KR102418590B1 - Method for preparing supported hybrid metallocene catalyst, and method for preparing polypropylene using supported hybrid metallocene catalyst - Google Patents

Abstract

The present invention relates to a method for preparing a hybrid supported metallocene catalyst, and to a method for preparing polypropylene using the hybrid supported metallocene catalyst. The method for preparing the hybrid supported metallocene catalyst according to the present invention increases the content of the meso isomer by heat-treating the catalyst composition in the presence of an aromatic hydrocarbon solvent. It is possible to provide polypropylene, which can be controlled, and has excellent catalytic activity, in particular, the content of xylene solubles being controlled to meet desired mechanical properties.

Description

Method for producing a hybrid supported metallocene catalyst, and a method for producing polypropylene using the hybrid supported metallocene catalyst

The present invention relates to a method for preparing a hybrid supported metallocene catalyst, and to a method for preparing polypropylene using the hybrid supported metallocene catalyst.

Catalysts for olefin polymerization can be classified into Ziegler-Natta catalysts and metallocene catalysts, and these two catalysts have been developed according to their characteristics.

Ziegler-Natta catalysts have been widely applied in conventional commercial processes since their invention in the 1950s. However, since the Ziegler-Natta catalyst is a multi-active site catalyst in which several active sites are mixed, the molecular weight distribution of the polymer formed using the Ziegler-Natta catalyst is wide and the composition distribution of the comonomer is not uniform, so there is a limit in securing desired physical properties. In particular, since polypropylene formed using the Ziegler-Natta catalyst has a high xylene soluble content (for example, more than 5% by weight), polypropylene having a low melting point (Tm) is obtained when using the Ziegler-Natta catalyst There are difficult limits.

The metallocene catalyst is composed of a combination of a main catalyst containing a transition metal compound as a main component and a cocatalyst containing aluminum as a main component, and this catalyst is a homogeneous complex catalyst and is a single site catalyst. Accordingly, the metallocene catalyst enables the formation of polypropylene having a small molecular weight distribution and a uniform composition distribution of comonomers. In addition, the metallocene catalyst has properties that can change the stereoregularity, copolymerization properties, molecular weight, crystallinity, and the like of polypropylene by changing the structure and polymerization conditions of the ligand.

Among them, the ansa-metallocene catalyst is an organometallic catalyst including two ligands connected to each other by a bridging group, and rotation of the ligand is prevented by the bridging group and the activity and structure of the metal center are determined.

In particular, in the polymerization of polypropylene, the ansa-metallocene catalyst forms a polymer having a low xylene soluble content (eg less than 1% by weight), which is advantageous for the production of polypropylene having a low melting point. However, polypropylene formed by using such an ansa-metallocene catalyst has a limit in that it is difficult to express mechanical properties such as heat sealing properties because the content of xylene solubles is too low.

As such, since polypropylene with too high or too low xylene soluble content is formed with the conventional catalyst system, it is necessary to develop a method for obtaining polypropylene capable of expressing an appropriate level of melting point and mechanical properties. do.

Therefore, in the prior art, a metallocene compound of a racemic body for producing an isotactic polymer having high crystallinity and melting point and high specific gravity and mechanical strength, and a meso isomer for producing an atactic polymer By using a catalyst in which a metallocene compound of

However, since the racemic body and the mirror-symmetric meso diastereomer are simultaneously prepared in the process of preparing the ansa-metallocene catalyst, in order to prepare the hybrid catalyst mixed in a predetermined ratio, the meso isomer and the racemic body are mixed It was essential to separate the metallocene compound of the meso isomer and the metallocene compound of the racemic form from the mixture, and then mix them again in a desired ratio.

However, in the above process, the mixture is dissolved in dichloromethane (DCM), crystallized, filtered to obtain a racemic metallocene compound, and the remaining filtrate is stirred under toluene and filtered to obtain a mesoisomeric metallocene compound, etc. , had to go through a complicated process.

Therefore, there is a need to develop a new method for preparing a catalyst that enables the provision of polypropylene in which the content of xylene solubles is controlled to match mechanical properties by a simpler method compared to the conventional method.

The present invention provides a hybrid supported metallocene catalyst capable of providing polypropylene with a controlled content of xylene solubles to match desired mechanical properties, a meso isomer of a metallocene catalyst and race It is intended to provide a method for controlling the content of the mixture.

Another object of the present invention is to provide a method for producing polypropylene using the hybrid supported metallocene catalyst.

According to the present invention,

Preparing a catalyst composition comprising the metallocene compound of Formula 1, the metallocene compound of Formula 2, or a mixture thereof;

heat-treating the catalyst composition in the presence of an aromatic hydrocarbon solvent at a temperature of 40 degrees Celsius or more for 2 hours or more to increase the content of the mesoisomer of Chemical Formula 1, Chemical Formula 2, or Chemical Formulas 1 and 2; and

There is provided a method for preparing a hybrid supported metallocene catalyst comprising the step of supporting the catalyst composition having an increased content of the meso isomer on a carrier:

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X ¹ and X ² are each independently halogen,

R ¹ and R ¹ ' are each independently an aryl having 6 to 20 carbon atoms substituted with an alkyl having 1 to 20 carbon atoms,

R ² , R ³ , R ⁴ , R ² ', R ³ ', and R ⁴ ' are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms. Silyl, C1-C20 silylalkyl, C1-C20 alkoxysilyl, C1-C20 ether, C1-C20 silylether, C1-C20 alkoxy, C6-C20 aryl, C7-C20 20 alkylaryl, or arylalkyl having 7 to 20 carbon atoms;

A is each independently carbon, silicon or germanium,

R ⁵ and R ⁵ ' are each independently alkyl having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms,

R ⁶ and R ⁶ ′ are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms.

And, according to the present invention, as a method for preparing the hybrid supported metallocene catalyst, when the catalyst composition is supported on a support, the metallocene compound of Formulas 1 and 2 is supported on the support. The hybrid supported metallocene catalyst is supported. A method of manufacturing is provided.

In addition, according to the present invention, there is provided a method for producing polypropylene, comprising the step of polymerizing a monomer containing propylene in the presence of the hybrid supported metallocene catalyst.

Throughout this specification, unless explicitly stated, terminology is for the purpose of referring to specific embodiments only, and is not intended to limit the present invention.

And, as used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite. As used herein, the meaning of 'comprising' specifies a particular characteristic, region, integer, step, operation, element and/or component, and other specific characteristic, region, integer, step, operation, element, component, and/or group. It does not exclude the existence or addition of

And, as used herein, the term "racemic form" refers to a plane in which the same substituents on two cyclopentadienyl moieties contain zirconium (Zr) or hafnium (Hf) and the center of the cyclopentadienyl moiety. It means the form on the opposite side.

And, as used herein, the term "meso isomer" is a stereoisomer of a racemic body, wherein the same substituent on two cyclopentadienyl moieties contains zirconium (Zr) or hafnium (Hf) and the cyclo It refers to the form coplanar with respect to the center of the pentadienyl moiety.

I. Preparation of Metallocene Catalyst for Polymerization of Propylene

According to one embodiment of the invention,

Preparing a catalyst composition comprising the metallocene compound of Formula 1, the metallocene compound of Formula 2, or the metallocene compound of Formula 1, the metallocene compound of Formula 2, or a mixture thereof ;

heat-treating the catalyst composition in the presence of an aromatic hydrocarbon solvent at a temperature of 40 degrees Celsius or more for 2 hours or more to increase the content of the mesoisomer of Chemical Formula 1, Chemical Formula 2, or Chemical Formulas 1 and 2; and

There is provided a method for preparing a hybrid supported metallocene catalyst comprising the step of supporting the catalyst composition having an increased content of the meso isomer on a carrier:

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X ¹ and X ² are each independently halogen,

R ¹ and R ¹ ' are each independently an aryl having 6 to 20 carbon atoms substituted with an alkyl having 1 to 20 carbon atoms,

R ² , R ³ , R ⁴ , R ² ', R ³ ', and R ⁴ ' are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms. Silyl, C1-C20 silylalkyl, C1-C20 alkoxysilyl, C1-C20 ether, C1-C20 silylether, C1-C20 alkoxy, C6-C20 aryl, C7-C20 20 alkylaryl, or arylalkyl having 7 to 20 carbon atoms;

A is each independently carbon, silicon or germanium,

R ⁵ and R ⁵ ' are each independently alkyl having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms,

R ⁶ and R ⁶ ′ are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms.

The metallocene compounds of Formulas 1 and 2 have an ansa-metallocene structure including two indenyl groups as ligands.

In the metallocene compounds of Formulas 1 and 2, a functional group capable of serving as a Lewis base as an oxygen-donor is substituted with a bridge group connecting the ligand, so that activity as a catalyst can be maximized.

In addition, the bulky groups (R ¹ and R ^{1 ′} ) substituted on the ligands impart steric hindrance, thereby basically inhibiting the formation of a mesoisomeric metallocene compound in the catalyst synthesis process.

However, as described above, the metallocene compound of the meso isomer forms atactic polypropylene, so unlike the existing use or avoidance, substantially, the metallocene compound of the meso isomer and the racemic form When a catalyst to which a metallocene compound is applied in a specific molar ratio is used, it is possible to provide polypropylene in which the content of xylene solubles is controlled to meet the desired mechanical properties. It is used as a catalyst.

Therefore, in order to satisfy the specific molar ratio of the mesoisomer and the racemic metallocene compound, the racemic metallocene compound and the mesoisomeric metallocene compound are separately purified and separated from the catalyst composition obtained from the mixture of materials. After mixing, it was necessary to mix again in the desired ratio.

On the other hand, according to the research results of the present inventors, a catalyst composition obtained from a mixture of a mesoisomeric metallocene compound and a racemic metallocene compound is heat-treated at a temperature of 40 degrees or more for 2 hours or more in the presence of an aromatic hydrocarbon solvent. case, it was confirmed that these ratios can be easily adjusted.

In this case, the catalyst composition includes a meso isomer and a racemic of the metallocene compound of Formula 1, includes a meso isomer and a racemic of the metallocene compound of Formula 2, or a meso isomer of the metallocene compound of Formula 1 And it may include both the racemic form, the meso isomer and the racemic form of the metallocene compound of Formula 2.

However, in the process of synthesizing the metallocene compound, since the racemic body and the meso isomer are simultaneously produced, the catalyst composition before heat treatment according to the present invention may be a mixture in which the mixing ratio of the meso isomer and the racemic body is not controlled, In the mixture, the molar ratio of the racemic body and the meso isomer is 50:1 or more, which is a very high rac-rich state.

Therefore, the content of the meso isomer can be increased by heat-treating the mixture in the presence of an aromatic hydrocarbon solvent to prepare a mixture having a desired content range.

The aromatic hydrocarbon solvent is not limited, and as an organic solvent that does not affect the reaction, a solvent such as toluene, benzene, or dichloromethane may be used, and specifically, toluene may be used.

In addition, the heat treatment is performed at 40 degrees or more for 2 hours or more, thereby controlling the ratio of the meso isomer and the racemic body in the catalyst composition.

In this regard, according to the research results of the present inventors, the metallocene compound of the meso isomer and the racemic body contains 1 to 5 wt. A polypropylene polymer having % xylene soluble content may be provided, and specifically, when the content of the meso isomer relative to the entire catalyst composition is 10 mol% to 35 mol%, more specifically 12 mol% to 25 mol% , since it is possible to provide polypropylene having a desired degree of xylene soluble content while exhibiting optimal catalytic activity, the content ratio of the metallocene compound of the meso isomer and the racemic body is adjusted to satisfy the above conditions desirable.

To this end, after the inventors of the present application have repeatedly studied in-depth, when the catalyst composition including the metallocene compound of Formula 1 or the metallocene compound of Formula 2 is heat-treated, the ratio of the meso isomer and the racemic body is controlled It was confirmed that the heat treatment temperature and time, and the ratio of the meso isomer and the racemic body are slightly different between the metallocene compound of Formula 1 and the metallocene compound of Formula 2, but a ratio that satisfies the content range of the meso isomer In order to obtain , a mixture of the desired ratio of the meso isomer and the racemic body was obtained when it was carried out at 40 degrees Celsius or higher for 2 hours or more, specifically at a temperature of 50 to 100 degrees Celsius, for 2 hours to 48 hours, More specifically, when carried out at a temperature of 50 degrees Celsius to 95 degrees Celsius, or 75 degrees Celsius to 95 degrees Celsius, for 4 hours to 24 hours, a mixture of the mesoisomer and the racemic body in the above content range was obtained.

In this case, the temperature and time may be selected in consideration of the mixing ratio of the meso isomer and the racemic body according to each purpose.

However, out of the above range, if the heat treatment is performed at less than 40 degrees Celsius, an increase in the desired degree of mesoisomer cannot be obtained, or an excessively long heat treatment time is required, which is not preferable.

According to the above preparation method, the molar ratio of the metallocene compound of the meso isomer and the metallocene compound of the racemic body applied to the catalyst can be more simply controlled, and through this, the xylene soluble content of the propylene polymer can be It can be easily controlled to suit the mechanical properties of the

On the other hand, the metallocene compound of Formula 1 may exhibit high catalytic activity by including zirconium (Zr) as a metal atom, and the metallocene compound of Formula 2 includes hafnium (Hf) as a metal atom, thereby having a high molecular weight poly propylene can be formed.

In particular, when polypropylene is prepared by increasing the comonomer content with a conventional catalyst, the melt flow index (MI) value increases instead of the melting point (Tm) of the polymer decreases, which may cause difficulties in the manufacturing process. However, when the compounds of Formulas 1 and 2 are applied together, it is possible to form polypropylene having a low melting point (Tm) and a small melt flow index (MI) value.

Accordingly, according to an embodiment of the present invention, in the supporting step of the method for preparing the hybrid supported metallocene catalyst, both the metallocene compounds of Chemical Formulas 1 and 2 may be supported on the carrier on the carrier.

That is, after increasing the content of the meso isomer of the metallocene compound of Formula 1, Formula 2, or Formula 1 and 2, the metallocene compound of Formula 1 and the metallocene compound of Formula 2 are supported together on a carrier. By preparing a supported hybrid catalyst, it can be used.

For example, after preparing a catalyst composition in which the content of the meso isomer of the metallocene compound of Formula 1 is increased, the metallocene compound of Formula 1 in which the meso isomer is increased is mixed with the metal of Formula 2 without such a process After preparing a catalyst composition in which the content of the meso isomer of the metallocene compound of Formula 2 is increased or supported on a carrier together with the placene compound, the metallocene compound of Formula 2 in which the meso isomer is increased, such a process A catalyst composition in which both the content of the meso isomer of the metallocene compound of Formulas 1 and 2 is increased, or supported on a carrier together with the untreated metallocene compound of Formula 1, may be directly supported on the carrier.

In other words, as the metallocene compound of Formula 1, a mixture of a meso isomer and a racemic body within the above range and a racemic compound of Formula 2 may be included together, or as the metallocene compound of Formula 2, a meso isomer and a racemic compound The mixture in which the mixture is mixed within the above range and the racemic compound of Formula 1 may be included together, or as the metallocene compound of Formula 1, the mixture in which the meso isomer and the racemic body are mixed within the above range and the metallocene compound of Formula 2 As such, a mixture in which the meso isomer and the racemic body are mixed within the above range may be included.

The carrier may have a hydroxyl group and a siloxane group having a high reactivity, which contains a hydroxyl group on the surface, and is specifically dried to remove moisture from the surface. As a non-limiting example, the carrier may be silica dried at high temperature, silica-alumina, silica-magnesia, or the like. In addition, the carrier may contain an oxide such as Na ₂ O, a carbonate such as K ₂ CO ₃ , a sulfate such as BaSO ₄ , and a nitrate component such as Mg(NO ₃ ) ₂ .

According to an embodiment of the present invention, in Formulas 1 and 2, X ¹ and X ² are each independently halogen; Specifically, each may be Cl.

And, in Formulas 1 and 2, R ¹ and R ^1′ are each independently an aryl having 6 to 20 carbon atoms substituted with an alkyl having 1 to 20 carbon atoms; Specifically, each may be phenyl substituted with tert-butyl; More specifically, it may be 4-tert-butylphenyl.

In Formulas 1 and 2, R ² , R ³ , R ⁴ , R ^2′ , R ^3′ , and R ^4′ are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, or al having 2 to 20 carbon atoms. Kenyl, C1-C20 alkylsilyl, C1-C20 silylalkyl, C1-C20 alkoxysilyl, C1-C20 ether, C1-C20 silylether, C1-C20 alkoxy, C6 aryl having to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; Specifically, each may be hydrogen.

In Formulas 1 and 2, A is each independently carbon, silicon, or germanium; Specifically, each may be silicon.

In Formulas 1 and 2, R ⁵ and R ^5' are each independently alkyl having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms; Specifically, it may be 6-tert-butoxyhexyl.

In Formulas 1 and 2, R ⁶ and R ^6' are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms; Specifically, each may be methyl.

According to an embodiment of the invention, representative examples of the metallocene compound of Formula 1 are as follows:

And, representative examples of the metallocene compound of Formula 2 are as follows:

.

.

Meanwhile, in the hybrid supported metallocene catalyst, the total content of the metallocene compounds of Formulas 1 and 2 may be supported in a mass ratio of 1: 0.001 to 1: 1 with respect to the support. That is, when the carrier and the metallocene compound are included in the above mass ratio, an appropriate catalytic activity may be exhibited, and it may be advantageous in terms of maintenance of catalytic activity and economic feasibility.

Meanwhile, the metallocene compound of Formula 1 may be prepared by the following method.

Step 1 is a step of preparing a compound of Formula 1-4 by reacting a compound of Formula 1-2 with a compound of Formula 1-3. The reaction of Step 1 may be performed under a temperature of -200 to 0° C. using alkyl lithium (eg, n-butyl lithium) as a catalyst, and toluene, THF, etc. may be used as a solvent. At this time, after separating the organic layer from the product, it is preferable to vacuum-dry the separated organic layer to remove excess reactants.

Step 2 is a step of preparing a compound of Formula 1 by reacting a compound of Formula 1-4 with a compound of Formula 1-5. The reaction of Step 2 may be performed under a temperature of -200 to 0°C using alkyl lithium (eg, n-butyllithium) as a catalyst, and ether, hexane, etc. may be used as a solvent.

In Step 2, the compound of Formula 1 is obtained in the form of a mixture of a meso isomer and a racemic body.

Similar to the above method, the metallocene compound represented by Chemical Formula 2 may be prepared by the following method.

Step 1' is a step of preparing a compound of Formula 2-4 by reacting a compound of Formula 2-2 with a compound of Formula 2-3. The reaction of Step 1' may be carried out under a temperature of -200 to 0°C using alkyl lithium (eg, n-butyllithium) as a catalyst, and toluene, THF, etc. may be used as a solvent. At this time, after separating the organic layer from the product, it is preferable to vacuum-dry the separated organic layer to remove excess reactants.

Step 2' is a step of preparing a compound of Formula 2 by reacting a compound of Formula 2-4 with a compound of Formula 2-5. The reaction of Step 2' may be carried out under a temperature of -200 to 0°C using alkyl lithium (eg, n-butyllithium) as a catalyst, and ether, hexane, etc. may be used as a solvent.

In Step 2', the compound of Formula 2 is obtained in the form of a mixture of a meso isomer and a racemic body.

Meanwhile, according to an embodiment of the invention, the hybrid supported metallocene catalyst may further include one or more cocatalysts selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5 in addition to the metallocene compound:

[Formula 3]

-[Al(R ³¹ )-O] _c -

In Formula 3,

c is an integer greater than or equal to 2,

each R ³¹ is independently halogen, hydrocarbyl having 1 to 20 carbon atoms, or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen;

[Formula 4]

D(R ⁴¹ ) ₃

In Formula 4,

D is aluminum or boron,

each R ⁴¹ is independently halogen, hydrocarbyl having 1 to 20 carbon atoms, or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen;

[Formula 5]

[LH] ⁺ [Q(E) ₄ ] ^-

In Formula 5,

L is a neutral Lewis base,

[LH] ⁺ is a Bronsted acid,

Q is boron or aluminum in the +3 formal oxidation state,

E is each independently an aryl having 6 to 20 carbon atoms, or alkyl having 1 to 20 carbon atoms in which one or more hydrogen atoms are unsubstituted or substituted with a halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy functional group.

Specifically, the compound represented by Chemical Formula 3 may be an alkylaluminoxane such as methylaluminoxane, ethylaluminoxane, butylaluminoxane, and isobutylaluminoxane. In addition, as the compound of Formula 3, modified methylaluminoxane (MMAO), which is a compound in which a part of the methyl group of the methylaluminoxane is substituted with another alkyl group, may be used. For example, the modified methylaluminoxane may be a compound in which 40 mol% or less, or 5 mol% to 35 mol% of the methyl groups of the methylaluminoxane are substituted with a straight-chain or branched alkyl group having 3 to 10 carbon atoms. Examples of the modified methylaluminoxane that are commercially available include MMAO-12, MMAO-3A and MMAO-7.

And, the compound represented by Formula 4 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethylchloroaluminum, triiso Propyl aluminum, triisobutyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p- tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like.

In addition, the compound represented by Formula 5 is triethylammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p-tolyl) Boron, tripropylammonium tetra(p-tolyl) boron, triethylammonium tetra(o,p-dimethylphenyl) boron, trimethylammonium tetra(o,p-dimethylphenyl) boron, tributylammonium tetra(p -Trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenyl boron, N,N- Diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron , triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium tetra (p -Tolyl) aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tri Butylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenyl Aluminum, diethylammonium tetrapentafluorophenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, triphenyl carbonium tetraphenyl boron, triphenyl carbonium tetraphenyl aluminum, triphenyl carbon umtetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetrapentafluorophenylboron, and the like.

Specifically, as the promoter, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethylaluminum sesquichloride ), diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and at least one compound selected from the group consisting of modified methylaluminoxane is preferably selected from the group consisting of can be applied.

And, the content of the co-catalyst may be determined in consideration of catalytic activity and the like. According to an embodiment of the present invention, the cocatalyst may be included in a molar ratio of 1: 1 to 1: 10000, or 1: 1 to 1: 5000, or 1: 1 to 1: 3000 with respect to the total amount of the metallocene compound. .

On the other hand, in this case, the hybrid supported metallocene catalyst includes, after the step of increasing the meso isomer content, supporting the cocatalyst on a carrier, and supporting the metallocene compound of Formulas 1 and 2 on the carrier. can be manufactured.

Hydrocarbon solvents such as pentane, hexane, and heptane; Alternatively, an aromatic solvent such as benzene or toluene may be used.

II. Method for producing polypropylene

On the other hand, according to another embodiment of the invention, there is provided a method for producing polypropylene, comprising the step of polymerizing a monomer containing propylene in the presence of the above-described hybrid supported metallocene catalyst.

The method for preparing the polypropylene may be carried out by applying a conventional apparatus and contacting technique using a monomer containing propylene as a raw material in the presence of the above-described hybrid supported metallocene catalyst.

As a non-limiting example, the method for preparing polypropylene may be carried out by using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor to homopolymerize propylene or random polymerization to copolymerize propylene and a comonomer. have. The comonomer includes ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1 -tetradecene, 1-hexadecene, 1-aitocene, etc. can be used.

In the preparation method, the hybrid supported metallocene catalyst may be used dissolved or diluted in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like.

And, the method for producing the polypropylene is carried out for 1 to 24 hours or 1 to 10 hours under a temperature of 20 to 500 ° C or 20 to 200 ° C, and a pressure of 1 to 100 kgf / cm 2 or 1 to 70 kgf / cm 2 can be

If necessary, the polymerization may be carried out under hydrogenation or non-hydrogenation conditions.

In particular, in the preparation method, the metallocene compound of the meso isomer included in the hybrid supported metallocene catalyst may be adjusted to 5 mol% to 40 mol% based on the total metallocene compound included. Accordingly, the content of xylene solubles in the propylene polymer prepared by the above method may be in the range of 1 to 5% by weight, or 1 to 4% by weight, or 1.3 to 3.9% by weight.

As such, the manufacturing method may be suitably applied to the production of polypropylene in which the content of xylene solubles is controlled to meet the desired mechanical properties.

The method for preparing the hybrid supported metallocene catalyst according to the present invention is a simpler method, and while having excellent catalytic activity, the content of xylene solubles is particularly controlled to meet the desired mechanical properties. It is possible to provide a hybrid supported metallocene catalyst that makes this possible.

1 is a graph showing the content of meso isomers according to heat treatment of a mixture prepared in Synthesis Example 1 of Test Example 1;
2 is a graph showing the content of the meso isomer according to the heat treatment of the mixture prepared in Synthesis Example 2 of Test Example 1.

Hereinafter, preferred embodiments are presented to help the understanding of the invention. However, the following examples are only for illustrating the invention, and do not limit the invention thereto.

Synthesis Example 1

rac-[(6-t-Butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride, and meso-[(6-t- Preparation of butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride

[Step 1]

2-methyl-4-tert-butylphenylindene (3000 g, 11.4 mol) was dissolved in toluene/THF=5/1 solution (10.3 kg/2.12 kg), and then n-butyllithium solution (2.5 M, hexanes) solvent, 4.8 L) was slowly added dropwise at -25°C, followed by stirring at room temperature for 12 hours. After that, 10 g of CuCN was added to a small amount of toluene slurry, and 30 minutes later, (6-t-butoxyhexyl)dichloromethylsilane (1.86 kg) was slowly added dropwise to the mixed solution at 0° C., at room temperature for 12 hours. stirred. Then, water (14.2 L) was added to separate the organic layer, and the organic material was separated again using a methyl tertbutyl ether (14.2 L) solvent, and then distilled under reduced pressure to [(6-t-butoxyhexyl) (methyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]silane was obtained.

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): -0.20-0.03 (3H, m), 1.26 (9H, s), 0.50-1.20 (4H, m), 1.20-1.31 (11H, m), 1.40 -1.62 (20H, m), 2.19-2.23 (6H, m), 3.30-3.34 (2H, m), 3.73-3.83 (2H, m), 6.89-6.91 (2H, m), 7.19-7.61 (14H, m)

[Step 2]

[(6-t-butoxyhexyl)(methyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]silane obtained in step 1 above was dissolved in toluene/THF=5/1 solution ( 95 mL), n-butyllithium solution (2.5 M, hexane solvent, 22 g) was slowly added dropwise at -78°C, followed by stirring at room temperature for one day. Bis(N,N'-diphenyl-1,3-propanediamido)dichlorozirconium bis(tetrahydrofuran) [Zr(C ₅ H ₆ NCH ₂ CH ₂ NC ₅ H ₆ )Cl ₂ (C ₄ H ₈ O) ₂ ] was dissolved in toluene (229 mL), and then slowly added dropwise at -78°C and stirred at room temperature for one day.

After the reaction solution was cooled to -78°C, HCl ether solution (1 M, 183 mL) was slowly added dropwise, and stirred at 0°C for 1 hour. After filtration and vacuum drying, hexane was added and stirred to precipitate crystals.

The precipitated crystals were filtered and dried under reduced pressure, and rac-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride and meso-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride (rac-rich) was obtained. (20.5 g, rac: meso ≥ 50: 1)

rac ^-1 H NMR (500 MHz, CDCl ₃ , 7.26 ppm): 1.20 (9H, s), 1.27 (3H, s), 1.34 (18H, s), 1.20-1.90 (10H, m), 2.25 (3H, s), 2.26 (3H, s), 3.38 (2H, t), 7.00 (2H, s), 7.09-7.13 (2H, m), 7.38 (2H, d), 7.45 (4H, d), 7.58 (4H) , d), 7.59 (2H, d), 7.65 (2H, d); meso ^-1 H NMR (500 MHz, CDCl ₃ , 7.26 ppm): 1.20 (9H, s), 1.33 (18H, s), 1.49 (3H, s), 140-1.85 (10H, m), 2.45 (3H, s), 3.37 (2H, t), 6.87 (2H, s), 6.86-6.89 (2H, m), 7.12 (2H, d), 7.42 (4H, d), 7.49 (4H, d), 7.66 (2H) , d).

Synthesis Example 2

rac-[(6-t-Butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]hafnium dichloride, and meso-[(6-t- Preparation of butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]hafnium dichloride

[Step 1]

150 g of 2-methyl-4-(4-t-butylphenyl)-indene was placed in a 3 L Schlenk flask, and a toluene/THF (10:1, 1.73 L) solution was added thereto and dissolved at room temperature. . After cooling the solution to -20°C, 240 mL of n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and stirred at room temperature for 3 hours.

Then, the reaction solution was cooled to -20°C, and then 82 g of (6-t-butoxyhexyl)dichloromethylsilane and 512 mg of CuCN were slowly added dropwise. After raising the temperature of the reaction solution to room temperature, the mixture was stirred for 12 hours, and 500 mL of water was added. After that, the organic layer was separated, dehydrated with MgSO ₄ and filtered. The filtrate was distilled under reduced pressure to obtain [(6-t-butoxyhexyl)(methyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]silane as a yellow oil.

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): -0.09 - -0.05 (3H, m), 0.40-0.60 (2H, m), 0.80-1.51 (26H, m), 2.12-2.36 (6H, m) ), 3.20-3.28 (2H, m), 3.67-3.76 (2H, m), 6.81-6.83 (2H, m), 7.10-7.51 (14H, m)

[Step 2]

[(6-t-butoxyhexyl)(methyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]silane prepared above in a 3 L Schlenk flask was Then, 1 L of diethyl ether was added and dissolved at room temperature. After the solution was cooled to -20°C, 240 mL of n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and stirred at room temperature for 3 hours.

After that, the reaction solution was cooled to -78°C, and then 92 g of hafnium chloride was added thereto. The reaction solution was heated to room temperature, stirred for 12 hours, and the solvent was removed under reduced pressure. 1 L of dichloromethane was added, and then undissolved inorganic salts were removed by filtration.

The filtrate was dried under reduced pressure, and 300 mL of dichloromethane was added thereto to precipitate crystals. The precipitated crystals were filtered and dried to obtain rac-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]hafnium dichloride; and meso-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]hafnium dichloride (rac-rich) was obtained. (80 g, rac: meso ≥ 50: 1).

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): 1.19-1.78 (37H, m), 2.33 (3H, s), 2.34 (3H, s), 3.37 (2H, t), 6.91 (2H, s) , 7.05-7.71 (14H, m)

Test Example 1

While the mixtures obtained in Synthesis Examples 1 and 2 were heat-treated at 50 degrees Celsius, 75 degrees and 95 degrees Celsius, the content of meso isomers over time was measured, and the results are shown in FIGS. 1 and 2 , respectively.

1 and 2 , it can be confirmed that a mixture of a desired composition ratio can be obtained by controlling the heat treatment temperature and time as the content of the mesoisomer increases as the heat treatment is performed in the above temperature range.

Example 1

The rac-rich mixture obtained in Synthesis Example 1 was heat-treated at 95 degrees Celsius for 4 hours to rac-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert) -Butylphenyl)indenyl)]zirconium dichloride, and meso-[(6-t-Butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)] A mixture in which the composition ratio (molar ratio) of zirconium dichloride was adjusted was obtained (rac: meso = 3: 1).

Example 2

The rac-rich mixture obtained in Synthesis Example 1 was heat-treated at 75 degrees Celsius for 4 hours to rac-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert) -Butylphenyl)indenyl)]zirconium dichloride, and meso-[(6-t-Butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)] A mixture in which the composition ratio (molar ratio) of zirconium dichloride was adjusted was obtained (rac: meso = 5: 1).

Example 3

The rac-rich mixture obtained in Synthesis Example 2 was heat-treated at 75 degrees Celsius for 8 hours to rac-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert) -Butylphenyl)indenyl)]hafnium dichloride, and meso-[(6-t-Butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)] A mixture in which the composition ratio (molar ratio) of hafnium dichloride was adjusted was obtained (rac: meso = 5.5: 1).

Example 4

The rac-rich mixture obtained in Synthesis Example 2 was heat-treated at 95 degrees Celsius for 12 hours to rac-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert) -Butylphenyl)indenyl)]hafnium dichloride, and meso-[(6-t-Butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)] A mixture in which the composition ratio (molar ratio) of hafnium dichloride was adjusted was obtained (rac: meso = 4 : 1).

Example 5

After weighing 3 g of silica in a shrink flask in advance, 39 mmol of methylaluminoxane (MAO) was added and reacted at 90° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene.

Here, rac-rich [(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]hafnium dichloride obtained in Synthesis Example 2 (75 micromolar, toluene solution) was added and reacted at 75° C. for 5 hours. When the precipitation was completed after the reaction was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

Then, rac-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride obtained in Example 1 above, and A mixture with a controlled composition ratio of meso-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride (45 micromolar , toluene solution) and reacted at 75° C. for 2 hours. When the precipitation was completed after the reaction was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

The reaction product was washed again with hexane and vacuum dried to obtain a supported hybrid catalyst in the form of solid particles. (rac: meso = 1: 0.1)

Example 6

After weighing 3 g of silica in a shrink flask in advance, 39 mmol of methylaluminoxane (MAO) was added and reacted at 90° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene.

Here, rac-rich [(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]hafnium dichloride obtained in Synthesis Example 2 (75 micromolar, toluene solution) was added and reacted at 75° C. for 5 hours. When the precipitation was completed after the reaction was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

Then, rac-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride obtained in Example 2, and A mixture with a controlled composition ratio of meso-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride (30 micromolar , toluene solution) and reacted at 75° C. for 2 hours. When the precipitation was completed after the reaction was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

The reaction product was washed again with hexane and vacuum dried to obtain a supported hybrid catalyst in the form of solid particles. (rac: meso = 1: 0.05)

Example 7

After weighing 3 g of silica in a shrink flask in advance, 39 mmol of methylaluminoxane (MAO) was added and reacted at 90° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene.

Here, rac-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]hafnium dichloride obtained in Example 3, and meso-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]hafnium dichloride in a controlled composition ratio (100 micrometers) mole, toluene solution) was added, and reacted at 75° C. for 5 hours. When the precipitation was completed after the reaction was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

Then, rac-rich [(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride ( 20 micromolar, toluene solution) was added and reacted at 75° C. for 2 hours. When the precipitation was completed after the reaction was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

The reaction product was washed again with hexane and vacuum dried to obtain a supported hybrid catalyst in the form of solid particles. ( rac: meso = 1: 0.14)

Example 8

After weighing 3 g of silica in a shrink flask in advance, 39 mmol of methylaluminoxane (MAO) was added and reacted at 90° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene.

Here, rac-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]hafnium dichloride obtained in Example 4, and meso-[(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]hafnium dichloride in a controlled composition ratio (100 micrometers) mole, toluene solution) was added, and reacted at 75° C. for 5 hours. When the precipitation was completed after the reaction was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

Then, rac-rich [(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride ( 20 micromolar, toluene solution) was added and reacted at 75° C. for 2 hours. When the precipitation was completed after the reaction was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

The reaction product was washed again with hexane and vacuum dried to obtain a supported hybrid catalyst in the form of solid particles. ( rac : meso = 1: 0.2)

Examples 9 to 12

After vacuum drying a 2 L stainless reactor at 65° C., 3.0 mmol of triethylaluminum, 2 bar of hydrogen, and 770 g of propylene were sequentially added at room temperature. After stirring for 10 minutes, 45 mg of each catalyst prepared in Examples 6 to 10 was dissolved in 20 mL of TMA hexane and added to the reactor under nitrogen pressure. Thereafter, the temperature of the reactor was raised to 70° C., and polymerization was performed for 1 hour to obtain a propylene homopolymer.

Examples 13 to 16

After vacuum drying a 2 L stainless reactor at 65° C., 3.0 mmol of triethylaluminum, 2 bar of hydrogen, and 770 g of propylene were sequentially added at room temperature. After stirring for 10 minutes, 45 mg of each catalyst prepared in Examples 6 to 10 was dissolved in 20 mL of TMA hexane and added to the reactor under nitrogen pressure. Thereafter, while raising the temperature of the reactor to 70° C., polymerization was performed for 1 hour while injecting 12000 cc of ethylene to obtain a propylene random polymer.

Test Example 2

The following physical properties were measured in the preparation of polypropylene according to Examples 9 to 16, and the results are shown in Table 1 below.

(1) Catalyst activity: It was calculated as the ratio of the weight (kg) of the polymer produced per the catalyst content (mmol and g of catalyst) used based on the unit time (h).

(2) Melt index (MFR, 2.16 kg): Measured temperature 230℃, ASTM 1238

(3) Melting point (Tm) of the polymer: The melting point of the polymer was measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 220 °C and maintained at that temperature for 5 minutes, then lowered to 20 °C, and then the temperature was increased again.

(4) Polymer crystallization temperature (Tc): Using DSC, the crystallization temperature was set as the crystallization temperature from the curve appearing while decreasing the temperature under the same conditions as the melting point.

(5) Xylene soluble content (XS) of polymer: Xylene was added to the sample, heated at 135° C. for 1 hour, and cooled for 30 minutes to pre-treat. After measuring a sample pretreated at a flow rate of 1 ml/min in OminiSec (FIPA equipment of Viscotek), the Refractive index peak area was calculated.

catalyst Category 1) activation
(kg PP/g Cat.hr) MFR
(g/10 min) Tm
(℃) Tc
(℃) XS
(weight%) Example 9 H 9.8 4.5 153.8 99.2 3.0 Example 10 H 9.7 15.1 153.0 99.2 1.6 Example 11 H 7.8 10.0 152.1 99.9 1.0 Example 12 H 6.9 13.6 151.8 100.8 1.5 Example 13 R 11.0 6.8 145.5 93.6 3.9 Example 14 R 12.0 7.4 146.1 89.1 1.8 Example 15 R 8.6 5.6 145.1 90.0 1.3 Example 16 R 7.7 7.3 143.3 89.7 2.6

1) H: homo polymerization, R: random polymerization

Referring to Table 1, even when a hybrid supported metallocene catalyst in which the mixing ratio of the meso isomer and the racemic is controlled is used by the preparation method according to the present invention, the molar ratio of the meso isomer and the racemic form of the metallocene compound Accordingly, it was confirmed that the xylene-soluble content of polypropylene can be controlled in the range of 1.0 to 3.9 wt%.

Claims (9)

Preparing a catalyst composition comprising the metallocene compound of Formula 1, the metallocene compound of Formula 2, or a mixture thereof;
heat-treating the catalyst composition in the presence of an aromatic hydrocarbon solvent at a temperature of 40 degrees Celsius or more for 2 hours or more to increase the content of the mesoisomer of Chemical Formula 1, Chemical Formula 2, or Chemical Formulas 1 and 2; and
Method for producing a hybrid supported metallocene catalyst comprising the step of supporting the catalyst composition having an increased content of the meso isomer on a carrier:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
X ¹ and X ² are each independently halogen,
R ¹ and R ¹ ' are each independently an aryl having 6 to 20 carbon atoms substituted with an alkyl having 1 to 20 carbon atoms,
R ² , R ³ , R ⁴ , R ² ', R ³ ', and R ⁴ ' are each independently hydrogen, halogen, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkyl having 1 to 20 carbons Silyl, C1-C20 silylalkyl, C1-C20 alkoxysilyl, C1-C20 ether, C1-C20 silylether, C1-C20 alkoxy, C6-C20 aryl, C7-C20 20 alkylaryl, or arylalkyl having 7 to 20 carbon atoms;
A is each independently carbon, silicon or germanium,
Zr is zirconium,
Hf is hafnium,
R ⁵ is each independently an alkyl having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms,
R ⁶ is each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms.
The method of claim 1,
The catalyst composition includes a meso isomer and a racemic of the metallocene compound of Formula 1, includes a meso isomer and a racemic of the metallocene compound of Formula 2, or includes a meso isomer and a racemic of the metallocene compound of Formula 1 A method for preparing a hybrid supported metallocene catalyst comprising both a mixture and a meso isomer and a racemic form of the metallocene compound of Formula 2.
The method of claim 1,
The method for producing a hybrid supported metallocene catalyst wherein the aromatic hydrocarbon solvent is toluene.
The method of claim 1,
The heat treatment, in consideration of the mixing ratio, at a temperature of 50 to 100 degrees Celsius, a method for producing a hybrid supported metallocene catalyst is performed for 2 hours to 48 hours.
5. The method of claim 4,
The heat treatment is, in consideration of the mixing ratio, at a temperature of 50 to 95 degrees Celsius, a method for producing a hybrid supported metallocene catalyst is performed for 4 hours to 24 hours.
The method of claim 1,
A method for producing a hybrid supported metallocene catalyst for increasing the content of the meso isomer to 5 mol% to 40 mol% relative to the total catalyst composition.
The method of claim 1,
The method for producing a hybrid supported metallocene catalyst in which all of the metallocene compounds of Formulas 1 and 2 are supported on the support.
A method for producing polypropylene comprising the step of polymerizing a monomer comprising propylene in the presence of the hybrid supported metallocene catalyst prepared according to claim 1 .
9. The method of claim 8,
The polypropylene has 1 to 5% by weight of xylene solubles (xylene solubles), the method for producing polypropylene.

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