KR102101878B1 - Supported hybrid catalyst system for propylene polymerization and method for preparing propylene polymer with the catalyst system - Google Patents

Abstract

The present invention relates to a hybrid supported catalyst system for producing a propylene polymer and a method for producing the propylene polymer using the same. The hybrid supported catalyst system according to the present invention enables the provision of a propylene polymer whose content of xylene solubles is controlled to be particularly suitable for a desired mechanical property while having excellent catalytic activity.

Description

Hybrid supported catalyst system for propylene polymerization and method for producing propylene polymer using the same {SUPPORTED HYBRID CATALYST SYSTEM FOR PROPYLENE POLYMERIZATION AND METHOD FOR PREPARING PROPYLENE POLYMER WITH THE CATALYST SYSTEM}

The present invention relates to a hybrid supported catalyst system for propylene polymerization and a method for producing a propylene polymer using the same.

Catalytic systems for olefin polymerization can be classified into Ziegler-Natta catalysts and metallocene catalysts, and these two catalysts have been developed to suit each feature.

Ziegler-Natta catalysts have been widely applied to existing commercial processes since being invented in the 1950s. However, since the Ziegler-Natta catalyst is a multi-activation catalyst having multiple active points, the molecular weight distribution of the polymer formed by using it is wide and the composition distribution of the comonomer is not uniform, thereby limiting the securing of desired physical properties. In particular, since the propylene polymer formed using a Ziegler-Natta catalyst has a high xylene soluble content (for example, more than 5% by weight), when using a Ziegler-Natta catalyst, a propylene polymer having a low melting point (Tm) is obtained. There are difficult limits.

The metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst composed mainly of aluminum, which is a homogeneous complex catalyst and is a single active point catalyst. Accordingly, the metallocene catalyst enables formation of a polymer having a folded 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, etc. of the polymer by changing the structure and polymerization conditions of the ligand.

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

In particular, in the polymerization of propylene, the ansa-metallocene catalyst has the advantage of forming a polymer having a low xylene soluble content (for example, less than 1% by weight), thereby producing a propylene polymer having a low melting point. However, the propylene polymer formed using the ansa-metallocene catalyst has a limit in that it is difficult to express mechanical properties such as heat sealing properties because the xylene soluble content is too low.

Since the propylene polymer having a content of xylene soluble or too low is formed in the conventional catalyst system, it is necessary to develop a method for obtaining a propylene polymer capable of exhibiting an appropriate level of melting point and mechanical properties. This is true.

The present invention is to provide a catalyst system that enables the provision of a propylene polymer whose xylene soluble content is controlled to match the desired mechanical properties.

In addition, the present invention is to provide a method for producing a propylene polymer using the catalyst system.

According to the invention,

A carrier and a metallocene compound supported on the carrier;

The metallocene compound may be one or more racemic metals selected from the group consisting of a mesotype metallocene compound represented by Formula 1, a compound represented by Formula 2a, and a compound represented by Formula 2b: A hybrid supported catalyst system for propylene polymerization is provided, comprising the locene compound in a molar ratio of 1: 0.5 to 1: 5:

[Formula 1]

[Formula 2a]

[Formula 2b]

In Chemical Formulas 1, 2a and 2b,

X ¹ and X ² are each independently halogen,

R ¹ and R ^{1 '} are each independently aryl having 6 to 20 carbons, substituted with alkyl having 1 to 20 carbons,

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, silylalkyl having 1 to 20 carbon atoms, alkoxysilyl having 1 to 20 carbon atoms, ether having 1 to 20 carbon atoms, silyl ether having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, 7 to 7 carbon atoms 20 alkylaryl, or aryl 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 carbons substituted with alkoxy having 1 to 20 carbons,

R ⁶ and R ^{6 '} are each independently alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons.

And, according to the present invention, there is provided a method for producing a propylene polymer, comprising the step of polymerizing an olefin monomer comprising propylene in the presence of the hybrid supported catalyst system.

Hereinafter, a method for oligomerization of an olefin to embodiments of the present invention will be described in more detail.

Prior to that, the terminology is only for referring to a specific embodiment, and is not intended to limit the present invention, unless expressly stated throughout this specification.

And, the singular forms used herein include plural forms unless the phrases express the opposite meaning. As used herein, the meaning of 'include' embodies a specific characteristic, region, integer, step, action, element, and / or component, and other specific characteristic, region, integer, step, action, element, component, and / or group. It does not exclude the existence or addition of.

And, in this specification, the term "racemic form" (racemic form) is the same substituent on the two cyclopentadienyl moieties zirconium (Zr) or hafnium (Hf) containing a plane and the center of the cyclopentadienyl portion It means the form on the other side.

And, in this specification, the term "meso form" (meso form) refers to a plane containing the same substituent on two cyclopentadienyl moieties of zirconium (Zr) or hafnium (Hf) and the center of the cyclopentadienyl moieties. It means the form on the same side.

I. Hybrid supported catalyst system for propylene polymerization

According to one embodiment of the invention,

A carrier and a metallocene compound supported on the carrier;

The metallocene compound may be one or more racemic metals selected from the group consisting of a mesotype metallocene compound represented by Formula 1, a compound represented by Formula 2a, and a compound represented by Formula 2b: A hybrid supported catalyst system for propylene polymerization is provided, comprising the locene compound in a molar ratio of 1: 0.5 to 1: 5:

[Formula 1]

[Formula 2a]

[Formula 2b]

In Chemical Formulas 1, 2a and 2b,

X ¹ and X ² are each independently halogen,

R ¹ and R ^{1 '} are each independently aryl having 6 to 20 carbons, substituted with alkyl having 1 to 20 carbons,

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, silylalkyl having 1 to 20 carbon atoms, alkoxysilyl having 1 to 20 carbon atoms, ether having 1 to 20 carbon atoms, silyl ether having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, 7 to 7 carbon atoms 20 alkylaryl, or aryl 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 carbons substituted with alkoxy having 1 to 20 carbons,

R ⁶ and R ^{6 '} are each independently alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons.

Propylene polymers can be classified into isotactic, syndiotactic or atactic according to their tacticity. Among them, the atactic propylene polymer has limited commercial use due to the limitation of physical properties due to disordered stereoregularity, while the isotactic propylene polymer has crystallinity and is widely used commercially.

This isotactic propylene polymer was made commercially available by Ziegler-Natta's study. However, the isotactic propylene polymer formed using a Ziegler-Natta catalyst is a xylene soluble component (i.e., contained in an isotactic polymer) when applied to a homopolypropylene of a high flow product or a random copolymer having a low melting point. Since the content of the atactic portion) usually exceeds 5% by weight, there are limitations that are difficult to commercially use.

Compared to such Ziegler-Natta catalysts, metallocene catalysts, particularly racemic ansa-metallocene catalysts, enable the formation of propylene polymers with a xylene solubles content of less than 1% by weight. However, propylene polymers having too low xylene solubles have limitations that are difficult to express mechanical properties such as heat sealing properties.

However, as a result of continuous research by the present inventors, when using a catalyst system in which a metallocene compound of racemic form and a metallocene compound of mesoform are applied in a specific molar ratio, the content of xylene solubles to meet the desired mechanical properties It has been found possible to provide this controlled propylene polymer.

In general, the metallocene compound in racemic form has been commercially favored by allowing the production of isotactic propylene polymer, whereas the mesotype metallocene compound is extremely limited or used because it forms atactic propylene polymer. come.

By the way, according to the research results of the present inventors, after separating and separating the compound of the meso form from the metallocene compound obtained by the mixture of the racemic form and the mesoform, the mesoform compound and the racemic form compound are separated. When applied to a catalyst system in a molar ratio of from 1: 0.5 to 1: 5, a propylene polymer having 1 to 5% by weight of xylene solubles can be provided, in particular the molar ratio of the compounds in the meso and racemic forms. According to the results, it was confirmed that the content of the xylene solubles can be easily controlled in the above range.

In particular, for the expression of the above-described effect, the catalyst system includes a metallocene compound of the meso form represented by Formula 1; One or more racemic metallocene compounds selected from the group consisting of the compound represented by Formula 2a and the compound represented by Formula 2b may be suitably used.

The compounds represented by Chemical Formulas 1, 2a and 2b have an ansa-metallocene structure including two indenyl groups as ligands.

In the compounds represented by Chemical Formulas 1, 2a and 2b, a functional group capable of serving as a Lewis base as an oxygen-donor is substituted in a bridge group connecting the ligands, thereby maximizing activity as a catalyst.

In addition, as the bulky groups (R ¹ and R ^{1 ′} ) substituted for the ligand impart steric hindrance, the formation of a meso-type metallocene compound can be basically suppressed in the synthesis of the catalyst.

In particular, according to an embodiment of the present invention, when the metallocene compound obtained as a mixture of racemic and mesoforms is subjected to selective recrystallization treatment under a solvent such as toluene, benzene, dichloromethane and a temperature of -20 ° C to room temperature, The meso-type metallocene compound can be selectively separated from the mixture. Accordingly, the molar ratio of the meso-type metallocene compound and the racemic-type metallocene compound applied to the catalyst system can be more precisely controlled, and through this, mechanical properties aiming at the xylene soluble component of the propylene polymer. It is easy to control and fit.

Furthermore, the compound represented by Chemical Formula 1 and Chemical Formula 2b can form a high molecular weight propylene polymer by including hafnium (Hf) as a metal atom. In addition, the compound represented by Chemical Formula 2a may exhibit high catalytic activity by including zirconium (Zr) as a metal atom. In addition, when the olefin-based polymer is prepared by increasing the content of the comonomer with a conventional catalyst, the melt flow index value is increased instead of the melting point of the polymer being reduced, which may cause difficulties in the manufacturing process. However, the catalyst system to which the compounds represented by Chemical Formulas 1, 2a, and 2b are applied as in the embodiment of the present invention enables formation of a propylene polymer having a low melt flow index and a low melt flow index.

Meanwhile, the hybrid supported catalyst system according to the embodiment of the present invention includes a carrier and a metallocene compound supported on the carrier.

As the carrier, the surface contains a hydroxy group, and preferably may be one having a highly reactive hydroxy group and a siloxane group, preferably dried to remove moisture on the surface. As a non-limiting example, the carrier may be silica dried at high temperature, silica-alumina, and silica-magnesia. And, 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 .

In addition, the hybrid supported catalyst system includes a meso-type metallocene compound and a racemic-type metallocene compound in a specific molar ratio.

According to an embodiment of the invention, the metallocene compound represented by Chemical Formula 1 may be preferably applied as the mesotype metallocene compound. Further, as the metallocene compound in the racemic form, one or more compounds selected from the group consisting of the compound represented by Chemical Formula 2a and the compound represented by Chemical Formula 2b may be preferably applied.

In particular, the metallocene compound in the meso form and the metallocene compound in the racemic form are 1: 0.5 to 1: 5, or 1: 0.5 to 1: 4.5, or 1: 0.55 to 1: 4, or 1: 0.6 to 1: 3.5, or 1: 0.6 to 1: 3 may be included in a molar ratio. That is, in order to provide a propylene polymer having xylene solubles of 1 to 5% by weight while providing optimum catalytic activity, the molar ratio of the meso and racemic metallocene compounds is adjusted within the above range. It is preferred.

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

And, in the formulas 1, 2a and 2b, R ¹ and R ^{1 ′} are each independently aryl having 6 to 20 carbons substituted with alkyl having 1 to 20 carbons; Preferably phenyl each substituted with tert-butyl; It may be more preferably 4-tert-butylphenyl.

In Formulas 1, 2a, and 2b, R ² , R ³ , R ⁴ , R ^{2 '} , R ^3' , and R ^{4 '} are each independently hydrogen, halogen, alkyl having 1 to 20 carbons, or 2 to 20 carbons Alkenyl of, alkylsilyl having 1 to 20 carbon atoms, silylalkyl having 1 to 20 carbon atoms, alkoxysilyl having 1 to 20 carbon atoms, ether having 1 to 20 carbon atoms, silyl ether having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, Aryl having 6 to 20 carbons, alkylaryl having 7 to 20 carbons, or arylalkyl having 7 to 20 carbons; Preferably, each may be hydrogen.

In Chemical Formulas 1, 2a and 2b, A is each independently carbon, silicon or germanium; Preferably, each may be silicon.

In Formulas 1, 2a and 2b, R ⁵ and R ^{5 '} are each independently alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons; Preferably 6-tert-butoxyhexyl.

In Formulas 1, 2a and 2b, R ⁶ and R ^{6 '} are each independently alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons; Preferably, each may be methyl.

According to an embodiment of the invention, a representative example of the metallocene compound in the meso form represented by Chemical Formula 1 is as follows:

And, a representative example of the racemic metallocene compound represented by Formula 2a is as follows:

.

.

And, a representative example of the racemic form of the metallocene compound represented by Formula 2b is as follows:

.

.

According to an embodiment of the invention, the metallocene compound in the hybrid supported catalyst system may be supported in a mass ratio of 1: 0.001 to 1: 1 with respect to the carrier. That is, when a carrier and a metallocene compound are included in the mass ratio, it exhibits appropriate catalytic activity, and can be advantageous in terms of maintaining catalytic activity and economic efficiency.

Meanwhile, the metallocene compound represented by Chemical Formulas 1 and 2b 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 and remove excess reactants.

Step 2 is a step of preparing a compound of Formula 1 and 2b 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 as a catalyst using alkyl lithium (eg, n-butyl lithium), and ether, hexane, and the like may be used as a solvent.

In Step 2, the compounds of Formulas 1 and 2b are obtained in the form of a mixture. In particular, according to an embodiment of the present invention, the mixture is a simple method for selectively recrystallizing under a temperature of -20 ° C to room temperature with a solvent such as toluene, benzene or dichloromethane, and the compound of the formula 1 in the form of meso It can be selectively separated.

Similar to the above manufacturing method, the metallocene compound represented by Chemical Formula 2a can 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 performed under a temperature of -200 to 0 ° C using a catalyst of alkyllithium (eg, n-butyllithium), 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 and remove excess reactants.

Step 2 'is a step of preparing a compound of Formula 2a and 2m 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 with a catalyst of alkyllithium (eg, n-butyllithium), and ether, hexane, etc. may be used as a solvent.

In step 2 ', the compounds of formulas 2a and 2m are obtained in the form of a mixture. According to an embodiment of the invention, the mixture is a simple method of selectively recrystallizing the mixture under a solvent such as toluene, benzene, and dichloromethane and a temperature of -20 ° C to room temperature. It can be selectively separated.

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

[Formula 3]

-[Al (R ³¹ ) -O] _c-

In Chemical Formula 3,

c is an integer of 2 or more,

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

[Formula 4]

D (R ⁴¹ ) ₃

In Chemical Formula 4,

D is aluminum or boron,

R ⁴¹ are each independently halogen, a C1-C20 hydrocarbyl or a C1-C20 hydrocarbyl substituted with halogen;

[Formula 5]

[LH] ⁺ [Q (E) ₄ ] ^-

In Chemical Formula 5,

L is a neutral Lewis base,

[LH] ⁺ is Bronsted acid,

Q is +3 type boron or aluminum in oxidation state,

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

Specifically, the compound represented by Chemical Formula 3 may be alkyl aluminoxane such as methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, and isobutyl aluminoxane. Further, as the compound of Formula 3, modified methylaluminoxane (MMAO), which is a compound in which a part of the methyl group of 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 straight or branched alkyl groups having 3 to 10 carbon atoms. Examples of the commercially available modified methylaluminoxane include MMAO-12, MMAO-3A and MMAO-7.

And, the compound represented by the formula (4) is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, dimethyl isobutyl aluminum, dimethyl ethyl aluminum, diethyl chloro aluminum, triiso Propyl aluminum, triisobutyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl 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 the formula (5) is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammoniumtetra (p-tolyl) Boron, tripropylammoniumtetra (p-tolyl) boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -Trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium tetrapentafluorophenyl boron, N, N-diethylanilinium tetraphenyl boron, N, N- Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtete Phenyl boron, 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, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (p-trifluoromethylphenyl) aluminum, trimethylammoniumtetra (p-trifluoromethylphenyl) aluminum , Tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapentaflo Low phenyl aluminum, diethyl ammonium tetrapentafluorophenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl alu It can be minium, triphenylcarbontetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenylcarboniumtetra (p-trifluoromethylphenyl) boron, triphenylcarboniumtetrapentafluorophenylboron, etc. have.

Preferably, the co-catalyst is trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethylaluminum sesquichloride ), Diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and one or more compounds selected from the group consisting of modified methylaluminoxane are preferably preferred. Can be applied.

And, the content of the co-catalyst can be determined in consideration of catalyst activity and the like. According to an embodiment of the invention, the co-catalyst 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 metallocene compound.

On the other hand, the hybrid supported catalyst system, the step of supporting a co-catalyst on a carrier; Supporting the metallocene compound of the meso form represented by Chemical Formula 1 on the carrier; And supporting a metallocene compound of at least one racemic form selected from the group consisting of the compound represented by Formula 2a and the compound represented by Formula 2b. However, the order of loading of the metallocene compound may be changed as necessary.

Hydrocarbon-based solvents such as pentane, hexane, and heptane are included in the preparation of the hybrid supported catalyst system; Alternatively, aromatic solvents such as benzene and toluene may be used.

II. Method for producing propylene polymer

Meanwhile, according to another embodiment of the present invention, there is provided a method for producing a propylene polymer, comprising the step of polymerizing an olefin monomer including propylene in the presence of the above-mentioned hybrid supported catalyst system.

The method for producing the propylene polymer may be performed by applying a conventional apparatus and contact technology as an raw material for an olefin monomer including propylene in the presence of the above-mentioned hybrid supported catalyst system.

As a non-limiting example, the method for producing the propylene polymer may be performed by homopolymerizing propylene using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor, or by copolymerizing propylene with a comonomer. 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 above manufacturing method, the hybrid supported catalyst system may be used dissolved or diluted in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, and chlorobenzene.

And, the production method of the propylene polymer 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 can be carried out under hydrogenation or non-addition conditions.

In particular, the molar ratio of the metallocene compound included in the hybrid supported catalyst system in the above production method may be adjusted to 1: 0.5 to 1: 5. Accordingly, in the propylene polymer prepared by the above method, the content of xylene solubles is 1 to 5% by weight, or 1 to 4% by weight, or or 1.3 to 4% by weight, or 1.3 to 3.5% by weight, Or 1.3 to 3% by weight.

As described above, the production method can be suitably applied to the production of a propylene polymer whose xylene soluble content is controlled to suit a desired mechanical property.

The hybrid supported catalyst system according to the present invention enables the provision of a propylene polymer whose content of xylene solubles is controlled to be particularly suitable for a desired mechanical property while having excellent catalytic activity.

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

Synthetic example  One

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)] Preparation of 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), followed by n-butyllithium solution (2.5 M, hexane Solvent, 4.8 L) was slowly added dropwise at -25 ° C, and then stirred at room temperature for 12 hours. Then, 10 g of CuCN was added with a small amount of toluene slurry, and after 30 minutes, (6-t-butoxyhexyl) dichloromethylsilane (1.86 kg) was slowly added dropwise to the mixed solution at 0 ° C. for 12 hours at room temperature. It was stirred. Then, water (14.2 L) was added to separate the organic layer, and then the organic material was separated again using a methyl tert-butyl ether (14.2 L) solvent, followed by distillation under reduced pressure [(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]

The [(6-t-butoxyhexyl) (methyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] silane obtained in step 1 above is toluene / Ether = 3/1 solution ( After dissolving in 12.4 kg / 4.78 L), n-butyllithium solution (2.5 M, hexane solvent, 4.8 L) was slowly added dropwise at -25 ° C, and then stirred at room temperature for 12 hours. Zirconium tetrachloride THF adduct (ZrCl ₄ · 2THF) was added dropwise to the reaction solution at -25 ° C and stirred at room temperature for 12 hours.

After vacuum drying, DCM (19.08 kg) was added and filtered under reduced pressure. The filtered solution was dried under reduced pressure to produce meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2- Methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride, and rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4- A mixture of tert-butylphenyl) indenyl)] zircorium dichloride was obtained (rac: meso = 1.5: 1).

; (rac)

(meso)

; (rac)

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).

[Step 3]

DCM (11 L) was added to the rac-, meso- mixture obtained in step 2 and completely dissolved at 40 ° C. After hexane (13.3 L) was added thereto, the mixture was stirred at 25 ° C. for 30 minutes, and then crystallized by standing at -20 ° C. for 48 hours. The supernatant was separated by decantation at -20 ° C and filtered using a filter. The filtered solid is rac rich (rac: meso = 23: 1). Then, the filtrate was dried under reduced pressure, and 20 L of toluene was added, followed by stirring for 6 hours at room temperature in a slurry state. Then, the slurry was filtered to selectively separate meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride. Did.

Synthetic 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 added to a 3 L Schlenk flask, and a toluene / THF (10: 1, 1.73 L) solution was added and dissolved at room temperature. . After the solution was cooled to -20 ° C, 240 mL of an n-butyl lithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and stirred at room temperature for 3 hours. Subsequently, 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. The reaction solution was heated to room temperature, stirred for 12 hours, and 500 mL of water was added. Thereafter, the organic layer was separated, and 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 in the form of 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]

The [(6-t-butoxyhexyl) (methyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] silane prepared before the 3 L Schlenk flask was added. It was added and 1 L of diethyl ether was added and dissolved at room temperature. After the solution was cooled to -20 ° C, 240 mL of an n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and stirred at room temperature for 3 hours. Thereafter, the reaction solution was cooled to -78 ° C, and then 92 g of hafnium chloride was added. After heating the reaction solution to room temperature, the mixture was stirred for 12 hours, and the solvent was removed under reduced pressure. After adding 1 L of dichloromethane, inorganic salts and the like that were not dissolved were filtered off. The filtrate was dried under reduced pressure, and 300 mL of dichloromethane was added again to precipitate crystals. The precipitated crystals were filtered and dried, and rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl) represented by the following formula: A mixture of hafnium dichloride and meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium dichloride was obtained. (80 g, rac: meso = 50: 1).

; (rac)

(meso)

; (rac)

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)

[Step 3]

The solvent was dried under reduced pressure in the filtrate excluding the product obtained in step 2, and 200 mL of toluene was added, stirred for 6 hours at room temperature in a slurry state, and filtered to filter meso-[(6-t-butoxyhexylmethylsilanediyl) ) -Bis (2-methyl-4- (4-t-butylphenyl) indenyl)] hafnium dichloride was selectively isolated.

Example  One

After 3 g of silica was previously weighed in a shrink flask, 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, meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl) obtained in Synthesis Example 2)] hafnium dichloride ( 30 micromolar, toluene solution) and rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium dichloride (75 Micromolar, toluene solution) was added and reacted at 75 ° C for 5 hours. After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

Subsequently, rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride obtained in Synthesis Example 1 ( 15 micromolar, toluene solution) and reacted at 75 ° C. for 2 hours. After the completion of the reaction and the precipitation was over, 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 dried under vacuum to obtain a hybrid supported catalyst in the form of solid particles (meso: rac = 1: 3).

Example  2

The content of the metallocene compound is 50 micromolar meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium Dichloride, 20 micromolar rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride, and 50 micromolar rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium dichloride , In the same manner as in Example 1, a hybrid supported catalyst (meso: rac = 1: 1.4) was obtained.

Example  3

The content of the metallocene compound is 69 micromolar meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium Dichloride, 20 micromolar rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride, and 31 micromolar rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium dichloride , In the same manner as in Example 1, a hybrid supported catalyst (meso: rac = 1: 0.74) was obtained.

Example  4

The content of the metallocene compound is 75 micromolar meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium Dichloride, 20 micromolar rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride, and Except for changing to 25 micromolar rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium dichloride , In the same manner as in Example 1, a hybrid supported catalyst (meso: rac = 1: 0.6) was obtained.

Comparative example  One

After 3 g of silica was previously weighed in a shrink flask, 52 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) obtained in Synthesis Example 1]] zirconium dichloride (270 micromolar, toluene solution) was added and reacted at 75 ° C for 5 hours. After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

To this, 216 micromol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added and reacted at 70 ° C for 5 hours. After the reaction was completed, the mixture was washed with toluene, washed again with hexane, and dried under vacuum to obtain a silica-supported metallocene catalyst in a solid particle state.

Comparative example  2

After 3 g of silica was previously weighed in a shrink flask, 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) obtained in Synthesis Example 2)] hafnium dichloride ( 270 micromolar, toluene solution) and reacted at 70 ° C. for 5 hours. After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

To this, 216 micromol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added and reacted at 70 ° C for 5 hours. After the reaction was completed, the mixture was washed with toluene, washed again with hexane, and dried under vacuum to obtain a silica-supported metallocene catalyst in a solid particle state.

Test example  One

After vacuum drying the 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. Thereafter, after stirring for 10 minutes, 45 mg of each catalyst prepared in Examples and Comparative Examples was dissolved in 20 mL of hexane TMA prescribed and introduced into the reactor under nitrogen pressure. Then, while raising the reactor temperature 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 the propylene polymer according to Test Example 1.

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

(2) 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, after heating the polymer to 220 ° C, the temperature was maintained for 5 minutes, the temperature was again increased to 20 ° C, and then the temperature was increased again.

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

Catalytic activity
(kg PP / g Cat. * hr) Polymer
Tm (℃) Polymer
XS (% by weight) Example 1 8.7 146.6 1.3 Example 2 8.6 145.1 2.2 Example 3 8.3 145.6 2.6 Example 4 7.7 143.3 2.7 Comparative Example 1 12.2 141.5 <1.0 Comparative Example 2 8.1 144.9 <1.0

 Referring to Table 1, Comparative Example 1 and Comparative Example 2, while the xylene solubles of the polymer were limited to less than 1% by weight, the examples were based on the molar ratio of the meso and racemic metallocene compounds used for polymerization. It was thus found that the xylene solubles of the polymer can be controlled in the range of 1.3 to 2.7% by weight.

Claims (9)

A carrier and a metallocene compound supported on the carrier;
The metallocene compound is a metallocene compound of the meso form represented by the following Chemical Formula 1, and a metallocene compound of the racemic form represented by the following Chemical Formula 2a and the following Chemical Formula 2b in a molar ratio of 1: 0.6 to 1: 3. A hybrid supported catalyst system for propylene polymerization, comprising:
[Formula 1]

[Formula 2a]

[Formula 2b]

In Chemical Formulas 1, 2a and 2b,
X ¹ and X ² are each independently halogen,
R ¹ and R ^{1 '} are each independently aryl having 6 to 20 carbons, substituted with alkyl having 1 to 20 carbons,
R ² , R ³ , R ⁴ , R ^{2 '} , R ^3' , and R ^{4 '} are each independently hydrogen, halogen, or alkyl having 1 to 20 carbon atoms,
A is each silicone,
R ⁵ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,
R ⁶ is alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons.
According to claim 1,
The R ¹ and R ^{1 ′} are 4-tert-butylphenyl, respectively, a hybrid supported catalyst system for propylene polymerization.
According to claim 1,
The R ² , R ³ , R ⁴ , R ^{2 '} , R ^3' , and R ^{4 '} are each hydrogen, a hybrid supported catalyst system for propylene polymerization.
delete According to claim 1,
Wherein R ⁵ is 6-tert-butoxyhexyl, and R ⁶ is methyl, a hybrid supported catalyst system for propylene polymerization.
According to claim 1,
The hybrid supported catalyst system further comprises at least one cocatalyst selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5, hybrid supported catalyst system for propylene polymerization:
[Formula 3]
-[Al (R ³¹ ) -O] _c-
In Chemical Formula 3,
c is an integer of 2 or more,
R ³¹ is each independently halogen, a hydrocarbyl having 1 to 20 carbons or a hydrocarbyl having 1 to 20 carbons substituted with halogen;
[Formula 4]
D (R ⁴¹ ) ₃
In Chemical Formula 4,
D is aluminum or boron,
R ⁴¹ are each independently halogen, a C1-C20 hydrocarbyl or a C1-C20 hydrocarbyl substituted with halogen;
[Formula 5]
[LH] ⁺ [Q (E) ₄ ] ^-
In Chemical Formula 5,
L is a neutral Lewis base,
[LH] ⁺ is Bronsted acid,
Q is +3 type boron or aluminum in oxidation state,
E each independently represents a halogen having 1 or more hydrogen atoms, a C1-C20 hydrocarbyl, an alkoxy or phenoxy functional group substituted or unsubstituted C6-C20 aryl, or C1-C20 alkyl.
The method of claim 6,
The cocatalysts are trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethylaluminum sesquichloride, diethyl aluminum Hybrid supported catalyst for propylene polymerization, at least one compound selected from the group consisting of diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane system.
A process for the production of a propylene polymer comprising polymerizing an olefin monomer comprising propylene in the presence of the hybrid supported catalyst system according to claim 1.
The method of claim 8,
The propylene polymer has 1 to 5% by weight of xylene solubles (xylene solubles), the production method of the propylene polymer.