalysts were charged into one reactor without air contact, Polymerization was carried out for one hour while continuously adding monomers and hydrogen. The termination of the polymerization was completed by first stopping the stirring and then removing ethylene by evacuation. Subsequently, the polymerization solvent was filtered to remove most of the solvent, followed by drying in an oven at 70 DEG C for 4 hours to obtain an ethylene / alpha olefin polymer.

The activity and bulk density (BD) and molecular weight of each polymer thus obtained were measured, and the results are shown in Table 1 below. The GPC graph of Example 3 and Comparative Example 2 of the present invention is shown in Fig. 1 (solid line, Comparative Example 2: dotted line).

Example 1 Example 2 Example 3 Comparative Example 1 Ethylene load (kg / hr) 30 28 31 31 Hydrogen input amount
(ppm) 100 120 248 35 activation 5.8 5.8 3.8 5.4 Setting efficiency 59 58 65 60 BD 0.41 0.40 0.44 0.42 HLMI 3.4 2.7 2.7 2.8 Mw 170,200 160,500 165,300 138,500 Mn 29,800 29,100 21,100 40,700 PDI 5.7 5.5 7.8 3.4

From the results shown in Table 1 and FIG. 1, it can be seen that Examples 1 to 3 of the present invention produced a polyolefin having a broad molecular weight distribution as compared with Comparative Example 1.

Claims (12)

Carrier, and
A first metallocene compound represented by the following formula (1) and a second metallocene compound represented by the following formula (2)
Wherein the ratio of the sum of the first metallocene and the second metallocene to the weight of the carrier is in the range of 0.005 to 0.30 weight ratio, the mixed metallocene catalyst for producing a polyolefin,
[Chemical Formula 1]
(R ^a ) _p (R ^b ) M'Q _3-p
In Formula 1,
p is an integer of 0 or 1;
M 'is a Group 4 transition metal;
R ^a and R ^b may be the same or different from each other and each independently represents hydrogen, alkyl of 1 to 20 carbon atoms, alkoxyalkyl of 2 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 40 carbon atoms, A cyclopentadienyl ligand substituted with at least one member selected from the group consisting of alkenyl having 1 to 20 carbon atoms, alkylaryl having 7 to 40 carbon atoms, arylalkyl having 7 to 40 carbon atoms, arylalkenyl having 8 to 40 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms ego;
Q is a halogen radical,
(2)

In Formula 2,
R ¹ to R ¹⁷ are the same or different from each other and each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms; Or R ¹ to R ¹⁷ are bonded to each other to form a cycloalkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms; ^At least one of R ¹ to R ¹⁷ is a substituent other than hydrogen and halogen in the substituent,
L is a straight or branched alkylene group having 1 to 10 carbon atoms,
D is -O-, -S-, -N (R ¹⁸ ) - or -Si (R ¹⁹ ) (R ²⁰ ) -, wherein R ¹⁸ to R ²⁰ are the same or different and each independently hydrogen, halogen , An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
A represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, An alkoxy group of 2 to 20 carbon atoms, a heterocycloalkyl group of 2 to 20 carbon atoms, a heteroaryl group of 5 to 20 carbon atoms,
M is a transition metal of Group 4,
X ¹ and X ² are the same or different from each other and each independently represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a nitro group, an amido group, An alkylsilyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or a sulfonate group of 1 to 20 carbon atoms.
The hybrid supported metallocene catalyst for producing a polyolefin according to claim 1, wherein the supported ratio of the first metallocene compound to the second metallocene compound to 1 g of the carrier is 100: 1 to 1: 100.
The hybrid supported metallocene catalyst for producing a polyolefin according to claim 1, wherein the first metallocene compound comprises a compound represented by the following general formula (1-1) or (1-2).
[Formula 1-1]

[Formula 1-2]

The hybrid supported metallocene catalyst for producing a polyolefin according to claim 1, wherein R1 to R17 in Formula 2 are each independently hydrogen or a methyl group, L is a C ₄ to C ₈ alkylene group, and A is a tert-butyl group.
The hybrid supported metallocene catalyst for producing a polyolefin according to claim 1, further comprising at least one cocatalyst selected from compounds represented by the following general formulas (3), (4) and (5)
(3)
^{- [Al (R 18) -O} ] a -
[Chemical Formula 4]
D ¹ (R ¹⁹ ) ₃
[Chemical Formula 5]
^{[LH] + [Z (E} ) 4] - or ^{[L] + [Z (E} ) 4] -
In this formula,
R ¹⁸ may be the same or different and each independently represents a halogen or a substituted or unsubstituted hydrocarbyl of 1 to 20 carbon atoms substituted with halogen, a is an integer of 2 or more,
R &lt; ¹⁹ &gt; may be the same or different from each other and are each independently halogen; A hydrocarbon having 1 to 20 carbon atoms or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen,
D ¹ is aluminum or boron,
L is independently a neutral Lewis base, [LH] + or [L] ⁺ is a Bronsted acid, H is a hydrogen atom,
Z are each independently a Group 13 element,
E is independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, and the aryl group or the alkyl group is an aryl group or an alkyl group in which at least one hydrogen atom is substituted with a halogen, a hydrocarbon having 1 to 20 carbon atoms, an alkoxy or phenoxy, will be.
The hybrid supported metallocene catalyst for producing a polyolefin according to claim 1, wherein the carrier contains a hydroxyl group and a siloxane group on its surface.
The hybrid supported metallocene catalyst for producing a polyolefin according to claim 1, wherein the carrier comprises at least one selected from silica, silica-alumina and silica-magnesia.
Supporting the first metallocene compound on the carrier,
Supporting the cocatalyst on the carrier, and
Supporting the second metallocene compound on the carrier
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
The method for producing a hybrid supported metallocene catalyst according to claim 8, wherein the supported amount of the promoter is 1 to 25 mmol based on 1 g of the carrier.
In one polymerization reactor equipped with a stirrer and a temperature controllable device,
Copolymerizing at least one olefin monomer under the mixed supported metallocene catalyst according to claim 1
&Lt; / RTI &gt;
The method of claim 10, wherein the olefin monomer is
Butene, 1-pentene, 1-pentene, 1-hexene, 1-heptene, , 1-hexadecene, 1-aidosene, norbornene, norbornene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1 , 6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.
The process for producing a polyolefin according to claim 10, wherein the dispersion degree (PDI) is 5 to 8 and the bulk density (BD) is 0.35 to 0.45.

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