WO2019132450A1 - Metallocene supported catalyst and method for preparing polypropylene using same - Google Patents

Abstract

The present invention relates to a novel supported catalyst containing a metallocene compound, the catalyst having excellent polymerization activity, and to a method for preparing polypropylene by polymerizing propylene in the presence of the catalyst. The metallocene-supported catalyst of the present invention can produce polypropylene having a relatively narrow molecular weight distribution and SPAN value.

Description

 Title of the Invention

 Metallocene supported catalyst and method for producing polypropylene using the same

 Cross-reference with related application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0180268, dated December 26, 2017, and Korean Patent Application No. 10-2018-0166737, dated December 20, 2018, The entire contents of which are incorporated herein by reference. The present invention relates to a process for preparing a supported catalyst and the polypropylene using the same metallocene. The present invention is by using a supported catalyst comprising a metallocene compound of a single _metal, the polypropylene has a relatively narrow molecular weight distribution and the SPAN value Can be produced with high activity.

BACKGROUND ART [0002]

 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, Is not uniform, so that it is difficult to secure desired properties. On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst, . The polymer has a narrow molecular weight distribution according to the single active site property and a homogeneous composition distribution of the comonomer is obtained. According to the modification of the ligand structure and the polymerization conditions of the catalyst, the stereoregularity of the polymer, Crystallinity and so on.

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

 U.S. Patent No. 5,552,678 discloses a method of using a catalyst system for olefin polymerization in which a metallocene compound and a non-metallocene compound are simultaneously supported on a carrier to polymerize a high molecular weight polymer and a low molecular weight polymer simultaneously . This is a disadvantage in that the metallocene compound and the non-metallocene compound must be supported separately and the carrier must be pretreated with various compounds for the supporting reaction.

 U.S. Patent No. 5,914,289 discloses a method of controlling the molecular weight and molecular weight distribution of a polymer by using a metallocene catalyst supported on each carrier. However, the amount of the solvent used in the preparation of the supported catalyst and the production time And it is troublesome to carry the metallocene catalyst to be used on the carrier, respectively.

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

 Accordingly, studies on metallocene catalysts for producing polypropylene having a narrow molecular weight distribution and SPAN value, while having high activity in the polymerization of propylene, have been carried out, but the degree of such metallocene catalysts is still insufficient. DETAILED DESCRIPTION OF THE INVENTION

 [Technical Problem]

The present invention aims to provide a metallocene supported catalyst comprising a novel metallocene compound capable of producing polypropylene having a relatively narrow molecular weight distribution and SPAN value with high activity. 2019/132450 1 »(: 1 ^ 1 {2018/016504

[Technical Solution]

 According to one embodiment of the present invention, there is provided a metallocene supported catalyst comprising a metallocene compound represented by the following formula (1) and a carrier.

 In Formula 1,

 II is an integer of 4 to 10,

 And each is independently an aryl having 6 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms and substituted with alkyl having 1 to 20 carbon atoms;

_¾ is an alkyl group having 1 to 20 carbon atoms;

 The show is carbon, silicon or germanium;

 Are each independently halogen or an alkyl group having 1 to 20 carbon atoms.

 For example, the group of Formula 1 may be dimethylamine, dipropylamine, diisopropylamine, diphenylamine, methylpropylamine, methylphenylamine, or isopropylphenylamine.

The compound represented by the formula (1) may be one of the compounds represented by the following structural formulas. \ ¥ 0 2019/132450 1 »(: 1/10 公 018/016504

The carrier may further comprise one or more promoter compounds selected from the group consisting of compounds represented by the following general formulas (2), (3) and (4) (2)

-, ₁₅ ) - " - In the above formula (2)

 May be the same or different and each independently represents a halogen;

1 to 20 hydrocarbons; Or a halogen-substituted C 1 -C 20 2019/132450 1 »(: 1 ^ 1 {2018/016504

Hydrocarbons;

 II is an integer of 2 or more;

 (3)

6 _{) 3}

 In Formula 3,

 May be the same or different and each independently represents a halogen; a hydrocarbon having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

 Is aluminum or boron;

 [Chemical Formula 4]

-11] ⁺ [ _4] - or [¾ ⁺ [ _24]

 The seedlings are neutral or cationic Lewis acids;

 II is a hydrogen atom;

 Is a Group 13 element;

 Are each independently an alkyl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with halogen, a hydrocarbon having 1 to 20 carbon atoms, an alkoxy or phenoxy, or an unsubstituted alkyl group having 1 to 20 carbon atoms. The carrier may be at least one selected from the group consisting of silica, alumina, magnesia, and mixtures thereof.

 In this case, the mass ratio of the transition metal to the carrier of the metallocene compound may be about 1:10 to about 1: 1,000.

 According to another embodiment of the present invention, there is provided a process for producing polypropylene comprising polymerizing propylene in the presence of the above metallocene supported catalyst.

Polymerization of such a profile X is from about 25 to about 5001: about 1 may be carried out by reaction for about 24 hours under a pressure of the temperature and from about 1 to _{§ £ / 011} ² to about 10, at this time, the weight of the propylene In the presence of a hydrogen (¾) gas of from about 30 to about 25 atm. 2019/132450 1 »(: 1 ^ 1 {2018/016504

【Effects of the Invention】

 The metallocene supported catalyst of the present invention can produce polypropylene having a relatively narrow molecular weight distribution and SPAN value with high activity.

₅ MODES FOR CARRYING OUT THE INVENTION

 In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

Also, the terminology used herein is used only to describe exemplary embodiments _{10 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 intended to mean that there exist features, numbers, steps, components or combinations thereof, integers, steps, components, or combinations thereof in the presence or addition of what will be the ₁₅ combinations are not intended to _preclude.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. This, however, is by no means to restrict the invention to the particular form disclosed, it is to be understood as embracing all included in the ₂₀ spirit and scope of the present invention changes, equivalents and substitutes.

Hereinafter, the present invention will be described in detail. According to one embodiment of the present invention, there is provided a metallocene supported catalyst comprising a metallocene ₂₅ compound represented by the following formula (1) and a carrier.

[Chemical Formula 1] 2019/132450 1 »(: 1 ^ 1 {2018/016504

In Formula ₁ ,

 Is an integer of 4 to 10,

 Are each independently an aryl having 6 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms and substituted with alkyl having 1 to 20 carbon atoms;

 ¾ is an alkyl group having 1 to 20 carbon atoms;

 And ¾ is a tertiary amine having an alkyl group having 1 to 10 carbon atoms;

 The show is carbon, silicon or germanium;

0 X are the same or different and each independently represents a halogen or an alkyl group having 1 to 20 carbon atoms.

 For example, the group of Formula 1 may be dimethylamine, dipropylamine, diisopropylamine, diphenylamine, methylpropylamine, methylphenylamine, or isopropylphenylamine.

5, the compound represented by Formula 1 may be one of the compounds represented by the following formulas. 2019/132450 1 »(: 1/10 公 018/016504

In general, the polypropylene polymerized metal for metallocene catalysts are the raw bulk (1 1均go through a loading process to be applied to the polymerization, when the process of the supported non-well-demanding and supporting step on the problem代_{0 1¾} etc.) wig Conventional metallocene catalysts have a problem in that they undergo prepolymerization (1 _¾ - ₁₅₀₁ >, _{11161 011} ) before the polymerization in order to avoid process problems.

The inventors of the present invention have found that by synthesizing a novel type catalyst in which a tethering catalyst having a specific structure capable of inducing a supported reaction is bonded, 2019/132450 1 »(: 1 ^ 1 {2018/016504

It was confirmed that the catalyst compound could be supported on the carrier effectively, and the present invention was completed.

 Particularly, in the metallocene compound used in the supported catalyst according to an example of the present invention, the alkylene group of a certain length is introduced in the bridge group connecting the indenyl groups, and then the alkylene group having a relatively high electron density Group and an amine group including nitrogen may be connected, which may have very large nucleophilicity.

 Therefore, it can be bonded more strongly to the carrier than the existing metallocene compound, and the single active species can be increased relative to the conventional one, so that the homogeneous activity can be exhibited in the propylene polymerization reaction.

₁₀ , the polypropylene weed in the presence of the supported catalyst according to an example of the present invention can have uniform physical properties such as a relatively narrow molecular weight distribution and a narrow SPAN value as compared with the prior art.

In the above formula ( _{1) ,?} Is an alkylene group for connecting a tether from an bridging group connecting an indenyl group, and is an integer of 4 to 10, preferably about _{15 to} about 5 to 8, more preferably about 6.

 By maintaining the alkylene linkage length as described above, electron deliquescence can be maintained in the phenylene group and the amine group contained in the tether group in the metallocene compound included in the supported catalyst of the present invention, The bond between the rossen compound and the carrier can be further strengthened, and the activity of the catalyst can be increased.

_In addition, due to the effect of increasing the activity, the metallocene supported catalyst according to one aspect of the present invention can exhibit high catalytic efficiency in the propylene polymerization reaction even when no extra promoter is added. According to one embodiment of the invention, the metallocene compound of the formula (I) is indene to prepare a ₂₅ derivative thereof connected to a bridge compound with a ligand compound, and then added to the metal precursor compound to the metal-ray line知₁ Seen _{10! 1)} it can be obtained by carrying _out, but is not limited to _this.

A more specifically, for example, is reacted with an organic compound such Lyrium the indene derivative and 0 ₁₁ to prepare a Li salt and 30 mix the halogenated compound of the bridge after the compound, the ligand compound is prepared by reacting a mixture thereof. The ligand 2019/132450 1 »(: 1 ^ 1 {2018/016504

The compound or its lithium salt and a metal precursor compound are mixed and reacted for about 12 hours to about 24 hours until the reaction is completed, and then the reaction product is filtered and dried under reduced pressure to obtain the metallocene compound represented by the formula The method for preparing the metallocene compound of Formula 1 will be described in the following Examples.

As the carrier in the metallocene supported catalyst according to one embodiment, a carrier containing a hydroxyl group or siloxane group on its surface may be used. Specifically, as the carrier, a carrier containing a hydroxyl group or a siloxane group having high reactivity by removing moisture on the surface by drying at a high temperature may be used. More specifically, examples of the carrier include silica, alumina, magnesia, and mixtures thereof. For example, the carrier may be at least one selected from the group consisting of silica, silica-alumina, and silica-magnesia. The support has a number of days will be dried at a high temperature, they typically can contain the Na _20, ¾00 _3, 6 _¾804 and Mg (N0 _{3) 2} such as an oxide, carbonate, sulfate, nitrate component.

The amount of the hydroxy group is controlled by the preparation method of the carrier, the preparation conditions, the drying conditions (temperature, time, drying method, etc.), and the like. number, and 0.1 to 10_ ₀₁ are preferred, more preferably from 0.1 to 1 _{11,111,101 /} silver, and more preferably from 0.1 to 0.5 _{11,111,101 /} it is. supported to reduce the side reaction by some of the hydroxy group remaining in the dry purpurea A siloxane group having high reactivity may be used while a carrier in which the hydroxyl group is chemically removed may be used.

 The carrier may further contain at least one compound represented by the following general formula (2), (3), or (4) as a promoter.

 (2)

_ [(11 ₅ ) -

 In Formula 2,

May be the same or different and each independently represents a halogen; a hydrocarbon having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen; 2019/132450 1 »(: 1 ^ 1 {2018/016504

₀₁ is an integer of 2 or more;

 (3)

) ₃

 In Formula 3,

 May be the same or different and each independently represents a halogen;

1 to 20 hydrocarbons; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen _;

 1 is aluminum or boron;

 [Chemical Formula 4]

[^ ^] ⁺ ^ ' _4] or] ⁺ _4]

 £ is a neutral or cationic Lewis acid;

 II is a hydrogen atom;

 Is a Group 13 element;

 Show 'may be the same or different from each other, and each independently at least one hydrogen atom is halogen, an aryl group having 6 to 20 carbon atoms substituted with a hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy, or an alkyl group having 1 to 20 carbon atoms. Non-limiting examples of the cocatalyst represented by the general formula (2) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and -butyl aluminoxane, and more preferred examples thereof include methyl aluminoxane.

Examples of the compound represented by the formula (3) include trimethyl aluminum, Tra-ethyl _aluminum, triisobutyl _aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro-aluminum, tri-isopropyl aluminum, tri-butyl aluminum, tri-cyclopentyl-aluminum, tri Triphenyl aluminum, tri- _1> tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triphenyl aluminum, triisopentyl aluminum, triisopentyl aluminum, trioctyl aluminum, Triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum. 2019/132450 1 »(: 1 ^ 1 {2018/016504

Examples of the compound represented by Formula 4 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra-tolyl) boron , Trimethylammoniumtetra ( _{0, / 7-} dimethylphenyl) boron, tributylammoniumtetra-trifluoromethylphenyl) boron, trimethylammoniumtetra-trifluoromethylphenyl) boron,

Tributylammonium tetrakis pentafluorophenylboron,

Diethylanilinium tetraphenylboron, when dimethylanilinium tetrakispentafluorophenylboron,

Diethylammonium tetrakispentafluorophenylboron,

Triphenylphosphonium tetraphenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra Tolyl) aluminum, triethylammoniumtetra (- dimethylphenyl) aluminum, tributylammonium tetrachloride - trifluoromethylphenyl) aluminum,

Trimethylammonium tetra-trichloromethylphenyl) aluminum,

Tributylammonium tetrakis pentafluorophenyl aluminum, diethyl anilinium tetraphenyl aluminum, diethyl anilinium tetrakis pentafluorophenyl aluminum,

Diethylammonium tetrakispentetetraphenyl aluminum,

Boron, triethylammonium tetra (dimethylphenyl) boron, tributylammonium tetra-trifluoromethylphenyl) boron, triphenylphosphonium tetraphenylboron, triphenylphosphonium tetraphenyl aluminum, Triphenylcarbonium tetra-trifluoromethylphenyl) boron,

Triphenylcarbonium tetrakis pentafluorophenylboron and the like.

As such a cocatalyst, aluminoxane may preferably be used, and more preferably alkyl aluminoxane such as methyl aluminoxane

The cocatalyst can be used in an appropriate amount so that the activation of the metallocene compound, which is a catalyst precursor, can proceed sufficiently. 2019/132450 1 »(: 1 ^ 1 {2018/016504

The metallocene catalyst of the present invention can be prepared by a method comprising: 1) contacting a metallocene compound represented by Formula 1 with a compound represented by Formula 2 or 3 to obtain a mixture; And 2) adding the compound represented by Formula 4 to the mixture.

 The metallocene supported catalyst according to the present invention can be prepared by a method of contacting the metallocene compound represented by Formula 1 and the compound represented by Formula 2 as a second method.

In the first method of the supported catalyst production method, the molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 2 or Formula 3 is preferably 1 / 5,000 to 1/2, More preferably from 1/1000 to 1/10, and most preferably from 1/500 to 1/20. When the molar ratio of the metallocene compound represented by the formula ( ₁ ) / the compound represented by the formula (2) or the formula (3) is more than 1/2, the amount of the alkylating agent is very small, If the molar ratio is less than 1/5000, the alkylation of the metal compound is performed, but the alkylated metal compound is not fully activated due to the side reaction between the excess alkylating agent and the activating agent. The molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 4 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1 / 5 to 1. When the molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 4 is more than 1, the amount of the activator is relatively small, There is a problem that the activity is inferior. When the molar ratio is less than 1/25, the activation of the metal compound is completely performed, but the unit price of the supported catalyst is insufficient due to the excess activating agent remaining or the purity of the produced polymer is low .

In the case of the second method in the method for producing an amine-supported catalyst, the molar ratio of the metallocene compound represented by the formula (1) / the compound represented by the formula (2) 2019/132450 1 »(: 1 ^ 1 {2018/016504

The ratio is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000 to 1/100, and most preferably 1/3 to 1/500. When the molar ratio exceeds 1/10 There is a problem in that the activation of the metal compound is not achieved completely due to the relatively small amount of the activator, and the activity of the supported catalyst is low. When the metal catalyst is less than 1 / 10,000, There is a problem that the unit price of the zero-supported catalyst is not economical or the purity of the resulting polymer is low.

 In the production of the supported catalyst, hydrocarbon solvents such as pentane, nucleic acid, heptane and the like or aromatic solvents such as benzene, toluene and the like may be used as a reaction solvent.

 When the metallocene compound and the co-catalyst compound are supported on the support in the supported catalyst, the amount of the metallocene compound is about 0.5 to about 20 parts by weight based on 100 parts by weight of the support, the cocatalyst is about 1 to about 1,000 parts by weight ≪ / RTI > Preferably, from about 1 to about 15 parts by weight of the metallocene compound and from about 10 to about 500 parts by weight of the cocatalyst may be included per 100 parts by weight of the support, and most preferably about 100 parts by weight of the support About 1 to about 100 parts by weight of the metallocene compound and about 40 to about 150 parts by weight of the cocatalyst. In the metallocene supported catalyst of the present invention, the mass ratio of the total transition metal to the carrier contained in the metallocene compound may be 1:10 to 1: 1,000. The weight ratio of the cocatalyst compound to the support may be in the range of 1: 1 to 1: 100. When the cocatalyst and the metallocene compound are contained in the mass ratio, the activity and the polymer microstructure can be optimized.

The metallocene supported catalyst may further include additives and adjuvants commonly employed in the art to which the present invention belongs, in addition to the above-mentioned components. According to another embodiment of the present invention, there is provided a process for producing polypropylene comprising polymerizing propylenes in the presence of the metallocene supported catalyst. 2019/132450 1 »(: 1 ^ 1 {2018/016504

As described above, the metallocene supported catalyst can provide a polypropylene having a narrow molecular weight distribution with high catalytic activity using a catalyst comprising a metallocene compound of the formula (1) containing an indene ligand having a specific substituent have.

 In the method for producing polypropylene according to an embodiment of the present invention. The supported catalyst comprising the metallocene compound of Formula 1 has improved catalytic activity over conventional Ziegler-Natta catalysts or metallocene catalysts, and is capable of supporting the metallocene compound, that is, the reaction temperature, the reaction time, the type of silica , The polypropylene can be produced with improved activity even when the amount of the supported metallocene compound is changed.

Wherein the polymerization of _propylenes can be carried out by reacting at a temperature of from about 25 to about 500 < 1 > and a pressure of from about 1 to about 1001 to about ₁₁₁ ² for about 1 to about 24 hours. At this time, the polymerization temperature is from about 25 to about 200 ^ 7} is preferable, (about 50 to about 100 °:. Preferable gaboda Further, the polymerization pressure is from about 1 to about 701 _{¾ £ ½11} ² are preferred, about 5 to about 501 _¾ «! ₁ ² is more preferable. The polymerization reaction time is preferably about 1 to about 5 hours.

 The process for producing the polypropylene of the present invention can be carried out by contacting propylenes with a catalyst containing a metallocene compound represented by the formula (1).

 Further, according to an embodiment of the present invention, the polymerization of propylenes can be carried out under hydrogen gas.

At this time, the hydrogen gas activates the inactive site of the metallocene catalyst,

To control the molecular weight. The metallocene compound of the present invention is excellent in hydrogen reactivity, and therefore, polypropylene having a desired molecular weight and melt index can be effectively obtained by adjusting the amount of hydrogen gas used in the polymerization process.

The hydrogen gas may be introduced at a rate of from about 30 to about 2,000 psi, or from about 50 to about 1,5001 psi, or from about 50 to about 500 psi, based on the weight of propylene. By controlling the amount of the hydrogen gas used, the molecular weight distribution of the polypropylene produced while exhibiting sufficient catalytic activity and the melt

MI) can be adjusted within a desired range, and accordingly, 2019/132450 1 »(: 1 ^ 1 {2018/016504

Polypropylene having physical properties can be produced. More specifically, the metallocene catalyst of the present invention has very good hydrogen reactivity, thereby increasing the amount of hydrogen gas used, thereby activating the chain transfer reaction. As a result, a polypropylene having a reduced molecular weight and a high melt index can be obtained have.

 The process for producing the polypropylene 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.

 In the process for producing polypropylene according to the present invention, the catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of the olefin monomer, such as pentane, nucleic acid, heptane, nonane, decane, An aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene, or the like. It is preferable to use a small amount of water or air, which acts as a catalyst poison, by using a small amount of alkylaluminum.

 The method for producing the polypropylene may further include a step that is commonly employed in the technical field to which the present invention belongs, in addition to the above-described steps. According to another embodiment of the present invention, there is provided a polypropylene obtained by the above-mentioned production method.

 As described above, according to the present invention, by using the catalyst containing the novel metallocene compound, it is possible to obtain polypropylene having a high polymerization activity without excellent processability and fouling, compared with the case of using a conventional metallocene compound Can be obtained.

 The polypropylene can be used as a packaging container, a film, a sheet, a neck-piece, a fiber product and the like which have low processing temperature and excellent transparency and fluidity and thus require such characteristics.

According to one embodiment of the present invention, when a polymerization process of propylene is carried out using a catalyst containing the metallocene compound, the weight average molecular weight

Depending on the amount of hydrogen used, it may vary from about 50,000 to about 1,000,000 / ₁₁₁₀ , or about 80,000, About 500,000 g / mol, preferably about 100,000 to about 300,000 g / mol. Further, the polypropylene produced according to the present invention can have a relatively narrow molecular weight distribution and a SPAN value. For example, the polypropylene prepared according to an embodiment of the present invention may have a molecular weight distribution value measured by GPC of about 3 or less, preferably about 2.6 or less, and a SPAN value measured by an optical diffraction particle size analyzer About 1 or less, preferably about 0.9 or less, more preferably about Q.1 to about 0.8. The SPAN value means the width of the particle size distribution diagram. The polypropylene has a small SPAN value and a uniform particle size. Accordingly, it is possible to manufacture a product having a high transparency and less problematic taste or smell problem have.

 The polypropylene produced according to an embodiment of the present invention has a weight-average molecular weight of about 1 to about 10 g / 10 min, preferably about 1 to about 7 g, as measured at 230 ° C and 2.16 kg, And a melt index (MI) of 10 min / 10 min. In particular, such properties can be easily controlled according to the amount of hydrogen used in the polymerization process, , A molecular weight distribution, and a melt property. Hereinafter, the functions and effects of the present invention will be described in more detail by way of specific examples of the present invention. However, these embodiments are merely given as examples of the present invention, and thus the scope of the present invention is not supposed.

. ≪ Examples &

 Manufacture of metallocene compounds

Preparation Example 1 2019/132450 1 »(: 1/10 公 018/016504

Step 1: 4- (6- (dichloro (methyl) silyl) hexyl) -N, N-

synthesis

4- (6-bromohexyl) _-N? N-Dimethylaniline (5.00 g, 25 mmol) (1.22 g, 50.2 mmol) was added to THF (25 mL) and stirred at 70 ^° C for 4 hours. To another flask was dissolved MeSiCB (7.47 g, 50.0 mmol) in THF (75 mL) and the mixture was slowly added dropwise at 0 ^° C for 1 h. The mixture was then stirred at room temperature overnight and then washed with sat. Of NaHC0 ₃ was added. After removing water with anhydrous MgSO ₄ , the resulting solution was subjected to vacuum distillation to obtain 4- (6- (dichloro (methyl) silyl) hexyl) -N, N-dimethylaniline (4.80 g, 82%) as a white solid.

_{^{] H NMR (500MHz, CDC1 3}} , 7.24ppm): 0.99 (3H, s), 3.01 (6H, s), 6.75 (2H, d), 7.57 (2H, d)

Step 1: Step 1: 4- (6- (bis (4- (4- (tert-butyl) phenyl) -2-methyl-1H- inden- -dimethylaniline synthesis

⁹⁷ mmol) and CuCN (176 mg, 1.97 mmol) were dissolved in toluene (90 mL) and THF (10 mL) under argon (Ar) (UmL). The solution was cooled to -30 ^° C (n-BuLi, 2.5 M in hexane, 16.5 mL) and slowly added. N, N-dimethylaniline (4.80 g, 20.5 mmol) was added to this solution, and the mixture was stirred at this temperature for about 10 minutes. mmol) in Toluene (30 mL) was added thereto, and the mixture was stirred at room temperature overnight. After the reaction was completed, MTBE and water were added and the organic layer was separated. The organic layer was dried over anhydrous MgSO ₄ and concentrated to give 4- (6- (bis (4- (4- (tert-butyl) phenyl) - 2-methyl-1H-inden-1-yl) (methyl) silyl) hexyl) -N, N-dimethylaniline (13.8 g, 100%) as a white solid.

_{'H NMR (500MHz, CDC1 3} , 7.24ppm): 0.00 - 0.07 (3H, m), 1.49 - 1.52 (18H, m), 2.46 - 2.49 (6H, m), 3.00 (3H, s), 3.02 (3H , s), 4.23-4.39 (2H, m), 6.50-7.52 (20H, m)

Step 1-3: Preparation of [4- (6- (bis (4- (4- (tert-butyl) phenyl) -2-

yl) (methyl) silyl) hexyl) -N, N-dimethylaniline] Zirconium dichloride Synthesis

Phenyl) -2-methyl-1H-inden-1-yl) (methyl) silyl) hexyl) -N, N-dimethylaniline (6.74 g, , 9.83 mmol) was dissolved in argon (Ar) in a 50 mL Schlenk flask and diethyl ether (8.2 mL) was poured in. The temperature was lowered to -78 ^° C and n-BuLi (2.5 M in hexane, 8.1 mL) was added thereto, followed by stirring at room temperature for 2 hours. A slurry of ZrC14 (2.29 g, 9.83 mmol) in Tol / diethyl ether (24.6 / 8.2 mL) was slowly added to the ligand solution at -78 ^° C and the temperature was raised to room temperature and stirred overnight. _. The solvent is distilled off under reduced pressure, dissolved in CH ₂ Cl ₂ , and filtered to remove LiCl. Concentrate the filtrate, saturate the crude with CH ₂ Cl ₂ , add hexane twice the volume and recrystallize for 15 h at -20 ^° C. After the yellow solid is formed, it is filtered and washed twice with hexane Respectively. [4- (6-

(methyl) silyl) hexyl) -N, N-dimethylaniline] Zirconium dichloride (225 mg, 30% , r / m > 20/1).

1 H NMR (500 MHz, CDCl ₃ , 7.24 ppm): 1.30-1.40 (21 H, m), 2.00 (3 H, s), 2.33

(3H, s), 3.10 (6H, s), 6.85-7.94 (18H, m)

 Example 1

 After supporting methylaluminoxane on silica by the following method,

And the metallocene compound obtained in the step 1-3 was supported to prepare a supported base. First, into a shrink flask (Schlenk flask) of 2 ⁵ 0mL silica (3g) under argon was slowly injected into the methyl aluminoxane (MAO, 19mL, 8mmol) at room temperature and the mixture was stirred at 90 ^° C for 18 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and allowed to stand for 15 minutes. Then, the solvent in the upper layer was removed. Toluene (25 mL) was added and the mixture was stirred for 3 minutes 2019/132450 1 »(: 1 ^ 1 {2018/016504

The metallocene compound (70 or 1 part 1) obtained in the above step 1-3 was dissolved in toluene (2011 part), and then the upper flask was equipped with a cannula _{rack 1111111} , And washed with toluene (511). After stirring at 501: for 5 hours, the mixture was cooled to room temperature, left for 15 minutes, and then the solvent in the upper layer was removed. Toluene (2511) was added, stirred for 3 minutes, left for 10 minutes, and the solvent in the upper layer was removed once. As another co-catalyst, dimethylaminoniumtetrakispentafluorophenylboron (13511/4) was dissolved in toluene (200 ° C) and then added to the flask using a cannula ( ₁₁ ) and washed with toluene Respectively. After stirring for 5 hours at 5 ° C, the reaction mixture was cooled to room temperature, left for 10 minutes, and then the solvent was removed from the upper layer. The reaction mixture was stirred for 3 minutes and then left for 10 minutes, followed by removing the solvent in the upper layer. The same procedure was followed by the addition of nucleic acid (2511), stirring for 1 minute,

 And vacuum dried for 4 hours.

 15

 Example 2

 The supported metallocene compound obtained in the above step 1-3 was supported on methyl aluminoxane supported on silica by the following method to prepare a supported catalyst. First, silica (3 was placed in a flask of 250 shore flasks in argon) was slowly injected at room temperature into methylaluminoxane show 0, 1911, 811111101)

The mixture was stirred at 90 [ ^deg.] (For 18 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and allowed to stand for 15 minutes. Then, the solvent in the upper layer was removed. Toluene (251) was added, stirred for 3 minutes, and allowed to stand for 10 minutes. Then, the solvent in the upper layer was removed. The metallocene compound (001) obtained in the above step 1-3 was dissolved in toluene (2011) On the flask

After stirring for 5 hours, it was cooled to room temperature and left for 15 minutes, and the solvent in the upper layer was removed. Toluene (2 liters) was added, stirred for 3 minutes, left for 10 minutes, and then the solvent in the upper layer was removed once. Nucleic acid (2511) was added in the same manner and stirred for 1 minute and left for 20 minutes. Then, the solvent in the upper layer was removed and dried overnight. Further, vacuum drying was performed at 45 ^° 0 for 4 hours. 2019/132450 1 »(: 1/10 公 018/016504

Manufacture of metallocene compounds

 Step 2-1: Preparation of (6- (tert-butoxy) hexyl) bis (4- (4- (tert- butyl) phenyl) -2-methyl-

1-yl) (methyl) silane < / RTI >

4- (4- (tert-butyl) phenyl) -2-methyl- 1 H-indene (10.3g, 39.3mmol) and under CuCN (176mg, 1.9 ⁷ mmol) and argon (Ar) in toluene ⁽⁹ 0mL) and THF (UmL). The solution was cooled to -30 ^° C (n-BuLi, 2.5 M in hexane, 16.5 mL) and slowly added. After stirring at this temperature for about 10 minutes, the temperature was raised to room temperature and then stirred for 2 hours. Dichloro (methyl) silane (5.56 g, 20.5 mmol) in Toluene (30 mL) was added to the solution, and the mixture was stirred overnight at room temperature. After the reaction was completed, MTBE and water were added and the organic layer was separated. The obtained organic layer was dried over anhydrous MgSCU and concentrated to obtain bis (4- (tert-butyl) phenyl) -2-methyl- (methyl) silane (14.8 g, 100%) as a pale yellow oil.

_{lH NMR (500MHz, CDC1 3,} 7.24ppm): -0.10 - 0.91 (3H, m), 1.25 - 1.40 (27H, m), 1.92 - 2.38 (6H, m), 4.11 - 4.52 (4H, m)? 6.44 - 7.91 (20H, m) 2-2 Step: [(6- (tert-Butoxy) hexyl) bis (4- (4- (tert- butyl) yl) (methyl) silane] Zirconium di chloride Synthesis

(6- (tert-butoxy) hexyl ) bis (4- (4- (tert-butyl) phenyl) -2-methyl-l H-inden- 1- yl) (methyl) silane (1.0g? 1.37mmol) to 50 mL shrink under argon (Ar) The mixture was placed in a Schlenk flask and dissolved by injecting diethyl ether (10 mL). The temperature was lowered to -78 ° C, n-BuLi (2.5 M in hexane, 1.1 mL) was added, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off under reduced pressure, and ZrC14 (THF) 2 (517 mg, 1.37 mmol) was added in a globe box and the temperature was lowered to -7 ^{8 °} C. Toluene (10 mL) was added to the mixture, the temperature was raised to room temperature, and the mixture was stirred overnight. The solvent was distilled off under reduced pressure and washed with hexane to obtain a yellow solid. The solid was dissolved in toluene and syringe filtered. The filtrate was distilled under reduced pressure, and the solid was washed with a nucleic acid to obtain yellow [(6- (tert-butoxy) hexyl) bis (4- (4- 2-methyl-1H-inden-1-yl) (methyl) silane] zirconium dichloride (225 mg, 18%, r / m ñ 10 / l).

^! _{H NMR (500MHZ, CDC1 3,} 7.24 ppm): 1.33 - 1.34 (21H, m), 1.37 (9H, s), 1.96 (3H, s), 2.33 (3H, s), 4.59 (2H, s), 6.86 (1H, s), 7.06 (1H, s), 7.17 (2H, m), 7.33 (1H, , 7.73 (1H, s), 8.06 (2H, d) Preparation of supported catalyst

 Comparative Example 1

The supported metallocene compound obtained in the step 2-2 was supported on silica supported on silica by the following method to prepare a supported catalyst. First, silica (3 g) was placed in a 250 mL Schlenk flask under argon, and methylaluminoxane (MAO, 19 mL, 8 mmol) was slowly added at room temperature and stirred at 90 ° C for 18 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and allowed to stand for 15 minutes. Then, the solvent in the upper layer was removed. The metallocene compound (70 or ₁₁₁₀₁₎ obtained in the above step 2-2 was dissolved in toluene (20 mL), and the solution was stirred at room temperature for 3 minutes. After the solution was stirred for 3 minutes, the solvent in the upper layer was removed. The can was added to the flask using a cannula and washed with toluene (5 mL). At 50 ^° C

After stirring for 5 hours, it was cooled to room temperature and left for 15 minutes, and the solvent in the upper layer was removed. Toluene (25 mL) was added and the mixture was stirred for 3 minutes and left for 10 minutes. Then, the solvent in the upper layer was removed once. As another co-catalyst, dimethylaniliniumtetrakis pentafluorophenylboron (135 mg) was dissolved in toluene (20 mL), and the mixture was added to the flask using a cannula. To the mixture was added toluene (5 mL) 2019/132450 1 »(: 1 ^ 1 {2018/016504

And washed. After stirring at 501: for 5 hours, it was cooled to room temperature and left for 15 minutes, and the solvent in the upper layer was removed. The mixture was stirred for 3 minutes and left for 10 minutes, and then the solvent in the upper layer was removed once. Nucleic acid (2511) was added in the same manner, and the mixture was stirred for 1 minute and left for 20 minutes The solvent in the upper layer was removed and dried overnight. And further vacuum dried at 45 V for 4 hours. Comparative Example 2

The supported metallocene compound obtained in the step 2-2 was supported on silica supported on silica by the following method to prepare a supported catalyst. First, the silica (3 L of argon and 250 < RTI ID = 0.0 > ₁ stop shin link flask

Into methyl aluminoxane (1 shows 0, 19, ₁₁₁ ^ 811 111 101) to 90 ° was slowly injected at room temperature (: is stirred for 18 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and allowed to stand for 15 minutes. Then, the solvent in the upper layer was removed. Toluene (solvent was removed at 25 into a ₁₁₁ you then allowed to stand for 10 minutes and stirred for 3 minutes upper layer. The metallocene compound (70 ^ ₁₁₁₀₁₎ on the metal obtained in the above 2-2 was dissolved in toluene (2011止) Then, a cannula 3 on the flask above! In using the ₁₁₁₁₁₎ and washed with toluene (5 ₁₁止). After stirring at 501: for 5 hours, it was cooled to room temperature and left for 15 minutes, and the solvent in the upper layer was removed. Put the toluene (25 ₁₁止) was stirred for 3 min and was carried out once the removal of the solvent in the upper layer was allowed to stand for 10 minutes. Into the nucleic acid (25 ₁₁止) in the same manner stirred for 1 minute and remove the solvent in the upper layer was allowed to stand for 20 minutes, and dried overnight then vacuum dried for 4 hours in an additional 45 ^° 0.

<Experimental Example>

 1) homopolymerization of propylene

2 stainless steel reactor was vacuum dried at 65 ° C and cooled. Triethylaluminum ( _III) ( ₁₁₁₀₁₎ was added at room temperature. Hydrogen was added to propylene at 33 ^ 1X1 and 77 propylene was added sequentially.

Since After stirring for 10 min, dissolved in the above Example 1 and Comparative Examples 1 and 2, each of the supported metallocene catalyst of 0.03 (the TMA prescribed nucleic acid 20 ₁₁止as manufactured by Nitrogen pressure was applied to the reactor. After the reactor temperature was gradually increased to 70 ^° C, the reactor was polymerized for 1 hour under a hydrogen input of 337 ppm and a pressure of 35 kg / cm ² .

2 ₎ Method of measuring physical properties of polymer

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

(2) Melt Index (MFR, 2.16 kg): Measured according to ASTM D1238 at 230 ^° C at a load of 2.16 kg and expressed as the weight (g) of the polymer melted for 10 minutes.

 (3) Molecular weight distribution: The molecular weight distribution value of the polypropylene prepared above was measured using GPC.

 (4) SPAN value: The average particle size (APS) and the SPAN value were confirmed by setting the method in the range of 50 to 3500 um after injecting the sample into the hopper using the optical diffraction particle size analyzer (Symatec HELOS). The reaction conditions of the above Examples and Comparative Examples and the physical properties of the resulting polypropylene are summarized in Table 1 below.

 [Table 1]

As shown in Table 1, the metallocene compound according to the present invention as a supported catalyst exhibited a high activity in the production of polypropylene. In particular, even when the aluminum borate-based co-catalyst was not used separately, Indicating that the activity was not significantly different.

In addition, Example 1 shows a relatively narrow molecular weight distribution even when compared with Comparative Example 1 in which other tether groups are introduced _. It was confirmed that a homogeneous polypropylene having a low value of VII and a high value of a value and a show value can be produced.

Claims

2019/132450 1 »(: 1 ^ 1 {2018/016504

Claims:

 [Claim 1]

A metallocene compound represented by the following formula ( ₁ ), and

 Metallocene supported catalyst comprising a carrier:

 [Chemical Formula 1]

 In Formula 1,

 II is an integer of 4 to 10,

 Are each independently an aryl having 6 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms and substituted with alkyl having 1 to 20 carbon atoms;

 ¾ is an alkyl group having 1 to 20 carbon atoms;

 And ¾ is a tertiary amine having an alkyl group having 1 to 10 carbon atoms;

 The show is carbon, silicon or germanium;

 Are each independently halogen or an alkyl group having 1 to 20 carbon atoms.

[Claim 2]

 The method according to claim 1,

Wherein the group of Formula 1 is dimethylamine, dipropylamine, diisopropylamine, diphenylamine, methylpropylamine, methylphenylamine, or isopropylphenylamine. 2019/132450 1 »(: 1/10 公 018/016504

[Claim 3]

 The method according to claim 1,

 The compound represented by the formula (1) is one of the compounds represented by the following formulas,

[4]

 The method according to claim 1,

Among the compounds represented by the following general formulas (2), (3) and (4) 2019/132450 1 »(: 1 ^ 1 {2018/016504

&Lt; / RTI &gt; further comprising at least one cocatalyst compound,

 (2)

 In Formula 2,

 May be the same or different and each independently represents a halogen;

1 to 20 hydrocarbons; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

 III is an integer of 2 or more;

 (3)

 (¾) 3

 In Formula 3,

_May be the same or different and each independently represents a halogen; a hydrocarbon having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

 Is aluminum or boron;

 [Chemical Formula 4]

[11] ⁺ [2 show, _{4 -} or ^Fe,

 In Formula 4,

 The seedlings are neutral or cationic Lewis acids;

 II is a hydrogen atom;

 Is a Group 13 element;

 Are each independently an alkyl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with halogen, a hydrocarbon having 1 to 20 carbon atoms, an alkoxy or phenoxy, or unsubstituted.

[Claim 5]

 The method according to claim 1,

Wherein the support is one type of catalyst selected from the group consisting of silica, alumina, magnesia, and mixtures thereof. 2019/132450 1 »(its 1 ^ {2018/016504

[Claim 6]

 The method according to claim 1,

Mass ratio of the transition metal to the carrier of The metallocene compound is from _1: 10 to 1: 1,000, metallocene supported catalyst to the metal.

7.

 7. A process for producing polypropylene comprising polymerizing propylene in the presence of the metallocene supported catalyst according to any one of claims 1 to 6. 8.

 8. The method of claim 7,

Wherein the polymerization of propylene is carried out by reacting at a temperature of 25 to 500 占 폚 and a pressure of 1 to 1001 占 퐉 / 011 ² for 1 to 24 hours.

9]

 8. The method of claim 7,

In the presence of a gas in the range of 30 to 2,000 (hydrogen field ₂ of cut 15111) with respect to the weight of the propylene.