KR102050573B1 - Transition metal complexes, catalyst compositions comprising the same, and method for preparing polyolefins therewith - Google Patents

Abstract

The present invention relates to a transition metal compound exhibiting high activity and improved copolymerization activity in the polymerization reaction of an olefin monomer to enable the production of low density and high molecular weight polyolefin, a catalyst composition comprising the same, and a method for producing a polyolefin using the composition.

Description

Transition metal compound, catalyst composition comprising the same, and method for producing polyolefin using same TECHNICAL FIELD

The present invention relates to a transition metal compound, a catalyst composition comprising the same, and a method for producing a polyolefin using the same.

In the existing commercial production process of polyolefins, Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used. However, the Ziegler-Natta catalyst has a high activity, but because it is a multi-active catalyst, the molecular weight distribution of the produced polymer is wide and the composition distribution of the comonomer is not uniform, thereby limiting the desired physical properties.

In order to overcome these limitations, metallocene catalysts in which a ligand including a cyclopentadiene functional group and a transition metal such as titanium, zirconium and hafnium have been developed and widely used.

Metallocene catalyst has a narrow molecular weight distribution of the resulting polymer as a single active site catalyst, and has the advantage of controlling the molecular weight, stereoregularity, crystallinity, etc. according to the structure of the catalyst and ligand. However, polyolefins polymerized with a metallocene catalyst generally have a low melting point and a narrow molecular weight distribution, and thus, when the polyolefin is applied to a product, there is a problem in that the application of the polyolefin is difficult due to the reduction in productivity due to the effect of extrusion load.

In particular, in order to solve the problems of the metallocene catalyst described above, a number of metallocene compounds in which a ligand compound including a hetero atom is coordinated have been proposed. However, among these attempts, only a few metallocene catalysts are actually used in commercial processes.

In particular, many catalysts have been proposed to obtain high molecular weight polymers with high reactivity to olefin monomers, but there are still limitations in preparing polyolefins having high molecular weight and low density due to their relatively low copolymerizable activity.

Republic of Korea Patent Publication No. 10-0820542 (2008. 04. 01)

The present invention is to provide a transition metal compound having a novel structure, which shows a high activity and an improved copolymerization activity for the polymerization reaction of the olefin monomer to enable the production of a polyolefin having a high molecular weight and a low density.

The present invention also provides a catalyst composition for olefin polymerization containing the transition metal compound.

In addition, the present invention is to provide a method for producing a polyolefin using the catalyst composition.

According to the present invention, a transition metal compound represented by the following Chemical Formula 1 is provided:

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁷ are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms;

M is a Group 4 transition metal;

Q ¹ and Q ² are each independently hydrogen, halogen, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, alkylaryl group of 7 to 20 carbon atoms, and 7 to 20 carbon atoms. An arylalkyl group, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;

Each X ¹ is independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms;

X ² is each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms.

In addition, according to the present invention, there is provided a catalyst composition for olefin polymerization comprising the transition metal compound and a promoter.

In addition, according to the present invention, there is provided a method for producing a polyolefin comprising the step of polymerizing the olefin monomer in the presence of the catalyst composition for olefin polymerization.

Hereinafter, the transition metal compound, the catalyst composition, and the method for preparing the polyolefin according to embodiments of the present invention will be described in detail.

Prior to this, the terminology used herein is for reference only to specific embodiments and is not intended to limit the invention.

As used herein, the singular forms “a,” “an” and “the” include plural forms as well, unless the phrases clearly indicate the opposite.

Also, as used herein, the meaning of “includes” specifies a particular characteristic, region, integer, step, operation, element or component, excluding the addition of other specific characteristics, region, integer, step, operation, element, or component. It is not meant to be.

I. Transition Metal Compounds

According to one embodiment of the invention,

Provided is a transition metal compound represented by Formula 1:

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁷ are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms;

M is a Group 4 transition metal;

Q ¹ and Q ² are each independently hydrogen, halogen, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, alkylaryl group of 7 to 20 carbon atoms, and 7 to 20 carbon atoms. An arylalkyl group, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;

Each X ¹ is independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms;

X ² is each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms.

The transition metal compound represented by Chemical Formula 1 has a structure in which ketimide ligands are connected to a derivative of cyclopentadiene having a heterocycle including sulfur.

As a result of continuous studies by the present inventors, the transition metal compound represented by Chemical Formula 1 has high activity and especially when used as a catalyst for copolymerization of ethylene, octene, hexene, butene, etc., due to the influence of cyclopentadiene derivatives having heterocycles. It was found that it was possible to exhibit improved copolymerization activity, thereby obtaining a polyolefin having a high molecular weight and a low density.

In Formula 1, M may be a Group 4 transition metal element on the periodic table; Preferably it may be titanium (Ti), zirconium (Zr) or hafnium (Hf).

In Formula 1, Q ¹ and Q ² are each independently hydrogen, halogen, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, alkylaryl group of 7 to 20 carbon atoms , An arylalkyl group having 7 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms. Preferably, Q ¹ and Q ² may be each independently halogen or an alkyl group having 1 to 10 carbon atoms.

In Formula 1, R ¹ to R ⁷ may be each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms. Preferably, each of R ¹ to R ⁷ is independently hydrogen, an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an alkynyl group of 2 to 10 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or 6 to 6 carbon atoms. It may be an aryl group of 20, a cycloalkyl group of 3 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, or an arylalkyl group of 7 to 20 carbon atoms.

In addition, in Formula 1, X ¹ may be each independently hydrogen, a C 1-20 hydrocarbyl group, or a C 1-20 heterohydrocarbyl group. Preferably, each of X ¹ is independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms. Group, a cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

In addition, in Formula 1, X ² may be each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms. Preferably, each X ² is independently hydrogen, halogen, alkyl group of 1 to 10 carbon atoms, alkenyl group of 2 to 10 carbon atoms, alkynyl group of 2 to 10 carbon atoms, alkoxy group of 1 to 20 carbon atoms, 6 to 20 carbon atoms It may be an aryl group, a cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

In the definition of the substituent, the alkyl group, alkenyl group, and alkynyl group may each have a structure that is linear or branched chain.

The aryl group is preferably an aromatic ring having 6 to 20 carbon atoms, and non-limiting examples may be phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like.

The alkylaryl group refers to an aryl group in which an alkyl group having at least one C 1-20 linear or branched chain is introduced. The arylalkyl group refers to an alkyl group which is a straight or branched chain into which at least one aryl group having 6 to 20 carbon atoms is introduced.

Halogen means fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

According to one embodiment of the invention, in view of the ease of synthesis of the transition metal compound, it may be advantageous that R ¹ to R ⁷ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms. In addition, it may be advantageous that each X ¹ is independently an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. In addition, it may be advantageous that each of X ² is independently hydrogen or halogen.

On the other hand, by way of non-limiting example, the transition metal compound of Formula 1 may be represented by the following Formula 1-1, Formula 1-2, Formula 1-3, or Formula 1-4:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-1 to 1-4,

Each Cy is a cyclohexyl group,

iPr is an isopropyl group, respectively.

In addition to the representative examples, the transition metal compound may have various structures in the range defined in Chemical Formula 1, and these compounds may exhibit equivalent functions and effects.

In addition, the transition metal compound may be synthesized according to Scheme 1, for example:

[Scheme 1]

In Scheme 1,

R ¹ to R ⁷ , M, Q ¹ , Q ² , X ¹ , and X ² are each as defined in Chemical Formula 1;

Q ³ is hydrogen, halogen, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, alkylaryl group of 7 to 20 carbon atoms, arylalkyl group of 7 to 20 carbon atoms, C1 to C20 An alkylamino group of 20, an arylamino group of 6 to 20 carbon atoms, or an alkylidene group of 1 to 20 carbon atoms;

X ³ is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms.

More detailed synthesis methods for the transition metal compounds are described in the Synthesis Examples section.

II. Catalyst composition for olefin polymerization

On the other hand, according to another embodiment of the invention, there is provided a catalyst composition for olefin polymerization comprising the above-described transition metal compound.

As described above, the transition metal compound can exhibit high activity and particularly improved copolymerization activity when used as a catalyst for the polymerization of olefin monomers, thereby enabling the provision of low density and high molecular weight polyolefins.

The catalyst composition may include a promoter. The cocatalyst is any organometallic compound capable of activating the transition metal compound, and may be applied without particular limitation as long as it can be generally used when polymerizing an olefin under a catalyst of the transition metal compound.

For example, the promoter may be at least one compound selected from the group consisting of compounds represented by Formulas 4 to 6 below:

[Formula 4]

-[Al (R ⁴¹ ) -O] _c-

In Formula 4, R ⁴¹ is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more, and ,

[Formula 5]

D (R ⁵¹ ) ₃

In Formula 5, D is aluminum or boron, R ⁵¹ is a hydrocarbyl having 1 to 20 carbon atoms or a hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

[Formula 6]

[LH] ⁺ [Q (E) ₄ ] ^-

In Chemical Formula 6,

L is a neutral Lewis base, [LH] ⁺ is a Bronsted acid, Q is boron or aluminum in a +3 type oxidation state, each E is independently at least one hydrogen atom is halogen, a hydrocarbyl having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an alkoxy functional group or a phenoxy functional group.

According to one embodiment, the compound represented by Formula 4 may be alkyl aluminoxane, such as methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane. In addition, the alkyl aluminoxane may be a modified alkyl aluminoxane (MMAO) mixed with two or more kinds.

According to one embodiment, the compound represented by Formula 5 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, di Ethylchloroaluminum, triisopropylaluminum, triisobutylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenyl Aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like.

Further, according to one embodiment, the compound represented by Formula 6 is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium Tetra (p-tolyl) boron, tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tri Butyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium tetrapentafluorophenyl boron, N, N-diethylanilinium tetraphenyl Boron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, Trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tri Propyl ammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoro Romethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilini Umtetrapentafluorophenylaluminum, diethylammonium tetrapentafluorophenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethyl Sponium tetraphenyl aluminum, triphenyl carbon tetra tetra boron, triphenyl carbon tetra tetra aluminum, triphenyl carbon tetra (p-trifluoromethylphenyl) boron, triphenyl carbon tetra tetra pentafluorophenyl May be boron and the like.

In addition, the promoter may be an organoaluminum compound, an organoboron compound, an organomagnesium compound, an organozinc compound, an organolithium compound, or a mixture thereof.

For example, the promoter is preferably an organoaluminum compound, more preferably trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum ), Ethylaluminum sesquichloride, diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane It may be one or more compounds selected from the group.

On the other hand, the content ratio of the components constituting the catalyst composition may be determined in consideration of the catalytic activity. In one example, the molar ratio of the transition metal compound: promoter in the catalyst composition is controlled to 1: 1 to 1: 10,000, or 1: 1 to 1: 5,000, or 1: 1 to 1: 3,000 to secure the catalytic activity May be advantageous.

In addition, the catalyst composition may be used while supported on a carrier. The carrier may be a metal, a metal salt, a metal oxide, or the like applied to a conventional supported catalyst. As a non-limiting example, the carrier may be silica, silica-alumina, silica-magnesia, and the like, and oxides, carbonates, sulfates, vaginas of metals such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , Mg (NO ₃ ) _2, and the like. It may comprise a trisalt component.

The components constituting the catalyst composition may be added simultaneously or in any order, in the presence or absence of a suitable solvent and olefin monomer, to act as a catalytic system having activity. In this case, hexane, heptane, toluene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone and the like may be used as a suitable solvent.

III. Process for producing polyolefin

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

The polymerization reaction of the olefin monomer may be carried out by any conventional process applicable to the polymerization of the olefin monomer such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, or emulsion polymerization.

The polymerization reaction of the olefin monomer may be performed under an inert solvent. As a non-limiting example, the inert solvent may be benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene and the like.

Ethylene, alpha-olefin, cyclic olefin, etc. may be used as the olefin monomer, and a diene olefin monomer or a triene olefin monomer having two or more double bonds may also be used. Specifically, the olefin 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, 1-hexadecene, 1-aitocene, norbornene, norbonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1 , 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. The olefin monomers may be used alone or in combination of two or more thereof. When the polyolefin is a copolymer of ethylene and other comonomers, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and the like may be used as the comonomer.

In addition, the polymerization reaction of the olefin monomer may be performed for 5 minutes to 24 hours at a temperature of 25 to 500 ℃ and a pressure of 1 to 100 bar. At this time, in consideration of the yield of the polymerization reaction, the temperature of the polymerization reaction is preferably 25 to 200 ℃, more preferably 120 to 160 ℃. In addition, the pressure of the polymerization reaction is preferably 1 to 70 bar, more preferably 5 to 40 bar. The polymerization reaction time may be 5 minutes to 5 hours, or 5 minutes to 1 hour, or 5 minutes to 10 minutes.

The transition metal compound according to the present invention exhibits high activity and improved copolymerization activity in the polymerization reaction of the olefin monomer, thereby enabling the production of polyolefins having high molecular weight and low density.

Hereinafter, preferred embodiments will be presented to aid in understanding the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

Synthesis Example  One

[Scheme 1-1]

(i) 1,2-dimethyl-1H-benzo [b] cyclopenta [d] thiophen-3 (2H) -one (15.854 g, 73.3 mmol) was dissolved in THF (180 mL), followed by MeMgBr (50 mL). , 146.6 mmol, 2 eq.) Was slowly added dropwise. Then, the mixture was slowly warmed up and stirred at room temperature for 12 hours. After confirming the disappearance of the starting material by TLC, distilled water (10 mL) was slowly added dropwise and stirred for 10 minutes. Then 6N HCl (180 mL) was added and stirred for 12 hours. TLC confirmed that the starting material in alcohol form was disappeared, hexane (50 mL) was added, the water layer was removed by extraction, excess water was removed through MgSO ₄ , and the solvent was filtered under reduced pressure. , 2,3-trimethyl-3H-benzo [b] cyclopenta [d] thiophene (15.4 g, 98%) was obtained.

¹ H NMR (500MHz, in Benzene): 7.83 (d, 1H), 7.71 (d, 1H), 7.35 (t, 1H), 7.20 (t, 1H), 3.33 (m, 1H), 2.09 (s, 3H ), 2.04 (s, 3 H), 1.40 (d, 3 H).

(ii) The 1,2,3-trimethyl-3H-benzo [b] cyclopenta [d] thiophene (14.57 g, 67.98 mmol) was dissolved in THF (230 mL) and n-BuLi (28.6 mL, 71.38) at 0 ° C. mmol, 1.05 eq.) was slowly added dropwise. Then, the mixture was slowly warmed up and stirred at room temperature for 12 hours. After confirming the disappearance of the starting material by NMR, TMSCl (12.9 mL, 101.97 mmol, 1.5 eq.) Was slowly added dropwise at room temperature and stirred at room temperature for 12 hours. The starting material was confirmed by NMR, and THF solvent was filtered under reduced pressure, and the reaction mixture was dissolved in hexane (150 mL). After filtration, LiCl was removed and the solvent was filtered under reduced pressure. Trimethyl (1,2,3-trimethyl-1H-benzo [b] cyclopenta [d] thiophen-1-yl) silane and trimethyl (1,2,3-trimethyl A mixture (18.5 g, 95%) of -3H-benzo [b] cyclopenta [d] thiophen-3-yl) silane was obtained.

¹ H NMR (500MHz, in Benzene): 8.00 (d, 1H), 7.87-7.84 (m, 2H), 7.73 (d, 1H), 7.37 (t, 1H), 7.32 (t, 1H), 7.25 (t , 1H), 7.18 (t, 1H), 2.38 (s, 3H), 2.14 (s, 3H), 2.05 (s, 3H), 2.02 (s, 3H), 1.66 (s, 3H), 1.49 (s, 3H), -0.04 (s, 9H), -0.08 (s, 9H).

(iii) trimethyl (1,2,3-trimethyl-1H-benzo [b] cyclopenta [d] thiophen-1-yl) silane and trimethyl (1,2,3-trimethyl-3H-benzo [b] cyclopenta [ a mixture of d] thiophen-3-yl) silane (19.65 g, 68.58 mmol) was dissolved in CH ₂ Cl ₂ (175 mL) and slowly added dropwise TiCl ₄ (68.60 g, 68.58 mmol, 1.0 eq.) at room temperature, Stir at room temperature for 12 hours. Then, CH ₂ Cl ₂ was removed by filtration under reduced pressure to obtain a compound (23.0 g, 91%) represented by Chemical Formula 2-1 as a black solid.

¹ H NMR (500MHz, in Benzene): 7.64 (d, 1H), 7.19 (d, 1H), 7.06 (t, 1H), 6.96 It, 1H), 2.24 (s, 3H), 2.10 (s, 3H) , 1.90 (s, 3 H).

(iv) The compound represented by Formula 2-1 (1.52 g, 4.14 mmol) and the ketimide ligand (1.33 g, 4.14 mmol) represented by Formula 3-1 were dissolved in toluene (20 mL), followed by TEA (0.74 mL). , 5.28 mmol) was slowly added dropwise. The reaction mixture was then stirred at room temperature for 12 hours. After confirming that the starting material disappears by NMR, amine salt was removed by filtration, and toluene solvent was removed by filtration under reduced pressure. Thereafter, the solid obtained in the glovebox was washed with hexane to obtain a transition orange compound (2.0 g, 75%) represented by Chemical Formula 1-1 of dark orange.

¹ H NMR (500MHz, in Benzene): 7.88 (d, 1H), 7.65 (d, 1H), 7.33-7.26 (m, 3H), 6.96-6.91 (m, 2H), 3.13-3.08 (m, 2H) , 2.47 (s, 3H), 2.15 (s, 3H), 2.14 (s, 3H), 1.79-0.85 (m, 20H).

Synthesis Example  2

[Scheme 1-2]

A transition metal compound represented by Chemical Formula 1-2 was prepared by the method of Synthesis Example 1, except that the compound represented by Chemical Formula 3-2 of Scheme 1-2 was added instead of the compound represented by Chemical Formula 3-1. Got it.

¹ H NMR (500MHz, in Benzene): 7.92 (d, 1H), 7.41 (d, 1H), 7.02 (m, 1H), 6.91 (t, 1H), 6.86 (t, 1H), 6.42 (m, 2H ), 2.49 (s, 3H), 2.16 (s, 3H), 2.11 (s, 3H), 1.84-1.10 (m, 20H).

Synthesis Example  3

[Scheme 1-3]

A transition metal compound represented by Chemical Formula 1-3 was prepared by the method of Synthesis Example 1, except that the compound represented by Chemical Formula 3-3 of Scheme 1-3 was added instead of the compound represented by Chemical Formula 3-1. Got it.

¹ H NMR (500 MHz, in Benzene): 7.74 (d, 1H), 7.42-7.35 (m, 3H), 7.09-7.06 (m, 3H), 7.01-6.97 (m, 2H), 3.11-2.99 (m, 2H), 2.31 (s, 3H), 2.04 (s, 3H), 1.74 (s, 3H), 1.53-0.80 (m, 20H).

Synthesis Example  4

[Scheme 1-4]

A transition metal compound represented by Chemical Formula 1-4 was prepared by the method of Synthesis Example 1, except that the compound represented by Chemical Formula 3-4 of Scheme 1-4 was added instead of the compound represented by Chemical Formula 3-1. Got it.

¹ H NMR (500MHz, in Benzene): 7.86 (d, 1H), 7.38 (d, 1H), 7.14 (t, 1H), 7.01 (t, 1H), 6.54 (m, 1H), 6.48 (t, 2H ), 2.41 (s, 3H), 2.12 (s, 3H), 2.07 (s, 3H), 1.28-1.17 (dd, 6H), 0.65-0.62 (m, 6H).

Synthesis Example  5

[Scheme 1-5]

A transition metal compound represented by Chemical Formula 1-F was prepared by the method of Synthesis Example 1, except that the compound represented by Chemical Formula 2-F of Scheme 1-5 was added instead of the compound represented by Chemical Formula 2-1. Got it.

¹ H NMR (500 MHz, in Benzene): 6.89-6.80 (m, 3H), 3.47-3.35 (m, 1H), 2.37 (s, 15H), 2.20-1.86 (m, 7H), 1.70-0.86 (m, 14H).

Example  One

After adding 1 L of hexane and 350 ml of 1-octene to a 2 L autoclave reactor, the temperature of the reactor was preheated to 150 ° C. and ethylene was saturated to 35 bar. 1 micromole of transition metal compound of Formula 1-1 according to Synthesis Example 1 (based on Ti), 10 equivalents of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and triisobutyl aluminum as scavenger (TIBAL, 1.0 M solution in hexane, Aldrich) was charged into the catalyst injection cylinder and then injected into the reactor. The copolymerization reaction proceeded for 8 minutes while continuously injecting ethylene to maintain the pressure in the reactor at 35 bar. The heat of reaction was removed through a cooling coil inside the reactor to keep the polymerization temperature as constant as possible.

After completion of the reaction, the remaining ethylene gas was removed and the polymer solution was added to excess ethanol to induce precipitation of the polymer. The obtained polymer was washed two to three times with ethanol and acetone, and then dried in a vacuum oven at 80 ° C. for at least 12 hours.

Example  2

A polymer was obtained in the same manner as in Example 1, except that the transition metal compound of Chemical Formula 1-2 according to Synthesis Example 2 was added instead of the transition metal compound of Synthesis Example 1.

Example  3

A polymer was obtained in the same manner as in Example 1, except that the transition metal compound of Chemical Formula 1-3 according to Synthesis Example 3 was added instead of the transition metal compound of Synthesis Example 1.

Example  4

A polymer was obtained in the same manner as in Example 1, except that the transition metal compound of Formula 1-4 according to Synthesis Example 4 was added instead of the transition metal compound of Synthesis Example 1.

Comparative example  One

A polymer was obtained in the same manner as in Example 1, except that the transition metal compound of Formula 1-F according to Synthesis Example 5 was added instead of the transition metal compound of Synthesis Example 1.

Test Example

Physical properties of the polymers according to Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

1) The yield was determined by the ratio of the weight (g) of the resulting polymer.

2) The melt index (MI) of the polymer was measured according to ASTM D-1238 (Condition E, 190 ° C., 2.16 kg load).

3) The density (g / cc) of the polymer was prepared from a sample treated with an antioxidant (1000 ppm) in a sheet having a thickness of 3 mm and a radius of 2 cm using a 180 ° C. press mold, and cooled to 10 ° C./min to METTLER. (Mettler) was measured on a balance.

4) The glass transition temperature (T _c ) and melting temperature (T _m ) of the polymer were measured using a differential scanning calorimeter (DSC 2920, TA instrument), respectively. Specifically, the polymer was heated to 220 ° C. and then maintained at that temperature for 5 minutes, cooled to 20 ° C. again and then increased again. At this time, the rising rate and the falling rate of the temperature were respectively adjusted to 10 ℃ / min.

Example 1 Example 2 Comparative Example 1 Yield (g) 12.9 13.9 12.9 MI (g / 10min) 0.54 0.05 0.02 Density (g / cc) 0.892 0.898 0.901 T _c (℃) 65.6 77.7 83.5 T _m (℃) 81.6 92.9 97.6

Referring to Table 1, it was confirmed that the polymer according to the examples are low-density polyolefins having a molecular weight equivalent to that of the polymer of Comparative Example 1.

Claims (7)

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

In Chemical Formula 1,
R ¹ to R ⁷ are each hydrogen or an alkyl group having 1 to 10 carbon atoms;
M is titanium (Ti), zirconium (Zr) or hafnium (Hf);
Q ¹ and Q ² are each halogen or an alkyl group having 1 to 10 carbon atoms;
X ¹ is each an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms;
X ² is hydrogen or halogen, respectively.
delete delete delete The method of claim 1,
The compound of Formula 1 is represented by the following Formula 1-1, Formula 1-2, Formula 1-3, or Formula 1-4, a transition metal compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-1 to 1-4,
Each Cy is a cyclohexyl group,
iPr is an isopropyl group, respectively.
A catalyst composition for olefin polymerization comprising a transition metal compound represented by the formula (1) of claim 1 and a promoter.
A method for producing a polyolefin, comprising the step of polymerizing the olefin monomer in the presence of the catalyst composition for olefin polymerization of claim 6.