KR20180044136A - Method for preparing supported hybrid metallocene catalyst - Google Patents

Abstract

The present invention relates to a method for preparing a mixed supported hybrid metallocene catalyst, which comprises a step of supporting a metallocene catalyst mainly contributing to the polymerization of high-molecular-weight polymer chains in a form of a pre-activated solution previously dissolved in an alkyl aluminoxane solution instead of directly supporting the metallocene catalyst on a carrier. Polyolefin having high catalytic activity, high molecular weight, and a broad molecular weight distribution can be produced through using the mixed supported hybrid metallocene catalyst prepared by the method of the present invention.

Description

METHOD FOR PREPARING SUPPORTED HYBRID METALLOCENE CATALYST [0002]

The present invention relates to a process for preparing a hybrid supported metallocene catalyst capable of producing a polyolefin having a high molecular weight while exhibiting high activity in the production of a polyolefin.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to conventional commercial processes since the invention of the 50's. However, since the Ziegler-Natta catalyst is a multi-site catalyst containing a plurality of active sites, the molecular weight distribution of the polymer is broad, There is a problem that the desired physical properties can not be secured.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst, . The polymer has a narrow molecular weight distribution according to the single active site property and a homogeneous composition distribution of the comonomer is obtained. According to the modification of the ligand structure and the polymerization conditions of the catalyst, the stereoregularity of the polymer, Crystallinity and so on.

U.S. Patent No. 5,032,562 discloses a method of preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. This is a method of producing a bimodal distribution polymer by supporting a Ziegler-Natta catalyst of a titanium (Ti) series which produces a high molecular weight and a zirconium (Zr) based metallocene catalyst which generates a low molecular weight on a support , The supporting process is complicated and the morphology of the polymer is deteriorated due to the co-catalyst.

U.S. Patent No. 5,525,678 discloses a method of using an olefin polymerization catalyst system capable of simultaneously polymerizing a high molecular weight polymer and a low molecular weight polymer by supporting a metallocene compound and a non-metallocene compound on a carrier simultaneously. This is a disadvantage in that the metallocene compound and the non-metallocene compound must be supported separately and the carrier must be pretreated with various compounds for the supporting reaction.

U.S. Patent No. 5,914,289 discloses a method of controlling the molecular weight and molecular weight distribution of a polymer by using a metallocene catalyst supported on each support. However, the amount of the solvent used for preparing the supported catalyst and the preparation time are long , And the metallocene catalyst used had to be carried on the carrier, respectively.

Korean Patent Application No. 2003-12308 discloses a method for controlling the molecular weight distribution by carrying a double-nucleated metallocene catalyst and a single nuclear metallocene catalyst together with an activating agent in a carrier to change and polymerize the combination of catalysts in the reactor have. However, this method has a limitation in simultaneously realizing the characteristics of the individual catalysts, and also disadvantageously causes fouling in the reactor due to liberation of the metallocene catalyst portion in the carrier component of the finished catalyst.

Accordingly, there is a continuing need for a process for preparing an olefin polymer of desired properties by preparing a hybrid supported metallocene catalyst having excellent activity in order to solve the above-mentioned disadvantages.

However, among all of these attempts, there are only a few catalysts currently being applied to commercial plants, and there is still a demand for a catalyst exhibiting improved polymerization performance.

The present inventors have found that a metallocene compound capable of contributing to the production of a high molecular weight polyolefin is preliminarily activated by dissolving it in an alkylaluminoxane solution before carrying it and then supported on a carrier to form a hybrid supported metallocene catalyst It was confirmed that the polyolefin activity of the catalyst was improved and that the polyolefin having a high molecular weight could be produced with a wide molecular weight distribution, thereby completing the present invention.

The present invention provides a process for preparing a hybrid supported metallocene catalyst which can exhibit high activity in the production of polyolefins and can produce polyolefins of high molecular weight.

The present invention also provides a process for producing a polyolefin comprising polymerizing an olefin monomer in the presence of the hybrid supported metallocene catalyst produced by the above production process.

In order to solve the above-mentioned problems, the present invention provides a process for producing a hybrid supported metallocene catalyst comprising the steps of:

1) carrying a cocatalyst on a carrier;

2) supporting the first metallocene compound on the support carrying the promoter; And

3) contacting the precatalyst and the preliminarily activated solution in which the first metallocene compound-carrying carrier and the second metallocene compound are dissolved in an alkylaluminoxane solution to form the co-catalyst and the first metallocene compound Supporting the second metallocene compound on the supported carrier.

The first metallocene compound may be at least one compound selected from compounds represented by the following general formulas (1) to (3), and the second metallocene compound may be at least one compound selected from the compounds represented by the following general formula to be.

Generally, the supported metallocene catalyst is prepared by contacting the metallocene compound with the carrier in a solution state in which the metallocene compound is dissolved in a solvent to carry the catalyst. This is because when the metallocene compound is brought into contact with the carrier in powder form, the metallocene compound is carried on the carrier in a non-uniform manner. However, when the metallocene compound is to be supported in a solution in which the metallocene compound is completely dissolved in a solvent, since the solubility of the metallocene compound in a commonly used solvent such as toluene is not high, The metallocene compound is unevenly supported on the carrier, and the polyolefin produced under such a supported catalyst is degraded in physical properties and morphology.

Accordingly, the present invention is characterized by using a preactivating solution in which a metallocene compound is preliminarily dissolved in an alkylaluminoxane solution before the metallocene compound is supported on a carrier, by supporting the metallocene compound on the carrier. In the case of using the preactivating solution, the problem that the metallocene compound is completely dissolved in the alkylaluminoxane solution while being non-uniformly supported can be prevented without using a large amount of solvent, and the catalytic activity of the supported catalyst is remarkably improved when the polyolefin is prepared .

In order to produce the hybrid supported metallocene catalyst of the present invention, two different first metallocene compounds and second metallocene compounds are successively carried on one carrier. The first metallocene compound mainly contributes to polymerizing a low molecular weight polymer chain in the production of polyolefin and the second metallocene compound mainly contributes to polymerizing a high molecular weight polymer chain. When the polyolefin is produced using the hybrid supported metallocene catalyst, a polyolefin having a high molecular weight distribution and a high molecular weight in a high molecular weight region can be obtained.

In particular, by preactivating and carrying only the second metallocene catalyst which mainly polymerizes high-molecular-weight polymer chains in the metallocene compound, the activity of the second metallocene catalyst is further increased, It is possible to prepare a polyolefin having a higher molecular weight and an increased molecular weight and molecular weight distribution. This is in contrast to the fact that the molecular weight and the molecular weight distribution of the polyolefin are not increased when the second metallocene catalyst is preliminarily activated as a single supported catalyst and then used, as can be seen from the comparative examples described later.

Hereinafter, the present invention will be described in detail.

On the carrier The co-catalyst Bearing  Step (Step 1)

The above step 1 is a step of supporting the promoter on the inside and on the surface of the carrier so that the activity of the catalyst is improved during the production of the polyolefin and the molecular weight distribution of the polyolefin finally prepared is more uniform.

As the carrier, a carrier containing a hydroxy group on the surface thereof can be used, and a carrier having a hydroxyl group and a siloxane group having high reactivity and dried on the surface of which moisture is removed can be used.

For example, the support may be at least one member selected from the group consisting of silica, silica-alumina, and silica-magnesia. They may typically contain oxides, carbonates, sulphates, and nitrate components such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ .

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° 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 amount of hydroxyl groups on the surface of the support is preferably from 0.1 to 10 mmol / g, more preferably from 0.5 to 5 mmol / g. The amount of the hydroxyl group on the surface of the carrier can be controlled by the preparation method and conditions of the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than 0.1 mmol / g, the number of sites of reaction with the co-catalyst is small. If the amount is more than 10 mmol / g, the hydroxyl group may be present in the water other than the hydroxyl group present on the surface of the carrier particle. not.

On the other hand, as the cocatalyst, any catalyst may be used as long as it is a catalyst used for polymerizing olefins 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.

More specifically, the promoter may be at least one member selected from the group consisting of compounds represented by the following formulas (6) to (8):

[Chemical Formula 6]

_{- [Al (R 21) -O} ] c -

In Formula 6,

Each R < ₂₁ > is independently halogen, _C1-20 alkyl or _C1-20 haloalkyl,

c is an integer of 2 or more,

(7)

D (R _{22) 3}

In Formula 7,

D is aluminum or boron,

R ₂₂ are each independently, a substituted C _1-20 hydrocarbyl hydrogen, halogen, C _1-20 hydrocarbyl or a halogen,

[Chemical Formula 8]

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

In Formula 8,

L is a neutral or cationic Lewis base,

[LH] ⁺ is Bronsted acid,

Q is Br ^{3 + 3 +} or Al,

Wherein each E is independently C _6-20 aryl or C _1-20 alkyl, wherein said C _6-20 aryl or C _1-20 alkyl is unsubstituted or substituted with one or more groups selected from halogen, C _1-20 alkyl, C _1-20 alkoxy and Lt; / RTI > is substituted by one or more substituents selected from the group consisting of phenoxy.

The compound represented by Formula 6 may be an alkyl aluminoxane such as modified methyl aluminoxane (MMAO), methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like.

The alkyl metal compound represented by the general formula (7) is, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethylchloro Aluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, Aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like.

The compound represented by the above formula (8) is, for example, triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra (p- (O, p-dimethylphenyl) boron, tributylammonium tetra (p-tolyl) boron, triethylammoniumtetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium Tetramethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra (aluminum) (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl) Aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapenta Triphenyl aluminum, diethyl ammonium aluminum tetrapentafluorophenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl Aluminum, triphenylcarboniumtetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenylcarboniumtetra (p-trifluoromethylphenyl) boron, triphenylcarboniumtetrapentafluorophenylboron, etc. .

More specifically, the same precursor as the alkylaluminoxane used in the preactivating solution described later as the cocatalyst can be used.

When the cocatalyst is carried on the carrier, the conditions for the cocatalyst are not particularly limited and may be carried out in 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.

And, the above step can be carried out under a solvent or a 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.

Through the above step 1, a support carrying a promoter can be produced. At this time, the amount of the cocatalyst to be supported can be appropriately controlled according to the physical properties or effects of the desired catalyst composition. Specifically, the amount of the cocatalyst to be supported may be 7 to 10 mmol based on 1 g of the carrier.

remind The co-catalyst Supported On the carrier  1st Metallocene  The compound Bearing  Step (Step 2)

Step 2 is a step of additionally supporting a first metallocene compound which mainly contributes to polymerizing a low molecular weight polymer chain on the support carrying the promoter.

The first metallocene compound is at least one selected from compounds represented by the following general formulas (1) to (3)

[Chemical Formula 1]

(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹³ _-n

In Formula 1,

M ¹ is a Group 4 transition metal;

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

R ^a and R ^b are the same or different and each independently hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;

Z ¹ is a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene , Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;

n is 1 or 0;

(2)

(Cp ³ R ^c ) _m B ¹ (Cp ⁴ R ^d ) M ² Z ² _3-m

In Formula 2,

M ² is a Group 4 transition metal;

Cp < ³ > and Cp < ⁴ > are the same or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical , Which may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ^c and R ^d are the same or different and each independently hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _1-20 silylalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;

Z ² represents a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene , Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;

B ¹ is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom containing radical which bridges the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or cross-links one Cp ⁴ R ^d ring to M ² Or a combination thereof;

m is 1 or 0;

(3)

(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂

In Formula 3,

M ³ is a Group 4 transition metal;

Cp < ⁵ > is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, which are substituted with hydrocarbons having 1 to 20 carbon atoms ;

R ^e is hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl , C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;

Z ³ is a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene , Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;

B ² is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radical which cross-links the Cp ⁵ R ^e ring with J, or a combination thereof;

J is any one selected from the group consisting of NR ^f , O, PR ^f and S, R ^f is C _1-20 alkyl, aryl, substituted alkyl or substituted aryl,

Examples of the Group 4 transition metal include, but are not limited to, titanium, zirconium, and hafnium.

R ^a to R ^e in the general formulas (1) to (3) are each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert- butyl, pentyl, hexyl, heptyl, octyl, , Methoxypentyl, ethoxypentyl, propoxypentyl, n-butoxypentyl, tert-butoxypentyl, methoxyhexyl, ethoxyhexyl, propoxyhexyl, n-butoxyhexyl, tert-butoxyhexyl, vinyl , But is more preferably, but not limited to, propenyl, butenyl, phenyl, halogen, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl or trimethylsilylmethyl.

The compound represented by Formula 1 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

In the formula (2), when m is 1, it means that a Cp ³ R ^c ring, a Cp ⁴ R ^d ring or a Cp ⁴ R ^d ring and M ² are bridged by B ¹ , and m is 0 Quot; refers to the structure of the non-crosslinked compound.

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.

The compound represented by the formula (3) may be, for example, a compound represented by the following structural formula, but is not limited thereto.

When the first metallocene compound is supported on the support carrying the promoter, the supporting conditions are not particularly limited and may be carried out within a range well known to those skilled in the art. For example, the support temperature can be in the range of -30 DEG C to 150 DEG C, preferably in the range of room temperature to 100 DEG C, more preferably in the range of room temperature to < RTI ID = 0.0 > 80 ° C. The deposition time can be appropriately controlled depending on the amount of the first metallocene compound to be supported.

Through the step 2, a support carrying the promoter and the first metallocene compound can be produced. At this time, the loading amount of the first metallocene compound may be 0.05 to 0.5 mmol based on 1 g of the carrier.

remind Co-catalyst  And the first Metallocene  The compound Supported The carrier  Second Metallocene  The compound Alkyl aluminoxane  To the solution Dissolved  Contacting the preactivating solution, The above-  And the first Metallocene  The compound Supported On the carrier  The second Metallocene  The step of supporting the compound (step 3)

In step 3, the preliminary activation solution is prepared in advance so that the second metallocene compound can be supported uniformly on the carrier, and then the solution is contacted with the carrier to form a second metallocene compound in the solution. To be carried. By carrying out only the second metallocene compound mainly contributing to polymerizing the high molecular weight polymer chain among the metallocene compounds to be mixed and supported in the carrier in the form of the preactivated solution through the above step, the polyolefin having a high molecular weight and a broad molecular weight distribution Can be prepared.

The preactivating solution may be prepared by dissolving the second metallocene compound in the alkylaluminoxane solution at a temperature of 10 to 40 DEG C for 1 minute to 12 hours. At this time, the dissolution is continued until the second metallocene compound is completely dissolved in the alkylaluminoxane solution. In particular, if the reaction proceeds in less than 1 minute, the second metallocene compound may not sufficiently dissolve, and if it exceeds 12 hours, the catalytic activity of the second metallocene compound may be lowered and the color of the solution may be discolored . Particularly, it is preferable that the dissolution is performed for 1 minute to 3 hours.

Also, the concentration of the alkylaluminoxane in the pre-activation solution may be 5 to 20 wt%, and the concentration of the second metallocene compound may be 3 to 15 wt%. In the above range, the second metallocene compound is uniformly supported on the carrier prepared in Step 2, and the catalytic activity effect can be effectively expressed.

The alkylaluminoxane solution used for preparing the preactivating solution may be one in which the alkylaluminoxane is dissolved in at least one solvent selected from the group consisting of toluene, xylene and isopropylbenzene. Toluene is particularly preferred from the viewpoint of compatibility with alkyl aluminoxane.

In this case, the concentration of the alkylaluminoxane in the alkylaluminoxane solution may be 5 to 20 wt%, and the alkylaluminoxane may include methylaluminoxane (MAO), ethylaluminoxane, butylaluminoxane, and isobutylaluminoxane. One or more selected from the group consisting of

Wherein the second metallocene compound is at least one selected from compounds represented by the following general formula (4)

[Chemical Formula 4]

In Formula 4,

A is selected from the group consisting of hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, C _7-20 arylalkyl, C _1-20 alkoxy, C _2-20 alkoxy Alkyl, C _3-20 heterocycloalkyl, or C _5-20 heteroaryl;

D is -O-, -S-, -N (R) - or -Si (R) (R ') - , in which R and R' are the same or different from each other, each independently hydrogen, halogen, C _{1 -20} alkyl, C _2-20 alkenyl, or C _6-20 aryl;

L is C _1-10 linear or branched alkylene;

B is carbon, silicon (Si) or germanium;

Q is hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl;

M is a Group 4 transition metal;

X ¹ and X ² are the same or different and are each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, nitro, amido, C _1-20 alkylsilyl, C _{1 -20} alkoxy, or C _1-20 sulfonate;

C ¹ And C ² are the same or different and each independently represents one of the following formulas (5a), (5b) or (5c);

[Chemical Formula 5a]

[Chemical Formula 5b]

[Chemical Formula 5c]

Wherein R ₁ to R ₁₇ and R ₁ 'to R ₉ ' are the same or different from each other and each independently represents hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 alkyl silyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 alkyl and aryl, wherein R _At least two adjacent to each other of R ₁₀ to R ₁₇ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

The substituents of the above formulas (1) to (4) will be described more specifically.

Examples of the C _1-20 alkyl include linear or branched alkyl, and specifically methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, , But is not limited thereto.

The C _2-20 alkenyl includes straight or branched chain alkenyl, and specific examples thereof include, but are not limited to, allyl, ethenyl, propenyl, butenyl, pentenyl and the like.

The C _6-20 aryl includes aryl of a monocyclic or condensed ring, and specifically includes, but is not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, and the like.

The C _5-20 heteroaryl includes a heteroaryl of a monocyclic or condensed ring and includes a heteroaryl such as carbazolyl, pyridyl, quinoline, isoquinoline, thiophenyl, furanyl, imidazole, oxazolyl, thiazolyl, Tetrahydropyranyl, tetrahydropyranyl, tetrahydrofuranyl, and the like, but are not limited thereto.

Examples of the C _1-20 alkoxy include, but are not limited to, methoxy, ethoxy, phenyloxy, cyclohexyloxy, and the like.

R ₁ to R ₁₇ and R ₁ 'to R ₉ ' in the general formulas 5a, 5b and 5c are each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert- butyl, pentyl, More preferably, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, phenyl, halogen, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, methoxy or ethoxy .

L in Formula 4 is more preferably C _4-8 straight chain or branched alkylene, but is not limited thereto. Further, the alkylene group may be substituted or unsubstituted with C _1-20 alkyl, C _2-20 alkenyl, or C _6-20 aryl.

In the formula (4), A represents 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, Tetrahydrofuranyl, tetrahydrofuranyl, tetrahydrofuranyl, tetrahydrofuranyl, tetrahydrofuranyl, tetrahydrofuranyl, tetrahydrofuranyl or tetrahydrofuranyl.

In addition, B of Formula 4 is preferably silicon (Si), but it is not limited thereto.

The second metallocene compound of Formula 4 forms a structure in which an indeno indole derivative and / or a fluorene derivative are bridged by a bridge, and a non-covalent electron pair which can act as a Lewis base in the ligand structure Thereby supporting the carrier on the surface having Lewis acid properties and exhibiting high polymerization activity even when carried. In addition, the activity is high due to the electron enrichment of the indenoindole group and / or the fluorene group, and not only the hydrogen reactivity is low due to the appropriate steric hindrance and the electronic effect of the ligand, and the high activity is maintained even in the presence of hydrogen. Also, it is possible to stabilize the beta-hydrogen of the polymer chain in which the nitrogen atom of the indenoindole derivative grows by hydrogen bonding to inhibit beta-hydrogen elimination and polymerize the ultra-high molecular weight olefin polymer.

According to one embodiment of the present invention, the compound represented by Formula 5a may be a compound represented by one of the following formulas, but the present invention is not limited thereto.

According to one embodiment of the present invention, the compound represented by Formula 5b may be a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

According to one embodiment of the present invention, the compound represented by Formula 5c may be a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

According to one embodiment of the present invention, a specific example of the second metallocene compound represented by the general formula (4) includes compounds represented by one of the following structural formulas, but is not limited thereto.

The second metallocene compound of Formula 4 is prepared by ligating an indenoindole derivative and / or a fluorene derivative with a bridging compound to prepare a ligand compound, and then adding a metal precursor compound to carry out metallation . The method for producing the second metallocene compound will be described in the following Examples.

When the precatalyst and the first metallocene compound-carrying carrier are brought into contact with the preactivating solution, and the second metallocene compound is carried on the carrier, the supporting condition is not particularly limited, Can be carried out in a range well known to those skilled in the art. For example, it is possible to proceed by suitably using a high temperature support and a low temperature support. For example, the support may be carried out at a temperature of 30 to 80 DEG C for 1 to 6 hours.

The mixed supported metallocene catalyst carrying the cocatalyst, the first metallocene compound and the second metallocene compound can be prepared through the above step 3. Further, by using the pre-activation solution, the alkylaluminoxane may be additionally supported on the hybrid supported metallocene catalyst. At this time, the loading amount of the second metallocene compound is 0.05 to 0.3 mmol based on 1 g of the carrier, and the loading amount of the alkylaluminoxane may be 7 to 10 mmol based on 1 g of the carrier.

The first metallocene compound and the second metallocene compound may be supported at a molar ratio of 1: 1 to 5: 1 based on 1 g of the support. In the case of the hybrid supported catalyst satisfying the above ratio, it is possible to provide a polyolefin having excellent catalytic activity and having a broad molecular weight distribution.

In addition, when the hybrid supported catalyst supported on the support in the order of the co-catalyst, the first metallocene compound and the second metallocene compound is used, the fouling of the polymer particles due to the presence of the co- The first metallocene compound having a high catalytic activity can be supported for a longer period of time than the second metallocene compound while exhibiting intrinsic properties of the metallocene compound without development, thereby further increasing the activity of the hybrid supported catalyst.

Process for producing polyolefin

The present invention also provides a process for producing a polyolefin comprising polymerizing an olefin monomer in the presence of a hybrid supported metallocene catalyst prepared according to the above process.

The olefin-based monomer may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, Norbornene, norbornene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-hexadiene, 1-hexadiene, - pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

The polymerization can be carried out by copolymerizing ethylene and alpha-olefins using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

The polymerization temperature may be about 25 to about 500 캜, preferably about 25 to about 200 캜, and more preferably about 50 to about 150 캜. The polymerization pressure may be from about 1 to about 100 Kgf / cm ^2, preferably about 1 to about 50 Kgf / cm ^2, more preferably from about 5 to about 30 Kgf / cm ^2.

The supported metallocene catalyst may be 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 and chlorobenzene A chlorine atom-substituted hydrocarbon solvent, or the like. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

The polyolefin prepared by the above-described method may have a weight average molecular weight of 50,000 to 300,000. The molecular weight distribution (Mw / Mn) of the polyolefin may be 2.5 or more, and more preferably 2.5 to 10. The weight average molecular weight and the molecular weight distribution of such a polyolefin exhibit significantly higher values as compared with the case where the preactivating solution like the present invention is not used, as can be seen from the test examples described later.

The present invention relates to a method of preparing a hybrid supported metallocene catalyst, in which a metallocene catalyst, which mainly contributes to polymerizing a high molecular weight polymer chain, is not directly supported on a carrier but a preactivated solution , And the hybrid supported metallocene catalyst prepared by the above method is characterized in that a polyolefin having a high catalytic activity and a high molecular weight and a broad molecular weight distribution can be produced.

Fig. 1 shows GPC curves of the polyolefins prepared in Example 1-1, Example 1-2 and Comparative Example 1. Fig.
Fig. 2 shows GPC curves of the polyolefins prepared in Examples 2-1, 2-2 and Comparative Example 2. Fig.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

Manufacturing example  1: 1st Metallocene  Preparation of compound (A1)

(Preparation of ligand compound)

(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).

(Preparation of first metallocene compound (A1)) [

The resulting t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 ° C and n-butyllithium (n-BuLi) was added slowly. After the temperature was raised to room temperature, the reaction was carried out for 8 hours . 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 The title compound was obtained (yield 92%).

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

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

Manufacturing example  2: 1st Metallocene  Preparation of compound (A2)

(Preparation of ligand compound)

4.05 g (20 mmol) of ((1H-inden-3-yl) methyl) trimethylsilane was added to the dried 250 ml schlenk flask and 40 ml of ether was introduced under argon. After cooling the solution to 0 ° C, 9.6 ml (20 mmol) of a 2.5 M n-BuLi hexane solution was added dropwise. Then, the temperature of the reaction mixture was slowly raised to room temperature and stirred until the next day.

In addition, a solution prepared by dissolving 2.713 g (10 mmol) of Silicon Tether in 30 ml of hexane in another dried 250 ml schlenk flask, cooling the schlenk flask to -78 ° C., adding the lithiated solution thereto Respectively. The temperature of the mixture was slowly raised to room temperature, stirred for one day, quenched by adding 50 ml of water in a flask, and the organic layer was separated and dried with MgSO ₄ . As a result, 6.1 g (10.05 mmol, 100.5%) of yellow oil was obtained.

NMR standard purity (wt%) = 100%

Mw = 603.11

¹ H NMR (500 MHz, CDCl ₃ ): 0.02 (18 H, m), 0.82 (3 H, m), 1.15 (3 H, m) m), 2.02 (2H, m), 3.21 (2H, m), 3.31 (1H, s), 3.44 (1H, s), 5.86 ), 7.16 (2H, m), 7.32 (3H, m)

(Preparation of first metallocene compound (A2)

The prepared ligand compound was dissolved in MTBE (methyl tert-butyl ether, 4 equivalents) and toluene solution, and then 2 equivalents of n-BuLi solution was added to the reaction solution for lithiation. After one day, all of the solvent in the flask was removed under vacuum and dissolved in the same amount of toluene. In addition, one equivalent of ZrCl ₄ (thf) ₂ in a glove box was placed in a 250 ml Schlenk flask and toluene was added to the suspension. Both flasks were cooled to -78 ° C and ligand anions were added to the Zr suspension. After the injection, the temperature of the reaction mixture was slowly raised to room temperature. After stirring for about one day, the toluene in the mixture was removed by vacuum decompression to about 1/5 volume, and recrystallized by adding hexane of about 5 times the volume of the remaining toluene. The mixture was filtered in a filter system that did not come in contact with outside air, and the obtained filter cake was washed on the top of the filter using a small amount of hexane. Then, the filter cake was weighed and sampled in a glove box to confirm the synthesis, yield and purity. 7.3 g (9.56 mmol, 95.6%) of the title compound in the form of a purple oil were obtained from 6.1 g (10 mmol) of the ligand, which was stored in toluene solution (0.733 mmol / mg).

NMR standard purity (wt%) = 100%

Mw = 763.23.

¹ H NMR (500 MHz, CDCl ₃ ): 0.03 (18H, m), 0.98, 1.28 (3H, d), 1.40 (9H, m), 1.45 (1H, m), 6.98 (1H, m), 6.94 (1H, m) m), 7.36 (2H, m), 7.43 (1H, m), 7.57 (1H, m).

Manufacturing example  3: 2nd Metallocene  Preparation of compound (B)

(Preparation of ligand compound)

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

Fluorene (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 in hexane) was slowly added thereto, followed by stirring at room temperature for 6 hours to obtain a fluorenyl lithium solution. After the 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) dissolved in hexane (100 ml) Was added slowly to the prepared fluorenyl lithium solution 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 ₁₀ ) ₂ compound (5.3 g , Yield: 100%).

^{1 H NMR (500 MHz, CDCl} 3): -0.35 (MeSi, 3H, s), 0.26 (Si-CH2, 2H, m), 0.58 (CH2, 2H, m), 0.95 (CH2, 4H, m), 1H-NMR (CDCl3): 1.17 (tert-BuO, 9H, s), 1.29 (CH2, 2H, 4H, m), 7.35 (Flu-H, 4H, m), 7.40 (Flu-H, 4H, m), 7.85 (Flu-H, 4H, d).

(Preparation of second metallocene compound (B)

To a solution of the ligand compound (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₁₀ ) ₂ (3.18 g, 6 mmol) / MTBE (20 ml) prepared at -20 ° C., 4.8 ml of n -BuLi (2.5 M in Hexane) was slowly added and the reaction was carried out at room temperature for 8 hours or longer to prepare a slurry solution of dilithium salts. The dilithium salt slurry solution prepared above was slowly added to the slurry solution of ZrCl ₄ (THF) ₂ (2.26 g, 6 mmol) / hexane (20 ml) at -20 ° C and further reacted at room temperature for 8 hours. The precipitate was filtered and washed several times with hexane to give the title compound (4.3 g, yield: 97%) in the form of a red solid (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₁₀ ) ₂ ZrCl _2. 94.5%).

^{1 H NMR (500 MHz, C} 6 D 6): 1.15 (tert-BuO, 9H, s), 1.26 (MeSi, 3H, s), 1.58 (Si-CH 2, 2H, m), 1.66 (CH 2, 4H, m), 1.91 (CH 2, 4H, m), 3.32 (tert-BuO-CH 2, 2H, t), 6.86 (Flu-H, 2H, t), 6.90 (Flu-H, 2H, t) , 7.15 (Flu-H, 4H, m), 7.60 (Flu-H, 4H, dd), 7.64

Example  1-1: Hybrid support Metallocene  Preparation of Catalyst (A1 + B)

As the carrier, silica (manufacturer: Grace Davision, product name: Sylopol 952) was prepared by firing at 200 ° C for 10 hours.

10 g of the silica carrier was stirred so as to be uniformly dispersed in 50 ml of toluene in the reactor shut off with air, and then 8 mmol / g SiO ₂ solution of 10 wt% methylaluminoxane (MAO) was added thereto. Followed by stirring to carry methylaluminoxane (MAO) used as a cocatalyst on the silica support. Thereafter, the reaction product was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed by decompression. 50 ml of toluene was again added and the temperature of the reactor was lowered to 30 ° C.

Next, 0.4 mmol / g SiO ₂ of the first metallocene compound (A1) prepared in Preparation Example 1 was dissolved in toluene, and the mixture was reacted for 3 hours.

After the reaction was completed, 0.2 mmol / g SiO ₂ of the second metallocene compound (B) prepared in Preparation Example 3 prepared in advance in the reactor was added to 20 ml of a 10 wt% methylaluminoxane (MAO) solution 20 ml of the preactivated solution completely dissolved by stirring at room temperature for 1 minute was added and reacted for 3 hours.

After the completion of the reaction, stirring was stopped, and the reaction solution was washed with a sufficient amount of toluene. Then, 50 ml of toluene was added thereto. After stirring for 10 minutes, the solution was stopped and washed with a sufficient amount of toluene to remove unreacted compounds. Thereafter, 50 ml of hexane was added, stirred, and then sampled into a flask, which was dried to prepare a mixed supported metallocene catalyst.

The amounts of methylaluminoxane (MAO), the first metallocene compound (A1) and the second metallocene compound (B) used as cocatalysts in the prepared mixed supported metallocene catalysts were 8 mmol / g SiO ₂ , 0.4 mmol / g SiO ₂ and was 0.2 mmol / g SiO _2.

Example  1-2: Hybrid support Metallocene  Preparation of Catalyst (A1 + B)

0.2 mmol / g SiO ₂ of the second metallocene compound (B) prepared in Preparation Example 3 was added to 20 ml of a 10 wt% solution of methylaluminoxane (MAO) in place of the preactivating solution of Example 1-1 The mixed supported metallocene catalyst was prepared in the same manner as in Example 1-1 except that the preactivated solution was completely dissolved by stirring at room temperature for 2 hours.

The amounts of methylaluminoxane (MAO), the first metallocene compound (A1) and the second metallocene compound (B) used as cocatalysts in the prepared mixed supported metallocene catalysts were 8 mmol / g SiO ₂ , 0.4 mmol / g SiO ₂ and was 0.2 mmol / g SiO _2.

Example  2-1: hybrid bearing Metallocene  Preparation of Catalyst (A2 + B)

The procedure of Example 1-1 was repeated except that the first metallocene compound (A2) prepared in Preparation Example 2 was used instead of the first metallocene compound (A1) of Example 1-1 To prepare a hybrid supported metallocene catalyst.

The amounts of methylaluminoxane (MAO), the first metallocene compound (A2) and the second metallocene compound (B) used as cocatalysts in the prepared mixed supported metallocene catalysts were 8 mmol / g SiO ₂ , 0.4 mmol / g SiO ₂ and was 0.2 mmol / g SiO _2.

Example  2-2: Hybrid support Metallocene  Preparation of Catalyst (A2 + B)

0.2 mmol / g SiO ₂ of the second metallocene compound (B) prepared in Preparation Example 3 was added to 20 ml of a 10 wt% solution of methylaluminoxane (MAO) in place of the preactivating solution of Example 2-1 The mixed supported metallocene catalyst was prepared in the same manner as in Example 2-1 except that the preliminarily activated solution completely dissolved by stirring at room temperature for 2 hours was used.

The amounts of methylaluminoxane (MAO), the first metallocene compound (A2) and the second metallocene compound (B) used as cocatalysts in the prepared mixed supported metallocene catalysts were 8 mmol / g SiO ₂ , 0.4 mmol / g SiO ₂ and was 0.2 mmol / g SiO _2.

Comparative Example  1: hybrid bearing Metallocene  Preparation of Catalyst (A1 + B)

Except that 0.2 mmol / g SiO ₂ of the second metallocene compound (B) prepared in Preparation Example 3 was dissolved in toluene and directly introduced into the reactor instead of using the pre-activation solution of Example 1-1 , A mixed supported metallocene catalyst was prepared in the same manner as in Example 1-1.

Comparative Example  2: hybrid bearing Metallocene  Preparation of Catalyst (A2 + B)

Except that 0.2 mmol / g SiO ₂ of the second metallocene compound (B) prepared in Preparation Example 3 was dissolved in toluene and directly introduced into the reactor instead of using the preactivating solution of Example 2-1 , A mixed supported metallocene catalyst was prepared in the same manner as in Example 2-1.

Comparative Example  3: Single carrier Metallocene  Preparation of Catalyst (B)

As the carrier, silica (manufacturer: Grace Davision, product name: Sylopol 952) was prepared by firing at 200 ° C for 10 hours.

10 g of the silica carrier was stirred in 50 ml of toluene to be dispersed evenly in the reactor shut off with air, and then 8 mmol / g SiO ₂ solution of 10 wt% methylaluminoxane (MAO) was added thereto. Followed by stirring to carry methylaluminoxane (MAO) on the silica support. Thereafter, the reaction product was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed by decompression. 50 ml of toluene was again added and the temperature of the reactor was lowered to 30 ° C.

Next, 0.1 mmol / g SiO ₂ of the second metallocene compound (B) prepared in Preparation Example 3 was added to 4 ml of a 10 wt% methylaluminoxane (MAO) solution in the reactor, and the mixture was stirred at room temperature for 1 hour 4 ml of the pre-activated solution completely dissolved by stirring was added and reacted for 5 hours.

After the completion of the reaction, stirring was stopped, and the reaction solution was washed with a sufficient amount of toluene. Then, 50 ml of toluene was added thereto. After stirring for 10 minutes, the solution was stopped and washed with a sufficient amount of toluene to remove unreacted compounds. Then, 50 ml of hexane was added thereto, stirred, sampled in a flask, and dried to prepare a single supported metallocene catalyst.

Comparative Example  4: Single carrier Metallocene  Preparation of Catalyst (B)

Except that 0.1 mmol / g SiO ₂ of the second metallocene compound (B) prepared in Preparation Example 3 was dissolved in toluene and directly added to the reactor instead of using the preactivating solution of Comparative Example 3 , A single supported metallocene catalyst was prepared using the same method as in Comparative Example 3.

Comparative Example  5: Single carrier Metallocene  Preparation of Catalyst (B)

Instead of using the preactivating solution of Comparative Example 3, 0.1 mmol / g SiO ₂ of the second metallocene compound (B) prepared in Preparation Example 3 was directly added to the reactor in the form of a suspension not dissolved in toluene , A single supported metallocene catalyst was prepared using the same method as in Comparative Example 3 above.

Test Example

1) ethylene polymerization

10 mg of each of the supported catalysts prepared in the above Examples and Comparative Examples was quantitatively measured in a dry box and immersed in a 50-mL glass bottle together with hexane, sealed with a rubber septum, and taken out from a dry box to prepare a catalyst to be injected. The polymerization was carried out in a 600 ml metal alloy reactor equipped with a mechanical stirrer and capable of temperature control and used at high pressure.

0.5 g of triethylaluminum and 0.1 ml of ASA were charged into the reactor, and 0.24 kg of hexane was added thereto. The mixture was heated to 80 DEG C while stirring at 500 rpm.

The above supported catalyst prepared with hexane was added to the reactor, and the mixture was stirred at 100 rpm while maintaining the temperature at 80 ° C. The polymerization reaction was carried out for 1 hour while continuously feeding gaseous ethylene monomer at a pressure of 9 bar. The termination of the polymerization was completed by first stopping the stirring and then removing unreacted ethylene by removing it. The polymerization solvent was removed from the obtained polymer by filtration, and the polymer was dried in a vacuum oven at 80 캜 for 4 hours to prepare polyethylene.

2) Evaluation of physical properties of polyethylene

The properties of the polyethylene prepared in the above Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 1 below. At this time, each sample was dissolved in 1,2,4-Trichlorobenzene containing 0.0125% of BHT at 160 DEG C for 10 hours by using PL-SP260, and then PL-GPC220 (Mw / Mn) And measuring the number-average molecular weight and the weight-average molecular weight at a measurement temperature of 160 ° C.

Supported
Metallocene compound Of the metallocene compound (B)
Input method Catalytic activity
(kg-PE / g-catalyst) Mw MWD Example 1-1 A1 + B
(A1: B = 2: 1 molar ratio) As a preactivating solution
input 12.5 75,000 2.5 Examples 1-2 A1 + B
(A1: B = 2: 1 molar ratio) As a preactivating solution
input 14 92,000 3.5 Comparative Example 1 A1 + B
(A1: B = 2: 1 molar ratio) Dissolve in toluene 11.2 68,000 2.4 Example 2-1 A2 + B
(A2: B = 2: 1 molar ratio) As a preactivating solution
input 6.8 120,000 6.04 Example 2-2 A2 + B
(A2: B = 2: 1 molar ratio) As a preactivating solution
input 8.4 173,000 8.54 Comparative Example 2 A2 + B
(A2: B = 2: 1 molar ratio) Dissolve in toluene 5.4 94,000 4.3 Comparative Example 3 B As a preactivating solution
input 3.2 612,000 2.30 Comparative Example 4 B Dissolve in toluene 1.5 665,000 2.43 Comparative Example 5 B Put in suspension Fouling in polymerization - -

As shown in Table 1, Fig. 1 and Fig. 2, the molar ratio of the metallocene compound (B) to the mixed supported metallocene catalyst of Comparative Examples 1 and 2 in which the metallocene compound (B) It can be confirmed that the hybrid supported metallocene catalyst exhibits high activity and can be used to produce a polyolefin having a high molecular weight and a high molecular weight distribution value.

On the other hand, in the case of the single supported metallocene catalyst of Comparative Example 3 in which the metallocene compound (B) is introduced in the form of the preactivated solution, the activity of the catalyst is higher than that of the catalyst of Comparative Example 4 which is dissolved and dissolved in toluene, The molecular weight and the molecular weight distribution value of the polyolefin produced by the method of the present invention are lowered.

Claims (11)

1) carrying a cocatalyst on a carrier;
2) supporting the first metallocene compound on the support carrying the promoter; And
3) contacting the precatalyst and the preliminarily activated solution in which the first metallocene compound-carrying carrier and the second metallocene compound are dissolved in an alkylaluminoxane solution to form the co-catalyst and the first metallocene compound Supporting the second metallocene compound on the supported carrier,
Wherein the first metallocene compound is at least one compound selected from compounds represented by the following Chemical Formulas 1 to 3,
Wherein the second metallocene compound is at least one compound selected from the group consisting of compounds represented by the following general formula (4)
METHOD FOR PRODUCING HYDROGEN SUPPORTED METALLOCENE CATALYST:
[Chemical Formula 1]
(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹³ _-n
In Formula 1,
M ¹ is a Group 4 transition metal;
Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^a and R ^b are the same or different and each independently hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;
Z ¹ is a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene , Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;
n is 1 or 0;
(2)
(Cp ³ R ^c ) _m B ¹ (Cp ⁴ R ^d ) M ² Z ² _3-m
In Formula 2,
M ² is a Group 4 transition metal;
Cp < ³ > and Cp < ⁴ > are the same or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical , Which may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^c and R ^d are the same or different and each independently hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _1-20 silylalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;
Z ² represents a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene , Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;
B ¹ is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom containing radical which bridges the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or cross-links one Cp ⁴ R ^d ring to M ² Or a combination thereof;
m is 1 or 0;
(3)
(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂
In Formula 3,
M ³ is a Group 4 transition metal;
Cp < ⁵ > is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, which are substituted with hydrocarbons having 1 to 20 carbon atoms ;
R ^e is hydrogen, C _1-20 alkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl , C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl;
Z ³ is a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene , Substituted or unsubstituted amino, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;
B ² is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radical which cross-links the Cp ⁵ R ^e ring with J, or a combination thereof;
J is any one selected from the group consisting of NR ^f , O, PR ^f and S, R ^f is C _1-20 alkyl, aryl, substituted alkyl or substituted aryl,
[Chemical Formula 4]

In Formula 4,
A is selected from the group consisting of hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, C _7-20 arylalkyl, C _1-20 alkoxy, C _2-20 alkoxy Alkyl, C _3-20 heterocycloalkyl, or C _5-20 heteroaryl;
D is -O-, -S-, -N (R) - or -Si (R) (R ') - , in which R and R' are the same or different from each other, each independently hydrogen, halogen, C _{1 -20} alkyl, C _2-20 alkenyl, or C _6-20 aryl;
L is C _1-10 linear or branched alkylene;
B is carbon, silicon or germanium;
Q is hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl;
M is a Group 4 transition metal;
X ¹ and X ² are the same or different and are each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, nitro, amido, C _1-20 alkylsilyl, C _{1 -20} alkoxy, or C _1-20 sulfonate;
C ¹ And C ² are the same or different and each independently represents one of the following formulas (5a), (5b) or (5c);
[Chemical Formula 5a]

[Chemical Formula 5b]

[Chemical Formula 5c]

Wherein R ₁ to R ₁₇ and R ₁ 'to R ₉ ' are the same or different from each other and each independently represents hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 alkyl silyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 alkyl and aryl, wherein R _At least two adjacent to each other of R ₁₀ to R ₁₇ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.
The method according to claim 1,
Wherein the carrier is at least one selected from the group consisting of silica, silica-alumina and silica-magnesia,
Gt;
The method according to claim 1,
Wherein the cocatalyst is at least one selected from the group consisting of compounds represented by the following formulas (6) to (8)
Manufacturing method:
[Chemical Formula 6]
_{- [Al (R 21) -O} ] c -
In Formula 6,
Each R < ₂₁ > is independently halogen, _C1-20 alkyl or _C1-20 haloalkyl,
c is an integer of 2 or more,
(7)
D (R _{22) 3}
In Formula 7,
D is aluminum or boron,
R ₂₂ are each independently, a substituted C _1-20 hydrocarbyl hydrogen, halogen, C _1-20 hydrocarbyl or a halogen,
[Chemical Formula 8]
^{[LH] + [Q (E} ) 4] - or ^{[L] + [Q (E} ) 4] -
In Formula 8,
L is a neutral or cationic Lewis base,
[LH] ⁺ is Bronsted acid,
Q is Br ^{3 + 3 +} or Al,
Wherein each E is independently C _6-20 aryl or C _1-20 alkyl, wherein said C _6-20 aryl or C _1-20 alkyl is unsubstituted or substituted with one or more groups selected from halogen, C _1-20 alkyl, C _1-20 alkoxy and Lt; / RTI > is substituted by one or more substituents selected from the group consisting of phenoxy.
The method according to claim 1,
Wherein the alkylaluminoxane solution is one in which the alkylaluminoxane is dissolved in at least one solvent selected from the group consisting of toluene, xylene and isopropylbenzene.
Gt;
The method according to claim 1,
Wherein the concentration of the alkylaluminoxane in the alkylaluminoxane solution is 5 to 20 wt%
Gt;
The method according to claim 1,
Wherein the alkyl aluminoxane is at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, and isobutyl aluminoxane,
Gt;
The method according to claim 1,
The preactivating solution is prepared by dissolving the second metallocene compound in the alkylaluminoxane solution at a temperature of 10 to 40 DEG C for 1 to 12 hours.
Gt;
The method according to claim 1,
Wherein the concentration of the alkylaluminoxane in the preactivating solution is 5 to 20 wt% and the concentration of the second metallocene compound is 3 to 15 wt%
Gt;
The method according to claim 1,
The supported amount of the promoter is 7 to 10 mmol based on 1 g of the carrier,
Gt;
The method according to claim 1,
The first metallocene compound and the second metallocene compound are supported in a molar ratio of 1: 1 to 5: 1 based on 1 g of the support,
Gt;
11. A process for preparing olefinic monomers, comprising polymerizing olefinic monomers in the presence of a hybrid supported metallocene catalyst prepared according to any one of claims 1 to 10,
A method for producing a polyolefin.

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