KR20190070724A - Method for preparing homopolypropylene - Google Patents

Abstract

The present invention relates to a method for preparing homo polypropylene, capable of suppressing an amorphous shape and an increase in fine particles, which comprises the steps of: preparing a catalyst composition; and mixing the catalyst composition with a propylene monomer to rise the temperature up to 60 to 85°C, and perform polymerization thereon.

Description

[0001] METHOD FOR PREPARING HOMOPOLYPROPYLENE [0002]

The present invention relates to a process for producing homopolypropylene which can inhibit an amorphous shape and an increase in fine particles due to hot spot formation through initial polymerization heat control.

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

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

In order to improve productivity in the production of polypropylene using such a metallocene catalyst, improvement of morphology should be given priority. If the morphology is not improved, the generation of fine particles in the process increases, resulting in fouling or lowering of process stability.

Accordingly, it is an object of the present invention to provide a method for producing polypropylene capable of suppressing an amorphous shape and an increase in an amount of fine particles due to hot spot formation through initial polymerization heat control.

According to an embodiment of the present invention,

Preparing a catalyst composition comprising a compound of Formula 1 and a metallocene compound of Formula 2; And

Mixing the catalyst composition with a propylene monomer in the presence of hydrogen gas in a temperature range of 15 to 40 占 폚 and polymerizing the mixture at 60 to 85 占 폚 for 8 to 15 minutes,

Wherein the compound of Formula 1 is contained in an amount of 0.5 to 2.5 equivalents.

[Chemical Formula 1]

[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-

In Formula 1,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a Group 13 element;

Q may be the same or different from each other and each independently represents an alkyl group having from 6 to 20 carbon atoms or an alkyl group having from 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with halogen, a hydrocarbon having 1 to 20 carbon atoms, ,

(2)

In Formula 2,

M is a Group 4 transition metal,

X ₁ and X ₂ are each independently halogen,

R ₁ and R ₅ are each independently C _6-20 aryl substituted with C _1-20 alkyl,

R ₂ to R _4, and R ₆ to R ₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 alkyl silyl, C _{1- 20} alkoxysilyl group, a C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

A is carbon, silicon or germanium,

R ₉ is C _1-20 alkyl substituted by C _1-20 alkoxy,

R ₁₀ is hydrogen, C _1-20 alkyl or C _2-20 alkenyl.

According to another embodiment of the present invention, there is provided a process for preparing a polymer having a bulk density in a polymer of 0.4 g / mL or more and a particle size of less than 75 탆 of 4 wt% or less, Homopolypropylene is provided.

The method for preparing homopolypropylene according to the present invention can improve the morphology of the produced homopolypropylene and reduce the generation of fine particles by obtaining the effect of the prepolymerization through the initial polymerization heat control during the polymerization reaction.

Fig. 1 is a graph showing changes in temperature during the production of homopolypropylene according to Examples 1 to 3 and Comparative Example 1. Fig.
2 to 6 are photographs of the homopolypropylene prepared in Examples 1 and 3 and Comparative Examples 1, 2 and 5, respectively, by scanning electron microscopy.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises", "comprising", or "having" are used to designate the presence of stated features, steps, components, or combinations thereof, and are not intended to preclude the presence of one or more other features, Components, or combinations thereof, as a matter of convenience, without departing from the spirit and scope of the invention.

The invention is capable of various modifications and may take various forms, which illustrate specific embodiments and are described in detail below. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, homopolypropylene according to a specific embodiment of the present invention, a method of manufacturing the homopolypropylene, and the like will be described.

Boron or aluminum-based compounds containing a bronsted acid ion are generally used as co-catalysts in the polymerization of polyolefins and are known to stabilize the catalytic compounds to maintain polymerization activity. In the present invention, it is found out that the boron or aluminum compound influences the initial polymerization heat during the polymerization reaction and maximizes the initial polymerization heat control effect in the polymerization reaction system by using the boron or aluminum compound, so that the effect of the prepolymerization, It was possible to prevent the occurrence of amorphous shape of the powder due to the formation of hot spots in propylene, thereby improving the morphology and reducing the generation of fine particles. Further, by using the boron or aluminum compound together with the metallocene compound of the following formula (2) having a tether, the bulk density in the produced homopolypropylene can be increased and the SPAN can be reduced.

Specifically, a method for producing homopolypropylene according to an embodiment of the present invention includes:

Preparing a catalyst composition comprising a compound of Formula 1 and a metallocene compound of Formula 2 (Step 1); And

Mixing the propylene monomer with the propylene monomer in the presence of hydrogen gas in a temperature range of from 15 to 40 占 폚 and then raising the temperature to 60 to 85 占 폚 for 8 to 15 minutes to carry out a polymerization reaction (Step 2)

The compound of Formula 1 is included in the catalyst composition in an amount of 0.5 to 2.5 equivalents:

[Chemical Formula 1]

[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-

In Formula 1,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a Group 13 element;

Q may be the same or different from each other and each independently represents an alkyl group having from 6 to 20 carbon atoms or an alkyl group having from 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with halogen, a hydrocarbon having 1 to 20 carbon atoms, ,

(2)

In Formula 2,

M is a Group 4 transition metal,

X ₁ and X ₂ are each independently halogen,

R ₁ and R ₅ are each independently C _6-20 aryl substituted with C _1-20 alkyl,

R ₂ to R ₄ and R ₆ to R ₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl group, a C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

A is carbon, silicon or germanium,

R ₉ is C _1-20 alkyl substituted by C _1-20 alkoxy,

R ₁₀ is hydrogen, C _1-20 alkyl or C _2-20 alkenyl.

Each step will be described in detail below.

(Step 1)

In the method for producing homopolypropylene according to an embodiment of the present invention, Step 1 is a step of preparing a catalyst composition comprising the compound of Formula 1 and the metallocene compound of Formula 2.

In the above catalyst composition, the compound of the formula (1) stabilizes the metallocene compound of the formula (2) and also lowers the initial polymerization heat by decreasing the catalyst heat generation in the polymerization reaction system during the polymerization reaction of the propylene monomer.

Specifically, the polymerization reaction of the propylene monomer can be carried out at 60 to 85 캜, more specifically at 65 to 75 캜, in which an elevated temperature treatment is carried out for the polymerization system comprising the catalyst composition and the propylene monomer. At this time, the longer the time to reach the polymerization reaction temperature becomes, the more the effect of the prepolymerization can be obtained while the temperature is increased. The time of arrival to the polymerization reaction temperature can be controlled by the initial polymerization heat in the polymerization reaction system and the initial polymerization heat in the polymerization reaction system can be controlled by the temperature at the time of introduction of the catalyst composition and the content of the compound of formula 1 in the catalyst composition Lt; / RTI >

Accordingly, in the method for preparing homopolypropylene according to an embodiment of the present invention, the catalyst composition contains 0.5 to 2.5 equivalents of the compound of the formula (1). When the content of the compound of the formula (1) is less than 0.5 equivalent, the effect of controlling the initial polymerization heat by the use of the compound of the formula (1) is insignificant. When the content of the compound exceeds 2.5 equivalents, the loading efficiency of the compound of the formula The polymerization heat control becomes difficult. As a result, the time to reach the polymerization temperature is short and it is difficult to obtain a sufficient prepolymerization effect, The morphology of homopolypropylene to be produced may be deteriorated. More specifically, the compound of Formula 1 may be contained in the catalyst composition in an amount of 0.8 to 2 equivalents, more specifically 0.8 to 1.5 equivalents.

Specifically, in Formula 1, Z may be B or Al.

Specific examples of the compound of Formula 1 include dimethylanilinium tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, methyl anilinium tetrakis (pentafluorodiphenyl) borate, tri Tetramethylammonium tetraphenylboron, trimethylammonium tetraphenylboron, trimethylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p- Dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, trimethylammoniumtetra (p -trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetra (P-tolyl) trimethylammonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, Aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra -Trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapentafluorophenyl aluminum, diethyl Ammonium tetraphenyltetra-phenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropyl phosphonium tetraphenyl aluminum, (P-tolyl) boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, triphenylcarboniumtetra Boron, triphenylcarbonium tetrapentafluorophenylboron and the like, and any one or a mixture of two or more of them may be used. Among them, such compounds as dimethylanilinium tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, or methyl anilinium tetrakis (pentafluorodiphenyl) borate and the like One or more anilinium borate compounds may preferably be used.

Meanwhile, the metallocene compound of Formula 2 used in the catalyst composition together with the compound of Formula 1 is an anhydrometallocene compound including two ligands connected to each other by a bridge group, The rotation of the ligand is prevented, and the activity and structure of the metal center are determined. The metallocene compound of the above formula (2) exhibits excellent activity by containing an indenyl group as a ligand, and polypropylene having improved stereoregularity can be produced.

The following terms in the above formula (2) can be defined as follows unless otherwise specified.

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

The C _1-20 alkyl group may be a straight chain, branched chain or cyclic alkyl group. Specifically, the C _1-20 alkyl group is a C _1-15 straight-chain alkyl group; A C _1-10 straight chain alkyl group; A C _1-5 straight chain alkyl group; A C _3-20 branched or cyclic alkyl group; C _3-15 branched or cyclic alkyl; Or a C _3-10 branched or cyclic alkyl group. More specifically, the C1-20 alkyl group may be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert- - pentyl group or cyclohexyl group and the like.

The C _2-20 alkenyl group may be a straight chain, branched chain or cyclic alkenyl group. Specifically, C _2-20 alkenyl groups are C _2-20 straight-chain alkenyl group, C _2-10 linear alkenyl, C _2-5 straight-chain alkenyl group, C _3-20 branched chain alkenyl, C _3-15 branched chain alkenyl A C _3-10 branched alkenyl group, a C _5-20 cyclic alkenyl group, or a C _5-10 cyclic alkenyl group. More specifically, may be a C _{2- 20} alkenyl group is ethenyl group, propenyl group, butenyl group, pentenyl group or cyclohexenyl group.

C _6-30 aryl can mean monocyclic, bicyclic or tricyclic aromatic hydrocarbons. Specifically, C _6-30 aryl may be phenyl, naphthyl or anthracenyl.

C _7-30 alkylaryl may mean a substituent wherein at least one hydrogen of the aryl is substituted by alkyl. Specifically, the C _7-30 alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl or cyclohexylphenyl.

C _7-30 arylalkyl may mean a substituent wherein at least one of the hydrogens of the alkyl is substituted by aryl. Specifically, the C _7-30 arylalkyl may be a benzyl group, phenylpropyl or phenylhexyl.

Specifically, the metallocene compound of Formula 2 includes hafnium (Hf) or zirconium (Zr) as a central metal.

In the metallocene compound of Formula 2, substituents other than hydrogen are introduced at positions 2 and 4 of the indenyl ligand. In the indenyl group, the 2-position is substituted with the methyl group, the 4-position (R ₁ and R ₅ ) are each substituted with a bulky group such as an alkyl-substituted phenyl group to thereby inhibit formation of a meso form by imparting a steric hindrance, and may have an anis-metallocene structure. More specifically, R ₁ and R ₅ in Formula 2 may each independently be C _6-12 aryl substituted with C _1-10 alkyl, more specifically C _3-6 branched such as tert-butylphenyl Or a phenyl group substituted with an alkyl group. The substitution position of the alkyl group with respect to the phenyl group may be a 4-position corresponding to the R ₁ or R ₅ position and the para position bonded to the indenyl group.

In the above formula (2), R ₂ to R ₄ , and R ₆ to R ₈ each independently may be hydrogen, and X ₁ and X ₂ each independently may be chloro.

The metallocene compound of Formula 2 is substituted with a functional group capable of acting as a Lewis base as an oxygen-donor in a bridge group connecting the ligand, thereby maximizing the activity as a catalyst.

Further, in a structure having no tether like a conventional metallocene compound, since the metallocene compound is supported on the carrier material, leaching of the catalyst precursor tends to occur. Further, when the compound of Formula 1 is further supported on the carrier on which the metallocene compound is supported, the compound of Formula 2 is leached together with the catalyst precursor, and the effect equivalent to that of not supporting the compound of Formula 1, And the effect of the prepolymerization is lowered. Further, there is a problem that fouling occurs or the morphology of the produced polymer is lowered due to the reaction of the leached catalyst precursor with the compound of formula (1). However, since the metallocene compound of Formula 2 in the present invention contains a tether group, the metallocene compound of Formula 2 is supported by a chemical reaction with the co-catalyst supported on the carrier, There is no occurrence of leaching and subsequent fouling, and excellent catalytic activity can be exhibited.

Specifically, in Formula 2, A may be silicon, and R _{9, which} is a substituent of A, is C _4-20 alkyl substituted with C _1-10 alkoxy, more specifically C _3-6 C _4-10 alkyl substituted with a branched chain alkoxy group, and still more specifically tert-butoxyhexyl. R _{10, which} is another substituent of A above, may be a C _1-10 alkyl group, more specifically a C _1-4 straight chain alkyl group, more particularly methyl.

More specifically, typical examples of the metallocene compound represented by the above-mentioned formula (2) are as follows:

The metallocene compound of formula (2) can be synthesized by applying known reactions, and a more detailed synthesis method can be referred to the following production examples.

The metallocene compound of formula (2) may be used in the catalyst composition itself, but may be used in a form supported on the carrier together with the compound of formula (1) since it exhibits high polymerization activity even when supported on a carrier.

As the carrier, a carrier containing a hydroxy group on its surface can be used, and preferably, a carrier having a hydroxyl group and a siloxane group having high reactivity and dried on the surface and having moisture removed can be used. Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components. In the case of being supported on a carrier such as silica, there is no catalyst released during the propylene polymerization process because the silica carrier and the functional group of the metallocene compound of the formula (2) are chemically bonded and carried so that the catalyst is free from slurry or gas phase polymerization There is no fouling on the walls of the reactor or polymer particles. In addition, when impregnated on a silica carrier, the shape and morphology of the polypropylene particles produced can be further improved.

In addition, the catalyst composition may further include an alkylaluminoxane-based cocatalyst in addition to the compound of Formula 1, the metallocene compound of Formula 2, and the carrier in order to enhance the high catalytic activity and process stability. The cocatalyst may also be contained on a carrier.

The alkylaluminoxane co-catalyst includes a metal element capable of serving as a Lewis acid capable of forming a bond through a Lewis acid-base interaction with a functional group introduced into a bridge group of the metallocene compound of Formula 2 .

Specifically, the alkylaluminoxane-based co-catalyst may include at least one compound represented by the following formula (3)

(3)

- [Al (R ₁₁ ) -O] _m -

In Formula 3,

R ₁₁ may be the same or different from each other, and each independently halogen; C _1-20 hydrocarbons; Or a C _1-20 hydrocarbon substituted with halogen;

m is an integer of 2 or more.

Examples of the compound represented by the general formula (3) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and any one or a mixture of two or more thereof may be used, Can be preferably used.

For example, when the catalyst composition has the form of the metallocene compound of Formula 2 and the compound of Formula 1 and the supported catalyst in which the cocatalyst is supported on the carrier, there is a step of supporting the cocatalyst on the carrier, Supporting the metallocene compound of Formula 2 on the support, and supporting the compound of Formula 1 on the support carrying the co-catalyst and the metallocene compound of Formula 2 The supporting sequence of the cocatalyst, the compound of formula (1) and the metallocene compound of formula (2) may be changed as needed, such as improvement of catalytic activity.

In the supported catalyst type catalyst composition, the metallocene compound of Formula 2 may be present in an amount of from about 10 to about 240 micromoles, more specifically from about 20 to about 160 micromoles, based on 1 g of silica, Can be carried in the content range. When the carrier and the metallocene compound of the formula (2) are contained in the above content range, they exhibit appropriate supported catalyst activity, which may be advantageous in terms of maintaining the activity of the catalyst and economical efficiency.

In the case of further including a cocatalyst, the alkylaluminoxane-based cocatalyst may be supported in an amount of 1 to 25 mmol, more specifically 3 to 15 mmol, per 1 wt. .

The compound of formula (1) may be used in the equivalent range as described above.

The catalyst composition may be used in a subsequent polymerization reaction in the state of being dissolved or diluted in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, etc., By treating with a small amount of alkylaluminum or the like, a small amount of water or air which can adversely affect the catalyst can be removed in advance.

(Step 2)

Next, Step 2 of the process for producing homopolypropylene according to an embodiment of the present invention is a step of mixing the catalyst composition prepared in Step 1 with propylene monomer in the presence of hydrogen gas, and then raising the temperature to effect polymerization.

In the step 2, the mixing process of the catalyst composition prepared in the step 1 and the propylene monomer is carried out in the usual manner except that the addition of the catalyst composition is carried out at a temperature in the range of 15 to 40 DEG C, . ≪ / RTI >

The feeding temperature of the catalyst composition influences the initial polymerization heat control in the polymerization reaction system. If the addition temperature is less than 15 ° C, the time to reach the polymerization reaction temperature and the polymerization process become longer, . When the addition temperature of the catalyst composition exceeds 40 캜, the time to reach the polymerization temperature is short and it is difficult to obtain a sufficient prepolymerization effect. In consideration of maximizing the effect of the prepolymerization according to the temperature control during the introduction of the catalyst composition, the catalyst composition may be added at 20 to 30 캜, more specifically.

Further, the mixing process of the catalyst composition and the propylene monomer may be carried out in the presence of hydrogen gas.

The hydrogen gas activates the inactive sites in the metallocene compound of formula (2) and controls the molecular weight by causing a chain transfer reaction. Since the metallocene compound of Formula 2 of the present invention has excellent hydrogen reactivity, the molecular weight distribution and the melt index of the homopolypropylene finally produced through the control of the amount of hydrogen gas used during polymerization can be easily controlled to a desired level . Specifically, the hydrogen gas may be supplied at a pressure of from 1 to 40 bar, more specifically from 1 to 10 bar, for the easy production of homopolypropylene satisfying the physical properties or morphological characteristics according to the present invention. When the hydrogen gas feed rate is controlled within such a range, the molecular weight of the homopolypropylene to be produced can be reduced and the melt index can be increased while exhibiting sufficient catalytic activity.

After the catalyst composition and the propylene monomer are mixed in the same manner as described above, the temperature in the polymerization reaction system is raised to a polymerization reaction temperature of 60 to 85 ° C, more specifically, to 65 to 75 ° C.

The temperature rise can be performed according to a conventional method such as heating.

However, in the present invention, the effect of the prepolymerization can be realized during the temperature rise by controlling the temperature rise time at the temperature rise. In detail, when the temperature rise time becomes long, the preliminary polymerization effect can be realized, and as a result, the morphology can be improved. In the present invention, the temperature rise time can be increased by reducing the catalyst heat generation by using the compound of formula (2), and the hot spot formation can be suppressed and the morphology can be improved due to the effect of the prepolymerization. Specifically, in the present invention, the temperature elevation can be performed for 8 to 15 minutes. If the heating time is less than 8 minutes, the hot spot is too hot to control the hot spot. Also, when the temperature is raised at the same heating rate, even if the amount of AB supported is increased, the supporting efficiency is lowered and can not exceed 15 minutes. More specifically, the temperature elevating process may be performed for 10 to 15 minutes.

The heating process for raising the temperature may be carried out at a temperature raising rate of 2 to 8 占 폚 / min, more specifically, 5 占 폚 / min under the conditions of satisfying the content condition and the raising time period of the compound of formula (2). When the polymerization is carried out at the above-mentioned heating rate, the effect of the prepolymerization can be maximized.

The polymerization reaction after the elevated temperature can be carried out by a solution polymerization process, a slurry process or a gas phase process using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor and the like.

The polymerization may be carried out at 60 to 85 ° C. When the polymerization temperature is lower than 60 ° C, sufficient polymerization reaction does not occur. If it exceeds 85 ° C, side reactions may occur and the morphology may deteriorate due to catalyst decomposition or damage due to high temperature. More specifically, the polymerization reaction may be carried out at a temperature of 70 to 80 캜.

The polymerization reaction may be carried out at a pressure of 1 to 100 kgf / cm ² for 1 to 24 hours, more specifically for 1 to 5 hours.

Through the polymerization process as described above, the homopolymerization takes place in the polymerization reaction system to form a powdered homopolypropylene.

According to the production method of the present invention, the effect of the prepolymerization can be realized through the initial polymerization heat control, and the produced homopolypropylene powder can suppress the occurrence of an amorphous shape due to hot spot formation, .

Accordingly, according to another embodiment of the present invention, there is provided homopolypropylene which is produced by the above production method and exhibits excellent morphology.

Specifically, the bulk density of the homopolypropylene has a high bulk density of 0.35 g / mL or more, more specifically 0.39 to 0.45 g / mL. Thus, the morphology improvement effect can be shown.

In the present invention, the bulk density (BD (g / mL)) is obtained by measuring the weight (A) of a flask having a volume of 100 mL, filling the homopolypropylene up to a scale of 100 mL into a flask filled with homopolypropylene The weight (B) can be measured and calculated according to the following equation:

[Equation 1]

Bulk density (g / mL) = (B - A) / 100

In the above formula (1), A represents the weight of the flask before homopolypropylene is filled, and B represents the weight of the flask filled with homopolypropylene.

Further, the homopolypropylene has a particle size distribution (PSD) of 900 to 1300 탆, more specifically 1000 to 1200 탆, and can exhibit excellent mechanical properties.

In addition, the homopolypropylene has a fine powder content of less than 75 占 퐉 of 4% by weight or less, and the generation of fine powder is small, and fouling caused by fine powder and the process instability caused thereby can be prevented. Can be reduced.

In addition, the homopropylene has a SPAN of less than 1, more specifically 0.5 to 0.9, which can increase the homogeneity of the homopropylene powder with a low SPAN.

In the present invention, the PSD of the homopropylene, the SPAN value, and the content of the fine powder having a particle diameter of less than 75 mu m can be measured by using an optical diffraction particle size analyzer. In the case of SPAN, Can be:

&Quot; (2) "

SPAN = {D [v, 0.9] - D [v, 0.1]} / D [

D [v, 0.9] denotes the diameter at a volume fraction of 0.1 and D [v, 0.9] and D [v, 0.5] denote diameters at volume fractions of 0.9 and 0.5, respectively it means.

The homopolypropylene has a melt index (MI) of 15 g / 10 min or more, more specifically 16 to 50 g / 10 min measured at 230 ° C under a load of 2.16 kg in accordance with ASTM D 1238, And has a melt index (MI), which can exhibit excellent processability.

Such homopolypropylene has excellent morphology and therefore can be used in various fields such as a packaging container, a film, a sheet, an injection molded article, and a fiber product.

Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Manufacturing example  1: Preparation of catalyst composition

Step 1) Synthesis of (6-t- Butoxyhexyl ) ( methyl ) - Bis (2- methyl -4- (4-t- Butylphenyl ) Indeny )) Silane  Produce

150 g of 2-methyl-4- (4-t-butylphenyl) indene was added to a 3 L Schlenk flask and dissolved in toluene / THF (10: 1, 1.73 L) at room temperature . After cooling the solution to -20 캜, 240 mL of n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise, and the mixture was stirred at room temperature for 3 hours. Thereafter, the reaction solution was cooled to -20 캜, and then 82 g of (6-t-butoxyhexyl) dichloromethylsilane and 512 mg of CuCN were slowly added dropwise. The reaction solution was warmed to room temperature, stirred for 12 hours, and 500 mL of water was added. Thereafter, the organic layer was separated, dehydrated with MgSO4 and filtered. The filtrate was distilled under reduced pressure to obtain a yellow oil.

M), 0.40 - 0.60 (2H, m), 0.80 - 1.51 (26H, m), 2.12 - 2.36 (6H, m) (2H, m), 3.67-3.76 (2H, m), 6.81-6.83 (2H, m), 7.10-7.51 (14H, m)

Step 2) rac - [(6-t- Butoxyhexylmethylsilandiyl ) - Bis (2- methyl -4- (4-t- Butylphenyl ) Indenyl)] hafnium dichloride (2a)

(6-t-butoxyhexyl) (methyl) bis (2-methyl-4- (4-t-butylphenyl)) indenylsilane prepared previously in a 3 L Schlenk flask, 1 L of ethyl ether was added and dissolved at room temperature. After the solution was cooled to -20 ° C, 240 mL of a n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and the mixture was stirred at room temperature for 3 hours. Thereafter, the reaction solution was cooled to -78 deg. C, and then 92 g of hafnium chloride was added thereto. The reaction solution was warmed to room temperature, stirred for 12 hours, and the solvent was removed under reduced pressure. 1 L of dichloromethane was added, and then the insoluble inorganic salts and the like were removed by filtration. The filtrate was dried under reduced pressure, and again 300 mL of dichloromethane was added to precipitate crystals. The precipitated crystals were filtered and dried to obtain rac - [(6-t-butoxyhexylmethylsilanediyl) -bis (2-methyl- 4- (4- t- butylphenyl) indenyl)] hafnium dichloride) 2a) (rac: meso = 50: 1).

(3H, s), 3.37 (2H, t), 6.91 (2H, s), 7.05 (2H, - < / RTI > 7.71 (14H, m)

Step 3) Preparation of Supported Catalyst

3 g of silica SP2410 was preliminarily weighed into a shrinkage flask, and 13 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C. for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. 70 [mu] mol of the compound (2a) prepared in the above step 2 was dissolved in toluene and reacted at 75 DEG C for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. 105 mol (1.5 eq.) Of dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) was reacted at 75 DEG C for 5 hours. After completion of the reaction, the reaction mixture was washed with toluene, washed again with hexane, and vacuum-dried to obtain 5 g of silica-supported metallocene catalyst in the form of solid particles.

Production Examples 2 to 5: Preparation of Catalyst Composition

A silica-supported catalyst was obtained in the same manner as in Preparation Example 1, except that the compound of Formula 2 in Preparation Example 1 was used in the AB equivalent amount shown in Table 1 below.

Production Example 6: Preparation of Catalyst Composition

Step 1) Catalyst Synthesis

After the ligand prepared in Step 1 of Preparation Example 1 was dissolved in a toluene / THF = 5/1 solution (95 mL), a n-butyllithium solution (2.5 M, hexane solvent, 22 g) The mixture was stirred at room temperature for one day. To the reaction solution of bis (N, N'- diphenyl-1,3-propane dia shown) dichloro zirconium 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), then slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for one day. After the reaction solution was cooled to -78 ° C, a HCl ether solution (1 M, 183 mL) was slowly added dropwise thereto, followed by stirring 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 to obtain [(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl- 4- (4- t- butylphenyl) indenyl)] zirconium dichloride (2b) (20.5 g, 61% total).

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 , 2.26 (3H, s), 3.38 (2H, t), 7.00 (2H, s), 7.09-7.13 ), 7.59 (2H, d), 7.65 (2H, d)

Step 2) Preparation of supported catalyst

3 g of silica SP2410 was preliminarily weighed in a shrinking flask, and 13 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. 70 [mu] mol of the compound (2b) prepared in the above Step 1 was dissolved in toluene and reacted at 75 DEG C for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. 105 mol (1.5 eq.) Of dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) was reacted at 75 DEG C for 5 hours. After completion of the reaction, the reaction mixture was washed with toluene, washed again with hexane, and vacuum-dried to obtain 5 g of silica-supported metallocene catalyst in the form of solid particles.

Manufacturing example  7: Preparation of catalyst composition

Step 1) Ligand Synthesis

2-Me-4-t-BuPh-indene were added to the reactor and dried under reduced pressure for 30 minutes. 50 g of Tolune and 5.2 g of THF were charged and completely dissolved by stirring. After cooling the reactor to -25 ° C, n-BuLi (2.5 M, 2.77 g) was slowly added dropwise with stirring. After stirring at 25 ^° C for 12 h, CuCN (18.0 mg) was added to a small amount of toluene slurry, and after 30 minutes, 1.6 g of dimethyldichlorosilane was added successively. After stirring at room temperature for 12 hours, water was added and further stirred. After the reactor was allowed to stand, the aqueous layer was separated, and the separated aqueous layer and toluene were re-introduced into the reactor, stirred and allowed to stand for 5 minutes, and the aqueous layer was separated and removed. After dehydrating the organic layer with MgSO ₄ and, filter and fed to the reactor again to give a ligand and dried (white, solid powder).

Step 2) Catalyst Synthesis

Toluene (13.7 g) and Et ₂ O (5.6 g) were poured into the ligand prepared in Step 1 and stirred. After cooling to -25 ° C, n-BuLi (2.5 M, 5.55 g) was slowly added dropwise and stirred. After stirring at 25 ° C for 12 hours and cooling to -20 ° C, ZrCl ₄ (2.22 g) was dissolved in toluene (6.9 g) and added. After stirring at 25 DEG C for 12 hours, all of the solvent was dried. After the filter was dried using DCM, it was recrystallized using DCM. As a result, a catalyst compound (i) of the following structure was obtained (yellow powder (only racemic), yield = 20%).

Step 3) Preparation of Supported Catalyst

3 g of silica SP2410 was preliminarily weighed into a shrinkage flask, and 13 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C. for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. After dissolving 70 탆 ol of the compound (i) prepared in the above step 2 in toluene, the reaction was carried out at 75 캜 for 5 hours. After the completion of the reaction, the upper layer solution was removed, and the remaining reaction product was washed with toluene, washed again with hexane, and vacuum dried to obtain 5 g of silica-supported metallocene catalyst in the form of solid particles.

Manufacturing example  8 and 9: Preparation of catalyst composition

A silica-supported catalyst was obtained in the same manner as in Production Example 6 except that Step 3 of Preparation Example 6 was conducted in the following manner.

Step 3) Preparation of Supported Catalyst

3 g of silica SP2410 was preliminarily weighed into a shrinking flask, and 13 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. 70 [mu] mol of the compound (2b) prepared in the step 2 was dissolved in toluene, and the mixture was reacted at 75 DEG C for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. Dimethylanilinium tetrakis (pentafluorophenyl) borate was added in the amounts shown in Table 1 and reacted at 75 DEG C for 5 hours. After completion of the reaction, the reaction mixture was washed with toluene, washed again with hexane, and vacuum-dried to obtain 5 g of silica-supported metallocene catalyst in the form of solid particles.

Manufacturing example  10: Preparation of catalyst composition

Step 1) Catalyst Synthesis

Toluene (13.7 g) and Et ₂ O (5.6 g) were poured into the ligand prepared in Step 1 of Preparation Example 6 and stirred. After cooling to -25 ° C, n-BuLi (2.5 M, 5.55 g) was slowly added dropwise and stirred. The mixture was stirred at 25 ° C for 12 hours, cooled to -20 ° C, and HfCl ₄ (3.05 g) was added to toluene (6.9 g). After stirring at 25 DEG C for 12 hours, all of the solvent was dried. After the filter was dried using DCM, it was recrystallized using DCM. As a result, a catalyst compound (ii) of the following structure was obtained (yellow powder (only racemic), yield = 15%).

Step 2) Preparation of supported catalyst

3 g of silica SP2410 was preliminarily weighed into a shrinkage flask, and 13 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C. for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. After dissolving 70 μmol of the compound (ii) prepared in the step 2 in toluene, the reaction was carried out at 75 ° C. for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. Dimethylanilinium tetrakis (pentafluorophenyl) borate was added in the amounts shown in Table 1 and reacted at 75 DEG C for 5 hours. After completion of the reaction, the reaction mixture was washed with toluene, washed again with hexane, and vacuum-dried to obtain 5 g of silica-supported metallocene catalyst in the form of solid particles.

Example  1: homopolymerization of propylene

The 2 L stainless steel reactor was vacuum dried at 65 占 폚, cooled, and then 1.5 mmol of triethylaluminum, 2 bar of hydrogen and 770 g of propylene were sequentially added at room temperature. After stirring for 10 minutes, the catalyst composition in the form of the supported catalyst prepared in Preparation Example 1 was dissolved in 20 mL of TMA-formulated hexane and introduced into the reactor under nitrogen pressure. At this time, the temperature of the catalyst composition was kept at 30 ° C. Then, the temperature of the reactor was elevated to 70 ° C., and polymerization was carried out for 1 hour. After the completion of the reaction, unreacted propylene was bubbled.

Example  2 to 4, and Comparative Example  1 to 6: homopolymerization of propylene

Homopolypropylene was prepared in the same manner as in Example 1 except for carrying out the supported catalyst and the polymerization conditions shown in Table 1 below.

Comparative Example  7: Homopolymerization of propylene

The 2 L stainless steel reactor was vacuum dried at 65 占 폚, cooled, and then 1.5 mmol of triethylaluminum, 2 bar of hydrogen and 770 g of propylene were sequentially added at room temperature. After stirring for 10 minutes, the temperature is raised to 70 ° C. The metallocene catalyst was dissolved in 20 mL of hexane prescribed TMA and charged to the reactor under nitrogen pressure. After 1 hour polymerization, unreacted propylene was vented.

catalyst AB equivalent
(eq.) Time to reach 70 ℃ (min) Example 1 Production Example 1 1.5 15 Example 2 Production Example 2 1.0 12 Example 3 Production Example 3 0.8 10 Example 4 Production Example 6 1.5 14 Comparative Example 1 Production Example 4 0 6 Comparative Example 2 Production Example 5 3.0 12 Comparative Example 3 Production Example 7 0 4 Comparative Example 4 Production Example 8 1.0 4 Comparative Example 5 Production Example 9 1.5 4 Comparative Example 6 Production Example 10 1.5 5 Comparative Example 7 Production Example 1 1.5 0

AB in Table 1 stands for dimethylanilinium tetrakis (pentafluorophenyl) borate.

Test Example 1

The temperature changes during the polymerization reaction in the production of homopolypropylene according to Examples 1 to 3 and Comparative Example 1 were observed, and the results are shown in Fig.

As shown in Fig. 1, the shorter the polymerization heat, the longer the time to reach the polymerization temperature (70 DEG C).

Test Example 2

The properties of the homopolypropylene prepared according to Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 2 below.

 (1) Catalytic activity: The ratio of the weight (kg) of the polymer produced per unit time (h) to the amount of catalyst (mmol and g of catalyst) used in the polymer synthesis reaction in the above Examples and Comparative Examples was calculated, Of the activity.

(2) Melt Index (MI, 2.16 kg): Measured according to ASTM D1238 at 230 占 폚 under a load of 2.16 kg and expressed as the weight (g) of the polymer melted for 10 minutes.

(3) Bulk density (BD) (g / mL): After measuring the weight (A) of the flask having a volume of 100 mL, the homopolypropylene prepared up to a 100 mL scale was filled and the weight of the homopolypropylene- B) can be measured and calculated according to the following equation:

[Equation 1]

Bulk density (g / mL) = (B - A) / 100

In the above formula (1), A represents the weight of the flask before homopolypropylene is filled, and B represents the weight of the flask filled with homopolypropylene.

(4) Polymer molecular weight distribution (MWD, polydispersity index): The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured using gel permeation chromatography (GPC) , And the molecular weight distribution (PDI) was calculated by dividing the weight average molecular weight by the number average molecular weight. At this time, the analysis temperature was 160 ° C, trichlorobenzene was used as a solvent, and the molecular weight was measured by standardizing with polystyrene.

(5) Sieving test

After injecting a sample into a hopper with a light diffraction particle size analyzer (Symatec HELOS), PDS, SPAN value, and fine particle content of less than 75 mu m in particle size were determined by setting the method in the range of 50 to 3500 mu m. At this time, the SPAN value was calculated according to the following equation (2).

&Quot; (2) "

SPAN = {D [v, 0.9] - D [v, 0.1]} / D [

D [v, 0.9] denotes the diameter at a volume fraction of 0.1 and D [v, 0.9] and D [v, 0.5] denote diameters at volume fractions of 0.9 and 0.5, respectively it means.

The homopolypropylene prepared in Examples 1 and 3 and Comparative Examples 1, 2 and 5 was observed with a scanning electron microscope, and the results are shown in Figs. 2 to 6. Fig.

AB equivalent
(eq.) activation
(g-PP / mg-Cat.hr) MI
(g / 10 min) BD
(g / mL)
Sieving test PSD
(탆) <75 μm
(weight%) SPAN Example 1 1.5 10.0 16.2 0.46 1027 1.07 0.79 Example 2 1.0 9.3 16.6 0.44 1020 2.38 0.85 Example 3 0.8 9.7 17.3 0.42 1018 3.38 0.88 Example 4 1.5 15.8 42.0 0.43 1120 1.19 0.83 Comparative Example 1 0 8.0 18.0 0.39 997 5.20 1.06 Comparative Example 2 3.0 9.2 15.2 0.40 1001 4.40 0.99 Comparative Example 3 0 11.0 2.5 0.38 1022 4.25 0.97 Comparative Example 4 1.0 7.6 8.9 0.35 925 6.20 1.20 Comparative Example 5 1.5 5.2 18.9 0.32 872 6.78 1.35 Comparative Example 6 1.5 3.2 1.25 0.32 855 7.55 1.30 Comparative Example 7 1.5 9.5 17.2 0.38 987 5.72 1.25

As a result of the test, the homopolypropylene of Examples 1 to 4 prepared using the supported catalyst carrying the metallocene compound of formula (2) together with the compound of formula (1) , Indicating a more improved morphology.

From the results of Examples 1 to 4 and Comparative Example 1, it has been found that as the amount of the compound of Formula 1 is increased, the time required for reaching the polymerization reaction temperature becomes longer and the MI of the homopolypropylene , The BD content was increased, and the SPAN was decreased.

On the other hand, in the case of using the supported catalyst in which the metallocene compound of formula (2) was supported in combination with the compound of formula (1), in the case of Comparative example 2 in which the compound of formula (1) was used in excess, The catalytic activity was lowered. As a result, the effect of improving the morphology was also lowered. From the results of Comparative Examples 1 and 2, it can be seen that optimization of the amount of the compound of Formula 1 is required for realizing the effect of the present invention.

In the case of Comparative Examples 3 to 6 in which a catalyst containing no tether group was used, the loading efficiency of the compound of Chemical Formula 1 was low and the catalytic activity was greatly lowered. As shown in Table 1, The prepolymerization effect due to the polymerization heat control was not sufficiently obtained. As a result, no improvement in morphology was observed. From these results, it can be seen that the combination of metallocene compounds having a tether which can enhance the supporting efficiency of the compound of formula (1) as well as showing excellent catalytic activity is required for realizing the effect of the present invention.

Further, in the case of Comparative Example 7 in which the temperature rise time up to the polymerization reaction temperature was 0 when the catalyst composition was added at the polymerization reaction temperature, the catalyst activity was the same level as that of the Example, but since the preliminary polymerization effect during the temperature rise was not obtained BD of the homopolypropylene produced decreased, and the fine particle content and the SPAN value were greatly increased.

From these results, it can be confirmed that control of the morphology is difficult as early control of polymerization heat is difficult, and it has been confirmed that homogeneity of homopolypropylene produced increases as the equivalent of the compound of Formula 1 in the catalyst composition increases.

Claims (13)

Preparing a catalyst composition comprising a compound of Formula 1 and a metallocene compound of Formula 2; And
Mixing the catalyst composition with a propylene monomer in a temperature range of 15 to 40 占 폚 and then raising the temperature to 60 to 85 占 폚 over 8 to 15 minutes,
Wherein the compound of Formula 1 is contained in an amount of 0.5 to 2.5 equivalents.
[Chemical Formula 1]
[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-
In Formula 1,
E is a neutral or cationic Lewis base;
H is a hydrogen atom;
Z is a Group 13 element;
Q may be the same or different from each other and each independently represents an alkyl group having from 6 to 20 carbon atoms or an alkyl group having from 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with halogen, a hydrocarbon having 1 to 20 carbon atoms, ,
(2)

In Formula 2,
M is a Group 4 transition metal,
X ₁ and X ₂ are each independently halogen,
R ₁ and R ₅ are each independently C _6-20 aryl substituted with C _1-20 alkyl,
R ₂ to R ₄ and R ₆ to R ₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl group, a C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,
A is carbon, silicon or germanium,
R ₉ is C _1-20 alkyl substituted by C _1-20 alkoxy,
R ₁₀ is hydrogen, C _1-20 alkyl or C _2-20 alkenyl.
The method according to claim 1,
Wherein the compound of Formula 1 is contained in an amount of 0.8 to 2 equivalents.
The method according to claim 1,
The compound of the above formula (1) may be prepared by reacting a compound represented by the formula (1) with a compound selected from the group consisting of dimethylanilinium tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, methyl anilinium tetrakis (pentafluorodiphenyl) (O, p-dimethylphenyl) boron, trimethylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammoniumtetra (p- Boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, trimethylammoniumtetra (p -trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium Tetraphenylboron, N, N-diethylanilium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylporo (P-tolyl) aluminum, tripropylammonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra ) Aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetra Phenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl ) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra And triphenylcarbonium tetrapentafluorophenylboron. 2. The process for producing homopolypropylene according to claim 1,
The method according to claim 1,
The compound of formula (1) is preferably selected from the group consisting of dimethylanilinium tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, and methyl anilinium tetrakis (pentafluorodiphenyl) Lt; RTI ID = 0.0 &gt; polypropylene. &Lt; / RTI &gt;
The method according to claim 1,
Wherein in Formula 2, M is Zr or Hf.
The method according to claim 1,
Wherein R ₁ and R ₅ are each independently a phenyl group substituted with a C _3-6 branched alkyl group.
The method according to claim 1,
Wherein R &lt; ₁ &gt; and R &lt; ₅ &gt; are each tert-butylphenyl.
The method according to claim 1,
In Formula 2, A is silicon,
R ₉ is C _4-10 alkyl substituted with a C _3-6 branched alkoxy group,
And R ₁₀ is C _1-4 straight chain alkyl.
9. The method of claim 8,
Wherein R &lt; ₉ &gt; is 6-tert-butoxy-hexyl and R &lt; ₁₀ &gt; is methyl.
The method according to claim 1,
Wherein the metallocene compound of formula (2) is a compound of formula (2a) or (2b).

The method according to claim 1,
Wherein the catalyst composition further comprises a silica carrier carrying the compound of formula (1) and the metallocene compound of formula (2).
The method according to claim 1,
Wherein the catalyst composition further comprises an alkylaluminoxane-based co-catalyst.
Homopolypropylene having a bulk density of 0.4 g / mL or more, a particle content of less than 75 mu m of 4 wt% or less, and a SPAN of 0.7 or more and less than 1.

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