KR102455610B1 - Transition metal compound used to prepare catalyst for polymerizing olefin and manufacturing method thereof - Google Patents

Abstract

A method for preparing a transition metal compound for an olefin polymerization catalyst, a transition metal compound for an olefin polymerization catalyst prepared using the same, and an olefin polymerization catalyst composition including the same are provided. The method for preparing a transition metal compound for an olefin polymerization catalyst includes the steps of preparing a first precursor represented by Formula A2, preparing a second precursor including at least one of compounds represented by Formulas B2-1 to B2-4 and reacting the first precursor with the second precursor to obtain one or more of the compounds represented by Chemical Formulas 1-1 to 1-5. Details of Formulas A2 to 1-5 are described in the specification.

Description

Transition metal compound for olefin polymerization catalyst and manufacturing method thereof

The present invention relates to a transition metal compound for an olefin polymerization catalyst and a method for preparing the same.

A metallocene catalyst, one of the catalysts used to polymerize olefins, is a compound in which ligands such as a cyclopentadienyl group, an indenyl group, and a cycloheptadienyl group are coordinated to a transition metal or transition metal halide compound. have

The metallocene catalyst is a single-site catalyst composed of the metallocene compound and a cocatalyst such as methylaluminoxane. The polymer polymerized with the metallocene catalyst has a narrow molecular weight distribution and The monomer distribution is uniform, and the copolymerization activity is higher than that of the Ziegler-Natta catalyst.

An object of the present invention is to provide a method for preparing a transition metal compound for an olefin polymerization catalyst having a novel structure, a transition metal compound prepared using the same, and an olefin polymerization catalyst composition including the same.

The problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

The method for producing a transition metal compound for an olefin polymerization catalyst according to an embodiment of the present invention for solving the above problems is a step of preparing a first precursor represented by the following formula A2, represented by the following formulas B2-1 to B2-4 One of the compounds represented by the following Chemical Formulas 1-1 to 1-5, including preparing a second precursor including at least one of the compounds to be used and reacting the first precursor with the second precursor get more

<Formula A2>

<Formula B2-1>

<Formula B2-2>

<Formula B2-3>

<Formula B2-4>

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

<Formula 1-5>

In Formulas A2 to 1-5, n and l are each independently an integer from 0 to 8, m1 and m2 are each independently an integer from 0 to 4, k is an integer from 0 to 2, and M is titanium ( Ti), zirconium (Zr) or hafnium (Hf), and each X is 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, C _6-20 arylamido or C _1-20 alkylidene, Q is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), R ¹ , R ⁶ and R ⁷ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene and R ² to R ⁵ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene, R ³ and R ⁴ are each independently a substituted or substituted by adjacent groups It may form an unsubstituted saturated or unsaturated C _4-20 ring.

The transition metal compound for an olefin polymerization catalyst according to an embodiment of the present invention for solving the other problems is represented by one or more of the following Chemical Formulas 1-1 to 1-5.

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

<Formula 1-5>

In Formulas 1-1 to 1-5, n and l are each independently an integer from 0 to 8, m1 and m2 are each independently an integer from 0 to 4, k is an integer from 0 to 2, and M is Titanium (Ti), zirconium (Zr) or hafnium (Hf), each X is 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, C _6-20 arylamido or C _1-20 alkylidene, Q is carbon (C ), silicon (Si), germanium (Ge), or tin (Sn), and R ¹ , R ⁶ and R ⁷ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkyl Nyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene, and R ² to R ⁵ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene, R ³ and R ⁴ are each independently an adjacent group connected A substituted or unsubstituted saturated or unsaturated C _4-20 ring may be formed.

The olefin polymerization catalyst composition according to an embodiment of the present invention for solving the above other problems includes a first transition metal compound, which is a transition metal compound for an olefin polymerization catalyst, and a second transition metal compound represented by the following Chemical Formula 3, , The content ratio of the first transition metal compound to the second transition metal compound is 100 parts by weight: 100 to 0 parts by weight.

<Formula 3>

In Formula 3, n and l are each independently an integer of 0 to 8, k is an integer of 0 to 2, M is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X is each independently By 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, C _6-20 arylamido or C _1-20 alkylidene, Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn), R ¹ , R ⁶ and R ⁷ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene, R ² , R ⁴ and R ⁵ are each independently 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 Alkylami Fig., C _6-20 arylamido or C _1-20 alkylidene, R ⁴ and R ⁵ may each independently be connected to adjacent groups to form a substituted or unsubstituted saturated C _4-20 ring.

The details of other embodiments are included in the detailed description and drawings.

According to the embodiments of the present invention, there are at least the following effects.

A transition metal compound for an olefin polymerization catalyst having a novel structure can be provided, and in particular, a transition metal compound for an olefin polymerization catalyst having a partially hydrogenated structure can be prepared alone.

Effects according to the embodiments of the present invention are not limited by the contents exemplified above, and more various effects are included in the present specification.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in a variety of different forms, only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the technical field to which the present invention belongs It is provided to fully inform the possessor of the scope of the invention, and the present invention is only defined by the scope of the claims.

In this specification, the term "C _AB " means "the number of carbon atoms is A or more and B or less", the term "A to B" means "A or more and B or less", and the term "substituted or unsubstituted""Substituted" in " means that at least one hydrogen of the hydrocarbon compound or hydrocarbon derivative is 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, C _6-20 arylamido or C _1-20 alkylidene "Unsubstituted" means that at least one hydrogen of the hydrocarbon compound or hydrocarbon derivative is halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl. not substituted with C _6-20 aryl, C _6-20 aryl, C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene.

According to an embodiment, the present invention includes the steps of preparing a first precursor represented by the following Chemical Formula A2, preparing a second precursor including at least one of the compounds represented by the following Chemical Formulas B2-1 to B2-4, and It provides a method for preparing a transition metal compound for an olefin polymerization catalyst comprising reacting a first precursor and a second precursor.

<Formula A2>

<Formula B2-1>

<Formula B2-2>

<Formula B2-3>

<Formula B2-4>

The first precursor may be obtained from a compound represented by the following Chemical Formula A1.

<Formula A1>

The second precursor may be obtained from one or more of the compounds represented by the following Chemical Formulas B1-1 to B1-4.

<Formula B1-1>

<Formula B1-2>

<Formula B1-3>

<Formula B1-4>

In Formulas A1, A2, B1-1 to B1-4, and B2-1 to B2-4, n and l are each independently an integer of 0 to 8, m1 and m2 are each independently an integer of 0 to 4, k may be an integer from 0 to 2. Specifically, n may be 0, and m1, m2, l, and k may be integers from 0 to 2.

X is 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, C _6-20 arylamido or C _1-20 alkylidene. Specifically, each X may be a halogen. More specifically, each of X may be chlorine (Cl).

Q may be carbon (C), silicon (Si), germanium (Ge), or tin (Sn). Specifically, Q may be silicon.

R ¹ , R ⁶ and R ⁷ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene. Specifically, R ¹ , R ⁶ and R ⁷ may each independently be C _1-20 alkyl. More specifically, R ¹ , R ⁶ , and R ⁷ may each be methyl.

R ² To R ⁵ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene, R ³ and R ⁴ are each independently adjacent groups connected to each other to be substituted or It may form an unsubstituted saturated or unsaturated C _4-20 ring. Specifically, R ³ may be C _1-20 alkyl or adjacent groups may be connected to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring, and R ⁴ may be adjacent groups joined to form an aromatic C _4-20 ring. can do. More specifically, R ³ may be tert -butyl or adjacent groups may be linked to form a substituted or unsubstituted aliphatic or aromatic C ₆ ring, and R ⁴ may be adjacent groups linked to form an aromatic C ₆ ring. can be formed

The first precursor is prepared by cyclizing the compound represented by Formula A1, reducing the cyclized compound to generate a hydroxyl group, dehydrating the reduced compound to form an unsaturated bond, and ionizing the dehydrated compound may be obtained through

The cyclization step may be a step of changing the carbon chain structure to a ring structure using an unsaturated bond in the compound, and the reduction step is a step of converting a carbonyl (C=O) group in the compound into a hydroxyl group (-OH) The dehydration step may be a step to remove a hydroxy group in the compound to generate an unsaturated bond, particularly a double bond, and the ionization step may be a step to remove hydrogen bound to the compound to remove an aromatic ion, particularly a cyclopentadiene ion. 1 may be a step of generating a precursor.

The following scheme shows exemplary examples of the method for preparing a transition metal compound for an olefin polymerization catalyst of the present invention. However, the following reaction scheme is merely an example for helping the understanding of the preparation method of the present invention, and the preparation steps or types of compounds used according to the embodiments of the present invention are not limited thereto.

<reaction formula>

According to another embodiment, the present invention provides a transition metal compound for an olefin polymerization catalyst, which may be represented by one or more of the following Chemical Formulas 1-1 to 1-5.

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

<Formula 1-5>

In Formulas 1-1 to 1-5, n and l are each independently an integer of 0 to 8, m1 and m2 are each independently an integer of 0 to 4, and k may be an integer of 0 to 2. Specifically, n may be 0, and m1, m2, l, and k may be integers from 0 to 2.

M may be titanium, zirconium or hafnium. Specifically, M may be zirconium.

each X is 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, C _6-20 arylamido or C _1-20 alkylidene. Specifically, each X may be a halogen. More specifically, each X may be chlorine.

Q may be carbon, silicon, germanium or tin. Specifically, Q may be silicon.

R ¹ , R ⁶ and R ⁷ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene. Specifically, R ¹ , R ⁶ and R ⁷ may each independently be C _1-20 alkyl. More specifically, R ¹ , R ⁶ and R ⁷ may each be methyl.

R ² To R ⁵ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene, R ³ and R ⁴ are each independently adjacent groups connected to each other to be substituted or It may form an unsubstituted saturated or unsaturated C _4-20 ring. Specifically, R ³ may be C _1-20 alkyl or adjacent groups may be connected to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring, and R ⁴ may be adjacent groups joined to form an aromatic C _4-20 ring. can do. More specifically, R ³ may be tert -butyl or adjacent groups may be joined to form a substituted or unsubstituted aliphatic or aromatic C ₆ ring, and R ⁴ may be adjacent groups joined to form an aromatic C ₆ ring.

In an exemplary embodiment, the transition metal compound may be one or more of the following Chemical Formulas 2-1 to 2-18.

<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>

<Formula 2-17>

<Formula 2-18>

The transition metal compound for an olefin polymerization catalyst of the present invention represented by at least one of Chemical Formulas 1-1 to 1-5 and/or 2-1 to 2-18 is prepared by the above-described transition metal compound for an olefin polymerization catalyst of the present invention. It may be prepared according to the method. However, the method for preparing the transition metal compound for the olefin polymerization catalyst of the present invention is not limited thereto.

According to another embodiment, the present invention provides a first transition metal compound represented by at least one of Formulas 1-1 to 1-5 and/or 2-1 to 2-18, and a second transition metal represented by Formula 3 below. An olefin polymerization catalyst composition comprising the compound is provided.

<Formula 3>

In Formula 3, n and l may each independently be an integer of 0 to 8, and k may be an integer of 0 to 2.

M may be titanium, zirconium or hafnium.

each X is 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, C _6-20 arylamido or C _1-20 alkylidene.

Q may be carbon, silicon, germanium or tin.

R ¹ , R ⁶ and R ⁷ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene.

R ² , R ⁴ and R ⁵ are each independently 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, C _6-20 arylamido or C _1-20 alkylidene.

R ⁴ and R ⁵ may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated C _4-20 ring.

The first transition metal compound and the second transition metal compound may have the same values of n, m1, m2, l and k and M, X, Q, R ¹ to R ⁷ of the above formula. That is, in the same transition metal compound structure represented by the following Chemical Formula 4, the first transition metal compound has a structure in which only hexane (the portion to which R ² is bonded) in a part of indenyl is hydrogenated, whereas the second transition metal compound is In all indenyl (indenyl), hexane (the portion to which R ² is bonded and the portion to which R ⁴ is bonded) may have a hydrogenated structure.

<Formula 4>

The olefin polymerization catalyst composition of the present invention described above may include the first transition metal compound and the second transition metal compound in a content ratio of 100 parts by weight: 100 to 0 parts by weight.

That is, conventionally, in order to obtain a transition metal compound in which only some indenyl or fluorenyl is hydrogenated, the partially hydrogenated compound and the fully hydrogenated compound have to be prepared in a mixed form, and it is practically impossible to separate them. However, according to the method for preparing a transition metal compound for an olefin polymerization catalyst of the present invention, a compound in which indenyl is only partially hydrogenated like the first transition metal compound can be obtained alone, so an olefin polymerization catalyst composition including the same is constituted When doing so, the first transition metal compound may be included in 100% by weight or more of the fully hydrogenated transition metal compound (second transition metal compound), and further, a catalyst composition including only the first transition metal compound may be prepared. .

The olefin polymerization catalyst composition of the present invention may further include a promoter compound.

The promoter compound may include at least one of a compound represented by the following formula (I), a compound represented by formula (II), and a compound represented by formula (III).

<Formula I>

In Formula I, n is an integer of 2 or more, and R _a may be a halogen atom, a C _1-20 hydrocarbon group, or a halogen-substituted C _1-20 hydrocarbon group. Specifically, R _a may be methyl, ethyl, n-butyl, or isobutyl, but is not limited thereto.

<Formula II>

In Formula II, 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, a halogen-substituted C _1-20 hydrocarbon group, or It may be a C _1-20 alkoxy group. Specifically, when D is aluminum, R _b , R _c and R _d may each independently be methyl or isobutyl, and when D is boron, R _b , R _c and R _d are each independently pentafluoro It may be phenyl, but is not limited thereto.

<Formula Ⅲ>

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

In Formula III, L is a neutral or cationic Lewis base, [LH] ⁺ or [L] ⁺ is a Bronsted acid, Z is a Group 13 element, A is each independently a substituted or unsubstituted C _6- It may be a ₂₀ aryl group or a substituted or unsubstituted C _1-20 alkyl group. Specifically, the [LH] ⁺ may be a dimethylanilinium cation, the [Z(A) ₄ ] ^- may be [B(C ₆ F ₅ ) ₄ ] ^- , and the [L] ⁺ may be [( C ₆ H ₅ ) ₃ C] ⁺ , but is not limited thereto.

The olefin polymerization catalyst composition may further include a carrier.

The carrier is not particularly limited as long as it can support the transition metal compound for the olefin polymerization catalyst and the cocatalyst compound. In an exemplary embodiment, the carrier may be carbon, silica, alumina, zeolite, magnesium chloride, or the like.

As a method of supporting the transition metal compound and the cocatalyst compound for an olefin polymerization catalyst on a carrier, a physical adsorption method or a chemical adsorption method may be used.

In an exemplary embodiment, the physical adsorption method is a method in which a solution in which a transition metal compound for an olefin polymerization catalyst is dissolved is contacted with a carrier and then dried, a solution in which a transition metal compound for an olefin polymerization catalyst and a cocatalyst compound are dissolved is brought into contact with a carrier A method in which the transition metal compound for an olefin polymerization catalyst is dissolved, or a solution in which the transition metal compound for the olefin polymerization catalyst is dissolved is brought into contact with the carrier and then dried to prepare a carrier on which the transition metal compound for the olefin polymerization catalyst is supported. Separately, a solution in which the promoter compound is dissolved It may be a method of contacting the carrier and drying the carrier to prepare a carrier on which the promoter compound is supported, and then mixing them.

In an exemplary embodiment, the chemical adsorption method is a method in which a promoter compound is first supported on the surface of a carrier, and then a transition metal compound for an olefin polymerization catalyst is supported on the promoter compound, or a functional group on the surface of the support (for example, In the case of silica, it may be a method of covalently bonding a hydroxy group (-OH)) on the silica surface and a catalyst compound.

The total loading amount of the main catalyst compound including the transition metal compound may be 0.001 mmol to 1 mmol based on 1 g of the carrier, and the supported amount of the cocatalyst compound may be 2 mmol to 15 mmol based on 1 g of the carrier.

However, such a carrier is not necessarily included, and whether to use the carrier may be appropriately selected according to necessity.

Polyolefin may be formed by polymerizing an olefinic monomer under the olefin polymerization catalyst composition of the present invention as described above.

Polyolefin is, for example, a free radical (free radical), cationic (cationic), coordination (coordination), condensation (condensation), a homopolymer or copolymer polymerized by polymerization such as addition (addition) ), but is not limited thereto.

In an exemplary embodiment, the polyolefin may be prepared by a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method. Examples of the solvent that can be used when the polyolefin is prepared by the solution polymerization method or the slurry polymerization method 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; mixtures thereof, and the like, but are not limited thereto.

Olefinic monomers are C _2-20 alpha-olefins, C _1-20 diolefins, C _3-20 cyclo-olefins and C _3-20 cyclodiolefins. It may be one or more selected from the group consisting of.

In an exemplary embodiment, the olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene , 1-dodecene, 1-tetradecene and 1-hexadecene, and the like, and the polyolefin may be a homopolymer containing only one type of the olefin-based monomers exemplified above, or a copolymer containing two or more types.

Preferably, the polyolefin may be a copolymer of ethylene and 1-octene, but is not limited thereto.

Since the olefin polymerization catalyst composition containing the transition metal compound of the present invention has high polymerization activity, it is possible to prepare polyolefins having excellent physical properties such as low density and high molecular weight.

Hereinafter, a specific preparation example for preparing the transition metal compound for olefin polymerization represented by Chemical Formula 2-1 will be described.

[Preparation Example 1] Preparation of the compound of Formula 2-1

The following scheme schematically shows the steps for preparing the compound of Formula 2-1 (Catalyst 1 in the scheme below).

<reaction formula>

Preparation Example 1-1: Preparation of 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-one (2-1) (Step 1)

Polyphosphoric acid (10 mL) was added to cyclohexyl methacrylate (1) (4.4 g, 26.15 mmol) and stirred overnight at 130 °C. The sticky solution was poured into ice water (5 mL) and stirred until the polyphosphoric acid was completely dissolved. 5 g of NH ₄ Cl solid was added to the brown solution, followed by extraction with ether (30 mL). After separating the organic layer and the water layer, the organic layer was washed with saturated NaHCO ₃ (10 mL) solution, and then washed again with saturated brine (10 mL). After drying with MgSO ₄ , the solvent was carefully removed with a rotary evaporator. 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-one (2-1) and 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-one (2-1) having ¹ H-NMR spectrum as shown below after short column chromatography purification with hexane solvent A 1:1 mixture of the product 2-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-1-one (2-2) was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): 2.70 (m. 1H), 2.37 (m, 1H), 2.29 (m, 2H), 2.11 (m. 2H), 1.69 (m, 5H), 1.17 (d, 3H)

Preparation 1-2: Preparation of 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-ol (3) (Step 2)

2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-one (2-1) and 2-methyl-3a,4,5, A mixture of 6,7,7a-hexahydro-1H-inden-1-one (2-2) (1.6 g, 10.65 mmol) was dissolved in ether (30 mL) and stirred at 0 °C. Here, LiAlH ₄ (162 mg, 4.27 mmol) was slowly added in three portions. After raising the temperature to room temperature and stirring for 3 hours, the reaction was confirmed by TLC, and the temperature was lowered to 0 °C again. Distilled water (30 mL) was slowly added thereto, extracted with ether (20 mL), and the organic layer and the water layer were separated. The obtained organic layer was washed once with saturated brine, dried over MgSO ₄ , and the solvent was removed using a rotary evaporator. Clean 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-ol having ¹ H-NMR spectrum as shown below after column chromatography purification with EA:Hex (1:4) solvent (3) was obtained with a yield of 28% in two steps.

¹ H NMR (300 MHz, C ₆ D ₆ ): 4.21 (br. 1H), 2.34 (m, 1H), 2.19 (m, 2H), 1.80 (m, 4H), 1.51 (m, 4H), 1.04 ( d, 3H)

Preparation Example 1-3: Preparation of 2-methyl-4,5,6,7-tetrahydro-1H-indene (4-1) (Step 3)

2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-ol (3) (1.1 g, 7.32 mmol) prepared in Preparation Example 1-2 was mixed with pentane (20 mL) was dissolved in MgSO ₄ (150 mg) and then reflux was performed for 8 hours. After slowly lowering the temperature, MgSO ₄ was removed with a filter, and 2-methyl-4,5,6,7-tetrahydro ^- 1H-indene (4-1) and 2-methyl-2, It was confirmed that 4,5,6-tetrahydro-1H-indene (4-2) was produced as a mixture in an almost 1:1 ratio.

¹ H NMR (300 MHz, CDCl ₃ ): 5.88 (s, 1H), 2.25 (m. 2H), 2.08 (m, 2H), 2.01 (s, 3H), 1.67 (m, 4H), 1.65 (m, 2H)

Preparation Example 1-4: Preparation of (2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl) lithium (5) (Step 4)

2-methyl-4,5,6,7-tetrahydro-1H-indene (4-1) and 2-methyl-2,4,5,6-tetrahydro-1H-indene (4-1) prepared in Preparation Example 1-3 ( After lowering the temperature of the pentane solution of 4-2) to -78 ℃, the flask was connected to a Schlenk line and degassing was performed to remove air. After injecting 7 mL of n -BuLi (1.6 M in hexane) solution, the temperature was slowly raised to room temperature and stirred overnight. The resulting white solid was obtained through a filter and washed thoroughly with hexane to remove 2-methyl-2,4,5,6-tetrahydro-1H-indene (4-2) and clean (2-methyl-4,5,6 ,7-tetrahydro-1H-inden-1-yl) lithium (5) was obtained in a yield of 37%.

Preparation Example 1-5: Preparation of Chloro(9H-fluoren-9-yl)dimethylsilane (7) (Step 5)

After fluorene (6) (3.33 g, 20 mmol) was dissolved in hexane (50 mL), 13 mL of n -BuLi (1.6 M in hexane) was slowly added at -30°C, followed by stirring at room temperature overnight. After cooling to -30 ℃, the mixed solution was slowly added to a hexane (50 mL) solution of dichlorodimethylsilane (5.16 g, 40 mmol) for 5 hours. After stirring at room temperature for 8 hours, LiCl was removed with a filter and dried to obtain clean Chloro(9H-fluoren-9-yl)dimethylsilane (7) having ¹ H-NMR spectrum as shown below in a yield of 74%.

¹ H NMR (300 MHz, CDCl ₃ ): 7.83 (d, 2H), 7.64 (d, 2H), 7.34 (m, 4H), 4.08 (s, 1H), 0.17 (s, 6H)

Preparation Example 1-6: Preparation of (9H-fluoren-9-yl)dimethyl(2-methyl-1H-inden-3-yl)silane (8) (Step 6)

A solution of Chloro(9H-fluoren-9-yl)dimethylsilane (7) (200 mg, 0.77 mmol) prepared in Preparation Example 1-5 in THF (10 mL) was cooled to -30 ° C. THF (10mL) solution of (2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl) lithium (5) (108 mg, 0.77mmol) prepared in 1-4 was slowly added and Stirring was carried out overnight at room temperature. After drying by evaporating the THF solvent, hexane (15 mL) was added, stirred for 30 minutes, LiCl was removed with a filter, and dried to obtain a yield of 97%, 9H-fluoren-9-yl having ¹ H-NMR spectrum as shown below. ) dimethyl(2-methyl-1H-inden-3-yl)silane (8) was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): 7.83 (d, 2H), 7.53 (d, 2H), 7.30 (m, 4H), 6.06 (s, 1H), 4.15 (s, 1H), 3.28 (s, 1H) ), 2.40 (m 2H), 2.34 (m, 2H), 2.08 (s, 3H), 1.84 (m, 2H), 1.58 (m, 2H), -0.30 (s, 3H), -0.41 (s, 3H) )

Preparation Example 1-7: Preparation of (9H-fluoren-9-yl)dimethyl(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)silyllithium (9) (Step 7)

9H-fluoren-9-yl)dimethyl(2-methyl-1H-inden-3-yl)silane (8) (268 mg, 0.76 mmol) prepared in Preparation Example 1-6 was dissolved in ether (15 mL) After cooling to -30 °C, 1 mL of n -BuLi (1.6 M in hexane) was slowly added thereto, followed by stirring at room temperature overnight. After removing all the solvent, adding hexane (20 mL), stirring for 30 minutes, filtering the lithium salt with a filter, washing with hexane several times, and purifying (9H-fluoren-9-yl)dimethyl with a yield of 68% (2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)silyllithium (9) was obtained.

Preparation Example 1-8: Rac-[Dimethylsilanediyl-(9-η) ⁵ -fluorenyl)(2-methyl-1-η ⁵ Preparation of -tetrahydroindenyl)]zirconium Dichloride (Catalyst 1) (Step 8)

(9H-fluoren-9-yl)dimethyl(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)silyllithium (9) (81 mg, 0.22 mmol) was added to toluene (15 mL), stirred, and then cooled to -30 °C. ZrCl ₄ (51 mg, 0.22 mmol) was added thereto, and the mixture was slowly raised to room temperature and stirred for 3 hours. After removing LiCl with a filter, the catalyst was extracted with toluene, dried, and clean Rac-[Dimethylsilanediyl-( ^{9-η 5 -fluorenyl} )(2-methyl-1- η ⁵ -tetrahydroindenyl)]zirconium Dichloride (Catalyst 1) (a compound of Formula 2-1 below) was obtained.

¹ H NMR (300 MHz, C ₆ D ₆ ): 7.82 (t, 2H), 7.50 (d, 2H), 7.37 (m, 4H), 6.00 (s, 1H), 2.94 (m, 2H), 2.38 (m) , 2H), 2.23 (m, 2H), 1.99 (s, 3H), 1.44 (m, 2H), 0.84 (s, 3H), 0.80 (s. 3H)

<Formula 2-1>

[Preparation Example 2] Synthesis of ethylene and 1-hexene copolymer using an olefin polymerization catalyst containing the compound of Formula 2-1

Ethylene was supplied at a pressure of 4 atm to a continuously stirred reactor containing hexane and 1-hexene, and copolymerization was carried out at 80° C. in the presence of an olefin polymerization catalyst containing the compound of Formula 2-1. . Copolymerization was carried out in a liquid phase process while increasing the input amount of 1-hexene to 15 mL, 30 mL, and 45 mL to obtain a [ethylene]-[1-hexene] copolymer.

Above, embodiments belonging to the spirit of the invention have been described in detail with reference to the exemplified chemical structural formulas and preparation examples. However, the spirit of the invention is not limited to the illustrated chemical structural formulas and preparation examples, and the spirit of the invention may be variously modified based on the illustrated chemical structural formulas and preparation examples. The exemplified chemical structural formulas and manufacturing examples are provided to fully inform those of ordinary skill in the art to which the invention belongs the scope of the spirit of the invention, and the scope of the invention is within the scope of the claims. It is only defined by Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (13)

preparing a first precursor represented by the following Chemical Formula A2;
Preparing a second precursor including at least one of the compounds represented by the following Chemical Formulas B2-1 to B2-4; and
A method for preparing a transition metal compound for an olefin polymerization catalyst to obtain one or more of the compounds represented by the following Chemical Formulas 1-1 to 1-5, including reacting the first precursor with the second precursor.
<Formula A2>

<Formula B2-1>

<Formula B2-2>

<Formula B2-3>

<Formula B2-4>

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

<Formula 1-5>

(In Formulas A2 to 1-5,
n and l are each independently an integer from 0 to 8, m1 and m2 are each independently an integer from 0 to 4, k is an integer from 0 to 2,
M is titanium (Ti), zirconium (Zr) or hafnium (Hf),
each X is 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, C _6-20 arylamido or C _1-20 alkylidene;
Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn),
R ¹ , R ⁶ and R ⁷ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene,
R ² To R ⁵ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene,
R ³ and R ⁴ are each independently adjacent groups may be linked to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring) The method of claim 1,
The first precursor is a method for preparing a transition metal compound for an olefin polymerization catalyst obtained from a compound represented by the following formula A1.
<Formula A1>

(In Formula A1,
n is an integer from 0 to 8,
each R ² is independently 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, C _6-20 arylamido or C _1-20 alkylidene) 3. The method of claim 2,
cyclizing the compound represented by Formula A1;
reducing the cyclized compound to form a hydroxyl group;
dehydrating the reduced compound to form unsaturated bonds; and
The method for producing a transition metal compound for an olefin polymerization catalyst further comprising the step of obtaining the first precursor by ionizing the dehydrated compound. The method of claim 1,
The second precursor is a method for preparing a transition metal compound for an olefin polymerization catalyst obtained from one or more of the compounds represented by the following Chemical Formulas B1-1 to B1-4.
<Formula B1-1>

<Formula B1-2>

<Formula B1-3>

<Formula B1-4>

(In the formulas B1-1 to B1-4,
l is an integer from 0 to 8, m1 and m2 are each independently an integer from 0 to 4, k is an integer from 0 to 2,
R ³ to R ⁵ are each independently 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, C _6-20 arylamido or C _1-20 alkylidene;
R ³ and R ⁴ are each independently adjacent groups may be linked to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring) The method of claim 1,
Wherein R ¹ is methyl (methyl) is a method for producing a transition metal compound for an olefin polymerization catalyst. The method of claim 1,
Formulas 1-1 to 1-5 are a method for preparing a transition metal compound for an olefin polymerization catalyst at least one of the following Formulas 2-1 to 2-18.
<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>

<Formula 2-17>

<Formula 2-18>

delete A transition metal compound for an olefin polymerization catalyst represented by the following Chemical Formula 1-2 or 1-3.
<Formula 1-2>

<Formula 1-3>

(In Formulas 1-2 and 1-3,
n and l are each independently an integer from 0 to 8, m1 and m2 are each independently an integer from 0 to 4, k is an integer from 0 to 2,
M is titanium (Ti), zirconium (Zr) or hafnium (Hf),
each X is 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, C _6-20 arylamido or C _1-20 alkylidene;
Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn),
R ¹ , R ⁶ and R ⁷ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene,
R ² to R ⁴ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene,
R ³ and R ⁴ are each independently adjacent groups may be linked to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring) 9. The method of claim 8,
wherein n is 0,
M is zirconium,
wherein each X is a halogen,
Wherein Q is silicon,
Wherein R ⁶ and R ⁷ are each independently C _1-20 A transition metal compound for an olefin polymerization catalyst. 10. The method of claim 9,
wherein R ³ is C _1-20 alkyl or adjacent groups are connected to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring,
Wherein R ⁴ is a transition metal compound for an olefin polymerization catalyst in which adjacent groups are connected to form an aromatic C _4-20 ring. delete delete A first transition metal compound which is a transition metal compound for an olefin polymerization catalyst according to any one of claims 8 to 10; and
Including a second transition metal compound represented by the following formula (3),
The content ratio of the first transition metal compound to the second transition metal compound is 100 parts by weight: 100 to 0 parts by weight of the olefin polymerization catalyst composition.
<Formula 3>

(In Formula 3,
n and l are each independently an integer from 0 to 8, k is an integer from 0 to 2,
M is titanium (Ti), zirconium (Zr) or hafnium (Hf),
each X is 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, C _6-20 arylamido or C _1-20 alkylidene;
Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn),
R ¹ , R ⁶ and R ⁷ are each independently hydrogen, 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, C _6-20 arylamido or C _1-20 alkylidene,
R ² , R ⁴ and R ⁵ are each independently 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, C _6-20 arylamido or C _1-20 alkylidene;
R ⁴ and R ⁵ are each independently adjacent groups may be connected to form a substituted or unsubstituted saturated C _4-20 ring)