KR102251397B1 - Transition metal compound, supported metallocene catalyst comprising the same, and method for preparing olefin polymer using the same - Google Patents

Abstract

The present invention relates to a transition metal compound and a metallocene supported catalyst comprising the same. According to an embodiment of the present invention, it is possible to exhibit high activity in the olefin polymerization reaction, and by easily controlling properties such as stereoregularity of the synthesized olefin polymer, in particular, to prepare a propylene polymer having a high glass transition temperature value. A transition metal compound, a metallocene-supported catalyst including the same, and a method of preparing an olefin polymer using the metallocene-supported catalyst may be provided.

Description

A transition metal compound, a metallocene-supported catalyst including the same, and a method for producing an olefin polymer using the same

The present invention relates to a transition metal compound, a metallocene supported catalyst including the transition metal compound, and a method for preparing an olefin polymer using the supported catalyst, and more specifically, it may exhibit high activity in an olefin polymerization reaction, By easily controlling properties such as stereoregularity of the synthesized olefin polymer, in particular, a transition metal compound capable of preparing a propylene polymer having a high glass transition temperature value, a metallocene supported catalyst including the same, and the metal It relates to a method for producing an olefin polymer using a strong supported catalyst.

Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used in the conventional commercial manufacturing process of polyolefins.The Ziegler-Natta catalyst has high activity, but since it is a multi-active point catalyst, the molecular weight distribution of the resulting polymer is wide and comonomers Since the composition distribution of is not uniform, there is a limit to securing the desired physical properties.

Accordingly, in recent years, a metallocene catalyst in which a transition metal such as titanium, zirconium, and hafnium is combined with a ligand including a cyclopentadiene functional group has been developed and has been widely used. The metallocene compound is generally used by activation with aluminoxane, borane, borate or other activating agent. For example, a metallocene compound having a ligand containing a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. This metallocene catalyst is a single active point catalyst having one type of active point, and has a narrow molecular weight distribution of the resulting polymer. Accordingly, the polyolefin polymerized with a metallocene catalyst has a narrow molecular weight distribution, and therefore, when applied to some products, there is a problem that it is difficult to apply in the field, such as productivity is significantly reduced due to the influence of extrusion load.

The present invention provides a transition metal compound capable of providing an olefin polymer having a high activity and a high glass transition temperature value.

In addition, the present invention provides a metallocene-supported catalyst including the transition metal compound and a method for producing an olefin polymer using the metallocene-supported catalyst.

According to an embodiment of the present invention, a transition metal compound represented by Formula 1 below is provided.

[Formula 1]

In Formula 1,

M is a Group 4 transition metal;

X1 and X2 are each independently, the same as or different from each other, a halogen atom;

A is silicon (Si) or germanium (Ge);

n is an integer from 4 to 10;

R is directly connected to an aromatic ring, and is an alicyclic ring having 4 to 7 carbon atoms in the entire ring;

R1 and R2 are each independently the same as or different from each other, and are linear or branched chain alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms;

R3, R4, R5, and R6 are each independently the same as or different from each other, and are linear or branched alkyl having 3 to 10 carbon atoms;

R7 is C1-C5 linear or branched-chain alkyl, or C6-C10 aryl.

In addition, the R3, R4, R5, and R6 are each independently the same or different from each other, and it may be preferable that they are branched chain alkyl having 3 to 10 carbon atoms.

In addition, R1, R2, and R7 may each independently be the same or different from each other, and may preferably be an alkyl having 1 to 3 carbon atoms, and M may be preferably a Group 4 transition metal, particularly zirconium or hafnium. .

On the other hand, according to another embodiment of the present invention, the transition metal compound; Cocatalyst; And a metallocene supported catalyst including a carrier is provided.

In this case, the cocatalyst may be at least one selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4.

[Formula 2]

R10-[Al(R9)-O] _m -R11

In Chemical Formula 2,

R9, R10 and R11 are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen,

m is an integer greater than or equal to 2,

[Formula 3]

D(R12) ₃

In Chemical Formula 3,

D is aluminum or boron,

R12 is each independently any one of halogen, a C1-C20 hydrocarbyl group, a C1-C20 hydrocarbyloxy group, and a C1-C20 hydrocarbyl group substituted with a halogen,

[Formula 4]

^{[LH] + [W (J} ) 4] - or ^{[L] + [W (J} ) 4] -

In Chemical Formula 4,

L is a neutral or cationic Lewis base,

W is a Group 13 element, and J is each independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And at least one hydrogen atom of these substituents is any one of substituents substituted with at least one substituent among halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms.

In addition, as the carrier, silica, alumina, magnesia, or a mixture thereof may be used.

Such a metallocene-supported catalyst may be used in a propylene polymerization reaction, in particular, to provide a propylene polymer having a high glass transition temperature.

According to another embodiment of the present invention, there is provided a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the metallocene supported catalyst.

In this case, the olefin polymer may preferably be a propylene homopolymer, and specifically, the olefin polymer may have a glass transition temperature of about 155°C or higher.

The transition metal compound and the metallocene-supported catalyst of the present invention can exhibit high activity in the olefin polymerization reaction, and easily control properties such as stereoregularity of the synthesized olefin polymer, and in particular, a high glass transition temperature value. It is possible to prepare a propylene polymer having.

In addition, terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise", "include", or "have" are intended to designate the existence of a feature, number, step, element, or combination of the implemented features, but one or more other features or It is to be understood that the possibility of the presence or addition of numbers, steps, elements, or combinations thereof is not preliminarily excluded.

The present invention will be described in detail below and exemplify specific embodiments, as various modifications can be made and various forms can be obtained. However, this is not intended to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, a transition metal compound according to a specific embodiment of the present invention, a metallocene supported catalyst including the same, and a method of preparing an olefin polymer using the same will be described.

According to an embodiment of the present invention, a transition metal compound represented by the following Formula 1 is provided.

[Formula 1]

In Formula 1,

M is a Group 4 transition metal;

X1 and X2 are each independently, the same as or different from each other, a halogen atom;

A is silicon (Si) or germanium (Ge);

n is an integer from 4 to 10;

R is directly connected to an aromatic ring, and is an alicyclic ring having 4 to 7 carbon atoms in the entire ring;

R1 and R2 are each independently the same as or different from each other, and are linear or branched chain alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms;

R3, R4, R5, and R6 are each independently the same as or different from each other, and are linear or branched alkyl having 3 to 10 carbon atoms;

R7 is C1-C5 linear or branched-chain alkyl, or C6-C10 aryl.

The halogen atom, specifically, means fluorine (F), chlorine (Cl), bromine (Br) or iodine (I), and is preferably chlorine, or bromine.

Straight or branched chain alkyl having 1 to 5 carbon atoms is, more specifically, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, or iso-pentyl, etc. I can.

The aryl having 6 to 10 carbon atoms means a monocyclic or bicyclic aromatic hydrocarbon, and specifically, may mean phenyl or naphnyl.

Linear or branched chain alkyl having 3 to 10 carbon atoms is, more specifically, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl; or,

One or more substituents such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, or iso-pentyl are attached to the side branch of the alkyl group. It may be formed to have 3 to 10 carbon atoms.

As described above, the transition metal compound represented by Formula 1 includes two indenyl groups into which a functional group of a specific structure is introduced as ligands, and in such indenyl groups, the substituents corresponding to R1 and R2, respectively, are indenyl The phenyl group into which each of R3 to R5 is introduced is bonded to the 2nd carbon position of, and is bonded to the 4th carbon position of indenyl, and in one of these indenyl groups, at the 5th and 6th carbon positions, a specific An alicyclic ring of a size is connected, and a functional group capable of serving as a Lewis base as an oxygen-donor is included in a bridge group connecting the two ligands. Due to this unique structure, the transition metal compound can have a specific electron density in the molecule, and can exhibit high activity in the polymerization reaction of the olefin monomer.

In addition, the transition metal compound represented by Chemical Formula 1 may have a structure that is difficult to sterically deform due to the introduction of the above-described substituent and alicyclic ring, that is, a structure with increased stereo-rigidity. Accordingly, when the transition metal compound represented by Formula 1 is used for olefin polymerization, an olefin polymer having a high stereoregularity and a high glass transition temperature value can be prepared.

In particular, as a result of the experiment of the present inventors, due to the unique structure of the transition metal compound represented by Formula 1, polypropylene having very improved stereoregularity can be prepared by using the transition metal compound as a polymerization catalyst for propylene. have.

More specifically, in Formula 1, R3, R4, R5, and R6 are each independently the same or different from each other, and may be a branched-chain alkyl having 3 to 10 carbon atoms, and R1, R2, and R7 are each independently As such, it is the same or different from each other, and is preferably an alkyl having 1 to 3 carbon atoms, and due to this structure, the above-described effect can be more remarkably increased.

In addition, the bridging group connecting each indenyl ligand in Formula 1 may affect the carrying stability of the transition metal compound. For example, R6 connected in an alkoxy form to the end of the bridge is connected in the form of a straight or branched chain alkyl having 3 to 10 carbon atoms, preferably, a branched chain alkyl having 3 to 10 carbon atoms, thereby increasing the carrying efficiency for bulk polymerization. I can make it. In addition, when n is an integer between 4 and 10, it can act as a tether for the carrier, thereby ensuring more excellent support stability, and effectively preventing fouling in the reactor during polymerization of olefin monomers. Can be prevented.

On the other hand, M in Formula 1 is any one of Group 4 transition metals; More specifically, storage stability of a transition metal compound and/or a metallocene-supported catalyst may be improved by using any one of titanium (Ti), zirconium (Zr), and hafnium (Hf).

The transition metal compound represented by Formula 1 may be synthesized by applying known reactions, and a more detailed synthesis method may be referred to Examples to be described later.

On the other hand, according to another embodiment of the invention, the transition metal compound represented by the formula (1); Cocatalyst; And a metallocene supported catalyst including a carrier.

The metallocene supported catalyst further includes a cocatalyst capable of activating a transition metal compound. As such a cocatalyst, those commonly used in the technical field to which the present invention pertains may be used without particular limitation. As a non-limiting example, the cocatalyst may be one or more compounds selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4.

[Formula 2]

R10-[Al(R9)-O] _m -R11

In Chemical Formula 2,

R9, R10 and R11 are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen,

m is an integer greater than or equal to 2,

[Formula 3]

D(R12) ₃

In Chemical Formula 3,

D is aluminum or boron,

R12 is each independently any one of halogen, a C1-C20 hydrocarbyl group, a C1-C20 hydrocarbyloxy group, and a C1-C20 hydrocarbyl group substituted with a halogen,

[Formula 4]

^{[LH] + [W (J} ) 4] - or ^{[L] + [W (J} ) 4] -

In Chemical Formula 4,

L is a neutral or cationic Lewis base,

W is a Group 13 element, and J is each independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And at least one hydrogen atom of these substituents is any one of substituents substituted with at least one substituent among halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms.

In the present specification, the following terms may be defined as follows unless there is a specific limitation.

Hydrocarbyl group is a monovalent functional group in the form of removing a hydrogen atom from a hydrocarbon, and is an alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, aralkenyl group, aralkynyl group, alkylaryl group, alkenylaryl group, and alkynyl group. It may include a nilaryl group and the like. In addition, the hydrocarbyl group having 1 to 20 carbon atoms may be a hydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. Specifically, the hydrocarbyl group having 1 to 20 carbon atoms is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group , a linear, branched or cyclic alkyl group such as an n-heptyl group and a cyclohexyl group; Or it may be an aryl group such as a phenyl group, a naphthyl group, or an anthracenyl group.

Hydrocarbyloxy group is a functional group in which a hydrocarbyl group is bonded to oxygen. Specifically, the hydrocarbyloxy group having 1 to 20 carbon atoms may be a hydrocarbyloxy group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. More specifically, the hydrocarbyloxy group having 1 to 20 carbon atoms is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentoxy group , a linear, branched or cyclic alkoxy group such as an n-hectoxy group, an n-heptoxy group, and a cyclohectoxy group; Or, it may be an aryloxy group such as a phenoxy group or a naphthalenoxy group.

The hydrocarbyl (oxy)silyl group is a functional group in which 1 to 3 hydrogens of -SiH3 are substituted with 1 to 3 hydrocarbyl groups or hydrocarbyloxy groups. Specifically, the hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms may be a hydrocarbyl (oxy)silyl group having 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms. More specifically, the hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms is an alkyl group such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a dimethylmethylsilyl group, and a dimethylpropylsilyl group. Silyl group; Alkoxysilyl groups such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group, and dimethoxyethoxysilyl group; Alkoxyalkylsilyl groups such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, and a dimethoxypropylsilyl group.

Non-limiting examples of the compound represented by Formula 2 above include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, tert-butylaluminoxane, and the like. And, non-limiting examples of the compound represented by Formula 3 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-sec-butyl aluminum, Tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide or dimethyl aluminum Toxide, etc. are mentioned. Finally, non-limiting examples of the compound represented by Formula 4 include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis ( Pentafluorophenyl) borate, N,N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N,N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N,N-dimethylanilinium Tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2,3 ,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis (Pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) ) Borate, hexadecyldimethylammonium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecylanilinium tetrakis (pentafluorophenyl) borate or methyldi (dodecyl) ammonium tetrakis (pentafluoro Phenyl) borate and the like.

The content of the cocatalyst used may be appropriately adjusted according to the properties or effects of the desired catalyst composition.

The catalyst composition may be a supported catalyst in which the above-described transition metal compound is supported on a carrier. The transition metal compound represented by Formula 1 has the above-described structural characteristics and can be stably supported on a carrier. In addition, such a supported catalyst on which the transition metal compound is supported exhibits high activity in olefin polymerization and can easily provide an olefin polymer having a high glass transition temperature value.

As the carrier, a carrier containing a hydroxy group or a siloxane group on the surface may be used. Specifically, as the carrier, a carrier containing a highly reactive hydroxyl group or a siloxane group may be used by drying at high temperature to remove moisture from the surface. More specifically, as the carrier, silica, alumina, magnesia, or a mixture thereof may be used. The carrier may be dried at high temperature, and these may include oxides, carbonates, sulfates, and nitrate components such _{as Na 2} O, K ₂ CO ₃ , BaSO ₄ and Mg(NO ₃ ) _2.

The above-described catalyst composition is used in the polymerization reaction of an olefin monomer to exhibit high catalytic activity and can provide an olefin polymer having a high glass transition temperature. In particular, the catalyst composition may be used in a propylene polymerization reaction to provide polypropylene having increased stereo regidity.

On the other hand, according to another embodiment of the invention, in the presence of the catalyst composition, there is provided a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer.

As described above, the catalyst composition provides an olefin polymer having a higher glass transition temperature than a polyolefin polymerized using a conventional metallocene catalyst due to a specific structure, and may exhibit higher activity during polymerization of the olefin monomer. have.

Examples of olefin monomers that can be polymerized with the catalyst composition include ethylene, alpha-olefins, cyclic olefins, and the like, and diene olefin monomers or triene olefin monomers having two or more double bonds can be polymerized. Specific examples of the monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like, and two or more of these monomers may be mixed and copolymerized.

In particular, the catalyst composition may be used in a propylene homopolymerization reaction due to the specific three-dimensional structure of the above-described transition metal compound of Formula 1 to provide a propylene homopolymer having high stereoregularity.

Therefore, for the polymerization reaction of the olefin monomer, various polymerization processes known as polymerization reactions of olefin monomers may be employed, such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process, or an emulsion polymerization process.

Specifically, the polymerization reaction may be performed under a temperature of about 50 to 110°C or about 60 to 100°C and a pressure of about 1 to 100kgf/cm2.

In addition, in the polymerization reaction, the catalyst composition may be used in a dissolved or diluted state in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like. At this time, by treating the solvent with a small amount of alkyl aluminum, etc., a small amount of water or air that may adversely affect the catalyst may be removed in advance.

The olefin polymer prepared by the above method has high stereoregularity and a high glass transition temperature, for example, about 155° C. or higher, or about 155° C. to 165° C., as it is manufactured using the above-described catalyst composition. It can have a transition temperature value.

Hereinafter, the action and effect of the invention will be described in more detail through specific embodiments of the invention. However, these embodiments are only presented as examples of the invention, and the scope of the invention is not determined thereby.

< Example >

Transition metal compounds and Metallocene Preparation of supported catalyst

< Example 1>

Ligand Synthesis:

8-(3,5-di-tert-butylphenyl)-6-methyl-1,2,3,4a,5,7a-hexahydros-indacene (27.90mmol) was added to a 50ml Schlenk flask to create an Ar atmosphere. After that, anhydrous hexane (96.90ml) and anhydrous methyl tert-butyl ether (MTBE) were added and cooled to -25°C. Here n-BuLi (2.5M in Hexane, 29.3mmol) was slowly injected, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 2 hours.

The mixture was again cooled to -25°C, and then (tert-butoxymethyl)dichloro(methyl)silane (33.48mmol) was injected into the flask at once, followed by stirring for 16 hours. A sample was taken, checked for the presence of unreacted silane by NMR, and dried in a vacuum state.

4-(4-tert-butylphenyl)-2-isopropyl-3a,7a-dihydro-1H-indene (25.11mmol) and CuCN (1.26mmol) were added to another Schlenk flask to create an Ar atmosphere. Anhydrous MTBE (62.78ml) was added and cooled to -25°C. Here n-BuLi (2.5M in Hexane, 26.37mmol) was slowly injected, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 2 hours.

This was again cooled to -25°C, and the previously dried mixture was dissolved in MTBE (60ml), and the two were mixed with each other. After mixing, the temperature was raised to room temperature and stirred at room temperature for 16 hours.

The reaction was worked up with haxane and distilled water, and the organic layer was collected to remove the solvent.

The residue was removed with haxane in column chromatography, and the ligand in the form of a light yellow solid was separated (EA:Hexane: 1:100).

(21.75mmol, yield: 78%)

¹ H NMR (500MHz, CDCl ₃ ): 7.6~7.0 (m, 11H), 6.8~6.6 (m, 2H), 3.9~3.4 (m, 2H), 3.4~3.2 (m, 2H), 3.0~2.4 ( m, 6H), 2.2~0.4 (m, 56H), 0.1~-0.1 (m, 3H)

Synthesis of transition metal compounds:

A 10ml Schlenk flask was polished in an Ar atmosphere. T-butylamine (1.18mmol), anhydrous toluene (1.30ml), and anhydrous THF (1.18mmol) were added and cooled to -25°C. n-BuLi (2.5M in hexane, 1.24 mmol) was slowly injected, and after the injection was completed, the temperature was raised to room temperature, followed by stirring at room temperature for 2 hours. After the stirring was over, this solution was _{injected into an Ar Schlenk flask (-25°C) containing ZrCl 4} -2 (THF) (1.18 mmol) and toluene (1 ml). After the injection was completed, the temperature was raised to room temperature and stirred at room temperature for 2 hours to prepare t-butylamide zirconium-slurry.

At the same time, the ligand (1.18 mmol) prepared above was put into a 25 ml Schlenk flask, and made into an Ar atmosphere. Then, anhydrous toluene (2.00ml) and anhydrous THF (0.20ml) were added and cooled to -25°C. BuLi (2.5M in hexane, 2.42mmol) was slowly injected, the temperature was raised to room temperature, and then stirred at room temperature for 2 hours.

This was cooled to -25°C again, and the t-butylamide zirconium-slurry prepared above was injected, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 16 hours.

This was cooled to -25°C again, HCl (2N in diethylether, 2.48mmol) was injected, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 2 hours.

Thereafter, it was filtered to remove the solid, and a solution containing the catalyst was obtained. After dissolving this in a minimum amount of anhydrous pentane and storing at room temperature, a solid was formed. Anhydrous pentane was further added thereto, followed by filtration to collect a transition metal compound in the form of a yellow solid.

(0.19 mmol, yield: 17%)

Metallocene Supported catalyst preparation:

Silca gel (3g) was placed in a 250ml Schlenk flask under Ar atmosphere, and methylaluminoxane (MAO, 30mmol) was slowly injected at room temperature, followed by stirring at 95°C for 18 hours. After completion of the reaction, the mixture was cooled to room temperature, left to stand for 15 minutes, and the solvent was removed using a cannula. Toluene (25ml) was added, stirred for 1 minute, left to stand for 20 minutes, and then the solvent was removed using a cannula again.

The transition metal compound (180 μmol) prepared above was dissolved in toluene (20 ml), transferred to the Schlenk flask using a cannula, washed with toluene (5 ml) and transferred again.

After stirring at 75° C. for 5 hours, cooling to room temperature and standing for 15 minutes, the solvent was removed again using a cannula.

Toluene (25ml) was added and stirred for 1 minute, then stirred at room temperature for 1 minute, and again, using a cannula, the operation of removing the solvent was performed twice.

After adding hexane (25ml) and stirring for 1 minute, the mixture was stirred at room temperature for 1 minute, and the solvent was removed using a cannula again.

It was dried under vacuum at room temperature for 24 hours, and further dried under vacuum at 45° C. for 4 hours to obtain a metallocene supported catalyst.

< Example 2>

Ligand Synthesis:

A ligand having the same structure as in Example 1 was used.

Synthesis of transition metal compounds:

A 10ml Schlenk flask was polished in an Ar atmosphere. T-butylamine (1.18mmol), anhydrous toluene (1.30ml), and anhydrous THF (1.18mmol) were added and cooled to -25°C. n-BuLi (2.5M in hexane, 1.24 mmol) was slowly injected, and after the injection was completed, the temperature was raised to room temperature, followed by stirring at room temperature for 2 hours. After the stirring was over, this solution was injected _{into an Ar Schlenk flask (-25°C) containing HfCl 4} -2 (THF) (1.18 mmol) and toluene (1 ml). After the injection was completed, the temperature was raised to room temperature and stirred at room temperature for 2 hours to prepare t-butylamide hafnium-slurry.

At the same time, the ligand (1.18 mmol) prepared above was put into a 25 ml Schlenk flask, and made into an Ar atmosphere. Then, anhydrous toluene (2.00ml) and anhydrous THF (0.20ml) were added and cooled to -25°C. BuLi (2.5M in hexane, 2.42mmol) was slowly injected, the temperature was raised to room temperature, and then stirred at room temperature for 2 hours.

This was cooled to -25°C again, and the t-butylamide hafnium-slurry prepared above was injected, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 16 hours.

This was cooled to -25°C again, HCl (2N in diethylether, 2.48mmol) was injected, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 2 hours.

Thereafter, it was filtered to remove the solid, and a solution containing the catalyst was obtained. When this is dissolved in a minimum amount of anhydrous pentane and stored at room temperature, a solid is formed. After adding anhydrous pentane to it, it is filtered to form a yellow solid. The metal compound was collected.

(0.28mmol, yield: 24%)

Metallocene Supported catalyst preparation:

Silca gel (3g) was placed in a 250ml Schlenk flask under Ar atmosphere, and methylaluminoxane (MAO, 30mmol) was slowly injected at room temperature, followed by stirring at 95°C for 18 hours. After completion of the reaction, the mixture was cooled to room temperature, left to stand for 15 minutes, and the solvent was removed using a cannula. Toluene (25ml) was added, stirred for 1 minute, left to stand for 20 minutes, and then the solvent was removed using a cannula again.

The transition metal compound (180 μmol) prepared above was dissolved in toluene (20 ml), transferred to the Schlenk flask using a cannula, washed with toluene (5 ml) and transferred again.

After stirring at 75° C. for 5 hours, cooling to room temperature and standing for 15 minutes, the solvent was removed again using a cannula.

Toluene (25ml) was added and stirred for 1 minute, then stirred at room temperature for 1 minute, and again, using a cannula, the operation of removing the solvent was performed twice.

After adding hexane (25ml) and stirring for 1 minute, the mixture was stirred at room temperature for 1 minute, and the solvent was removed using a cannula again.

It was dried under vacuum at room temperature for 24 hours, and further dried under vacuum at 45° C. for 4 hours to obtain a metallocene supported catalyst.

< Comparative example 1>

Ligand Synthesis:

4-(4-tert-butylphenyl)-2-methyl-3a,7a-dihydro-1H-indene (25.00mmol) was added to a 50ml Schlenk flask to create an Ar atmosphere. After that, anhydrous hexane (96.90ml) and anhydrous methyl tert-butyl ether (MTBE) were added and cooled to -25°C. Here n-BuLi (2.5M in Hexane, 29.3mmol) was slowly injected, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 2 hours.

This was again cooled to -25°C, and dichlorodimethylsilane (12.5 mmol) was injected into the flask at once, followed by stirring for 16 hours. A sample was taken, checked for the presence of unreacted silane by NMR, and dried in a vacuum state.

The residue was removed with haxane in column chromatography, and a ligand in the form of a yellow solid was separated (EA:Hexane: 1:100).

(12.5mmol, yield: 99%)

Synthesis of transition metal compounds:

The ligand (1.18mmol) prepared above was placed in a 25ml Schlenk flask, and made into an Ar atmosphere. Then, anhydrous toluene (2.00ml) and anhydrous THF (0.20ml) were added and cooled to -25°C. BuLi (2.5M in hexane, 2.42mmol) was slowly injected, the temperature was raised to room temperature, and then stirred at room temperature for 2 hours.

This was cooled to -25°C again _{, and injected into an Ar Schlenk flask (-25°C) containing ZrCl 4} -2 (THF) (1.18 mmol) and toluene (1 ml). After the injection was completed, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 16 hours. After the reaction, it was recrystallized in MC/Hexane to obtain a transition metal compound in the form of an orange solid.

(0.35mmol, yield: 30%)

Metallocene Supported catalyst preparation:

Silca gel (3g) was placed in a 250ml Schlenk flask under Ar atmosphere, and methylaluminoxane (MAO, 30mmol) was slowly injected at room temperature, followed by stirring at 95°C for 18 hours. After completion of the reaction, the mixture was cooled to room temperature, left to stand for 15 minutes, and the solvent was removed using a cannula. Toluene (25ml) was added, stirred for 1 minute, left to stand for 20 minutes, and then the solvent was removed using a cannula again.

The transition metal compound (180 μmol) prepared above was dissolved in toluene (20 ml), transferred to the Schlenk flask using a cannula, washed with toluene (5 ml) and transferred again.

After stirring at 75° C. for 5 hours, cooling to room temperature and standing for 15 minutes, the solvent was removed again using a cannula.

Toluene (25ml) was added and stirred for 1 minute, then stirred at room temperature for 1 minute, and again, using a cannula, the operation of removing the solvent was performed twice.

After adding hexane (25ml) and stirring for 1 minute, the mixture was stirred at room temperature for 1 minute, and the solvent was removed using a cannula again.

It was dried under vacuum at room temperature for 24 hours, and further dried under vacuum at 45° C. for 4 hours to obtain a metallocene supported catalyst.

< Comparative example 2>

Ligand Synthesis:

4-(4-tert-butylphenyl)-2-methyl-3a,7a-dihydro-1H-indene (25.00mmol) was added to a 50ml Schlenk flask to create an Ar atmosphere. After that, anhydrous hexane (96.90ml) and anhydrous methyl tert-butyl ether (MTBE) were added and cooled to -25°C. Here n-BuLi (2.5M in Hexane, 29.3mmol) was slowly injected, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 2 hours.

The mixture was again cooled to -25°C, and then (tert-butoxymethyl)dichloro(methyl)silane (12.50 mmol) was injected into the flask at once, followed by stirring for 16 hours. A sample was taken, checked for the presence of unreacted silane by NMR, and dried in a vacuum state.

The reaction was worked up with haxane and distilled water, and the organic layer was collected to remove the solvent.

The residue was removed with haxane in column chromatography, and a ligand in the form of a yellow solid was separated (EA:Hexane: 1:100).

(12.50 mmol, yield: 99%)

Synthesis of transition metal compounds:

The ligand (1.18mmol) prepared above was placed in a 25ml Schlenk flask, and made into an Ar atmosphere. Then, anhydrous toluene (2.00ml) and anhydrous THF (0.20ml) were added and cooled to -25°C. BuLi (2.5M in hexane, 2.42mmol) was slowly injected, the temperature was raised to room temperature, and then stirred at room temperature for 2 hours.

This was cooled to -25°C again _{, and injected into an Ar Schlenk flask (-25°C) containing ZrCl 4} -2 (THF) (1.18 mmol) and toluene (1 ml). After the injection was completed, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 16 hours. After the reaction, it was recrystallized in MC/Hexane to obtain a transition metal compound in the form of an orange solid.

(0.35mmol, yield: 30%)

Metallocene Supported catalyst preparation:

Silca gel (3g) was placed in a 250ml Schlenk flask under Ar atmosphere, and methylaluminoxane (MAO, 30mmol) was slowly injected at room temperature, followed by stirring at 95°C for 18 hours. After completion of the reaction, the mixture was cooled to room temperature, left to stand for 15 minutes, and the solvent was removed using a cannula. Toluene (25ml) was added, stirred for 1 minute, left to stand for 20 minutes, and then the solvent was removed using a cannula again.

The transition metal compound (180 μmol) prepared above was dissolved in toluene (20 ml), transferred to the Schlenk flask using a cannula, washed with toluene (5 ml) and transferred again.

After stirring at 75° C. for 5 hours, cooling to room temperature and standing for 15 minutes, the solvent was removed again using a cannula.

Toluene (25ml) was added and stirred for 1 minute, then stirred at room temperature for 1 minute, and again, using a cannula, the operation of removing the solvent was performed twice.

After adding hexane (25ml) and stirring for 1 minute, the mixture was stirred at room temperature for 1 minute, and the solvent was removed using a cannula again.

It was dried under vacuum at room temperature for 24 hours, and further dried under vacuum at 45° C. for 4 hours to obtain a metallocene supported catalyst.

Preparation of olefin polymer

First, a 2L stainless steel reactor was vacuum-dried at 65°C, cooled, and 1.5 mmol of triethylaluminum was added at room temperature, and 770 g of propylene was added. After stirring this for 10 minutes, the silica-supported metallocene catalyst prepared in Examples and Comparative Examples was added to the reactor under nitrogen pressure. At this time, about a certain amount of hydrogen gas was added together with the catalyst. Thereafter, the temperature of the reactor was gradually increased to 70° C. and polymerization was performed for 1 hour. After completion of the reaction, unreacted propylene was vented.

Test example : Catalyst activity and Olipine Evaluation of polymer properties

<Method of evaluating physical properties>

(1) Catalyst activity: Calculate the ratio of the weight (kg) of the produced polymer per unit time (h) based on the catalyst content (mmol and g of catalyst) used in the polymer synthesis reactions of Examples and Comparative Examples It was defined as the activity of And, the results are shown in Table 1 below.

(2) Glass transition temperature (Tm): The glass transition temperature (Tm) of the polymers prepared in Examples and Comparative Examples was measured using a Differential Scanning Calorimeter (DSC). Specifically, the polymer sample was heated to 220° C., maintained at the temperature for 5 minutes, cooled to 20° C., and the temperature was increased again. At this time, the rate of increase and decrease of temperature were 10° C./min, respectively It was adjusted to.

(3) Melt Index (MFR): According to ISO 1133, the melt mass flow index was measured.

The reaction conditions and results are summarized in Tables 1 and 2, respectively.

Remark Catalyst used Amount of catalyst used
(mg) Hydrogen supply
(mol·ppm) Catalytic activity
(kg/g·hr) Comparative Example 1-1 Comparative Example 1 45 300 8.3 Comparative Example 2-1 Comparative Example 2 30 300 12 Example 1-1 Example 1 45 0 2.2 Example 1-2 Example 1 45 300 5.3 Example 1-3 Example 1 45 700 5.3 Example 2-1 Example 2 45 300 10.8

Remark Yield
(g) MFR
(g/10min) Tm
(℃) Comparative Example 1-1 365 0.4 152 Comparative Example 2-1 370 6.2 150 Example 1-1 100 1.8 155 Example 1-2 239 12.8 156 Example 1-3 238 More than 100 156 Example 2-1 484 7.7 160

Referring to Table 1, the metallocene-supported catalyst used in the example polymerization reaction is capable of tethering the carrier to the t-butoxyhexyl group located at the bridge portion, so that the catalytic activity is equivalent to or equal to the existing one. You can see that it appears as above.

In addition, in the case of the embodiment, it can be clearly confirmed that the glass transition temperature value is relatively higher than that of the comparative example due to the structure in which a specific position is substituted, so that an olefin polymer having a glass transition temperature of about 155°C or higher can be prepared.

Claims (10)

Transition metal compound represented by the following formula (1):
[Formula 1]

In Formula 1,
M is a Group 4 transition metal;
X1 and X2 are each independently, the same as or different from each other, a halogen atom;
A is silicon (Si) or germanium (Ge);
n is an integer from 4 to 10;
R is directly connected to an aromatic ring, and is an alicyclic ring having 4 to 7 carbon atoms in the entire ring;
R1 and R2 are each independently different from each other and are at least one selected from the group consisting of methyl, ethyl, n-propyl, and iso-propyl;
R3, R4, R5, and R6 are each independently the same or different from each other, and the group consisting of n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl At least one selected from among;
R7 is at least one selected from the group consisting of methyl, ethyl, n-propyl, and iso-propyl.
delete delete The method of claim 1,
M is zirconium (Zr) or hafnium (Hf), a transition metal compound.
The transition metal compound of claim 1;
Cocatalyst; And
A metallocene-supported catalyst comprising a carrier.
The method of claim 5,
The cocatalyst is at least one selected from the group consisting of compounds represented by the following formulas 2 to 4, a metallocene supported catalyst:
[Formula 2]
R10-[Al(R9)-O] _m -R11
In Chemical Formula 2,
R9, R10 and R11 are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen,
m is an integer greater than or equal to 2,
[Formula 3]
D(R12) ₃
In Chemical Formula 3,
D is aluminum or boron,
R12 is each independently any one of halogen, a C1-C20 hydrocarbyl group, a C1-C20 hydrocarbyloxy group, and a C1-C20 hydrocarbyl group substituted with a halogen,
[Formula 4]
^{[LH] + [W (J} ) 4] - or ^{[L] + [W (J} ) 4] -
In Chemical Formula 4,
L is a neutral or cationic Lewis base,
W is a Group 13 element, and J is each independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And at least one hydrogen atom of these substituents is any one of a substituent substituted with at least one substituent among halogen, a C1-C20 hydrocarbyloxy group, and a C1-C20 hydrocarbyl (oxy)silyl group.
The method of claim 5,
The carrier is a metallocene supported catalyst of silica, alumina, magnesia, or a mixture thereof.
In the presence of the metallocene supported catalyst of claim 5, a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer.
The method of claim 8,
The olefin polymer is a propylene homopolymer, a method for producing an olefin polymer.
The method of claim 8,
The method for producing an olefin polymer, wherein the olefin polymer has a glass transition temperature of 155°C or higher.