KR20230109257A - Polyolefin and Process for Preparing the Same - Google Patents

Abstract

The present invention relates to an olefin-based polymer and a method for preparing the same. The olefin-based polymer prepared by a metallocene catalyst according to an embodiment of the present invention has low density and low melt index, so it can be effectively used for polymer modifiers and automobile compounds.

Description

Olefin polymer and manufacturing method thereof {Polyolefin and Process for Preparing the Same}

The present invention relates to an olefin-based polymer and a method for preparing the same. Specifically, the present invention relates to an olefin-based polymer produced by polymerization of ethylene and at least one alpha-olefin in the presence of a metallocene catalyst and having a low density and melt index, and a method for preparing the same.

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

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

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

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

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

On the other hand, the polyolefin-based elastomer resin is a copolymer of ethylene and alpha-olefin, and has elasticity and exhibits excellent transparency. The physical properties of these polyolefin-based elastomer resins are affected by the content of comonomers. As the content of comonomers in the resin increases, density decreases, elasticity increases, and transparency increases. Such a resin having a low density and a low melt index is mainly used for polymer modifiers and automobile compounds.

An object of the present invention is to provide an olefinic polymer prepared by polymerization of ethylene and at least one alpha-olefin in the presence of a metallocene catalyst and having a low density and melt index, and a method for preparing the same.

According to one embodiment of the present invention for achieving the above object, it is an olefinic polymer prepared by polymerization of ethylene and at least one alpha-olefin in the presence of a metallocene catalyst, and has a density of 0.850 to 0.905 g/cm 3 , Melt index (I _2.16 ) measured at 190 ° C. under a load of 2.16 kg is 0.1 to 20.0 g / 10 min, and an olefinic polymer having an unsaturated group content of 0.4 mol% or less is provided.

In an embodiment of the present invention, the density of the olefin-based polymer is 0.850 to 0.880 g/cm 3 , the melt index (I _2.16 ) measured under a load of 2.16 kg at 190° C. is 0.1 to 5.0 g/10 min, and the content of unsaturated groups is may be 0.39 mol% or less.

In an embodiment of the present invention, the molecular weight distribution (MWD) according to the polydispersity index (Mw/Mn) of the olefin-based polymer may be 0.5 to 5, preferably 0.5 to 4.5.

In an embodiment of the present invention, the metallocene catalyst includes at least one transition metal compound represented by Formula 1 below and a cocatalyst compound.

[Formula 1]

In Formula 1 above, l is each independently an integer from 0 to 5, but at least one is not 0, m and n are each independently an integer from 0 to 4,

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

X is each independently halogen, nitro, 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, C _1-20 sulfonate or C _1-20 sulfonamide;

At least one of R ₁ and R ₂ is substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _2-20 cycloalkenyl, or substituted or unsubstituted C _1-20 alkenyl C _6-20 aryl , substituted or unsubstituted C _6-20 aryl C _1-20 alkenyl, substituted or unsubstituted C _1-20 cycloalkenyl C _6-20 aryl, and substituted or unsubstituted C _6-20 aryl C _{1- 20} An alkenyl group selected from cycloalkenyl, but when only one of R ₁ and R ₂ is an alkenyl group, the other of R ₁ and R ₂ is hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl , substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene , Substituted or unsubstituted C _1-20 It may be silyl,

R ₃ to R ₅ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylami , substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, substituted or unsubstituted C _1-20 silyl, but R ₃ to R ₅ may each independently form a substituted or unsubstituted saturated or unsaturated C _4-20 ring by connecting adjacent groups.

In an embodiment of the present invention, in Formula 1 above, l is each 1, m and n are each 0 or 1, M is zirconium or hafnium, and X is each halogen or substituted or unsubstituted C _1-20 alkyl. And, R ₁ and R ₂ are each substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _2-20 cycloalkenyl, or substituted or unsubstituted C _6-20 aryl C _1-20 alkenyl kenyl, and R ₃ to R ₅ may each be hydrogen or substituted or unsubstituted C _1-20 alkyl.

In a preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above may be at least one of transition metal compounds represented by Formulas 1-1 to 1-12 below.

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

[Formula 1-3] [Formula 1-4]

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

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

[Formula 1-9] [Formula 1-10]

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

In the above formula, Me is methyl and t -Bu is t -butyl.

In an embodiment of the present invention, the cocatalyst may include at least one selected from the group consisting of a compound represented by Formula 10, a compound represented by Formula 11, and a compound represented by Formula 12 below.

[Formula 10]

[Formula 11]

[Formula 12]

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

In Formula 10 above, n is an integer of 2 or more, R _a is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen,

In Formula 11, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen. A hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms,

In Formula 12, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a Group 13 element, and A is each independently substituted or unsubstituted 6 carbon atoms It is an aryl group of ~20 or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In a preferred embodiment of the present invention, the compound represented by Formula 10 is at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane.

In a preferred embodiment of the present invention, the compound represented by Formula 11 above is trimethylaluminum, triethylaluminium, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s -butyl Aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl It is at least one selected from the group consisting of aluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron and tributylboron.

In a preferred embodiment of the present invention, the compound represented by Formula 12 above is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium Tetra ( p -tolyl) boron, trimethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra ( p -trifluoromethylphenyl) boron, trimethylammonium tetra ( p -trifluoromethylphenyl) boron , tributylammonium tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenyl Boron, triphenylphosphonium tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium Umtetra ( p -tolyl) aluminum, tripropylammonium tetra ( p -tolyl) aluminum, triethylammonium tetra ( o , p -dimethylphenyl) aluminum, tributylammonium tetra ( p -trifluoromethylphenyl) aluminum , trimethylammonium tetra( p -trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetrapenta Florophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra ( p -tolyl) boron, triethylammonium tetra ( o , as p -dimethylphenyl)boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarboniumtetra( p -trifluoromethylphenyl)boron and triphenylcarbonium tetrapentafluorophenylboron It is at least one selected from the group consisting of.

In an embodiment of the present invention, the metallocene catalyst may further include a carrier supporting a transition metal compound, a cocatalyst compound, or both.

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

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

According to one embodiment of the present invention, ethylene and at least one alpha-olefin are polymerized in the presence of a metallocene catalyst comprising at least one transition metal compound represented by Formula 1 and a cocatalyst compound to obtain an olefinic polymer obtaining, wherein the density of the olefin-based polymer is 0.850 to 0.905 g/cm 3 , the melt index (I _2.16 ) measured under a load of 2.16 kg at 190° C. is 0.1 to 20.0 g/10 min, and the content of unsaturated groups is It is 0.4 mol% or less, and the molecular weight distribution (MWD) by polydispersity index (Mw / Mn) is 0.5 to 5, a method for producing an olefin-based polymer is provided.

In an embodiment of the invention, the alpha-olefin is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, It may be at least one selected from the group consisting of 1-dodecene, 1-tetradecene and 1-hexadecene. Preferably, the alpha-olefin may be 1-octene.

The olefin-based polymer prepared by a metallocene catalyst according to an embodiment of the present invention has low density and low melt index, so it can be effectively used for polymer modifiers and automobile compounds.

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

Olefin polymer

According to one embodiment of the present invention, the density is 0.850 ~ 0.905 g / cm 3, the melt index (I _2.16 ) measured under a load of 2.16 kg at 190 ° C. is 0.1 ~ 20.0 g / 10 minutes, and the content of unsaturated groups is 0.4 An olefin-based polymer that is mol% or less is provided.

The olefin-based polymer according to an embodiment of the present invention has a density of 0.850 to 0.905 g/cm 3 . Preferably, the density of the olefin-based polymer may be 0.850 to 0.880 g/cm 3 , 0.850 to 0.875 g/cm 3 , 0.850 to 0.870 g/cm 3 or 0.850 to 0.865 g/cm 3 .

The olefin-based polymer according to an embodiment of the present invention has a melt index (I _2.16 ) of 0.1 to 20.0 g/10 minutes measured at 190° C. under a load of 2.16 kg. Preferably, the melt index of the olefin-based polymer measured under a load of 2.16 kg at 190° C. may be 0.1 to 5.0 g/10 min, 0.1 to 2.5 g/10 min, or 0.1 to 1.5 g/10 min.

The olefin-based polymer according to an embodiment of the present invention has an unsaturated group content of 0.4 mol% or less. Preferably, the content of the unsaturated group of the olefin-based polymer may be 0.39 mol% or less or 0.38 mol% or less.

In an embodiment of the present invention, the molecular weight distribution (MWD) according to the polydispersity index (Mw/Mn) of the olefin-based polymer may be 0.5 to 5.0. Preferably, the molecular weight distribution according to the polydispersity index of the olefin-based polymer may be 0.5 to 4.5, 0.5 to 4.0, or 0.5 to 3.5.

Olefinic polymers according to embodiments of the present invention are prepared by polymerization of ethylene and at least one alpha-olefin.

In an embodiment of the present invention, the olefinic polymer is prepared by polymerization of ethylene and at least one alpha-olefin in the presence of a metallocene catalyst comprising at least one transition metal compound represented by Formula 1 below and a cocatalyst compound It can be.

[Formula 1]

In Formula 1 above, l is each independently an integer of 0 to 5, but at least one is not 0, and m and n are each independently an integer of 0 to 4. Specifically, l is 0 or 1, but at least one is not 0, and m and n are 0 or 1, respectively. Preferably, l is each 1, and m and n are each 0 or 1.

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

X is each independently halogen, nitro, 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, C _1-20 sulfonate or C _1-20 sulfonamide. Specifically, each X may be a halogen or a substituted or unsubstituted C _1-20 alkyl.

At least one of R ₁ and R ₂ is substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _2-20 cycloalkenyl, or substituted or unsubstituted C _1-20 alkenyl C _6-20 aryl , substituted or unsubstituted C _6-20 aryl C _1-20 alkenyl, substituted or unsubstituted C _1-20 cycloalkenyl C _6-20 aryl, and substituted or unsubstituted C _6-20 aryl C _{1- 20} An alkenyl group selected from cycloalkenyl, but when only one of R ₁ and R ₂ is an alkenyl group, the other of R ₁ and R ₂ is hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl , substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene , It may be a substituted or unsubstituted C _1-20 silyl.

R ₃ to R ₅ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylami , substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl.

Also, R ₃ to R ₅ may each independently form a substituted or unsubstituted saturated or unsaturated C _4-20 ring by connecting adjacent groups.

In an embodiment of the present invention, in Formula 1 above, l is each 1, m and n are each 0 or 1, M is zirconium or hafnium, and X is each halogen or substituted or unsubstituted C _1-20 alkyl. And, R ₁ and R ₂ are each substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _2-20 cycloalkenyl, or substituted or unsubstituted C _6-20 aryl C _1-20 alkenyl kenyl, and R ₃ to R ₅ may each be hydrogen or substituted or unsubstituted C _1-20 alkyl.

In a preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above may be at least one of transition metal compounds represented by Formulas 1-1 to 1-12 below.

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

[Formula 1-3] [Formula 1-4]

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

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

[Formula 1-9] [Formula 1-10]

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

In the above formula, Me is methyl and t -Bu is t -butyl.

The metallocene catalyst comprising at least one transition metal compound represented by Formula 1 and a cocatalyst compound has high reactivity toward comonomers, and is prepared by polymerization of ethylene and at least one alpha-olefin in the presence of the catalyst. The olefin-based polymer that becomes may have a low density. In addition, the above metallocene catalyst has excellent high-temperature stability, so that a resin can be produced so that the physical properties of the olefin-based polymer are not biased.

The transition metal compound of Chemical Formula 1 is prepared by: (1a) reacting a compound represented by Chemical Formula 2h with a compound represented by Chemical Formula 3m to obtain a compound represented by Chemical Formula 4h; (2a) reacting a compound represented by Chemical Formula 5 with at least one of a lithium compound, a potassium compound, and a sodium compound to obtain a compound represented by Chemical Formula 5m; (3a) reacting a compound represented by Chemical Formula 4h with a compound represented by Chemical Formula 5m to obtain a compound represented by Chemical Formula 6h; (4a) a compound represented by Formula 6 by reacting a compound represented by Formula 6h with an organic boron compound substituted with R ₁ or R ₂ (where R ₁ and R ₂ are as described in the section on the transition metal compound above); obtaining; (5) reacting the compound represented by Chemical Formula 6 with at least one of a lithium compound, a potassium compound and a sodium compound to obtain a compound represented by Chemical Formula 6m below; and (6) reacting a compound represented by Chemical Formula 6m with a compound represented by Chemical Formula 7 below or a complex thereof to obtain a transition metal compound represented by Chemical Formula 1h below.

[Formula 2h]

[Formula 3m]

[Formula 4h]

[Formula 5]

[Formula 5m]

[Formula 6h]

[Formula 6]

[Formula 6m]

[Formula 7]

M(X _a ) ₄

[Formula 1h]

In the above formula, l, m, n, M, R ₁ to R ₅ are as described in the above transition metal compound, Mt is one of lithium, potassium and sodium, Y ₁ and Y ₂ are halogen, C _1-20 sulfonate or C _1-20 sulfonamide, wherein either Y ₁ or Y ₂ can be R ₁ or R ₂ , X _a is halogen, C _1-20 sulfonate, C _1-20 sulfonamide , C _1-20 aryl C _1-20 alkyl or C _1-20 alkylamido.

Step (1a)

In the above step (1a), the compound represented by the above formula 2h and the compound represented by the above formula 3m are reacted to obtain the compound represented by the above formula 4h.

In an embodiment of the present invention, in the above formula, l is each 1, m is 0, and Y ₁ and Y ₂ may be bromine.

In an embodiment of the present invention, the compound represented by the above formula 2h and the compound represented by the above formula 3m may be dissolved in a solvent before the reaction. Here, the solvent is an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an ether solvent such as diethyl ether or tetrahydrofuran, acetone and ethyl It may include at least one selected from the group consisting of acetate, but is not particularly limited thereto. Preferably, the above solvent may be tetrahydrofuran.

The temperature at the time of mixing the compound represented by Formula 2h and the compound represented by Formula 3m is preferably in the range of -78°C to 30°C. More preferably, the temperature at the time of mixing these two compounds may be -40 ℃ to 10 ℃. Most preferably, the temperature when mixing these two compounds may be about -30 °C.

After mixing the compound represented by formula 2h and the compound represented by formula 3m, the temperature is gradually raised to a temperature of -78 ° C to 80 ° C, preferably -40 ° C to 60 ° C, more preferably room temperature, The reaction is carried out under stirring for 1 to 24 hours, preferably 1 to 12 hours, more preferably 1 to 6 hours.

For example, distilled water is added to terminate the reaction, the product is extracted with a solvent such as dichloromethane, and after removing moisture with, for example, anhydrous sodium sulfate, it is concentrated under reduced pressure. Subsequently, the product may be recrystallized using, for example, dichloromethane and methanol to obtain the compound represented by the above formula 4h.

Step (2a)

In the above step (2a), the compound represented by the above formula 5 is reacted with at least one of a lithium compound, a potassium compound and a sodium compound to obtain a compound represented by the above formula 5m.

In an embodiment of the present invention, in the above formula, each n is 1, and R ₄ and R ₅ may each be a substituted or unsubstituted C _1-20 alkyl. Preferably, R ₄ and R ₅ may each be t -butyl.

In an embodiment of the present invention, at least one of the lithium compound, the potassium compound and the sodium compound is n -butyl lithium, methyl lithium, sodium amide and potassium hydroxide may include at least one of them. Preferably, at least one of the lithium compound, potassium compound and sodium compound may be n -butyllithium.

In an embodiment of the present invention, at least one of the compound represented by Formula 5 and a lithium compound, a potassium compound, and a sodium compound may be dissolved in a solvent before the reaction. Here, the solvent is an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an ether solvent such as diethyl ether or tetrahydrofuran, acetone and ethyl It may include at least one selected from the group consisting of acetate, but is not particularly limited thereto. Preferably, the compound represented by Chemical Formula 5 may be dissolved in a mixed solution of hexane and ether, and at least one of a lithium compound, a potassium compound, and a sodium compound may be dissolved in hexane.

The temperature at the time of mixing the compound represented by Formula 5 with at least one of a lithium compound, a potassium compound and a sodium compound is preferably in the range of -78°C to 30°C. More preferably, the temperature at the time of mixing these two compounds may be -40 ℃ to 10 ℃. Most preferably, the temperature when mixing these two compounds may be about -30 °C.

After mixing the compound represented by Formula 5 with at least one of a lithium compound, a potassium compound and a sodium compound, the temperature is -78 ° C to 80 ° C, preferably -40 ° C to 60 ° C, more preferably It is gradually raised to room temperature and reacted under stirring for 1 to 48 hours, preferably 12 to 32 hours, more preferably 18 to 30 hours.

The product is concentrated under reduced pressure, the solvent is removed under vacuum, and then washed with, for example, hexane to obtain a compound represented by Formula 5m above.

Step (3a)

In the above step (3a), the compound represented by the above formula 6h is obtained by reacting the compound represented by the above formula 4h with the compound represented by the above formula 5m.

In an embodiment of the present invention, the compound represented by the above formula 4h and the compound represented by the above formula 5m may be dissolved in a solvent before the reaction. Here, the solvent is an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an ether solvent such as diethyl ether or tetrahydrofuran, acetone and ethyl It may include at least one selected from the group consisting of acetate, but is not particularly limited thereto. Preferably, the above solvent may be diethyl ether.

The temperature at the time of mixing the compound represented by Formula 4h and the compound represented by Formula 5m is preferably in the range of -78°C to 30°C. More preferably, the temperature at the time of mixing these two compounds may be -40 ℃ to 10 ℃. Most preferably, the temperature when mixing these two compounds may be about -30 °C.

After mixing the compound represented by Formula 4 and the compound represented by Formula 6, the temperature is gradually raised to a temperature of -78 ° C to 80 ° C, preferably -40 ° C to 60 ° C, more preferably room temperature, The reaction is carried out under stirring for 1 to 48 hours, preferably 12 to 32 hours, more preferably 18 to 30 hours. An excess of distilled water is then added and stirred for about 10 minutes.

The resulting slurry is filtered and washed with a solvent such as hexane to obtain a compound represented by the above formula 6h.

Step (4a)

In step (4a), the compound represented by Chemical Formula 6h is reacted with an organic boron compound substituted with R ₁ or R ₂ to obtain a compound represented by Chemical Formula 6 above. Here, R ₁ and R ₂ are as described in the above transition metal compound.

In an embodiment of the present invention, R ₁ and R ₂ substituted in the organic boron compound may be the same or different, and are preferably the same. Specifically, R ₁ and R ₂ are substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _2-20 cycloalkenyl, or substituted or unsubstituted C _6-20 aryl C _1-20 alkenyl could be Neil.

The organic boron compound substituted with R ₁ or R ₂ may be selected from boronic acid, boronic ester, potassium trifluoride, alkylborane, boronic acid, and boronic ester substituted with R ₁ or R ₂ .

In a preferred embodiment of the present invention, the organic boron compound is boronic acid substituted with R ₁ or R ₂ , isopropenyl boronic acid, vinyl boronic acid, 3-methyl-2-butene-2yl boronic acid (3-methyl -2-buten-2-ylboronic acid), 1-phenylvinylboronic acid, cyclopenten-1-ylboronic acid and 1-cyclohexen-1-ylboronic acid It may include at least one of nic acid (1-cyclohexen-1-yl-boronic acid), but is not particularly limited thereto.

In an embodiment of the present invention, the reaction between the compound represented by Formula 6h and the organic boron compound substituted with R ₁ or R ₂ is potassium carbonate, potassium phosphate, potassium t-butoxide, sodium methoxide, sodium hydroxide, cesium carbonate, Basic substances such as triethylamine, sodium carbonate, sodium phosphate, t-butylamine, diisopropylethylamine, tetrakis(triphenylphosphine)palladium, palladium(II)acetate, Na ₂ PdCl ₄ , tris( It can be carried out in the presence of a catalyst such as dibenzylideneacetone) dipalladium(0).

In an embodiment of the present invention, the reaction of step (4a) may be carried out in a solvent. Here, the solvent is not particularly limited, but may be a mixed solvent of tetrahydrofuran and water.

After mixing the above-mentioned compounds in a solvent, at a temperature of 0 ° C to 120 ° C, more preferably at a temperature of 25 ° C to 80 ° C, most preferably at a temperature of about 70 ° C, for 1 to 24 hours, preferably is reacted under stirring for 1 to 12 hours, more preferably 1 to 5 hours.

After the reaction is complete, the organic layer is collected using a separatory funnel, concentrated under reduced pressure, and water is removed with, for example, anhydrous sodium sulfate. Then, the product can be purified using column chromatography to obtain the compound represented by Formula 6 above.

step (5)

In the above step (5), the compound represented by the above formula 6 is reacted with at least one of a lithium compound, a potassium compound and a sodium compound to obtain a compound represented by the above formula 6m.

Here, at least one of the lithium compound, the potassium compound and the sodium compound is as described in step (2a) above.

In an embodiment of the present invention, at least one of the compound represented by Formula 6 and a lithium compound, a potassium compound, and a sodium compound may be dissolved in a solvent before the reaction. Here, the solvent is as described in step (2a) above.

The temperature at which the compound represented by Formula 6 is mixed with at least one of the lithium compound, potassium compound, and sodium compound, and the reaction temperature and time after mixing them are the same as described in step (2a) above.

After completion of the reaction, the solvent is removed under vacuum, and the obtained product is washed with, for example, hexane to obtain a compound represented by Formula 6m above.

step (6)

In the above step (6), the compound represented by the above formula 6m and the compound represented by the above formula 7 or a complex thereof are reacted to obtain the transition metal compound represented by the above formula 1h.

In an embodiment of the present invention, the compound represented by Chemical Formula 7 above may include at least one of HfCl ₄ and ZrCl ₄ . More preferably, the compound represented by Formula 7 above may be HfCl ₄ or ZrCl ₄ . In this case, in Formula 1h above, X _a may be chlorine.

In an embodiment of the present invention, the compound represented by the above formula 6m and the compound represented by the above formula 7 or a complex thereof may be dissolved in a solvent before the reaction. Here, the solvent is an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an ether solvent such as diethyl ether or tetrahydrofuran, acetone and ethyl It may include at least one selected from the group consisting of acetate, but is not particularly limited thereto. Preferably, the above solvent may be toluene.

The temperature at the time of mixing the compound represented by formula 6m and the compound represented by formula 7 or its complex is preferably in the range of -78°C to 30°C. More preferably, the temperature at the time of mixing these two compounds may be -40 ℃ to 10 ℃. Most preferably, the temperature when mixing these two compounds may be about -30 °C.

After mixing the compound represented by Formula 6m and the compound represented by Formula 7 or a complex thereof, the temperature is -78°C to 80°C, preferably -40°C to 60°C, more preferably room temperature. and reacted under stirring for 1 to 96 hours, preferably 18 to 78 hours, more preferably 24 to 72 hours.

The product is filtered through, for example, celite, and the solvent is removed under vacuum to obtain the transition metal compound represented by Formula 1h above.

In an optional embodiment of the present invention, in the method for producing a transition metal compound according to an embodiment of the present invention, the compound represented by Formula 6 above may be obtained by another method.

Specifically, the method for preparing a transition metal compound according to an embodiment of the present invention, instead of steps (3a) and (4a), (3b) an organic boron substituted with R ₁ or R ₂ for the compound represented by Formula 4h above Obtaining a compound represented by Formula 4 below by reacting with a compound (where R ₁ and R ₂ are as described in the above transition metal compound); and (4b) reacting the compound represented by Chemical Formula 4 with the compound represented by Chemical Formula 5m to obtain the compound represented by Chemical Formula 6.

[Formula 4]

In the above formula, l, m, R ₁ to R ₃ are as described in the above transition metal compound.

Step (3b)

In step (3b), the compound represented by Chemical Formula 4h is reacted with an organic boron compound substituted with R ₁ or R ₂ to obtain a compound represented by Chemical Formula 4 above. Here, the organic boron compound substituted with R ₁ or R ₂ is as described in step (4a) above. In addition, specific reaction conditions between the compound represented by Chemical Formula 4h and the organic boron compound are substantially the same as those in step (4a) above.

Step (4b)

In step (4b) above, the compound represented by the above formula (6) is obtained by reacting the compound represented by the above formula (4) with the compound represented by the above formula (5m). Here, specific reaction conditions between the compound represented by Formula 4 and the compound represented by Formula 5m are substantially the same as those in step (3a) above.

In an optional embodiment of the present invention, in the method for producing a transition metal compound according to an embodiment of the present invention, the compound represented by Formula 6 above can be obtained by another method.

Specifically, the method for producing a transition metal compound according to an embodiment of the present invention, instead of steps (1a) to (4a), (2c) reacts the compound represented by Formula 2 with the compound represented by Formula 3m above Obtaining a compound represented by Formula 4; (3c) reacting the compound represented by Chemical Formula 5 with at least one of a lithium compound, a potassium compound and a sodium compound to obtain a compound represented by Chemical Formula 5m; (4c) reacting the compound represented by Chemical Formula 4 with the compound represented by Chemical Formula 5m to obtain the compound represented by Chemical Formula 6 above.

[Formula 2]

In the above formula, l, R ₁ and R ₂ are as described in the above transition metal compound.

Step (2c)

In the above step (2c), the compound represented by the above formula (2) is reacted with the compound represented by the above formula (3m) to obtain the compound represented by the above formula (4). Here, the specific reaction conditions of the compound represented by Formula 2 above and the compound represented by Formula 3m above are substantially the same as the reaction conditions of step (1a) above.

Step (3c)

In the above step (3c), the compound represented by Chemical Formula 5 is reacted with at least one of a lithium compound, a potassium compound and a sodium compound to obtain a compound represented by Chemical Formula 5m below. The specific conditions of step (3c) are substantially the same as those of step (2a) above.

step (4c)

In the above step (4c), the compound represented by the above formula (4) and the compound represented by the formula (5m) are reacted to obtain the compound represented by the above formula (6). The specific conditions of step (4c) are substantially the same as those of step (3a) above.

In an embodiment of the present invention, the method for preparing the above transition metal compound is (7a) reacting a compound represented by formula 1h with a compound represented by formula 8a or a compound represented by formula 9 to obtain a compound represented by formula 1a below An obtaining step may be further included.

[Formula 8a]

X _b Mg X _c

[Formula 9]

X _b Li

[Formula 1a]

In the above formula, l, m, n, M, R ₁ to R ₅ are as described in the above transition metal compound, and X _b 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, X _c is halogen.

In an embodiment of the present invention, the method for preparing the above transition metal compound may further include the step of (7b) reacting a compound represented by Formula 1h with a compound represented by Formula 8b to obtain a compound represented by Formula 1b below. can

[Formula 8b]

(R _n ) ₃ SiX _d

[Formula 1b]

In the above formula, l, m, n, M, R ₁ to R ₅ are as described in the above transition metal compound, and R _n 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 or C _6-20 aryl C _1-20 alkyl, and X _d is halogen.

In an embodiment of the present invention, the compound represented by Chemical Formula 8a may be MeMgBr, and the compound represented by Chemical Formula 9 may be MeLi. In addition, the compound represented by Formula 8b above may be (Me) ₃ SiCl.

In an embodiment of the present invention, the compound represented by Chemical Formula 1h and the compound represented by Chemical Formula 8a or 8b or the compound represented by Chemical Formula 9 may be dissolved in a solvent before the reaction. Here, the solvent is an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an ether solvent such as diethyl ether or tetrahydrofuran, acetone and ethyl It may include at least one selected from the group consisting of acetate, but is not particularly limited thereto. Preferably, the compound represented by Formula 1h may be dissolved in toluene, and the compound represented by Formula 8a or 8b or the compound represented by Formula 9 may be dissolved in hexane.

The temperature at the time of mixing the compound represented by Formula 1h and the compound represented by Formula 8a or 8b or the compound represented by Formula 9 is preferably in the range of -78°C to 30°C. More preferably, the temperature at the time of mixing these two compounds may be -40 ℃ to 10 ℃. Most preferably, the temperature when mixing these two compounds may be about -30 °C.

After mixing the compound represented by Formula 1h with the compound represented by Formula 8a or 8b or the compound represented by Formula 9, the temperature is -78°C to 80°C, preferably -40°C to 60°C, More preferably, the temperature is gradually raised to room temperature and reacted under stirring for 1 to 48 hours, preferably 4 to 30 hours, and still more preferably 6 to 24 hours.

After completion of the reaction, the solvent is removed under vacuum, dissolved in, for example, hexane, and filtered through, for example, celite. The transition metal compound represented by Chemical Formula 1a may be obtained by removing the solvent from the obtained solution under vacuum.

In an embodiment of the present invention, the cocatalyst compound may include at least one selected from the group consisting of a compound represented by Formula 10, a compound represented by Formula 11, and a compound represented by Formula 12 below.

[Formula 10]

In Formula 10, n is an integer of 2 or greater, and R _a may be a halogen atom, a C _1-20 hydrocarbon, or a C _1-20 hydrocarbon substituted with a halogen. Specifically, R _a can be methyl, ethyl, n -butyl or isobutyl.

[Formula 11]

In Formula 11, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. or a C _1-20 alkoxy group. Specifically, when D is aluminum (Al), R _b , R _c and R _d may each independently be methyl or isobutyl, and when D is boron (B), R _b , R _c and R _d are Each may be pentafluorophenyl.

[Formula 12]

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

In Formula 12 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C ₆ It is _{a -20} aryl group or a substituted or unsubstituted C _1-20 alkyl group. Specifically, [LH] ⁺ may be a dimethylanilinium cation, [Z(A) ₄ ] ^- may be [B(C ₆ F ₅ ) ₄ ] ^- , and [L] ⁺ may be [(C ₆ H ₅ ) ₃ C] ⁺ .

In an embodiment of the present invention, examples of the compound represented by Formula 10 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and methylaluminoxane is preferred, but is limited thereto. It is not.

In an embodiment of the present invention, examples of the compound represented by Formula 11 above include trimethylaluminum, triethylaluminium, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s- Butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are preferred, but are limited thereto. It is not.

In an embodiment of the present invention, examples of the compound represented by Formula 12 above include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium Umtetra ( p -tolyl) boron, trimethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra ( p -trifluoromethylphenyl) boron, trimethylammonium tetra ( p -trifluoromethylphenyl) Boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluoro Phenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethyl Ammonium tetra ( p -tolyl) aluminum, tripropylammonium tetra ( p -tolyl) aluminum, triethylammonium tetra ( o , p -dimethylphenyl) aluminum, tributylammonium tetra ( p -trifluoromethylphenyl) Aluminum, trimethylammonium tetra( p -trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetra Pentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra ( p -tolyl) boron, triethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarboniumtetra( p -trifluoromethylphenyl)boron, triphenylcarbonium tetrapentafluorophenylboron etc. can be mentioned.

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

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

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

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

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

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

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

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

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

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

In an embodiment of the present invention, as a method for supporting the transition metal compound and/or cocatalyst compound, a physical adsorption method or a chemical adsorption method may be used.

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

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

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

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

In addition, the process of supporting the transition metal compound and/or cocatalyst compound on the carrier is performed by sufficiently stirring the mixture of the transition metal compound and/or cocatalyst compound and the carrier for 1 minute to 24 hours, preferably 5 minutes to 15 hours. can be performed

In an embodiment of the present invention, the olefin-based polymer may be a homopolymer of olefin-based monomers or a copolymer of olefin-based monomers and comonomers. Preferably, the olefinic polymer is a copolymer of olefinic monomers and olefinic comonomers.

Here, the olefinic monomer is C _2-20 alpha-olefin (α-olefin), C _1-20 diolefin (diolefin), C _3-20 cycloolefin (cycloolefin) and C _3-20 cyclodiolefin (cyclodiolefin). It is at least one selected from the group consisting of.

For example, olefinic monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 -dodecene, 1-tetradecene or 1-hexadecene, and the like.

In an exemplary embodiment, the olefin-based polymer may be a copolymer of ethylene and C _3-20 alpha-olefin. Preferably, the olefinic polymer may be low density polyethylene in which the olefinic monomer is ethylene and the olefinic comonomer is 1-octene.

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

Method for producing olefin-based polymers

According to one embodiment of the present invention, ethylene and at least one alpha-olefin are polymerized in the presence of a metallocene catalyst comprising at least one transition metal compound represented by Formula 1 and a cocatalyst compound to obtain an olefinic polymer A method for producing an olefin-based polymer comprising the step of obtaining is provided.

[Formula 1]

In Formula 1 above, l, m, n, M, X, R ₁ to R ₅ are as described in the transition metal compound section above.

As described above, the olefin-based polymer prepared by the manufacturing method according to one embodiment of the present invention has a density of 0.850 to 0.905 g/cm 3 , and a melt index (I _2.16 ) measured at 190° C. under a load of 2.16 kg. 0.1 ~ 20.0 g / 10 minutes, the content of unsaturated groups is 0.4 mol% or less, and the molecular weight distribution (MWD) by polydispersity index (Mw / Mn) is 0.5 ~ 5.0.

As an embodiment of the present invention, the olefin-based polymer may be prepared by gas phase polymerization, solution polymerization or slurry polymerization. Preferably, polymerization of the olefinic monomers may be carried out by solution polymerization.

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

In an embodiment of the invention, the alpha-olefin is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, It may be at least one selected from the group consisting of 1-dodecene, 1-tetradecene and 1-hexadecene. Preferably, the alpha-olefin may be 1-octene.

Example

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

manufacturing example 1: Preparation of transition metal compound of Formula 1-1

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

[Scheme 1]

step 1:6 ,6- Di (4-bromophenyl) fulvene (6,6-di (4- bromophenyl ) fulvene ; Synthesis of Chemical Formula 4-1)

A solution of 4,4'-dibromobenzophenone (Formula 2-1h) (10 g, 29 mmole) in tetrahydrofuran (THF) (73.5 ml) was heated to -30 ° C. After cooling, a solution of sodium pentamethylcyclopentadienide (NaCp; Formula 3-1m) (2.0 M in THF, 17.6 mL) was added slowly. After slowly raising the temperature to room temperature and stirring for 3 hours, the reaction was terminated by adding distilled water (10 ml). The product was extracted with dichloromethane, dried with anhydrous sodium sulfate, and then concentrated under reduced pressure. The product was recrystallized from dichloromethane and methanol to obtain a red crystalline solid compound (Formula 4-1) (8.7 g, yield 75%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.52 (m, 4 H), 7.17 (m, 4 H), 6.62 (m, 2 H), 6.23 (m, 2 H).

step 2:3 Synthesis of 6-di-tert-butylfluorenyl lithium (3,6-di-tert-butylfluorenyl lithium; Formula 5-1m)

A solution of 3,6-di-tert-butylfluorene (Formula 5-1) (8.4 g, 30 mmole) in hexane (55 ml) and ether (75 ml) After cooling to -30 °C, n -butyllithium solution (1.6 M in hexane, 20.8 mL) was slowly added. The temperature was gradually raised to room temperature and stirred for 24 hours. The obtained yellow solution was concentrated under reduced pressure, the solvent was removed under vacuum, and washed with hexane to obtain a yellow solid compound (Formula 5-1m) (9.6 g, yield 100%).

Step 3: Synthesis of Formula 6-1h Compound

A solution of 3,6-di-tert-butylfluorenyl lithium (formula 5-1m) (7.0 g, 22 mmole) in ether (30 ml) was cooled to -30 ° C, and 6,6-di( A solution of 4-bromophenyl)fulvene (Formula 4-1) (8.7 g, 22 mmole) dissolved in ether (120 ml) cooled to -30 °C was slowly added. After slowly raising the temperature to room temperature and stirring for 24 hours, an excess amount of distilled water was added and the mixture was stirred for 10 minutes. The resulting slurry was filtered and washed with hexane to obtain a pale yellow solid compound (Formula 6-1h) (6.2 g, yield 42%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.60-6.95 (m, 14 H), 6.55-5.30 (m, 4 H), 3.09 (br s, 2 H), 1.36 (s, 18 H).

Step 4: Synthesis of Compound of Formula 6-1

Compound of Formula 6-1h (800 mg, 1.2 mmole), potassium carbonate (663 mg, 4.8 mmole), isopropenyl boronic acid (1.9 g, 16% by weight in THF), tetrakis(triphenylphosphine)palladium ( 69 mg, 0.06 mmole) was added to THF (6 ml) and distilled water (6 ml) and stirred at 70°C for 2.5 hours. The organic layer was collected using a separatory funnel, concentrated under reduced pressure, and water was removed using anhydrous sodium sulfate. The product was purified using column chromatography to obtain a pale yellow solid compound (Formula 6-1) (283 mg, yield 40%).

¹ H NMR (300 MHz, CDCl ₃ ): δ7.65-7.11 (m, 14 H), 6.50-5.41 (m, 6 H), 5.16 (s, 2H), 3.07 (br s, 2H), 2.24 ( s, 6H), 1.46 (s, 18H).

Step 5: Synthesis of Formula 6-1m Compound

A solution of the compound of Formula 6-1 (209 mg, 0.35 mmole) in ether (3.5 ml) was cooled to -30°C, and n -butyllithium solution (1.6 M in hexane, 0.47 ml) was slowly added. After slowly raising the temperature to room temperature and stirring for 24 hours, hexane (3 ml) was added and the solvent was removed under vacuum. The obtained solid compound was washed with hexane to obtain an orange solid compound (Formula 6-1m) (147 mg, yield 75%).

Step 6: Synthesis of Formula 1-1h Compound

A solution of the compound of Formula 6-1m (70 mg, 0.12 mmole) in toluene (0.8 mL) was cooled to -30 °C, and hafnium tetrachloride (HfCl ₄ ) (37 mg, 0.12 mmole) was added to toluene (1.5 mL). After dissolving in ), a solution cooled to -30 ° C was added. The temperature was gradually raised to room temperature and stirred for 24 hours. The product was filtered through celite, and the solvent was removed under vacuum to obtain a yellow solid compound (Formula 1-1h) (78 mg, yield 66%).

¹ H NMR (300 MHz, C ₆ D ₆ ): δ8.29 (s, 2H), 7.68 (d, 4H, J=9 Hz), 7.38-6.82 (m, 6 H), 6.55 (m, 2H) , 6.14 (m, 2H), 5.59 (m, 2H), 5.36 (s, 2H), 4.97 (s, 2H), 1.91 (s, 6H), 1.33 (s, 18H).

Step 7: Synthesis of Formula 1-1 Compound

A solution of Compound 1-1h (78 mg, 0.077 mmole) in toluene (1.6 mL) was cooled to -30 °C and a solution of MeMgBr (3.0 M in ether, 0.08 mL, 0.24 mmole) was added slowly. The temperature was gradually raised to room temperature and stirred for 19 hours. After removing the solvent under vacuum, the mixture was filtered through Celite while dissolved in hexane. The solvent was removed from the obtained solution under vacuum to obtain a yellow solid (Formula 1-1) (53.9 mg, yield 78%).

¹ H NMR (300 MHz, C ₆ D ₆ ): δ8.36 (s, 2H), 7.86 (d, 2H, J = 7.8 Hz), 7.75 (d, 2H, J = 8.4 Hz), 7.47-6.68 ( m, 6H), 6.46 (d, 2H, J = 9.0 Hz), 6.12 (m, 2H), 5.52 (m, 2H), 5.34 (s, 2H), 4.95 (s, 2H), 1.90 (s, 6H) ), 1.33 (s, 18 H), −1.35 (s, 6 H).

manufacturing example 2: Preparation of the transition metal compound of Formula 1-9

Transition metal compounds of Chemical Formulas 1-9 were prepared according to the synthetic procedure outlined in Reaction Scheme 2 below.

[Scheme 2]

A compound represented by Chemical Formula 6-1h was obtained in the same manner as in Steps 1 to 3 of Example 1 above.

Step 4: Synthesis of Compounds of Formula 6-9

Compound of formula 6-1h (300 mg, 0.45 mmole), potassium carbonate (249 mg, 1.8 mmole), cyclopentyl boronic acid (151 mg, 1.35 mmole), tetrakis(triphenylphosphine)palladium (26 mg, 0.023 mole) into THF (3 ml) and distilled water (3 ml) and stirred at 65°C for 4.5 hours. The organic layer was collected using a separatory funnel, concentrated under reduced pressure, and water was removed using anhydrous sodium sulfate. The product was purified using column chromatography to obtain a pale yellow solid compound (Formula 6-9) (132 mg, yield 46%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.85-6.96 (m, 16 H), 6.11 (m, 2 H), 5.45 (m, 2 H), 2.65 (m, 2 H), 2.49 (m, 2 H), 1.98 (m, 2 H), 1.30 (s, 18 H).

Step 5: Synthesis of Compounds of Formula 6-9m

A solution of the compound of Formula 6-9 (70 mg, 0.11 mmole) in ether (2.5 mL) was cooled to -30°C, and n -butyllithium solution (1.6 M in hexane, 0.16 mL) was slowly added. The temperature was gradually raised to room temperature and stirred for 24 hours to obtain an orange solution (6-9 m).

Step 6: Synthesis of Compounds of Formula 1-9h

The solution of formula 6-9m obtained in step 5 was cooled to -30 °C and hafnium tetrachloride (HfCl ₄ ) (35 mg, 0.11 mmole) was added. After slowly raising the temperature to room temperature and stirring for 16 hours, the solvent was removed under vacuum. A solution obtained by dissolving the obtained solid compound in toluene was filtered through celite, and the solvent was removed under vacuum to obtain a yellow solid compound (Formula 1-9h) (84 mg, yield 87%).

¹ H NMR (300 MHz, C ₆ D ₆ ): δ 8.32 (m, 2 H), 7.73 (m, 2 H), 7.42-7.32 (m, 2 H), 7.20-6.88 (m, 6 H), 6.55 (d, J = 9.3 Hz, 2 H), 6.17 (m, 2 H), 6.05 (m, 2 H), 5.64 (t, J = 2.7 Hz, 2 H), 2.55 (m, 4 H), 2.35 (m, 4 H), 1.83 (m, 4 H), 1.37 (s, 18 H).

Step 7: Synthesis of Compounds of Formulas 1-9

A solution of Compound 1-9h (84 mg, 0.095 mmole) in toluene (1.8 mL) was cooled to -30 °C and a solution of MeMgBr (3.0 M in ether, 0.10 mL, 0.30 mmole) was added slowly. The temperature was gradually raised to room temperature and stirred for 4 hours. After removing the solvent under vacuum, the mixture was filtered through celite while dissolved in toluene. The solvent was removed from the obtained solution under vacuum to obtain a yellow solid (Formula 1-9) (73.8 mg, yield 92%).

¹ H NMR (300 MHz, C ₆ D ₆ ): δ 8.39 (m, 2 H), 7.91 (m, 2 H), 7.79 (m, 2 H), 7.45-6.77 (m, 6 H), 6.56 ( d, J = 9.3 Hz, 2 H), 6.15 (s, 2 H), 6.02 (s, 2 H), 5.57 (s, 2 H), 2.52 (m, 4 H), 2.35 (m, 4 H) , 1.82 (m, 4 H), 1.36 (s, 18 H), −1.33 (s, 6 H).

Example

Confinement based on each transition metal compound catalyst obtained in the above preparation and known dimethylsilylene (t-butylamido) (tetramethylcyclopentadienyl) titanium dimethyl Ethylene/1-octene copolymers were prepared in a 2-liter autoclave reactor using a constrained geometry catalyst (CGC) (see US Pat. No. 5,272,236), respectively.

First, moisture and impurities in the reactor were removed using a vacuum pump. The vacuum state was maintained to be at least 3.0 × 10 ^-1 torr or less. Thereafter, the temperature of the reactor was raised to 60° C. while purging the reactor for 30 minutes or more using argon (Ar) gas. At the same time, the catalyst, cocatalyst, scavenger and 1-octene were quantified in a glove box.

The purified solvent (hexane) and copolymer (1-octene) were introduced into the reactor, and 2.085 ml of 1M triisobutyl aluminum (TiBAL) was used as a scavenger to remove oxygen, moisture, and impurities remaining in the solvent. put in. Thereafter, the stirrer of the reactor was set to 500 rpm, and when the reaction temperature was reached, stirring was stopped and the catalyst and ethylene were introduced into the reactor at 20 bar. When the introduction of the catalyst and ethylene was completed, the pressure of the reactor was maintained at an argon pressure of 25 bar. A pressurized cocatalyst (dimethylanilinium tetrakis(pentafluorophenyl)borate) was added and the reaction was started simultaneously with stirring. The reaction was carried out in a semi-batch manner by continuously introducing the argon pressure at 25 bar. The reaction temperature was maintained in the range of 60 to 120 °C.

When the reaction time was 5 minutes, the reaction was terminated by stopping the injection of argon and stirring. The molten polymer in the reactor was transferred to a separator through the reactor discharge port, unreacted ethylene and 1-octene were separated from the hexane solvent, and then the polymer was dried in a vacuum oven at 80° C. for 12 hours or longer to obtain polyolefin.

Specific polymerization conditions of each Example and Comparative Example are as shown in Table 1 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 catalyst Preparation Example 1 Preparation Example 1 Preparation Example 2 CGC CGC Polymerization temperature (℃) 120 120 120 120 120 Catalyst injection amount (μmol) 2 2 2 2 2 Cocatalyst Injection Amount (μmol) 12 12 12 12 12 Dosage of 1-octene (M) 0.8 0.8 0.8 0.8 0.8

test example

The olefin polymer obtained in the above examples was measured according to the following methods and standards. The results are shown in Tables 2 and 3 below.

(1) Density

Measured according to ASTM D1505.

(2) Melt index

In accordance with ASTM D 1238, the melt index was measured at 190 ° C. under a load of 21.6 kg and 2.16 kg, respectively, and the ratio (MI _21.6 / MI _2.16 ) was obtained.

(3) molecular weight and polydispersity index

Polymer Char's model name GPC-6 product gel permeation chromatography-FTIR (GPC-FTIR) was used. The measurement was performed at a temperature of 160° C., and trichlorobenzene was used as the solvent.

(4) Unsaturated group content in the molecule

After preparing a specimen in the form of a film by melting the polymer at 190 ° C, it was analyzed by ¹ H-NMR (AS400 from Agilent) at a high temperature (120 ° C) using a trichloroethane-d2 solvent. Each unsaturated The content was calculated through interval integration at the corresponding chemical shift of the group.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Density (g/cm) 0.855 0.857 0.8553 0.869 0.868 MI (g/10 min) 0.17 0.195 0.16 too high
not measurable too high
not measurable Mn 136,653 141,875 120,733 7,549 13,792 Mw 263,138 266,416 253,073 33,107 35,195 MWD 1.9 1.9 2.1 4.4 2.6

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 vinylene 0.428 0.357 0.292 0.997 1.081 trisubstituted olefin 1.312 0.779 0.582 1.146 1.209 vinyl 0.072 0.021 0.009 0.203 0.214 vinylidene 0.098 0.230 0.350 0.135 0.187 Sum 1.910 1.387 1.233 2.481 2.691 Total (mole %) 0.3820 0.2774 0.2466 0.4962 0.5382

As shown in Tables 2 and 3, the polyolefins of Examples belonging to the scope of the present invention have a low density and a low melt index and a narrow molecular weight distribution (low polydispersity value), so they can be effectively used for polymer modifiers and automobile compounds. .

Claims (16)

An olefinic polymer prepared by polymerization of ethylene and at least one alpha-olefin in the presence of a metallocene catalyst, having a density of 0.850 to 0.905 g / cm 3 and a melt index (I _2.16 ) is 0.1 to 20.0 g/10 min, and the content of unsaturated groups is 0.4 mol% or less. The method of claim 1, wherein the density is 0.850 ~ 0.880 g / cm 3, the melt index (I _2.16 ) measured under a load of 2.16 kg at 190 ° C is 0.1 ~ 5.0 g / 10 minutes, and the content of unsaturated groups is 0.39 mol% or less Olefinic polymers. The olefin-based polymer according to claim 1, wherein the molecular weight distribution (MWD) according to the polydispersity index (Mw/Mn) of the olefin-based polymer is 0.5 to 5. The olefin-based polymer of claim 1, wherein the metallocene catalyst comprises at least one transition metal compound represented by Formula 1 below and a cocatalyst compound:
[Formula 1]

In Formula 1 above, l is each independently an integer from 0 to 5, but at least one is not 0, m and n are each independently an integer from 0 to 4,
M is titanium (Ti), zirconium (Zr) or hafnium (Hf);
X is each independently halogen, nitro, 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, C _1-20 sulfonate or C _1-20 sulfonamide;
At least one of R ₁ and R ₂ is substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _2-20 cycloalkenyl, or substituted or unsubstituted C _1-20 alkenyl C _6-20 aryl , substituted or unsubstituted C _6-20 aryl C _1-20 alkenyl, substituted or unsubstituted C _1-20 cycloalkenyl C _6-20 aryl, and substituted or unsubstituted C _6-20 aryl C _{1- 20} An alkenyl group selected from cycloalkenyl, but when only one of R ₁ and R ₂ is an alkenyl group, the other of R ₁ and R ₂ is hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl , substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene , Substituted or unsubstituted C _1-20 It may be silyl,
R ₃ to R ₅ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylami , substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, substituted or unsubstituted C _1-20 silyl, but R ₃ to R ₅ may each independently form a substituted or unsubstituted saturated or unsaturated C _4-20 ring by connecting adjacent groups. The method of claim 4, wherein l is each 1, m and n are each 0 or 1, M is zirconium or hafnium, X is each halogen or substituted or unsubstituted C _1-20 alkyl, R ₁ and R ₂ is each substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _2-20 cycloalkenyl, or substituted or unsubstituted C _6-20 aryl C _1-20 alkenyl, and R ₃ to wherein each R ₅ is hydrogen or substituted or unsubstituted C _1-20 alkyl. The olefin-based polymer according to claim 4, wherein the transition metal compound represented by Formula 1 above is at least one of transition metal compounds represented by Formulas 1-1 to 1-12 below:
[Formula 1-1] [Formula 1-2]

[Formula 1-3] [Formula 1-4]

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

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

[Formula 1-9] [Formula 1-10]

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

In the above formula, Me is methyl and t -Bu is t -butyl. The olefin-based polymer according to claim 4, wherein the cocatalyst compound is at least one selected from the group consisting of a compound represented by Formula 10, a compound represented by Formula 11, and a compound represented by Formula 12:
[Formula 10]

[Formula 11]

[Formula 12]
[LH] ⁺ [Z(A) ₄ ] ^- or [L] ⁺ [Z(A) ₄ ] ^-
In Formula 10 above, n is an integer of 2 or greater, R _a is a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with a halogen,
In Formula 11, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. Or a C _1-20 alkoxy group,
In Formula 12 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C ₆ It is _{a -20} aryl group or a substituted or unsubstituted C _1-20 alkyl group. The olefin-based polymer according to claim 7, wherein the compound represented by Formula 10 is at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane. The method of claim 7, wherein the compound represented by Formula 11 is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri- s -butyl aluminum, tri Cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxy At least one olefin-based polymer selected from the group consisting of seed, trimethylboron, triethylboron, triisobutylboron, tripropylboron and tributylboron. The method of claim 7, wherein the compound represented by Formula 12 is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetraphenylboron ( p -Tolyl) boron, trimethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra ( p -trifluoromethylphenyl) boron, trimethylammonium tetra ( p -trifluoromethylphenyl) boron, tributyl Ammonium tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethylammonium tetrapentafluorophenyl boron, tri Phenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra( p -tolyl) aluminum, tripropylammonium tetra( p -tolyl) aluminum, triethylammonium tetra( o , p -dimethylphenyl) aluminum, tributylammonium tetra( p -trifluoromethylphenyl) aluminum, trimethylammonium Umtetra ( p -trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenyl Aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra( p -tolyl) boron, triethylammonium tetra( o , p -dimethyl The group consisting of phenyl) boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarboniumtetra( p -trifluoromethylphenyl)boron and triphenylcarbonium tetrapentafluorophenylboron At least one selected from, olefin-based polymer. The olefin-based polymer according to claim 7, wherein the metallocene catalyst further comprises a carrier supporting a transition metal compound, a cocatalyst compound, or both. The olefin-based polymer according to claim 11, wherein the support includes at least one selected from the group consisting of silica, alumina, and magnesia. The method of claim 11, wherein the total amount of the transition metal compound supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the total amount of the cocatalyst compound supported on the carrier is 2 to 15 mmole based on 1 g of the carrier. Olefinic polymers. Obtaining an olefin-based polymer by polymerizing ethylene and at least one alpha-olefin in the presence of a metallocene catalyst comprising at least one transition metal compound represented by Formula 1 below and a cocatalyst compound, wherein the olefin-based polymer has a density of 0.850 to 0.905 g/cm 3 , a melt index (I _2.16 ) measured at 190 ° C and a load of 2.16 kg is 0.1 to 20.0 g / 10 min, an unsaturated group content of 0.4 mol% or less, and a polydispersity index Method for producing an olefin-based polymer having a molecular weight distribution (MWD) of 0.5 to 5.0 by (Mw/Mn):
[Formula 1]

In Formula 1 above, l, m, n, M, X, R ₁ to R ₅ are as defined in claim 4. 15. The method of claim 14, wherein the alpha-olefin is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 -A method for producing an olefin-based polymer, which is at least one selected from the group consisting of dodecene, 1-tetradecene and 1-hexadecene. 16. The method for producing an olefin-based polymer according to claim 15, wherein the alpha-olefin is 1-octene.