KR20190055551A - Transition metal compound used to prepare catalyst for polymerizing olefin and manufacturing method thereof - Google Patents

Abstract

Provided are: a method for manufacturing a transition metal compound for an olefin polymerization catalyst; the transition metal compound for the olefin polymerization catalyst manufactured using the same; and an olefin polymerization catalyst composition comprising the same. The method for manufacturing the transition metal compound for the olefin polymerization catalyst comprises following steps of: preparing a first precursor represented by chemical formula A2; preparing a second precursor comprising at least one of compounds represented by chemical formulas B2-1 to B2-4; and conducting a reaction of the first precursor with the second precursor to obtain at least one of the compounds represented by chemical formulas 1-1 to 1-5. Details of the chemical formulas A2 to 1-5 are described in the specification. The present invention can provide the transition metal compound for the olefin polymerization catalyst having a novel structure.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transition metal compound for an olefin polymerization catalyst and a method for producing the same. BACKGROUND ART < RTI ID = 0.0 >

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

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

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

SUMMARY OF THE INVENTION The present invention provides a process 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 containing the same.

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method of manufacturing the same.

According to an embodiment of the present invention, there is provided a method for preparing a transition metal compound for an olefin polymerization catalyst, comprising the steps of preparing a first precursor represented by the following general formula (A2) Preparing a second precursor comprising at least one of the compounds represented by the following formulas 1-1 to 1-5, and reacting the first precursor with the second precursor, Or more.

≪

≪ Formula (B2-1)

<B2-2>

<B2-3>

<B2-4>

&Lt; Formula 1-1 >

(1-2)

<Formula 1-3>

<Formula 1-4>

&Lt; Formula 1-5 >

M and m are each independently an integer of 0 to 4, k is an integer of 0 to 2, and M is an element selected from the group consisting of titanium ( Ti), and 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, and Fig or C _1-20 alkylidene amino C _6-20 aryl C _1-20 alkyl amino, Q is carbon (C), Wherein R ¹ , R ⁶ and R ⁷ are each independently selected from the group consisting of 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 selected from the group consisting of 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, also C _1-20 alkyl amino, C _6-20 aryl or C _1-20 amino is also alkylidene, R ³ and R ⁴ are each independently selected from the adjacent groups are connected to a substituted or unsubstituted, saturated or unsaturated C ₄ ring _-20 ring can be formed.

The transition metal compound for an olefin polymerization catalyst according to one embodiment of the present invention for solving the above-mentioned other problems is represented by at least one of the following formulas (1-1) to (1-5).

&Lt; Formula 1-1 >

(1-2)

<Formula 1-3>

<Formula 1-4>

&Lt; Formula 1-5 >

M and m are each independently an integer of 0 to 4, k is an integer of 0 to 2, and M is an integer of 0 to 3. In the above formulas 1-1 to 1-5, n and 1 are each independently an integer of 0 to 8, Wherein each of X is independently selected from the group consisting of 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 alkyl, amido, C _6-20 aryl or C _1-20 alkylidene amino Fig, 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 alkynyl carbonyl, C _6-20 aryl, C _1-20 alkyl, C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkyl, amido, C _6-20 aryl or C _1-20 amido And R ² to R ⁵ are each independently selected from the group consisting of 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 alkyl, amido, C _6-20 aryl or C _1-20 amino is also alkylidene, R ³ and R ⁴ are each independently of the adjacent groups are connected by a substituted or unsubstituted, saturated or unsaturated ring C _4-20 rings can be formed.

According to another aspect of the present invention, there is provided an olefin polymerization catalyst composition comprising a first transition metal compound, which is a transition metal compound for the olefin polymerization catalyst, and a second transition metal compound represented by the following formula (3) , And the content ratio of the first transition metal compound and the second transition metal compound is 100 parts by weight: 100 to 0 parts by weight.

(3)

In Formula 3, n and 1 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) 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, , also C _1-20 alkyl amino, C _6-20 aryl or C _1-20 alkylidene amido and also, Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn), R ¹ , R ⁶ and R ⁷ are each independently selected from the group consisting of 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 alkylamino C _6-20 arylamido or C _1-20 alkyl And R ⁴ and R ⁵ are each independently 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.

The embodiments of the present invention have at least the following effects.

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

The 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 specification.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

As used herein, the term " C _AB " means " the number of carbon atoms is not less than A and not more than B &quot;, and the terms " A to B ""inthe" substituted "means" at least one hydrogen of the hydrocarbon compound or a hydrocarbon derivative 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 alkyl, amido, C _6-20 aryl or C _1-20 amido substituted with alkylidene "means, and" unsubstituted "means" hydrocarbon compounds or at least one hydrogen, halogen, C _1-20 alkyl hydrocarbon derivatives, 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 ".

According to one embodiment, the present invention provides a method for preparing a precursor, comprising the steps of preparing a first precursor represented by the following formula (A2), a second precursor comprising at least one of compounds represented by the following formulas (B2-1) to And reacting the first precursor and the second precursor to produce a transition metal compound for an olefin polymerization catalyst.

&Lt;

&Lt; Formula (B2-1)

<B2-2>

<B2-3>

<B2-4>

The first precursor may be obtained from a compound represented by the following formula (A1).

&Lt; Formula (A1)

The second precursor may be one derived from at least one of the compounds represented by the following formulas (B1-1) to (B1-4).

&Lt; Formula (B1-1)

<Formula (B1-2)

&Lt; Formula (B1-3)

&Lt; Formula (B1-4)

In the above formulas A1, A2, B1-1 to B1-4 and B2-1 to B2-4, n and 1 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 is 0, and m1, m2, l, and k may be an integer of 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, X may each be a halogen. More specifically, each 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 selected from the group consisting of 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 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, respectively _-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 selected from the group consisting of Can form an unsubstituted saturated or unsaturated C _4-20 ring. Specifically, R ³ is 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 to adjacent groups to form an aromatic C _4-20 ring can do. More specifically, R ³ may be tert -butyl or adjacent groups may be connected to form a substituted or unsubstituted aliphatic or aromatic C ₆ ring, and R ⁴ may be an adjacent C ₆ group to form an aromatic C ₆ ring .

The first precursor may be prepared by cyclizing the compound represented by the formula (A1), reducing the cyclized compound to generate a hydroxy group, dehydrating the reduced compound to generate an unsaturated bond, and ionizing the dehydrated compound . &Lt; / RTI &gt;

The cyclization step may be a step of converting the carbon chain structure into a cyclic structure using an unsaturated bond in the compound, and the reducing step is a step of converting a carbonyl (C = O) group in the compound to a hydroxyl group (-OH) And the dehydration step may be a step of removing the hydroxyl groups in the compound to produce an unsaturated bond, especially a double bond, and the ionization step may be a step of removing hydrogen bonded to the compound to form an aromatic ion, especially a cyclopentadiene ion- 1 &lt; / RTI &gt; precursor.

The following reaction formula shows an exemplary embodiment of the method for producing a transition metal compound for an olefin polymerization catalyst of the present invention. However, the following reaction formula is only an example for helping understanding of the production method of the present invention, and the production step according to the embodiments of the present invention and the kinds of the used compounds are not limited thereto.

<Reaction Scheme>

The present invention provides a transition metal compound for an olefin polymerization catalyst, which may be represented by one or more of the following formulas (1-1) to (1-5), according to another embodiment.

&Lt; Formula 1-1 >

(1-2)

<Formula 1-3>

<Formula 1-4>

&Lt; Formula 1-5 >

In the above formulas 1-1 to 1-5, n and 1 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 is 0, and m1, m2, l, and k may be an integer of 0 to 2.

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

X is independently selected from the group consisting of 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 alkyl, amido, may indenyl C _6-20 aryl or C _1-20 amido alkali. Specifically, X may each be a halogen. More specifically, X may each be chlorine.

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

R ¹ , R ⁶ and R ⁷ are each independently selected from the group consisting of 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 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, respectively _-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 selected from the group consisting of Can form an unsubstituted saturated or unsaturated C _4-20 ring. Specifically, R ³ is 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 to adjacent groups to form an aromatic C _4-20 ring can do. More specifically, R ³ may be tert -butyl or adjacent groups may be connected to form a substituted or unsubstituted aliphatic or aromatic C ₆ ring, and R ⁴ may be adjacent to form an aromatic C ₆ ring.

In an exemplary embodiment, the transition metal compound may be at least one of the following structural formulas (2-1) to (2-18).

&Lt; Formula (2-1)

&Lt; Formula (2-2)

<Formula 2-3>

<Formula 2-4>

<Formula 2-5>

<Formula 2-6>

<Formula 2-7>

<Formula 2-8>

&Lt; Formula 2-9 >

&Lt; Formula 2-10 >

&Lt; Formula (2-11)

<Formula 2-12>

&Lt; Formula (2-13)

<Formula 2-14>

&Lt; Formula (2-15)

<Formula 2-16>

&Lt; Formula 2-17 &

(2-18)

The transition metal compound for an olefin polymerization catalyst of the present invention represented by at least one of the above-mentioned formulas 1-1 to 1-5 and / or 2-1 to 2-18 can be obtained by preparing the transition metal compound for an olefin polymerization catalyst of the present invention Or may be made according to the method. However, the method for producing the transition metal compound for an olefin polymerization catalyst of the present invention is not limited thereto.

The present invention provides, in accordance with still another embodiment, a first transition metal compound represented by one or more of Formulas 1-1 to 1-5 and / or 2-1 to 2-18 and a second transition metal represented by Formula 3 below The present invention provides an olefin polymerization catalyst composition comprising the compound.

(3)

In Formula 3, n and 1 are each independently an integer of 0 to 8, and k may be an integer of 0 to 2.

M may be titanium, zirconium or hafnium.

X is independently selected from the group consisting of 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 alkyl, amido, may indenyl C _6-20 aryl or C _1-20 amido alkali.

Q can be carbon, silicon, germanium or tin.

R ¹ , R ⁶ and R ⁷ are each independently selected from the group consisting of 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 selected from the group consisting of 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 connected to adjacent groups to form a substituted or unsubstituted saturated C _4-20 ring.

The transition metal compound may be one and the second transition metal compound is the same all n, m1, m2, k, and l values of the M, X, Q, R ¹ to R ⁷ of Formula is. That is, in the same transition metal compound structure represented by the following formula (4), the first transition metal compound has a structure in which only a part of hexene in the indenyl (the moiety to which R ² is bonded) is hydrogenated, while the second transition metal compound All hexenyl in indenyl (the moiety where R &lt; ² &gt; and R &lt; ⁴ &gt; join) may be hydrogenated.

&Lt; Formula 4 >

The olefin polymerization catalyst composition of the present invention may contain the first transition metal compound and the second transition metal compound in a 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 a part of indenyl or fluorenyl is hydrogenated, it has been inevitable to produce the partially hydrogenated compound and the fully hydrogenated compound in a mixed form, and it is practically impossible to separate them However, according to the method for producing a transition metal compound for an olefin polymerization catalyst of the present invention, a compound in which indenyl is partially hydrogenated as in the case of a first transition metal compound alone can be obtained. Therefore, an olefin polymerization catalyst composition comprising the same , The first transition metal compound may be contained in an amount of 100 wt% or more of the fully hydrogenated transition metal compound (second transition metal compound), and further, a catalyst composition containing only the first transition metal compound may be prepared .

The olefin polymerization catalyst composition of the present invention may further comprise a cocatalyst compound.

The promoter compound may include at least one of a compound represented by the formula (I), a compound represented by the formula (II) and a compound represented by the 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 C _1-20 hydrocarbon group substituted with halogen. Specifically, R _a may be methyl, ethyl, n-butyl or isobutyl, but is not limited thereto.

&Lt; Formula (II)

R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, a C _1-20 hydrocarbon group substituted with halogen, or a group represented by the formula 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 pentafluoro Phenyl, but is not limited thereto.

&Lt; Formula (III)

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

Wherein L is a neutral or cationic Lewis base, [LH] ⁺ or [L] ⁺ is a Bronsted acid, Z is a Group 13 element, and A is independently a substituted or unsubstituted C _{6- 20} aryl group or a substituted or unsubstituted C _1-20 alkyl group. Specifically, the [LH] ⁺ may be a dimethylanilinium cation dimethyl, wherein [Z (A) _4] ^- is _{[B (C 6 F 5)} 4] - can be a, the [L] ⁺ is [( C ₆ H ₅ ) ₃ C] ⁺ , but is not limited thereto.

The olefin polymerization catalyst composition may further comprise 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 can be carbon, silica, alumina, zeolite, magnesium chloride, and the like.

As a method of supporting a transition metal compound and a promoter 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 includes 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 method in which a solution in which a transition metal compound for olefin polymerization catalyst and a co- Or 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 dried to prepare a carrier carrying thereon a transition metal compound for an olefin polymerization catalyst, To contact the carrier and drying the carrier to prepare a carrier carrying the promoter compound 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 support, and then a transition metal compound for an olefin polymerization catalyst is supported on the promoter compound, or a method in which a functional group (e.g., A method of covalently bonding a catalyst compound with a hydroxyl group (-OH) on the silica surface in the case of silica).

The total amount of the main catalyst compound containing 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 promoter compound may be 2 mmol to 15 mmol based on 1 g of the carrier.

However, such carrier does not necessarily have to be included, and can be appropriately selected depending on necessity.

The polyolefin can be formed by polymerizing the olefin monomer under the olefin polymerization catalyst composition of the present invention as described above.

Polyolefins can be homopolymers or copolymers that are polymerized by polymerization reactions, such as, for example, free radicals, cationic, coordination, condensation, ), But is not limited thereto.

In an exemplary embodiment, the polyolefin may be produced by vapor phase polymerization, solution polymerization, slurry polymerization or the like. Examples of the solvent that can be used when the polyolefin is prepared by solution polymerization or slurry polymerization 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. However, the present invention is not limited to these.

The olefinic monomer may be selected from the group consisting of C _2-20 alpha-olefins, C _1-20 diolefins, C _3-20 cyclo-olefins, and C _3-20 cyclodiolefins. And may be one or more selected from the group consisting of

In an exemplary embodiment, the olefinic monomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, , 1-dodecene, 1-tetradecene, 1-hexadecene, and the like, and the polyolefin may be a homopolymer containing only one of the above-exemplified olefin-based monomers, or a copolymer containing two or more thereof.

Preferably, the polyolefin may be a copolymer in which ethylene and 1-octene are copolymerized, but is not limited thereto.

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

Hereinafter, a specific example of production of the transition metal compound for olefin polymerization represented by the above formula (2-1) will be described.

[Preparation Example 1] Preparation of compound of formula (2-1)

The following scheme schematically illustrates the steps of preparing the compound of formula (II-1) (Catalyst 1 of the following reaction formula).

<Reaction Scheme>

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

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 polyphosphoric acid was completely dissolved. To the brown solution was added 5 g of NH ₄ Cl solid and extracted 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 with saturated brine (10 mL). After drying with MgSO ₄ , the solvent was carefully removed with a rotary evaporator. Hexane solvent to obtain 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-one (2-1) having a ¹ H- 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)

Production Example 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- (1.6 g, 10.65 mmol) of 6,7,7a-hexahydro-1H-inden-1-one (2-2) was dissolved in ether (30 mL) and stirred at 0 ° C. LiAlH ₄ (162 mg, 4.27 mmol) was slowly added thereto in three portions. The temperature was raised to room temperature and stirred for 3 hours. After confirming that the reaction had proceeded completely by TLC, the temperature was lowered to 0 ° C again. The 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 with saturated brine, dried over MgSO _4, and then the solvent was removed using a rotary evaporator. EA: Hex (1: 4) solvent in column chromatography pure 2-methyl-2,3,4,5,6,7-hexahydro- 1H-inden-1-ol having the ¹ H-NMR spectrum as described below, to obtain (3) was obtained at a yield of 28% in two stages.

^{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)

Production 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 dissolved in pentane And MgSO ₄ (150 mg) was added thereto, followed by refluxing for 8 hours. Lower the temperature slowly remove the filter with MgSO _4, and through the following ¹ H NMR spectrum as 2-methyl-4,5,6,7-tetrahydro- 1H-indene (4-1) and 2-methyl-2, 4,5,6-tetrahydro-1H-indene (4-2) was almost 1: 1.

^{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)

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

2-methyl-4,5,6,7-tetrahydro-1H-indene (4-1) and 2-methyl-2,4,5,6-tetrahydro- 4-2) pentane solution was cooled to -78 ° C., and the flask was connected to the Schlenk line to degass the air. To this was added 7 mL of n- BuLi (1.6 M in hexane) solution, and the temperature was slowly raised to room temperature and stirred overnight. The resulting white solid was filtered and washed 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%.

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

Fluorene 6 (3.33 g, 20 mmol) was dissolved in hexane (50 mL), 13 mL of n- BuLi (1.6 M in hexane) was added slowly at -30 ° C, and the mixture was stirred overnight at room temperature. After cooling to -30 ° C, the mixed solution was slowly added to 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 by filtration and dried to obtain clean Chloro (9H-fluoren-9-yl) dimethylsilane (7) having a ¹ H-NMR spectrum at a yield of 74% as follows.

_{^{1 H NMR (300MHz, 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-

A solution of the above-prepared 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 (10 mL) solution of (2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl) lithium (5) (108 mg, 0.77 mmol) The mixture was stirred overnight at room temperature. 9H-fluoren-9-yl After drying and evaporation of the THF solvent is added to hexane (15 mL) to remove the LiCl by after stirring for 30 minutes the filter and dried with a ¹ H-NMR spectrum as described below in a yield of 97% ) dimethyl (2-methyl-1H-inden-3-yl) silane (8).

¹ H NMR (300 MHz, CDCl ₃ ): 7.83 (d, 2H), 7.53 (d, 2H), 7.30 (m, 4H), 6.06 (s, 2H), 1.50 (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)

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 After cooling to -30 ° C, 1 mL of n- BuLi (1.6 M in hexane) was slowly dropped and stirred at room temperature overnight. The solvent was removed and hexane (20 mL) was added. After stirring for 30 minutes, the lithium salt was filtered off and washed several times with hexane. The solution was purified to yield 68% of (9H-fluoren-9-yl) dimethyl (2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl) silyllithium (9).

Preparation 1-8: Rac- [Dimethylsilanediyl- (9-侶 ⁵ lt; / RTI &gt; fluorenyl) (2-methyl-1- ⁵ -tetrahydroindenyl)] zirconium dichloride (Catalyst 1) (Step 8)

1H-inden-1-yl) silyllithium (9) (81 mg, prepared as described in Preparation Example 1-7, 0.22 mmol) were added to toluene (15 mL), and the mixture was stirred and cooled to -30 ° C. ZrCl ₄ (51 mg, 0.22 mmol) was added thereto, slowly warmed to room temperature, and stirred for 3 hours. Rac- clean with a ¹ H-NMR spectrum, such as to remove the LiCl filter to extract the catalyst with toluene and dried and to a 54% yield ^{[Dimethylsilanediyl- (9-η 5 -fluorenyl} ) (2-methyl-1- η ⁵ -tetrahydroindenyl)] zirconium dichloride (Catalyst 1) (compound of the following formula (2-1)).

_{^{1 H NMR (300MHz, 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

&Lt; 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 equipped with hexane and 1-hexene, and copolymerization was carried out at 80 DEG C in the presence of an olefin polymerization catalyst containing the compound of the formula (2-1) . Copolymerization was carried out in a liquid phase process while increasing the amount of 1-hexene to 15 mL, 30 mL, and 45 mL to obtain an [ethylene] - [1-hexene] copolymer.

Hereinafter, embodiments belonging to the spirit of the invention will be described with reference to the above-described chemical structures, production examples, and the like. However, the spirit of the invention is not limited to the exemplary chemical structures and the production examples, and the ideas of the invention can be variously modified based on the exemplified chemical structures and the manufacturing examples. It is to be understood that both the foregoing general description and the appended claims are intended to provide further understanding of the scope of the inventive concept to those skilled in the art and do not limit the scope of the inventive idea to the scope of the claims . It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (13)

Preparing a first precursor represented by the following formula (A2);
Preparing a second precursor comprising at least one of compounds represented by the following formulas B2-1 to B2-4; And
And reacting the first precursor and the second precursor to obtain at least one of compounds represented by the following general formulas (1-1) to (1-5).
&Lt;

&Lt; Formula (B2-1)

<B2-2>

<B2-3>

<B2-4>

&Lt; Formula 1-1 >

(1-2)

<Formula 1-3>

<Formula 1-4>

&Lt; Formula 1-5 >

(In the formulas (A2) 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, k is an integer of 0 to 2,
M is titanium (Ti), zirconium (Zr), or hafnium (Hf)
X is independently selected from the group consisting of 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 alkyl, amido, C _6-20 aryl or C _1-20 amido FIG alkylidene,
Q is carbon (C), silicon (Si), germanium (Ge), or tin (Sn)
R ¹ , R ⁶ and R ⁷ are each independently selected from the group consisting of 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 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, respectively _-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 connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring) The method according to claim 1,
Wherein the first precursor is obtained from a compound represented by the following formula (A1).
&Lt; Formula (A1)

(In the formula (A1)
n is an integer of 0 to 8,
R ² is each independently selected from the group consisting of 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 the formula (A1);
Reducing the cyclized compound to produce a hydroxyl group;
Dehydrating the reduced compound to produce an unsaturated bond; And
Further comprising the step of ionizing the dehydrated compound to obtain the first precursor. The method according to claim 1,
Wherein the second precursor is obtained from at least one of compounds represented by the following general formulas (B1-1) to (B1-4).
&Lt; Formula (B1-1)

<Formula (B1-2)

&Lt; Formula (B1-3)

&Lt; Formula (B1-4)

(In the formulas (B1-1) to (B1-4)
l is an integer of 0 to 8, m1 and m2 are each independently an integer of 0 to 4, k is an integer of 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 connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring) The method according to claim 1,
Wherein R &lt; ¹ &gt; is methyl. The method according to claim 1,
Wherein the structural formulas 1-1 through 1-5 are at least one of the following structural formulas 2-1 through 2-18.
&Lt; Formula (2-1)

&Lt; Formula (2-2)

<Formula 2-3>

<Formula 2-4>

<Formula 2-5>

<Formula 2-6>

<Formula 2-7>

<Formula 2-8>

&Lt; Formula 2-9 >

&Lt; Formula 2-10 >

&Lt; Formula (2-11)

<Formula 2-12>

&Lt; Formula (2-13)

<Formula 2-14>

&Lt; Formula (2-15)

<Formula 2-16>

&Lt; Formula 2-17 &

(2-18)

A transition metal compound for an olefin polymerization catalyst produced by the method according to any one of claims 1 to 6. The transition metal compound for an olefin polymerization catalyst represented by one or more of the following formulas (1-1) to (1-5).
&Lt; Formula 1-1 >

(1-2)

<Formula 1-3>

<Formula 1-4>

&Lt; Formula 1-5 >

(In the above 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, k is an integer of 0 to 2,
M is titanium (Ti), zirconium (Zr), or hafnium (Hf)
X is independently selected from the group consisting of 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 alkyl, amido, C _6-20 aryl or C _1-20 amido FIG alkylidene,
Q is carbon (C), silicon (Si), germanium (Ge), or tin (Sn)
R ¹ , R ⁶ and R ⁷ are each independently selected from the group consisting of 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 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, respectively _-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 connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring) 9. The method of claim 8,
Wherein n is 0,
Wherein M is zirconium,
Each X is independently halogen,
Wherein Q is silicon,
And R ⁶ and R ⁷ are each independently C _1-20 alkyl. 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,
And R &lt; ⁴ &gt; is a transition metal compound for an olefin polymerization catalyst in which adjacent groups are connected to form an aromatic C &lt; ₄ &gt; 11. The method of claim 10,
The transition metal compound for an olefin polymerization catalyst according to any one of the above-mentioned Formulas 1-1 to 1-5 is at least one of the following Chemical Formulas 2-1 to 2-18.
&Lt; Formula (2-1)

&Lt; Formula (2-2)

<Formula 2-3>

<Formula 2-4>

<Formula 2-5>

<Formula 2-6>

<Formula 2-7>

<Formula 2-8>

&Lt; Formula 2-9 >

&Lt; Formula 2-10 >

&Lt; Formula (2-11)

<Formula 2-12>

&Lt; Formula (2-13)

<Formula 2-14>

&Lt; Formula (2-15)

<Formula 2-16>

&Lt; Formula 2-17 &

(2-18)

12. The method of claim 11,
Wherein R &lt; ¹ &gt; is methyl. A first transition metal compound which is a transition metal compound for an olefin polymerization catalyst according to any one of claims 8 to 12; And
A second transition metal compound represented by the following formula (3)
Wherein the content ratio of the first transition metal compound and the second transition metal compound is 100 parts by weight: 100 to 0 parts by weight.
(3)

(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)
X is independently selected from the group consisting of 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 alkyl, amido, C _6-20 aryl or C _1-20 amido an alkylidene,
Q is carbon (C), silicon (Si), germanium (Ge), or tin (Sn)
R ¹ , R ⁶ and R ⁷ are each independently selected from the group consisting of 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 selected from the group consisting of 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 &lt; ⁵ &gt; may each independently be connected to adjacent groups to form a substituted or unsubstituted saturated C _4-20 ring)