KR20230023196A - Transition Metal Compound, Catalyst Comprising the Same, and Processes for Preparing the Same - Google Patents

Abstract

The present invention relates to a transition metal compound, a catalyst for olefin polymerization, including the same, and a preparation method thereof. More specifically, the present invention relates to a transition metal compound having a framework of 2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-indene], a catalyst for olefin polymerization, including the same, and a preparation method of the corresponding transition metal compound and the catalyst. The transition metal compound and the catalyst for olefin polymerization, including the same according to an embodiment of the present invention has a unique three-dimensional structure to allow physical properties of the polymer to be controlled.

Description

Transition metal compounds, catalysts containing them and methods for preparing them {Transition Metal Compound, Catalyst Comprising the Same, and Processes for Preparing the Same}

The present invention relates to a transition metal compound, a catalyst for olefin polymerization comprising the same, and a method for preparing the same. Specifically, the present invention is 2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-indene] (2'-methyl-1',5',6 It relates to a transition metal compound having a ',7'-tetrahydrospiro[cyclohexane-1,4'-indene]) skeleton, a catalyst for olefin polymerization including the same, and a method for preparing the transition metal compound and catalyst.

Polyolefin-based polymers are widely used in real life as materials such as shopping bags, vinyl houses, fishing nets, cigarette wrappers, ramen bags, yogurt bottles, battery cases, automobile bumpers, interior materials, shoe soles, and washing machines.

Conventional polyolefin polymers such as polyethylene, polypropylene, and ethylene-alpha olefin copolymers and copolymers thereof are prepared by a heterogeneous catalyst such as a Ziegler-Natta catalyst composed of a titanium compound and an alkyl aluminum compound.

Recently, a method for producing polyolefin using a metallocene catalyst, which is a homogeneous catalyst having very high catalytic activity, has been studied. A metallocene catalyst is a compound in which a ligand such as cyclopentadienyl, indenyl, or cycloheptadienyl is coordinated with a transition metal or transition metal halide compound, and has a sandwich structure as a basic form. . At this time, it has various molecular structures depending on the shape of the ligand and the type of the central metal.

Whereas the Ziegler-Natta catalyst, which is a heterogeneous catalyst, has a non-uniform nature of the active site because the metal component, which is the active site, is dispersed on an inert solid surface, the metallocene catalyst is a compound with a certain structure. Therefore, it is known as a single-site catalyst having the same polymerization characteristics at all active sites.

In general, since a metallocene catalyst is inactive as a polymerization catalyst by itself, it is used together with a cocatalyst such as methyl aluminoxane. The metallocene catalyst is activated as a cation by the action of the cocatalyst, and at the same time, the cocatalyst stabilizes the unsaturated cationic active species as an anion that is not coordinated to the metallocene catalyst to form a catalyst system having activity in various olefin polymerizations.

Such a metallocene catalyst is easy to copolymerize and can control the three-dimensional structure of the polymer according to the symmetry of the catalyst, and the polymer prepared therefrom has the advantage of having a narrow molecular weight distribution and a uniform distribution of comonomers.

However, there is still a need for a metallocene catalyst for olefin polymerization capable of preparing a resin having high activity, improved copolymerizability, and improved physical properties.

An object of the present invention is to provide a transition metal compound for olefin polymerization catalyst having a novel structure and a catalyst for olefin polymerization including the same, which can prepare a resin having high activity and excellent physical properties.

Another object of the present invention is to provide a method for preparing the above transition metal compound and a catalyst for olefin polymerization comprising the same.

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

[Formula 1]

In Formula 1 above, l is an integer from 0 to 2, m is an integer from 0 to 3, n is an integer from 0 to 5,

M is titanium (Ti), zirconium (Zr) or hafnium (Hf);

X is each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido or C _6-20 arylamido;

R ₁ to R ₃ are each independently substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 Alkyl C _6-20 Aryl, substituted or unsubstituted C _6-20 Aryl C _1-20 Alkyl, substituted or unsubstituted C _1-20 Heteroalkyl, substituted or unsubstituted C _3-20 Heteroaryl, substituted or unsubstituted substituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl, wherein R _One to R ₃ may each independently form a substituted or unsubstituted saturated or unsaturated C _4-20 ring by connecting adjacent groups;

R ₄ is substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _{6- 20} Aryl, substituted or unsubstituted C _6-20 Aryl C _1-20 Alkyl, substituted or unsubstituted C _1-20 Heteroalkyl, substituted or unsubstituted C _3-20 Heteroaryl or substituted or unsubstituted C _{1 -20} It is an alkylidene.

Specifically, in Formula 1 above, l is 1 or 2, m and n are each 0 or 1, M is zirconium, X is each halogen or substituted or unsubstituted C _1-20 alkyl, R ₁ to R ₃ are each substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, or substituted or unsubstituted C _6-20 aryl, and R ₄ is substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, or substituted or unsubstituted C _1-20 alkylidene.

Preferably, the transition metal compound represented by Formula 1 above is at least one of transition metal compounds represented by Formulas 1-1 to 1-21 below.

[Formula 1-1] [Formula 1-2] [Formula 1-3]

[Formula 1-4] [Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8] [Formula 1-9]

[Formula 1-10] [Formula 1-11] [Formula 1-12]

[Formula 1-13] [Formula 1-14] [Formula 1-15]

[Formula 1-16] [Formula 1-17] [Formula 1-18]

[Formula 1-19] [Formula 1-20] [Formula 1-21]

According to one embodiment of the present invention, (1) reacting the compound represented by the formula (2) and the compound represented by the formula (3) to obtain a compound represented by the formula (4); (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6; (3) reacting the compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; and (4) reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 below to obtain a transition metal compound represented by Chemical Formula 1 above.

[Formula 2]

[Formula 3]

Me ₂ Si(X _a ) ₂

[Formula 4]

[Formula 5]

R ₄ NH ₂

[Formula 6]

[Formula 7]

[Formula 8]

_MX4

In the above formula, l, m, n, M, X, R ₁ to R ₄ are as described in the above transition metal compound, Me is methyl, and X _a is halogen.

Preferably, the compound represented by Formula 2 above is at least one of the compounds represented by Formulas 2-1 to 2-16 below.

[Formula 2-1] [Formula 2-2] [Formula 2-3]

[Formula 2-4] [Formula 2-5] [Formula 2-6]

[Formula 2-7] [Formula 2-8] [Formula 2-9]

[Formula 2-10] [Formula 2-11] [Formula 2-12]

[Formula 2-13] [Formula 2-14] [Formula 2-15]

[Formula 2-16]

In an embodiment of the present invention, the reactions of the above steps (1) to (4) are independently selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate. It may be performed in the presence of at least one solvent selected from.

In an embodiment of the present invention, the reaction of step (4) may be carried out in the presence of an amine-based compound.

According to one embodiment for achieving another object of the present invention, the transition metal compound represented by Formula 1 above; And a catalyst for olefin polymerization comprising a cocatalyst compound is provided.

Here, the cocatalyst compound may be at least one selected from the group consisting of a compound represented by Formula 9, a compound represented by Formula 10, and a compound represented by Formula 11 below.

[Formula 9]

[Formula 10]

[Formula 11]

[LH] ⁺ [Z(A) ₄ ] ^- or [L] ⁺ [Z(A) ₄ ] ^-

In Formula 9 above, n is an integer of 2 or greater, R _a is a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with a halogen,

In Formula 10, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. Or a C _1-20 alkoxy group,

In Formula 11 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C ₆ It is _{a -20} aryl group or a substituted or unsubstituted C _1-20 alkyl group.

Specifically, the compound represented by Formula 9 is at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane.

In addition, the compound represented by Formula 10 is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri- s -butyl aluminum, tricyclopentyl aluminum, Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron , At least one selected from the group consisting of triethyl boron, triisobutyl boron, tripropyl boron and tributyl boron.

In addition, the compound represented by Formula 11 above is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra ( p -tolyl) Boron, trimethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra ( p -trifluoromethylphenyl) boron, trimethylammonium tetra ( p -trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra( p -tolyl) ) Aluminum, tripropylammonium tetra ( p -tolyl) aluminum, triethylammonium tetra ( o , p -dimethylphenyl) aluminum, tributylammonium tetra ( p -trifluoromethylphenyl) aluminum, trimethylammonium tetra ( p -trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenyl aluminum, di Ethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra( p -tolyl)boron, triethylammoniumtetra( o , p -dimethylphenyl)boron , Tributylammonium tetra ( p -trifluoromethylphenyl) boron, triphenylcarbonium tetra ( p -trifluoromethylphenyl) boron and triphenylcarbonium tetrapentafluorophenyl boron selected from the group consisting of at least one

In an embodiment of the present invention, the catalyst for olefin polymerization further includes a carrier supporting a transition metal compound. Specifically, the carrier may support both the transition metal compound and the cocatalyst compound.

In an embodiment of the present invention, the carrier may include at least one selected from the group consisting of silica, alumina and magnesia.

Here, the total amount of the transition metal compound supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the total amount of the cocatalyst compound supported on the carrier is 2 to 15 mmole based on 1 g of the carrier.

According to another embodiment of the present invention, (1) reacting the compound represented by the above formula (2) and the compound represented by the above formula (3) to obtain a compound represented by the above formula (4); (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 to obtain a compound represented by Chemical Formula 6; (3) obtaining a compound represented by Chemical Formula 7 by reacting a compound represented by Chemical Formula 6 with an organic lithium compound; and (4) reacting the compound represented by Chemical Formula 7 with the compound represented by Chemical Formula 8 to obtain a transition metal compound represented by Chemical Formula 1 above; and (5) supporting the transition metal compound, cocatalyst compound, or both obtained in step (4) on a carrier.

Since the transition metal compound and the catalyst for olefin polymerization including the same according to an embodiment of the present invention have a unique three-dimensional structure, physical properties of the polymer can be controlled.

Hereinafter, the present invention will be described in more detail.

transition metal compound

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

[Formula 1]

In Formula 1 above, l is an integer from 0 to 2, m is an integer from 0 to 3, and n is an integer from 0 to 5. Specifically, l may be 1 or 2, and m and n may be 0 or 1, respectively.

M is titanium (Ti), zirconium (Zr) or hafnium (Hf). Specifically, M may be hafnium or zirconium, preferably zirconium.

X is each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido or C _6-20 arylamido. Specifically, each X may be a halogen or a substituted or unsubstituted C _1-20 alkyl. More specifically, each X may be a halogen, preferably chlorine (Cl).

R ₁ to R ₃ are each independently substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 Alkyl C _6-20 Aryl, substituted or unsubstituted C _6-20 Aryl C _1-20 Alkyl, substituted or unsubstituted C _1-20 Heteroalkyl, substituted or unsubstituted C _3-20 Heteroaryl, substituted or unsubstituted substituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl. Here, R ₁ to R ₃ may each independently form a substituted or unsubstituted saturated or unsaturated C _4-20 ring by connecting adjacent groups. Specifically, R ₁ to R ₃ may each be substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, or substituted or unsubstituted C _6-20 aryl.

R ₄ is substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _{6- 20} Aryl, substituted or unsubstituted C _6-20 Aryl C _1-20 Alkyl, substituted or unsubstituted C _1-20 Heteroalkyl, substituted or unsubstituted C _3-20 Heteroaryl or substituted or unsubstituted C _{1 -20} It is an alkylidene. Specifically, R ₄ is substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl or substituted or unsubstituted C _1-20 alkylidene.

In an embodiment of the present invention, in Formula 1 above, l is 1 or 2, m and n are each 0 or 1, M is zirconium, X is each halogen or substituted or unsubstituted C _1-20 alkyl, and , R ₁ to R ₃ are each substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, or substituted or unsubstituted C _6-20 aryl, and R ₄ is substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, or substituted or unsubstituted C _1-20 alkylidene.

In a preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above may be at least one of transition metal compounds represented by Formulas 1-1 to 1-21 below.

[Formula 1-1] [Formula 1-2] [Formula 1-3]

[Formula 1-4] [Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8] [Formula 1-9]

[Formula 1-10] [Formula 1-11] [Formula 1-12]

[Formula 1-13] [Formula 1-14] [Formula 1-15]

[Formula 1-16] [Formula 1-17] [Formula 1-18]

[Formula 1-19] [Formula 1-20] [Formula 1-21]

Method for preparing transition metal compound

According to another embodiment of the present invention, (1) reacting the compound represented by the formula (2) and the compound represented by the formula (3) to obtain a compound represented by the formula (4); (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6; (3) reacting the compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; and (4) reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 below to obtain a transition metal compound represented by Chemical Formula 1 below.

[Formula 1]

[Formula 2]

[Formula 3]

Me ₂ Si(X _a ) ₂

[Formula 4]

[Formula 5]

R ₄ NH ₂

[Formula 6]

[Formula 7]

[Formula 8]

_MX4

In the above formula, l, m, n, M, X, R ₁ to R ₄ are as described in the above transition metal compound, Me is methyl, and X _a is halogen.

Preferably, the compound represented by Formula 2 above may be at least one of the compounds represented by Formulas 2-1 to 2-16 below.

[Formula 2-1] [Formula 2-2] [Formula 2-3]

[Formula 2-4] [Formula 2-5] [Formula 2-6]

[Formula 2-7] [Formula 2-8] [Formula 2-9]

[Formula 2-10] [Formula 2-11] [Formula 2-12]

[Formula 2-13] [Formula 2-14] [Formula 2-15]

[Formula 2-16]

Preferably, the compound represented by Formula 8 above may be ZrCl ₄ .

In an embodiment of the present invention, the reactions of the above steps (1) to (4) are independently selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate. It may be performed in the presence of at least one solvent selected from, but the solvent is not particularly limited thereto.

step (1)

In step (1) above, the compound represented by Chemical Formula 2 is reacted with the compound represented by Chemical Formula 3 to obtain the compound represented by Chemical Formula 4. Preferably, the compound represented by Formula 3 may be Me ₂ SiCl ₂ .

The reaction of step (1) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate, The solvent is not particularly limited to these. Preferably, the solvent may be toluene.

When the compound represented by Formula 2 and the compound represented by Formula 3 are dissolved in a solvent, the order of adding each compound is not particularly limited. That is, the compound represented by Chemical Formula 2 may be first added to a solvent to be dissolved, and then the compound represented by Chemical Formula 3 may be added to a solvent to be dissolved, or may be dissolved in the reverse order. Alternatively, these two compounds may be dissolved in a solvent and then slowly mixed.

When mixing the compound represented by Formula 2 and the compound represented by Formula 3 respectively dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Formula 2 and the compound represented by Formula 3 dissolved in a solvent, respectively, are dissolved at a temperature of -78 to 30 ° C, preferably at a temperature of -78 to -30 ° C, more preferably at about -30 ° C. It can be mixed slowly at a temperature of °C.

After mixing the compound represented by the formula (2) and the compound represented by the formula (3) respectively dissolved in a solvent, the resulting solution is stirred to obtain the compound represented by the formula (4).

At this time, the temperature and time during stirring are not particularly limited. For example, at a temperature of 25 to 150 ° C, preferably at a temperature of 80 to 110 ° C, more preferably at a temperature of about 90 ° C for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours. It can be reacted by stirring for a period of time.

After completion of the reaction in step (1), the solvent is removed from the reaction solution under vacuum, a new solvent is added to extract the product, and then the solvent is removed again under vacuum to obtain the product. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.

step (2)

In the above step (2), the compound represented by formula 6 is obtained by reacting the compound represented by formula 4 with the compound represented by formula 5. Preferably, the compound represented by Formula 5 may be t -butylamine.

The reaction of step (2) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate, The solvent is not particularly limited to these. Preferably, the solvent may be tetrahydrofuran.

When the compound represented by Formula 4 and the compound represented by Formula 5 are dissolved in a solvent, the order of adding each compound is not particularly limited. That is, the compound represented by Chemical Formula 4 may be first added to a solvent to be dissolved, and then the compound represented by Chemical Formula 5 may be added to a solvent to be dissolved, or may be dissolved in the reverse order. Alternatively, these two compounds may be dissolved in a solvent and then slowly mixed.

When mixing the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5 respectively dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5 respectively dissolved in a solvent at a temperature of -78 to 30 ° C, preferably at a temperature of -78 to -30 ° C, more preferably at about -30 ° C. It can be mixed slowly at a temperature of °C.

After mixing the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5 respectively dissolved in a solvent, the resulting solution is stirred to obtain the compound represented by Chemical Formula 6.

At this time, the temperature and time during stirring are not particularly limited. For example, stirring at a temperature of -30 to 100 ° C, preferably at a temperature of 0 to 50 ° C, more preferably at room temperature for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours can react.

After completion of the reaction in step (2), the solvent is removed from the reaction solution under vacuum, a new solvent is added to extract the product, and then the solvent is removed again under vacuum to obtain the product. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.

step (3)

In the above step (3), the compound represented by Chemical Formula 6 is reacted with an organolithium compound to obtain a compound represented by Chemical Formula 7. Preferably, the organolithium compound may be n -butyllithium.

The reaction of step (3) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate, The solvent is not particularly limited to these. Preferably, the solvent may be hexane.

When dissolving the compound represented by Formula 6 and the organolithium compound in a solvent, the order of adding each compound is not particularly limited. That is, the compound represented by Formula 6 may be first added to a solvent to be dissolved, and then the organolithium compound may be added to a solvent to be dissolved, or may be dissolved in the reverse order. Alternatively, these two compounds may be dissolved in a solvent and then slowly mixed. Specifically, it is preferable to slowly add a solution in which the organolithium compound is dissolved in a solvent to a solution in which the compound represented by Formula 6 is dissolved in a solvent.

When mixing the compound represented by Formula 6 and the organolithium compound each dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Formula 6 and the organic lithium compound respectively dissolved in a solvent at a temperature of -78 to 30 ° C, preferably at a temperature of -78 to -30 ° C, more preferably at a temperature of about -30 ° C can be mixed slowly.

After mixing the compound represented by Chemical Formula 6 and the lithium compound respectively dissolved in a solvent, the resulting solution is stirred to obtain a compound represented by Chemical Formula 7.

At this time, the temperature and time during stirring are not particularly limited. For example, stirring at a temperature of -30 to 100 ° C, preferably at a temperature of 0 to 50 ° C, more preferably at room temperature for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours can react.

After completion of the reaction in step (3), the solvent is removed from the reaction solution under vacuum, a new solvent is added to extract the product, and then the solvent is removed again under vacuum to obtain the product. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.

step (4)

In the above step (4), the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 are reacted to obtain a transition metal compound represented by Chemical Formula 1. Preferably, the compound represented by Chemical Formula 8 may be zirconium chloride (ZrCl ₄ ).

The reaction of step (4) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate, The solvent is not particularly limited to these. Preferably, the solvent may be toluene.

The reaction of step (4) may be carried out in the presence of an amine-based compound. The amine-based compound stabilizes the unstable compound represented by Chemical Formula 7 by maintaining a basic reaction environment and prevents the compound from being protonated. Preferably, the amine compound may be triethylamine, but is not particularly limited thereto.

When the compound represented by Formula 7 and the compound represented by Formula 8 are dissolved in a solvent, the order of adding each compound is not particularly limited. That is, the compound represented by Chemical Formula 7 may be first added to a solvent to be dissolved, and then the compound represented by Chemical Formula 8 may be added to a solvent to be dissolved, or may be dissolved in the reverse order. Alternatively, these two compounds may be dissolved in a solvent and then slowly mixed.

Here, the order of adding the amine-based compound is not particularly limited. Preferably, after adding the amine-based compound to a solution in which the compound represented by Formula 7 is dissolved, it can be dissolved by sufficiently stirring.

When mixing the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 respectively dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 respectively dissolved in a solvent at a temperature of -78 to 30 ° C, preferably at a temperature of -78 to -30 ° C, more preferably at about -30 ° C. It can be mixed slowly at a temperature of °C.

After mixing the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 respectively dissolved in a solvent, the resulting solution is stirred to obtain a transition metal compound represented by Chemical Formula 1.

At this time, the temperature and time during stirring are not particularly limited. For example, stirring at a temperature of -30 to 100 ° C, preferably at a temperature of 0 to 50 ° C, more preferably at room temperature for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours can react.

After completion of the reaction in step (4), the reaction solution is passed through a filter to remove impurities. The product can be obtained by removing the solvent from the reaction solution under vacuum, adding a new solvent to extract the product, and then removing the solvent under vacuum again. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.

Catalyst for olefin polymerization

According to another embodiment of the present invention, a transition metal compound represented by Formula 1 below; And a catalyst for olefin polymerization comprising a cocatalyst compound is provided.

[Formula 1]

In Formula 1 above, l, m, n, M, X, R ₁ to R ₄ are as described in the transition metal compound section above.

In a preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above may be at least one of transition metal compounds represented by Formulas 1-1 to 1-21 below.

[Formula 1-1] [Formula 1-2] [Formula 1-3]

[Formula 1-4] [Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8] [Formula 1-9]

[Formula 1-10] [Formula 1-11] [Formula 1-12]

[Formula 1-13] [Formula 1-14] [Formula 1-15]

[Formula 1-16] [Formula 1-17] [Formula 1-18]

[Formula 1-19] [Formula 1-20] [Formula 1-21]

Meanwhile, the cocatalyst compound may include at least one of a compound represented by Formula 9, a compound represented by Formula 10, and a compound represented by Formula 11 below.

[Formula 9]

In Formula 9, n is an integer of 2 or greater, and R _a may be a halogen atom, a C _1-20 hydrocarbon, or a C _1-20 hydrocarbon substituted with a halogen. Specifically, R _a can be methyl, ethyl, n -butyl or isobutyl.

[Formula 10]

In Formula 10, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. or a C _1-20 alkoxy group. Specifically, when D is aluminum (Al), R _b , R _c and R _d may each independently be methyl or isobutyl, and when D is boron (B), R _b , R _c and R _d are Each may be pentafluorophenyl.

[Formula 11]

[LH] ⁺ [Z(A) ₄ ] ^- or [L] ⁺ [Z(A) ₄ ] ^-

In Formula 11 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C ₆ It is _{a -20} aryl group or a substituted or unsubstituted C _1-20 alkyl group. Specifically, [LH] ⁺ may be a dimethylanilinium cation, [Z(A) ₄ ] ^- may be [B(C ₆ F ₅ ) ₄ ] ^- , and [L] ⁺ may be [(C ₆ H ₅ ) ₃ C] ⁺ .

Specifically, examples of the compound represented by Formula 9 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and methyl aluminoxane is preferable, but is not limited thereto.

Examples of the compound represented by Formula 10 above are trimethylaluminum, triethylaluminium, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminium, tri- s -butylaluminum, tricyclopentylaluminum , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and trimethylaluminum, triethylaluminum and triisobutylaluminum are preferred, but not limited thereto.

Examples of the compound represented by Formula 11 above are triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra ( p -tolyl) Boron, trimethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra ( p -trifluoromethylphenyl) boron, trimethylammonium tetra ( p -trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra( p -tolyl) ) Aluminum, tripropylammonium tetra ( p -tolyl) aluminum, triethylammonium tetra ( o , p -dimethylphenyl) aluminum, tributylammonium tetra ( p -trifluoromethylphenyl) aluminum, trimethylammonium tetra ( p -trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenyl aluminum, di Ethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra( p -tolyl)boron, triethylammoniumtetra( o , p -dimethylphenyl)boron , tributylammonium tetra( p -trifluoromethylphenyl) boron, triphenylcarbonium tetra( p -trifluoromethylphenyl)boron, triphenylcarbonium tetrapentafluorophenylboron, and the like.

In a preferred embodiment of the present invention, the catalyst for olefin polymerization may further include a carrier supporting a transition metal compound. Specifically, the carrier may support both the transition metal compound and the cocatalyst compound.

At this time, the carrier may include a material containing a hydroxyl group on the surface, and preferably, a material having a highly reactive hydroxyl group and a siloxane group, from which moisture is removed from the surface by drying, may be used. For example, the carrier may include at least one selected from the group consisting of silica, alumina, and magnesia. Specifically, silica dried at high temperature, silica-alumina, silica-magnesia, and the like can be used as carriers, which are usually oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) ₂ . , carbonate, sulfate, and nitrate components. In addition, they may contain carbon, zeolites, magnesium chloride, and the like. However, the carrier is not limited thereto, and is not particularly limited as long as it can support the transition metal compound and the cocatalyst compound.

The carrier may have an average particle size of 10 to 250 μm, preferably 10 to 150 μm, and more preferably 20 to 100 μm.

The micropore volume of the carrier may be 0.1 to 10 cc/g, preferably 0.5 to 5 cc/g, and more preferably 1.0 to 3.0 cc/g.

The specific surface area of the carrier may be 1 to 1,000 m2/g, preferably 100 to 800 m2/g, and more preferably 200 to 600 m2/g.

In a preferred embodiment, when the carrier is silica, the drying temperature of the silica may be from room temperature to 900°C. The drying temperature may be preferably from room temperature to 800°C, more preferably from room temperature to 700°C. When the drying temperature is lower than room temperature, too much moisture causes the surface moisture to react with the cocatalyst, and when the drying temperature exceeds 900° C., the structure of the carrier may collapse.

The concentration of the hydroxy group in the dried silica may be 0.1 to 5 mmole/g, preferably 0.7 to 4 mmole/g, and more preferably 1.0 to 2 mmole/g. If the concentration of the hydroxy group is less than 0.1 mmole/g, the supported amount of the cocatalyst is low, and if it exceeds 5 mmole/g, a problem of inactivation of the catalyst component may occur.

The total amount of the transition metal compound supported on the carrier may be 0.001 to 1 mmole based on 1 g of the carrier. When the ratio of the transition metal compound and the carrier satisfies the above range, it exhibits appropriate supported catalyst activity, which is advantageous in terms of maintaining the activity of the catalyst and economic efficiency.

The total amount of the cocatalyst compound supported on the carrier may be 2 to 15 mmole based on 1 g of the carrier. When the ratio of the cocatalyst compound and the carrier satisfies the above range, it is advantageous in terms of maintaining the activity of the catalyst and economic efficiency.

One or two or more carriers may be used. For example, both the transition metal compound and the cocatalyst compound may be supported on one carrier, or the transition metal compound and the cocatalyst compound may be supported on two or more carriers, respectively. In addition, only one of the transition metal compound and the cocatalyst compound may be supported on the carrier.

Method for preparing a catalyst for olefin polymerization

According to another embodiment of the present invention, (1) reacting the compound represented by the formula (2) and the compound represented by the formula (3) to obtain a compound represented by the formula (4); (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6; (3) reacting the compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; and (4) reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 to obtain a transition metal compound represented by Chemical Formula 1 below; and (5) supporting the transition metal compound, cocatalyst compound, or both obtained in step (4) on a carrier.

[Formula 1]

[Formula 2]

[Formula 3]

Me ₂ Si(X _a ) ₂

[Formula 4]

[Formula 5]

R ₄ NH ₂

[Formula 6]

[Formula 7]

[Formula 8]

_MX4

In the above formula, l, m, n, M, X, R ₁ to R ₄ are as described in the above transition metal compound, Me is methyl, and X _a is halogen.

Details of the above steps (1) to (4) are substantially the same as steps (1) to (4) of the above transition metal compound preparation method.

step (5)

In the above step (5), the transition metal compound, the cocatalyst compound or both are supported on the carrier.

As a method for supporting the transition metal compound and/or cocatalyst compound, a physical adsorption method or a chemical adsorption method may be used.

For example, the physical adsorption method is a method of contacting a solution in which a transition metal compound is dissolved with a carrier and then drying it, a method of bringing a solution in which a transition metal compound and a cocatalyst compound are dissolved into contact with a carrier, and drying the solution, or a transition metal compound The dissolved solution is brought into contact with a carrier and dried to prepare a carrier supported with a transition metal compound, and separately, the solution in which the cocatalyst compound is dissolved is brought into contact with a carrier and then dried to prepare a carrier supported with a cocatalyst compound. After that, it may be a method of mixing them.

The chemical adsorption method is a method in which a cocatalyst compound is first supported on the surface of a carrier and then a transition metal compound is supported on the cocatalyst compound, or a functional group on the surface of the carrier (for example, in the case of silica, a hydroxyl group on the silica surface (-OH) )) and a method of covalently bonding a transition metal compound.

Here, the solvent used for supporting the transition metal compound and/or the cocatalyst compound is not particularly limited. For example, the solvent is an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an ether solvent such as diethyl ether or tetrahydrofuran, or acetone. And it may include at least one selected from the group consisting of ethyl acetate.

In a preferred embodiment, the process of supporting the transition metal compound and/or cocatalyst compound on the support in step (5) may be performed at a temperature of 0 to 100°C, preferably from room temperature to 90°C.

In addition, in the process of supporting the transition metal compound and/or cocatalyst compound on the carrier in step (5), the mixture of the transition metal compound and/or cocatalyst compound and the carrier is maintained for 1 minute to 24 hours, preferably 5 minutes to 15 hours. It can be performed by sufficiently stirring for a period of time.

polymerization of olefins

An olefin-based polymer may be prepared by polymerizing an olefin-based monomer in the presence of a catalyst for olefin polymerization according to an embodiment of the present invention.

Here, the olefin-based polymer may be a homopolymer of olefin-based monomers or a copolymer of olefin-based monomers and comonomers.

The olefinic monomer is composed of C _2-20 alpha-olefin, C _1-20 diolefin, C _3-20 cycloolefin and C _3-20 cyclodiolefin. It is at least one selected from the group.

For example, olefinic monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 It may be dodecene, 1-tetradecene or 1-hexadecene, etc., and the olefinic polymer may be a homopolymer containing only one olefinic monomer or a copolymer containing two or more of the olefinic monomers exemplified above.

In an exemplary embodiment, the olefin-based polymer may be a copolymer of ethylene and C _3-20 alpha-olefin, preferably a copolymer of ethylene and 1-hexene, but is not limited thereto.

In this case, the content of ethylene is preferably 55 to 99.9% by weight, more preferably 90 to 99.9% by weight. The content of the alpha-olefin comonomer is preferably 0.1 to 45% by weight, more preferably 0.1 to 10% by weight.

In an exemplary embodiment, the olefin-based polymer may be polymerized by a polymerization reaction such as free radical, cationic, coordination, condensation, or addition, but is limited to these it is not going to be

As a preferred embodiment, the olefin-based polymer may be prepared by gas phase polymerization, solution polymerization or slurry polymerization. When the olefinic polymer is produced by solution polymerization or slurry polymerization, examples of solvents that can be used include C _5-12 aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof; aromatic hydrocarbon solvents such as toluene and benzene; hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; and mixtures thereof, but are not limited thereto.

Example

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only for exemplifying the present invention, and the scope of the present invention is not limited only to these.

Example 1:N- tert -Butyl-1,1-dimethyl-1-(2'- methyl -1',5',6',7'- tetrahydrospiro [Cyclohexane-1,4'-indenyl]) Silanamine Zirconium dichloride (N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7' -tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine zirconium dichloride; 1) of manufacturing

A transition metal compound of Chemical Formula 1-1 was prepared according to the synthesis procedure outlined in Reaction Scheme 1 below.

[Scheme 1]

Step 1: Spiro[5.5]undecane -1-one ( spiro[5.5]undecan -1-one; chemical formula b ) synthesis of

To a solution in which potassium tert-butoxide (11.43 g, 102 mmole) was dispersed in toluene (80 ml), cyclohexanone (Formula a ) (5.0 g, 51 mmole) was added to toluene (50 ml). ) and a diluted solution of 1,5-dibromopentane (11.71 g, 51 mmole) in toluene (70 ml) were slowly added. After that, the mixture was stirred at 110°C for 12 hours. After neutralization by adding 1 M hydrochloric acid at 0 °C to terminate the reaction, the organic layer was separated using a separatory funnel. After removing the remaining water with magnesium sulfate (MgSO ₄ ) and removing the solvent under vacuum, it was separated by column chromatography (hexane: ethyl acetate = 20/1, v/v) to give 5.59 g (66%) of a white solid compound. got

¹ H NMR (300 MHz, CDCl ₃ ): δ 2.40 (t, 2 H), 1.80-1.93 (m, 4 H), 1.66-1.75 (m, 4 H), 1.45-1.53 (m, 4 H), 1.30-1.45 (m, 4 H).

step 2:2 - bromospiro[5,5]undecane -1-one (2- bromospiro[5,5]undecan -1-one; chemical formula c ) synthesis of

To a solution of the compound of Formula b (5.59 g, 34 mmole) diluted in diethyl ether (50 mL), a solution of bromine (5.37 g, 34 mmole) diluted in diethyl ether (50 mL) was slowly added at 0 ° C. After that, the temperature was gradually raised to room temperature and stirred for 12 hours. To terminate the reaction, a saturated solution of sodium thiosulfate (Na ₂ S ₂ O ₃ ) was added to remove bromine remaining after the reaction, and the organic layer was separated using a separatory funnel. The remaining water was removed with magnesium sulfate, and the solvent was removed under vacuum, followed by column chromatography (hexane:ethyl acetate = 20/1, v/v) to obtain 9.23 g (equivalent yield) of a yellow liquid compound.

¹ H NMR (300 MHz, CDCl ₃ ): δ 4.94 (dd, 1 H), 2.57-2.66 (m, 1 H), 2.09 (dd, 1 H), 1.85-2.01 (m, 4 H), 1.64- 1.78 (m, 4 H), 1.37–1.61 (m, 6 H), 1.20–1.34 (m, 2 H).

Step 3: Ethyl 3-oxo-2- (1-oxospiro[5,5]undecen-2-yl)butyrate (ethyl 3-oxo-2- (1-oxospiro[5.5]undecen-2-yl)butyrate; chemical formula d ) synthesis of

A solution obtained by dispersing ethyl acetoacetate sodium salt (11.45 g, 75 mmole) in toluene (70 ml) and diluting the compound of formula c (9.23 g, 38 mmole) in toluene (30 ml). was added. It was then stirred at 110° C. for 12 hours. After neutralization by adding 1 M hydrochloric acid at 0 °C to terminate the reaction, the organic layer was separated using a separatory funnel. The remaining water was removed with magnesium sulfate, and the solvent was removed under vacuum to obtain 12.30 g (equivalent yield) of a yellow liquid mixture of the compound of formula d and ethylacetoacetate.

step 4:2 - (2-oxopropyl)spiro[5,5]undecane -1-one (2- (2-oxopropyl)spiro[5.5] undecan-1-one; chemical formula e ) synthesis of

A 3.0 M aqueous solution of potassium hydroxide (120 ml) was added to a solution of a mixture of the compound of formula d and ethyl acetoacetate diluted in methanol (120 ml), and the mixture was stirred at 65° C. for 12 hours. After neutralization by adding 1 M hydrochloric acid at 0 °C to terminate the reaction, the organic layer was separated using a separatory funnel. The remaining water was removed with magnesium sulfate, and the solvent was removed under vacuum, followed by column chromatography (hexane:ethyl acetate = 20/1, v/v) to obtain 3.46 g (31%) of a yellow liquid compound.

¹ H NMR (300 MHz, CDCl ₃ ): δ 3.25-3.36 (m, 1 H), 2.94 (dd, 1 H), 2.22 (s, 3 H), 2.12 (dd, 1 H), 1.85-2.04 ( m, 4 H), 1.55–1.70 (m, 4 H), 1.24–1.52 (m, 7 H), 1.01–1.10 (m, 1 H).

step 5:5 ',6',7',7a'- tetrahydrospiro [ cyclohexane -1,4'- inden ] 2' (1'H) -one (5', 6', 7', 7a'-tetrahydrospiro [cyclohexane-1,4'-inden] 2' ( 1'H ) - one; chemical formula f ) synthesis of

Potassium t -butoxide (2.10 g, 19 mmole) was added to a solution of the compound of formula e (3.46 g, 16 mmole) diluted in toluene (35 ml), and the mixture was stirred at room temperature for 4 hours. The reaction was terminated by adding distilled water, extracted with ethyl acetate, and the organic layer was separated using a separatory funnel. After removing the remaining water with magnesium sulfate, removing the solvent under vacuum, and separating by column chromatography (hexane: ethyl acetate = 20/1, v/v), 1.65 g of a compound obtained as a mixture of a yellow needle-like solid and a yellow liquid was obtained. (52%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 5.90 and 5.81 (s, 1 H), 2.85-2.93 and 2.75-2,81 (m, 1 H), 2.59 and 2.75 (d, 1 H), 2.15- 2.38 (m, 3 H), 0.92–2.02 (m, 14 H).

Step 6: 2'-methyl-1', 2', 5', 6', 7', 7a'-hexahydrospiro [cyclohexane-1,4'-indene] -2'-ol (2'-methyl -1',2',5',6',7',7a'-hexahydrospiro[cyclohexane-1,4'-inden]-2'-ol; g ) synthesis of

After cooling the solution of the compound of formula f (1.0 g, 4.89 mmole) in tetrahydrofuran (20 ml) to -30 ° C, a 1.6 M methyllithium solution (4.6 ml, 7.34 mmole) was slowly injected, The mixture was stirred at room temperature for 16 hours. The reaction was terminated by adding distilled water, extracted with ethyl acetate, and the organic layer was separated using a separatory funnel. After removing remaining water with magnesium sulfate and removing the solvent under vacuum, the obtained compound of formula g was used in the next reaction as it is.

step 7:2 '- methyl -5',6',7',7a'- tetrahydrospiro [ cyclohexane -1,4'- inden ](2'-methyl-5',6',7',7a'-tetrahydrospiro[cyclohexane-1,4'-indene; chemical formula h ) synthesis of

A solution of the compound of Formula g dissolved in diethyl ether (10 ml) was cooled to 0°C, then 1 M hydrochloric acid (6 ml) was added thereto, and the mixture was stirred for 2 hours while maintaining the temperature. Then, it was diluted with distilled water (10 ml), extracted with ethyl acetate, and the organic layer was separated with a separatory funnel. The remaining water was removed with magnesium sulfate, the solvent was removed under vacuum, and then separated by column chromatography (hexane) to give 466 mg (47%) of compound h as a clear colorless liquid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 6.10 and 5.85 (s, 1 H), 2.83 and 2.77 (s, 2 H), 2.23-2.10 (m, 2 H), 2.00 (s, 3 H), 1.71-1.54 (m, 4 H), 1.54-1.41 (m, 10 H).

step 8:2 '- methyl -5',6',7',7a'- tetrahydrospiro [ cyclohexane -1,4'- indenyl ] Lithium (2'-methyl-5',6',7',7a'- tetrahydrospiro [ cyclohexane -1,4'- indenyl ] lithium; chemical formula i ) synthesis of

A solution of the compound of formula h (51 mg, 0.25 mmole) in tetrahydrofuran (5 ml) was cooled to -30 ° C, and then a 1.6 M n- butyllithium solution (0.2 ml, 0.31 mmole) was slowly injected. Then, the mixture was stirred at room temperature for 16 hours. After removing the tetrahydrofuran solvent under vacuum, hexane was added to filter out the lithium salt compound (Formula i ) produced through a separatory funnel, and then washed several times with hexane to obtain 42 mg (79%).

Step 9: Chlorodimethyl(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-indene]-1'-yl)silane (chlorodimethyl(2'- methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silane; j ) synthesis of

After cooling a solution of dimethyldichlorosilane (Me ₂ SiCl ₂ ) (35 mg, 0.17 mmole) in toluene (1 ml) to -30 ° C, the compound of formula i (35 mg, 0.17 mmole) was added to toluene (1 ml). ) After slowly injecting the dissolved solution, the mixture was stirred at 90° C. for 16 hours. After removal of toluene under vacuum, the product was extracted by addition of pentane and removal of pentane under vacuum to give 39 mg (78%) of the compound as a white solid.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ 6.19 (s, 1H), 2.91 (s, 1H), 2.05 (s, 3H), 1.61-1.18 (m, 16H), 0.18-0.09 (m, 6H).

Step 10: N- tert -Butyl-1,1-dimethyl-1-(2'- methyl -1', 5', 6', 7'- tetrahydrospiro [cyclohexane-1,4'-indene] -1'-yl) silaneamine (N-tert-butyl-1,1-dimethyl-1- (2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine; k ) synthesis of

After cooling the solution of the compound of formula j (39 mg, 0.13 mmole) in tetrahydrofuran (1 ml) to -30 ° C, t -butylamine ( t -butylamine) (38 mg, 0.53 mmole) was added to tetrahydro After slowly injecting a solution dissolved in furan (1 ml), the mixture was stirred at room temperature for 16 hours. After removing tetrahydrofuran under vacuum, pentane was added to extract the product, and pentane was removed under vacuum to obtain 43 mg (97%) of the compound as a white solid.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ 6.24 (s, 1H), 2.75 (s, 1H), 2.11 (s, 3H), 1.91 (m, 2H), 1.70-1.58 (m, 7H) , 1.51–1.45 (m, 7H), 1.07 (s, 9H), 0.13 (d, 6H).

Step 11: N- tert -Butyl-1,1-dimethyl-1-(2'- methyl -1',5',6',7'- tetrahydrospiro [Cyclohexane-1,4'-indene] -1'-yl) silaneamine dilithium Salt (N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl )silanamine dilithium salt; chemical formula l ) synthesis of

After cooling a solution of the compound of formula k (43 mg, 0.13 mmole) in hexane (1 ml) to -30 ° C, a 1.6 M t -butyllithium (121 mg, 0.28 mmole) solution was slowly injected therein, It was stirred for 16 hours at room temperature. After removing the hexane under vacuum, it was washed several times with pentane and dried to be used in the next step.

Step 12: N- tert -Butyl-1,1-dimethyl-1-(2'- methyl -1',5',6',7'- tetrahydrospiro [Cyclohexane-1,4'-indene] -1'-yl) silaneamine zirconium dichloride (N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6 ',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine zirconium dichloride; 1) of synthesis

Trimethylamine (52 mg, 0.52 mmole) was added to a solution of the compound of Formula 1 in toluene (2 ml), stirred for 30 minutes, and then the solution was cooled to -30 °C. Zirconium chloride (ZrCl ₄ ) (30 mg, 0.12 mmole) was added thereto, and the mixture was stirred at room temperature for 16 hours. The reaction mixture was passed through a filter to remove impurities and toluene was removed under vacuum. Then, pentane was added to extract the product, and pentane was removed under vacuum to give 30 mg (47%) of the compound of Formula 1-1.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ 6.39 (s, 1H), 2.08 (s, 3H), 1.71-1.09 (m, 16H), 1.34 (s, 9H), 0.39 (s, 3H) , 0.34 (s, 3H).

Since the transition metal compound and the catalyst for olefin polymerization containing the same according to an embodiment of the present invention have a unique three-dimensional structure, the physical properties of the polymer can be controlled.

Claims (16)

A transition metal compound represented by Formula 1 below:
[Formula 1]

In Formula 1 above, l is an integer from 0 to 2, m is an integer from 0 to 3, n is an integer from 0 to 5,
M is titanium (Ti), zirconium (Zr) or hafnium (Hf);
X is each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido or C _6-20 arylamido;
R ₁ to R ₃ are each independently substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 Alkyl C _6-20 Aryl, substituted or unsubstituted C _6-20 Aryl C _1-20 Alkyl, substituted or unsubstituted C _1-20 Heteroalkyl, substituted or unsubstituted C _3-20 Heteroaryl, substituted or unsubstituted substituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl, wherein R _One to R ₃ may each independently form a substituted or unsubstituted saturated or unsaturated C _4-20 ring by connecting adjacent groups;
R ₄ is substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _{6- 20} Aryl, substituted or unsubstituted C _6-20 Aryl C _1-20 Alkyl, substituted or unsubstituted C _1-20 Heteroalkyl, substituted or unsubstituted C _3-20 Heteroaryl or substituted or unsubstituted C _{1 -20} It is an alkylidene. The method of claim 1, wherein l is 1 or 2, m and n are each 0 or 1, M is zirconium, X is each halogen or substituted or unsubstituted C _1-20 alkyl, R ₁ to R ₃ are each substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, or substituted or unsubstituted C _6-20 aryl, and R ₄ is substituted or unsubstituted C A transition metal compound that is _1-20 alkyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, or substituted or unsubstituted C _1-20 alkylidene. The transition metal compound according to claim 1, wherein the transition metal compound represented by Formula 1 is at least one of transition metal compounds represented by Formulas 1-1 to 1-21 below:
[Formula 1-1] [Formula 1-2] [Formula 1-3]

[Formula 1-4] [Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8] [Formula 1-9]

[Formula 1-10] [Formula 1-11] [Formula 1-12]

[Formula 1-13] [Formula 1-14] [Formula 1-15]

[Formula 1-16] [Formula 1-17] [Formula 1-18]

[Formula 1-19] [Formula 1-20] [Formula 1-21]

. (1) reacting a compound represented by Chemical Formula 2 with a compound represented by Chemical Formula 3 below to obtain a compound represented by Chemical Formula 4; (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6; (3) reacting the compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; and (4) reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 to obtain a transition metal compound represented by Chemical Formula 1 below:
[Formula 1]

[Formula 2]

[Formula 3]
Me ₂ Si(X _a ) ₂
[Formula 4]

[Formula 5]
R ₄ NH ₂
[Formula 6]

[Formula 7]

[Formula 8]
_MX4
In the above formula, l, m, n, M, X, R ₁ to R ₄ are as described in the above transition metal compound, Me is methyl, and X _a is halogen. The method of claim 4, wherein the compound represented by Formula 2 is at least one of the compounds represented by Formulas 2-1 to 2-16 below:
[Formula 2-1] [Formula 2-2] [Formula 2-3]

[Formula 2-4] [Formula 2-5] [Formula 2-6]

[Formula 2-7] [Formula 2-8] [Formula 2-9]

[Formula 2-10] [Formula 2-11] [Formula 2-12]

[Formula 2-13] [Formula 2-14] [Formula 2-15]

[Formula 2-16]

. The method of claim 4, wherein the reactions of steps (1) to (4) are each independently selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate Method for producing a transition metal compound carried out in the presence of at least one solvent that is. The method for preparing a transition metal compound according to claim 4, wherein the reaction of step (4) is performed in the presence of an amine-based compound. The transition metal compound according to any one of claims 1 to 3; And a catalyst for olefin polymerization comprising a cocatalyst compound. The catalyst for olefin polymerization according to claim 8, wherein the cocatalyst compound is at least one selected from the group consisting of a compound represented by Formula 9, a compound represented by Formula 10, and a compound represented by Formula 11:
[Formula 9]

[Formula 10]

[Formula 11]
[LH] ⁺ [Z(A) ₄ ] ^- or [L] ⁺ [Z(A) ₄ ] ^-
In Formula 9 above, n is an integer of 2 or greater, R _a is a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with a halogen,
In Formula 10, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. Or a C _1-20 alkoxy group,
In Formula 11 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C ₆ It is _{a -20} aryl group or a substituted or unsubstituted C _1-20 alkyl group. The catalyst for olefin polymerization according to claim 9, wherein the compound represented by Formula 9 is at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane. The method of claim 9, wherein the compound represented by Formula 10 is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri- s -butyl aluminum, tri Cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxy A catalyst for olefin polymerization that is at least one selected from the group consisting of seed, trimethylboron, triethylboron, triisobutylboron, tripropylboron and tributylboron. The method of claim 9, wherein the compound represented by Formula 11 is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetraphenylboron ( p -Tolyl) boron, trimethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra ( p -trifluoromethylphenyl) boron, trimethylammonium tetra ( p -trifluoromethylphenyl) boron, tributyl Ammonium tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethylammonium tetrapentafluorophenyl boron, tri Phenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra( p -tolyl) aluminum, tripropylammonium tetra( p -tolyl) aluminum, triethylammonium tetra( o , p -dimethylphenyl) aluminum, tributylammonium tetra( p -trifluoromethylphenyl) aluminum, trimethylammonium Umtetra ( p -trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenyl Aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra( p -tolyl) boron, triethylammonium tetra( o , p -dimethyl The group consisting of phenyl) boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarboniumtetra( p -trifluoromethylphenyl)boron and triphenylcarbonium tetrapentafluorophenylboron At least one catalyst for olefin polymerization selected from The catalyst for olefin polymerization according to claim 8, further comprising a carrier supporting the transition metal compound, the cocatalyst compound, or both. The catalyst for olefin polymerization according to claim 13, wherein the support includes at least one selected from the group consisting of silica, alumina, and magnesia. The olefin according to claim 13, wherein the total amount of the transition metal compound supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the total amount of the cocatalyst compound supported on the carrier is 2 to 15 mmole based on 1 g of the carrier. Catalyst for polymerization. (1) reacting a compound represented by Chemical Formula 2 with a compound represented by Chemical Formula 3 below to obtain a compound represented by Chemical Formula 4; (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6; (3) reacting the compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; (4) reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 to obtain a transition metal compound represented by Chemical Formula 1 below; and (5) supporting a transition metal compound, a cocatalyst compound, or both obtained in step (4) on a carrier.
[Formula 1]

[Formula 2]

[Formula 3]
Me ₂ Si(X _a ) ₂
[Formula 4]

[Formula 5]
R ₄ NH ₂
[Formula 6]

[Formula 7]

[Formula 8]
_MX4
In the above formula, l, m, n, M, X, R ₁ to R ₄ are as described in the above transition metal compound, Me is methyl, and X _a is halogen.