WO2015046995A1

WO2015046995A1 - Polyolefin

Info

Publication number: WO2015046995A1
Application number: PCT/KR2014/009119
Authority: WO
Inventors: 금돈호; 이충훈; 박상은; 정승환; 조윤희; 도영실; 박해웅; 이영우
Original assignee: 주식회사 엘지화학
Priority date: 2013-09-30
Filing date: 2014-09-29
Publication date: 2015-04-02

Abstract

The present invention relates to a polyolefin having a molecular weight distribution of 1.5 to 3.0, and a branch gradient number (BGN) value of 0.01 to 1.0. According to the present invention, it is possible to provide a polyolefin having excellent impact strength and mechanical physical properties by having a narrow molecular weight distribution and presenting an inherent comonomer distribution.

Description

【Specification】

[Name of invention]

Polyolefin

Technical Field

The present invention relates to polyolefins, and more particularly, to polyolefins having a narrow molecular weight distribution and exhibiting a characteristic comonomer distribution.

This application is filed with the Korean Patent Application No. 10 # ² 013-0116760 filed with the Korean Patent Office on September 30, 2013 and the Korean Patent Application No. 10-2014-0129367 filed with the Korean Patent Office on September 26, 2014. Claims the benefit of the entire contents are included herein.

Background Art

Dow (Dow) Saga ¹⁹ early 90's _{_{[Me 2 Si (Me 4 C}} 5) NtBu] TiCl 2 were published (Constrained- Geometry Catalyst, CGC) (US Patent 5,064,802), in the copolymer of ethylene and an alpha olefin banung The advantages of CGC in comparison to metallocene catalysts known in the art are largely summarized in two ways: (1) to produce high molecular weight copolymers with high activity even at high polymerization temperatures, (2 ) It is also very good for co-polymerization of alpha-olefins with high steric hindrances such as 1-nuxene and 1-octene. In addition, various characteristics of CGC are gradually known during the polymerization reaction, and its derivatives are synthesized and used as polymerization catalysts. Efforts are being made in academia and industry. ―

One approach has been the synthesis of metal compounds in which various bridges and nitrogen substituents have been introduced in place of silicon bridges, and polymerization using them. Representative metal compounds known to date are listed (Ozem. I? Ev. 2003, 103, 283).

SUBSTITUTE SHEET (RULE 26) Compounds listed in the above figure have a phosphorus (1), ethylene or propylene (2), methylidene (3) and methylene ( ⁴ ) bridges instead of the CGC-structured silicon bridges, but ethylene polymerization or ethylene and alphalephine are introduced, respectively. When applied to the copolymerization did not show excellent results in terms of polymerization activity and co-polymerization performance compared to CGC.

In another approach, many compounds composed of an oxido ligand instead of the amido ligand of CGC have been synthesized, and some polymerization has been attempted using the compound.

Of all these attempts, however, only a few catalysts are actually used in commercial plants. In most cases, the copolymers of ethylene and alpha-olefins to be polymerized using a transition metal compound, in a narrow molecular weight distribution as compared with LDPE obtained through a conventional high pressure process ^"shown or a polymer structure side does not contain long chain branching, relative In recent years, efforts have been actively made in academia and industry to obtain polyolefin-based co-polymers having a polymer structure having a long chain branch and various characteristics, and to develop new catalysts and processes. This is still required.

[Content of invention]

[Problem to solve]

The present invention uses a metallocene catalyst to control the distribution of comonomers according to the molecular weight. The present invention controls the distribution of comonomers according to the molecular weight by using a metallocene catalyst. Eggplant is to provide a polyolefin.

[Measures of problem]

One aspect of the present invention for achieving the above object, provides a polyolefin having a molecular weight distribution of 1.5 to 3, the branch gradient number (BGN) value of 0.01 to 1.0 calculated by the following formula (1):

[Equation 1] Branch Gradient Number (BGISI)

(Side molecular weight of low molecular weight)

In Formula 1,

When the log value (log Mw) of the molecular weight (Molecular weight, Mw) is the x-axis, and the molecular weight distribution (dwt / dlog Mw) with respect to the log value is the y-axis,

The low molecular weight grain content means the grain content at the left boundary of 80%, except for the left and right ends 10% of the total area (branch content of 2 or more carbon atoms per 1,000 carbons, unit: 1,000 C). And, the high molecular weight side branch content means the content of the branch at the right boundary.

【Effects of the Invention】

According to the present invention, it is possible to provide a polyolefin having a narrow molecular weight distribution and exhibiting a unique comonomer distribution having excellent impact strength and mechanical properties. Accordingly, the polyolefins of the present invention can be used in various fields, such as household articles, automobiles, shock absorbers, which alone or blended with other polymers, requiring high laminar strength and elasticity.

[Brief Description of Drawings]

1 is a graph showing the results of GPC-FTIR measurement of the polyolefin of Example 1. FIG.

2 is a graph showing the results of GPC-FTIR measurement of polyolefin of Example 2. FIG.

3 is a graph showing the results of GPC-FTIR measurement of polyolefin of Comparative Example 1. FIG.

4 is a graph showing the results of GPC-FTIR measurement of polyolefin of Comparative Example 2.

[Specific contents to carry out invention]

In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.

In addition, the terminology used herein is for illustrative purposes only. It is used for the purpose of illustration and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, number, step, component, or combination thereof, and one or more other features, It is to be understood that the present invention does not exclude the possibility of adding or presenting numbers, steps, components, or combinations thereof.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific form disclosed, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, a polyolefin according to a specific embodiment of the present invention will be described in detail.

According to one embodiment of the present invention, the molecular weight distribution is 1.5 to 3, and the BGN (Branch gradient number) value calculated by the following Equation 1 provides 0.01 to 1.0 polyolefin.

[Equation 1]

Branch Gradient Number (BGN) = High Molecular Weight Side Branch Content-Low Molecular Weight

(Low molecular weight defect)

In the term branch gradient number (BGN) used in the specification of the present invention, BGN is a measure showing how the content of a comonomer such as alpha olepin is distributed according to molecular weight. The branch referred to in the BGN is attached to the main chain, which is derived from an alpha olefin such as propylene, 1-butene, 1-nuxene, 1-octene, etc. as a comonomer in the polyolefin polymerization process. The side branches that are present. In addition, the defect is to include both a short carbon branch (SCB) having 2 to 6 carbon atoms and a long carbon branch (LCB) having 7 or more carbon atoms.

Molecular weight, molecular weight distribution and defect content using GPC-FTIR It can be measured continuously at the same time.

The BGN (Branch gradient number) value is measured by using the GPC-FTIR equipment to measure the molecular weight, molecular weight distribution, and defect content at the same time continuously, and log-log (w / w) of the molecular weight (Molecular weight, Mw) as the x-axis. When the molecular weight distribution curve is plotted using the logarithmic molecular weight distribution (dwt / dlog Mw) as the y-axis, the low-molecular weight content of the low-molecular weight defect is determined at the left boundary of 80% except for the left and right ends 10% of the total area. The content (unit: dog / 1,000C), and the high molecular weight side branch content means the value calculated according to the following formula 1 as the content of the defect at the right boundary of the middle 80%. Here, the content of the grains is to mean the content of two or more carbon atoms per 1,000 carbons.

[Equation 1]

Branched Gradient Number (BGN) = ：

(Low molecular weight defect)

If the BGN value is positive, it means that the low content of grains is low in the low molecular weight region according to the molecular weight distribution curve for the logarithm of the molecular weight, and that the side branch content is relatively high in the high molecular weight region. If the value is negative (-), it means a structure that has a high content of grains in a low molecular weight region and a relatively low content of grains in a high molecular weight region. The polyolefin of the present invention has a BGN value measured and calculated in the same manner as 0.01 to 1.0, or about 0.01 to about 0.9, or about 0.01 to about 0.5, or about 0.01 to about 0.2, or about 0.01 to about 0.1, or From about 0.03 to about 0.1. That is, the polyolefin of the present invention has a low branched content in the low molecular weight region, a relatively high branched content in the high molecular weight region, and the slope thereof is within the above-described range.

When the BGN value is within the above range and simultaneously satisfies a narrow range of molecular weight distribution, the physical properties of the polyolefin can be optimized to achieve high impact strength and good mechanical properties. This results in high layer strength and good mechanical properties when compounded with other polymers such as polypropylene resins. Can be achieved.

In addition, the polyolefin of the present invention may have a range of about 20 to about 120 carbon atoms, preferably about 50 to about 100 carbon atoms per 1,000 carbon atoms.

The polyolefins of the invention also have a range ¾ ^{■ in} which the molecular weight distribution (weight average molecular weight / number average molecular weight) is from about 1.0 to about 3.0, or from about 1.5 to about 3.0, or from about 1.5 to about 2.8, or from about 2.0 to about 18. As such, the polyolefin of the present invention may exhibit high layer strength by having a very narrow molecular weight distribution.

In addition, the polyolefin has a melt flow index (Ml) measured at 190 ^° C. and a 2.16 kg load condition in accordance with ASTM D1238 of about 0.1 to about 2000 g / 10 min, preferably about 0.1 to about 1000 g / 10 min, Preferably about 0.1 to 500 g / 10min, but is not limited thereto.

In addition, the melt flow rate ratio (MFRR) of the polyolefin may be about 5 to about 15, preferably about 6 to about 13, but is not limited thereto. In addition, the density of the polyolefin can be about 0.85 to about 0.91 g cc, preferably about 0.86 to about 0.91 g / cc, more preferably about 0.86 to about 0.90 g / cc, but is not limited thereto. It is not.

However, when the melt flow index, the melt flow rate ratio, the density, and the like are in the above-described ranges, the physical properties may be more optimized to achieve high laminar strength and good mechanical properties.

It is preferable that the polyolefin which concerns on this invention is a copolymer of ethylene which is an olefinic monomer, and an alpha olefin comonomer.

Alpha olefins having 3 or more carbon atoms may be used as the alpha olefin copolymer. Alpha olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, ₄ -methylxopentene, 1'nucleene, 1-heptene, 1'octene, μdecene, 1-undecene, 1-dodecene and 1- Tetradecene, 1-nuxadecene, 1-octadecene, or 1-eicosene.

Ateo a copolymer of said ethylene and alpha-olefin comonomer on, alpha eulre content of the pins co-monomer is from about 5 to about 70 parts by weight ^_0/0, preferably from about 5 to about 60 Increased ⁰ /., And more preferably About 10 to about 50 weight%. The weight average molecular weight of the polyolefin according to the present invention may be about 10,000 to about 500,000 g / mol, preferably about 20,000 to about 200,000 g / m, but is not limited thereto.

The polyolefin according to the present invention has excellent layer strength when mixed with other polymers, and can be used in various fields such as household articles, automobiles, layer absorbers, and the like.

Polyolefins according to the present invention having the above characteristics can be obtained by copolymerization with ethylene and alpha olepin using a common metallocene compound including two metallocene compounds of different structures as catalysts, The polyolefin may have a molecular weight distribution and a BGN value as described above. More specifically, the polyolefin of the present invention, the first metallocene compound represented by the formula (1); And in the presence of a common metallocene catalyst comprising a second metallocene compound represented by the formula (2), it can be obtained by combining the ethylene and alpha olepin comonomer.

[

In Chemical Formula 1,

R1 and R2 may be the same as or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid of a Group 4 metal substituted with hydrocarbyl; R 1 and R 2 or two R 2 may be connected to each other by an alkylidine including an alkyl having 1 to 20 carbon atoms or an aryl functional group having 6 to 20 carbon atoms to form a ring;

R3, 3 'and R3 "may be the same or different from each other, and each independently Hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an amido group; Two or more of said R3, R3 ', and R3 "may be linked to each other to form an aliphatic ring or an aromatic ring;

CY is a substituted or unsubstituted aliphatic or aromatic ring, and the substituents substituted in CY are halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an alkyl amido group having 1 to 20 carbon atoms; An aryl amido group having 6 to 20 carbon atoms, and when there are a plurality of substituents, two or more substituents in the substituents may be linked to each other to form an aliphatic or aromatic ring;

Ml is a Group 4 transition metal;

Q1 and Q2 may be the same as or different from each other, and each independently halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkyl amido having 1 to 20 carbon atoms; Aryl amido having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms.

[

In Chemical Formula 2,

M 2 is a Group 4 transition metal;

Q3 and Q4 may be the same or different from each other, and each independently halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Carbon number 1 Alkyl amido of from 20 to 20; Aryl amido having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms;

R4 to R10 may be the same as or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Or alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms;

B is carbon, silicon, or germanium, and is a bridge that binds a cyclopentadienyl-based ligand and JR10 _zy by a covalent bond;

J is a periodic table group 15 element or group 16 element;

z is the oxidation number of the element J;

y is the bond number of the J element;

n is an integer of 0-10.

When polymerizing ethylene and alpha olepin comonomer using a common metallocene catalyst comprising the first metallocene compound of Formula 1 and the second metallocene compound of Formula 2, the low molecular weight region as described above Polyolefins having a low side branch content and a relatively high defect content in a high molecular weight region can be obtained.

On the other hand, the polymerization reaction of the ethylene and alpha olefin comonomer may be made at about 130 to about 250 ^° C, preferably about 140 to about 200 ^° C. When the second metallocene compound is used in combination with the first metallocene compound, the activity of the catalyst may be maintained even in a high temperature synthesis process of 130 ^° C. or higher, so that the active point of the catalyst in the synthesis reaction of the polyolefin is 2 Make it ideal. In particular, the metallocene catalyst for synthesizing the high-density pleurepine is generally not used in the solution polymerization step of applying a high reaction resistance due to its low activity in the high temperature region, but the second metallocene compound of Chemical Formula 2 is represented by Chemical Formula 1 When mixed with the first metallocene compound of the excellent catalytic activity can be exhibited even in a high temperature region of 130 ° C or more.

In addition, the reaction reaction of the ethylene and alpha olefin comonomer may be carried out in a continuous solution polymerization process, bulk polymerization process, suspension polymerization process or emulsion polymerization process. It may proceed, but preferably by solution polymerization reaction in a single reactor. In the method for preparing polyolefin, polyolefin can be synthesized in a single reactor even though two different metallocene catalysts are used, and thus a simple manufacturing process can be configured to reduce process time and cost.

Specific examples of the first metallocene compound of Formula 1 include, but are not limited to, the compound of Formula 3 or Formula 4.

In Chemical Formula 3,

R1, R2, Q1, Q2 and Ml are the same as defined in Formula 1, and R11 may be the same as or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or amido group; Two or more of the R 11 may be connected to each other to form an aliphatic ring or an aromatic ring.

[Formula 4]

In Chemical Formula 4,

R1, R2, Q1, Q2 and Ml are the same as defined in Formula 1, and R12 may be the same or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an amido group; Two or more of the R 12 may be connected to each other to form an aliphatic ring or an aromatic ring.

In addition, specific examples of the compound that is more preferred for controlling the electronic stereo environment around the metal in the compound of Formula 1 are as follows. In the following formulae, R2 may be each independently hydrogen or methyl group, Q1 or Q2 may be the same or different from each other, and each independently may be a methyl group _: dimethylamido group or chloride group.

Specific examples of the second metallocene compound of Chemical Formula 2 may include a compound of the following chemical formula, but are not limited thereto.

According to one embodiment of the present invention, in the method for preparing the polyolefin, the common metallocene catalyst may further include a cocatalyst compound in addition to the first and second metallocene compounds described above.

The cocatalyst compound includes a Group 13 metal of the periodic table, and may be at least one selected from the group consisting of a compound of Formula 5, a compound of Formula 6, and a compound of Formula 7.

[Formula 5]

-[Al (R 13) -0] c- In Formula 5, R13 is 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,

[Formula 6]

D (R14) ₃

In Chemical Formula 6,

D is aluminum or boron, R14 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

[Formula 7]

[LH] ⁺ [ZE ₄ ] ^" or [L] ⁺ [ZE ₄ ]-in the above Formula 7,

L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 element, E may be the same or different from each other, and each independently one or more hydrogen atoms is halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or Or an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with phenoxy.

A compound represented by the above formula (V) may, for example, such as methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane may ^be.

As the alkyl metal compound represented by the formula (6), for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum,. Tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethylchloroaluminum, triisopropylaluminum tri-S-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum trinuclear silaluminum, Ethyl dimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-P-rylyl aluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron tributyl boron, etc. Can be. Examples of the compound represented by the formula (7) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (P). -Lryl) boron, tripropylammonium tetra (P-lryl) boron, triethylammonium tetra (ο, ρ-dimethylphenyl) boron, trimethylammonium tetra (ο, ρ-dimethylphenyl) boron, tributylammonium Tetra (Ρ-trifluoromethylphenyl) boron, trimethylammonium tetra (Ρ-trifluoromethylphenyl) boron,

Tributylammonium tetrapentafluorophenylboron, Ν, Ν- diethylanilinium tetraphenylboron, Ν, Ν-diethylanilinium tetraphenylboron, Ν, Ν- diethylanilinium tetrapentapolluo Rophenylboron,

Diethylammonium tetrapentafluorophenylboron,

Triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum,

Tripropylammonium tetraphenylaluminum, trimethylammonium tetra (Ρ-rylryl) aluminum, tripropylammonium tetra (Ρ-rylryl) aluminum, triethylammonium tetra (ο, ρ-dimethylphenyl) aluminum, tributylammonium Tetra (Ρ-trifluoromethylphenyl) aluminum, trimethylammonium tetra (Ρ- trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, Ν, Ν-diethylanilinium tetraphenylaluminum, Ν, Ν- diethylanilinium tetraphenylaluminum, Ν, Ν- diethylanilinium tetrapentafluorophenylaluminum,

Diethylammonium tetrapentafluorophenylaluminum,

Triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra (Ρ-trifluoromethylphenyl) boron,

Triphenylcarbonium tetrapentafluorophenylboron and the like.

In addition, the content of the promoter is the amount of the first and second metallocene compound

The molar ratio of the Group 13 metals to Group 4 metals may be about 1 to about 10,000, preferably about 1 to about 1,000, more preferably about 1 to about 500. remind If the molar ratio is less than 1, the effect of the addition of the promoter is insignificant. If the molar ratio exceeds 10,000, the excess alkyl group, which does not participate in the reaction and the residual alkyl group, rather inhibits the catalytic reaction and may act as a catalyst poison. This may cause a problem that excess aluminum or boron will remain in the polymer.

In the preparation of the common metallocene catalyst, a hydrocarbon solvent such as pentane, nucleic acid, heptane, or an aromatic solvent such as benzene or toluene may be used as the reaction solvent, but is not necessarily limited thereto, and may be used in the art. Any solvent can be used.

In the preparation method of polyolefin according to the present invention, the common metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for an olefin polymerization process, for example, pentane, nucleic acid, heptane, nonane, decane, and isomers thereof. It can be injected by dissolving or diluting with aromatic hydrocarbon solvents such as and toluene and benzene, and hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter. By using the common metallocene catalyst, a polyolefin satisfying the above-described physical properties may be manufactured. Copolymerization with alpha olefins when using a mixed metallocene catalyst is particularly induced by the second metallocene compound that makes the high molecular weight moiety, which enables the production of high performance polyolefins in which alpha olefin comonomers are concentrated on the high molecular weight chain side. do.

The polyolefin production can be carried out by solution polymerization, for example, can be carried out according to the conventional method while continuously supplying ethylene and alpha olefin comonomer at a constant ratio.

When copolymerizing alpha olepin as ethylene and comonomer using the common metallocene catalyst, the alpha olephine comonomer is, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nucleene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-nuxadecene, 1-octadecene or 1-eicosene may be used. However, the present invention is not limited thereto. The polymerization temperature when copolymerizing alpha olefin as a comonomer with the common metallocene catalyst may range from about 130 to about 250 ^° C., preferably from about 140 to about 200 ^° C. As described above, when the second metallocene compound is used in combination with the first metallocene compound, the activity of the catalyst can be maintained even in a high temperature synthesis process of 130 ^° C. or higher, so that the catalyst in the synthesis reaction of polyolefin Let the active point of be at least 2. In particular, the metallocene catalyst for synthesizing high-density polyolefin is not generally used in the solution thickening step of applying a high reaction temperature because of its low activity in the high temperature region, but the second metallocene compound of Formula 2 is When mixed with the first metallocene compound, excellent catalytic activity may be exhibited even in a high temperature region of 130 ^° C or higher.

In addition, the polymerization pressure is preferably performed at about 1 to about 150 bar, more preferably about 1 to about 120 bar, most preferably about 10 to about 120 bar.

On the other hand, in the polymerization reaction of the ethylene and the alpha olefin pin comonomer can control the physical properties of the polyolefin prepared by adjusting the content of the second metallocene compound.

In particular, the common metallocene catalyst includes a second metallocene compound in a relatively low content. More specifically, the second metallocene compound is more than 0 mol% to less than about 50 mol%, preferably about 5 to about 30 mol%, based on the total amount of the first and second metallocene compounds, More preferably from about 5 to about 25 mol%. When the second metallocene compound is included in such a content ratio, it is possible to provide a polyolefin having a narrow molecular weight distribution but having a BGN value in the above-described range.

The invention is explained in more detail in the following examples. However, the following examples are only for exemplifying the present invention, and the contents of the present invention are not limited to the following examples. ^'

<Production Example of Metallocene Compound> Preparation Example 1 Synthesis of First Metallocene Compound

Preparation Example 1-1

8-ί2,3,4,5-tetramethyl-1.3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline ((8- (2,3,4,5-Tetramethyl-l, 3 -cvclopentadienyr) -l, 2,3,4-tetrahydroquinoline))

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a Schlenk flask. The shield tank was immersed in a -78 ^° C. low temperature bath made of dry ice and acetone and stirred for 30 minutes. Subsequently, n-BuLi (n-butyllithium, 39.3 mL, 2.5M, 98.24 mmol) was introduced into a syringe under a nitrogen atmosphere to form a pale yellow slurry. Then, after the flask was stirred for 2 hours, the flask was cooled to room temperature while removing the generated butane gas. The flask was again immersed in a -78 ^° C low temperature bath to lower the silver and added CO ₂ gas. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler to raise the temperature to room temperature while removing carbon dioxide gas. Thereafter, excess C0 ₂ gas and solvent were removed under vacuum. The flask was transferred to a dry box, pentane was added thereto, stirred vigorously, and filtered to obtain lithium carbamate of a white solid compound. The white solid compound is coordinated with diethyl ether. The yield is 100%.

1 H NMR (C6D6, C5D5N): δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH ₂ ), 2.34 (br s, 2H, quin-CH ₂ ), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quin-CH ₂ ), 6.76 (br d, J = 5.6 Hz, lH, quin-CH) ppm

13 C NMR (C6D6): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09 (C = O) ppm. The lithium carbamate compound (8.47 g, 42.60 mmol) prepared above was placed in a shield tank flask. Subsequently, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were added sequentially. Immerse the Schlenk flask in a -20 ^° C low-silver bath made of acetone and a small amount of dry ice for 30 minutes. After stirring, tert-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture It turned red and stirred for 6 hours while maintaining -20 ^° C. CeCl 2LiCl solution (129 mL, 0.33 M, 42.60 mmol) and tetramethylcyclopentinone (5.89 g, 42.60 mmol) dissolved in tetrahydrofuran were mixed in a syringe and then charged into a flask under nitrogen atmosphere. The flask was slowly cooled to room temperature, and after 1 hour, the thermostat was removed and the temperature was kept at room temperature. Subsequently, water (15 mL) was added to the flask, ethyl acetate was added and filtered to obtain a filtrate. The filtrate was transferred to a separatory funnel and hydrochloric acid (2N, 80 mL) was added thereto, followed by shaking for 12 minutes. After neutralizing with saturated aqueous sodium hydrogen carbonate solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to this organic layer to remove moisture and filtered, and the filtrate was taken out and the solvent was removed. The obtained filtrate was purified by column chromatography using nucleic acid and ethyl acetate (v / v, 10: 1) solvent to give a yellow oil. Yield 40%.

1 H NMR (C6D6): δ 1.00 (br d, 3H, Cp-CH 3), 1.63-1.73 (m, 2H, quin-CH ₂ ), 1.80 (s, 3H, Cp-CH ₃ ), 1.81 (s, 3H , Cp-CH ₃ ), 1.85 (s, 3H, Cp-CH ₃ ), 2.64 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 2.84-2.90 (br, 2H, quin-CH ₂ ), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, N-H), 6.77 (t, J = 7.2 Hz, 1H, quin-CH), 6.92 (d, J = 2.4 Hz, 1H , quin-CH), 6.94 (d, J = 2.4 Hz, 1 H, quin-CH) ppm. Preparation Example 1-2

"0,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-

vDtetramethylcvclopentadienyl-etaS-kapa-Nltita ^ dimethyl)

In a dry box, compound (8.07 g, 32.0 mmol) prepared in Preparation Example 1-1 and 140 mL of diethyl ether were placed in a constant flask, and the temperature was decreased to -30 ^° C, and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was added slowly with stirring. The reaction was carried out for 6 hours while raising the temperature to room temperature. Thereafter, the mixture was washed with diethyl ether several times to obtain a solid. Removal of the remaining solvent through vacuum yielded a dilithium compound (Compound 4a) (9.83 g) as a yellow solid. Yield 95%. IH NMR (C6D6, C5D5N): δ 2.38 (br s, 2H, quin-CH ₂ ), 2.53 (br s, 12H, Cp-CH ₃ ), 3.48 (br s, 2H, quin-CH ₂ ), 4.19 ( br s, 2H, quin-CH ₂ ), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 (br s, IH, quin-CH), 7.75 (brs, IH, quin-CH) ppm .

In a dry box, TiC14 * DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were added to an isometric flask, and MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added while stirring at -30 ^° C. After stirring for 15 minutes [[1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, kappa-N] dilithium compound (Compound 4a) ( [(l, 2,3,4-Tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta5, kapa-N] dilithium) (5.30 g, 15.76 mmol) was added to the flask. It stirred for 3 hours while raising the temperature to room temperature. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, and filtered to obtain a filtrate. Removal of pentane through vacuum gave a dark brown compound (3.70 g). The yield was 71.3%. ^'

IH NMR (C6D6): δ 0.59 (s, 6H, Ti-CH ₃ ), 1.66 (s, 6H, Cp-CH ₃ ), 1.69 (br t, J = 6.4 Hz, 2H, quin-CH ₂ ), 2.05 (s, 6H, Cp-CH ₃ ), 2.47 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 4.53 (m, 2H, quin-CH ₂ ), 6.84 (t, J = 7.2 Hz, IH , quin-CH), 6.93 (d, J = 7.6 Hz, quin-CH), 7.01 (d, J = 6.8 Hz, quin-CH) ppm.

13 C NMR (C 6 D 6): δ 12.12, 23.08, 27.30, 48.84, 51.01, 1 19.70, 1 19.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm. Preparation Example 2 Synthesis of Second Metallocene Compound

rmethyl (6-t-buthoxyhexyl) silyl (n 5 -tetramethylCp) ( After adding Mg (s) of 50 g in a manufacturing room temperature for 10 L reactor was added 300 mL THF. After the ₁₂ was added about 0.5 g ， Reactor temperature was maintained at 50 ^° C. After the reaction period was stabilized, 250 g of 6-t-buthoxyhexyl chloride was added to the tank 5 mL / using a feeding pump. It was added to the reactor at a rate of min It was observed that the reaction temperature increased by about 4 to 5 ^° C. with the addition of 6-t-subspecific nucleus chloride. After stirring for 12 hours, a reaction solution of black color was obtained after 12 hours. After adding water, the organic layer was obtained, and 6-t-buthoxyhexane was confirmed by ^ -NMR, and the Grignard reaction proceeded well from 6-t-butoxynucleic acid. . Thus 6-t-buthoxyhexyl magnesium chloride was synthesized.

After adding 500 g of MeSiCl ₃ and 1 L of THF to the reactor, the reaction temperature was-

Cooled to 20 ^° C. 560 g of the synthesized 6-t-butyroxylmagnesium chloride was added to the reactor at a rate of 5 mL / min using an injecting pump. After completion of the Grignard reagent injection, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours, it was confirmed that a white MgCl ₂ salt was produced. 4 L of nucleic acid was added to remove the salt through a laboratory pressure dewatering filtration apparatus (labdori, Han River Engineering Co., Ltd.) to obtain a filter solution. After the obtained filter solution was added to the reaction vessel, the nucleic acid was removed at 70 ^° C. to obtain a pale yellow liquid. The obtained liquid was confirmed to be the desired methyl (6-t- appendixyl) dichlorosilane compound through 1 H-NMR.

Ή-NMR (CDC1 ₃ ): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m,

2H), 0.7 (s, 3H)

1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reaction vessel, followed by cooling the reaction temperature to -20 ^° C. 480 mL of n-BuLi was added to the reactor at a rate of 5 mL / min using an infusion pump. After n-BuLi was added, the reactor temperature was slowly stirred to room temperature and stirred for 12 hours. After 12 hours, an equivalent amount of Methyl (6-t-buthoxy hexyl) dichlorosilane (326 g, 350 mL) was quickly added to the reactor. After stirring for 12 hours while slowly raising the reactor temperature to room temperature, the reaction mixture was again stirred at 0 ^° C., and 2 equivalents of t-BuNH ₂ was added thereto. Stirring the reactor temperature slowly to room temperature and stirring for 12 hours. After 12 hours of reaction, THF was removed and 4 L of nucleic acid was added to obtain a filter solution from which salt was removed through labdori. After adding the filter solution back to the reactor, the nucleic acid was removed at 70 ^° C to obtain a yellow solution. The obtained yellow solution was confirmed to be Methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane compound through 1 H-NMR.

THF from n-BuLi and Ligand Dimethyl (tetramethylCpH) t-Butylaminosilane TiCl ₃ (THF) ₃ (10 mmol) was quickly added to the dilithium salt of the ligand synthesized in the solution at -78 ^° C. Banung solution was slowly stirred for 12 hours while slowly raising the room temperature at -78 ^° C. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, blue colored vaginal black solution was obtained. After removing THF from the reaction solution, nucleic acid was added to filter the product. The nucleic acid was removed from the obtained filter solution, and the desired [methyl (6-t-buthoxyhexyl) silyl (n ⁵ -tetrametliylCp) (t-

Butylamido)] TiCl ₂ compound.

Ή-NMR (CDC1 ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), 0.7 (s, 3 H)

Polymerization Examples of Polyolefins

Example 1

The 2 L autoclave continuous process reactor was charged with nucleic acid solvent (5.38 kg / h) and 1-butene (0.82 kg / h), then the temperature at the top of the reactor was preheated to 160 ^° C. Triisobutylaluminum compound (0.05 mmol / min), the first metallocene compound obtained above (0.45 μηιοΐ / ιηϊη), the crab 2 metallocene compound (0.05 μπιοΐ / min), and dimethylanilinium tetrakis (penta Florophenyl) borate cocatalyst (1.5 μηιοΐ / ηι) was simultaneously introduced into the reaction vessel. Subsequently, ethylene (0.87 kg / h) was introduced into the autoclave reactor and maintained at 160 ^° C. for 30 minutes or more in a continuous process at a pressure of 89 bar, followed by copolymerization to obtain a copolymer. Next, the remaining ethylene gas was removed and the polymer solution was dried in a vacuum oven for at least 12 hours, and then physical properties were measured. Example 2

After a 2 L autoclave continuous process reactor was filled with nucleic acid solvent (5.9 kg / h) and 1-butene (1.01 kg / h), the temperature at the top of the reactor was preheated to 160 ^° C. Triisobutylaluminum compound (0.05 mmol / min), the first metallocene compound (() .4 μιηοΐ / min) obtained above, the second metallocene compound (0.1 μηιοΐ / ηιΐη), and dimethylanilinium tetra Kiss (pentafluorophenyl) borate promoter (1.5 μιηοΐ / πώι) At the same time into the reactor. Subsequently, ethylene (1.0 kg / h) was introduced into the autoclave reaction vessel and maintained at 160 ^° C. for 30 minutes or more in a continuous process at a pressure of 89 bar, followed by copolymerization to obtain a copolymer. Next, the remaining ethylene gas was removed and the polymer solution was dried in a vacuum oven for at least 12 hours, and then physical properties were measured. Comparative Example 1

LG Chem's LLDPE (product name: SN318) prepared with a Ziegler-Natta catalyst was prepared. Comparative Example 2

LG Chem's ethylene-1-butene copolymer (product name: LC565) prepared using only the first metallocene catalyst was prepared. Experimental Example

The physical properties of the polyolefins of Examples 1 and 2 and Comparative Examples 1 and 2 were measured by the following methods, and are shown in Table 1 below.

1) Density: ASTM 1505

2) Melt Flow Index ^{^{(MI, 2 .1 6 kg /}} 10 min): The silver is measured ^{^{1 9 0 ° C, ASTM 1}} 8 3) the molecular weight, and molecular weight distribution: Measuring temperature 160 ^° C, measured by gel permeation chromatography - FT ahyial The number average molecular weight, the weight average molecular weight, and the Z average molecular weight were measured using (GPC-FTIR). The molecular weight distribution is It is represented by the ratio of the weight average molecular weight and the number average molecular weight.

4) BGN (Branch gradient number): In the GPC-FTIR measurement result, the log value (log Mw) of the molecular weight (Mw) is the X-axis, and the molecular weight distribution (dwt / dlog Mw) is y for the log value. When the molecular weight distribution curve is plotted as an axis, the content of low molecular weight side branches is 80% at the left boundary, except for the left and right ends 10% of the total area. The amount of grains was determined as the amount of grains at the right boundary of 80%, and the BGN value was obtained by calculating the value of the following formula (1). [Expression i] ^'

(Side molecular weight of high molecular weight-defect content of low molecular weight)

Branch Gradient Number (BGN)

(Low molecular weight defect)

Table 1

GPC-FTIR measurement results of the polyolefins of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in FIGS. 1 to 4, respectively.

Referring to FIGS. 1 and 2, the content of the carbon content of 2 or more carbon atoms at the left boundary point (point A) and the carbon content of 2 or more carbon atoms at the right boundary point (point B) in the middle 80% region of the molecular weight distribution curve area. By measuring the content it can be seen that the BGN value calculated according to 1 has a positive value.

Referring to FIG. 3, the polyolefin of Comparative Example 1 had a negative BGN value of −0.14 and a molecular weight distribution exceeded 3.

In addition, referring to Figure 4, ^' polylefin of Comparative Example 2 shows a BGN value close to 0, it can be seen that does not show the characteristic comonomer distribution as in the present invention.

Claims

【Patent Claims】【Claim 1】 A polyolefin having a molecular weight distribution of 1.5 to 3.0 and a BGN (Branch gradient number) value of 0.01 to 1.0 calculated by the following equation 1:

[Equation 1]

(Missing branch content of high molecular weight -X1 Missing branching content of molecular weight)

Branch Gradient iNumber (BGN) =

^' (Low molecular weight missing branch content)

In equation 1 above,

When a molecular weight distribution curve is drawn with the logarithmic value (log Mw) of molecular weight (Mw) as the x-axis and the molecular weight distribution (dwt/dlog Mw) for the logarithmic value as the y-axis,

The low molecular weight branch content is calculated as the branch content at the left border of 80% of the total area, excluding ₁₀ % of the left and right ends (content of branches with 2 or more carbon atoms per 1,000 carbons, unit: branch/1,000C). This means that the high molecular weight side branch content means the missing branch content at the right border.

【Claim 2】

2. The polyolefin of claim 1, wherein the polyolefin has a density of 0.85 to 0.91 g/cc.

【Claim 3】

The polyolefin according to claim 1, wherein the number of branched branches having 2 or more carbon atoms per 1,000 carbons is 20 to 120.

【Claim 4】

The polyolefin according to claim 1, which is a copolymer of ethylene and an alpha olefin comonomer, wherein the content of the alpha olefin comonomer is 5 to 70 ^% by _weight based on the total polyolefin.

【Claim 5】

The method of claim 1, wherein the polyolefin is represented by the following formula (1): A polyolefin obtained by polymerizing ethylene and alpha olefin comonomer in the presence of a common metallocene catalyst comprising 1 metallocene compound and a second metallocene compound represented by the following formula (2):

[Formula 1]

In Formula 1,

R1 and R2 may be the same or different from each other, and each independently represents hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; or a metalloid of a Group 4 metal substituted with hydrocarbyl; R1 and R2 or two R2s may be linked to each other by an alkylidine containing an alkyl functional group having 1 to 20 carbon atoms or an aryl functional group having 6 to 20 carbon atoms to form a ring;

R3, R3' and R3" may be the same or different from each other, and each independently represents hydrogen; halogen; alkyl with 1 to 20 carbon atoms; alkenyl with 2 to 20 carbon atoms; aryl with 6 to 20 carbon atoms; alkyl with 7 to 20 carbon atoms. Aryl; Arylalkyl with 7 to 20 carbon atoms; Alkoxy with 1 to 20 carbon atoms; Aryloxy with 6 to 20 carbon atoms; Or an amido group; Two or more of R3, R3' and R3" are connected to each other to form ^an aliphatic ring or may form an aromatic ring;

CY is a substituted or unsubstituted aliphatic or aromatic ring,

The substituent substituted in CY is halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; or an alkyl amido group having 1 to 20 carbon atoms or an aryl amido group having 6 to 20 carbon atoms, and when there are multiple substituents, the substituents Among them, two or more substituents may be connected to each other to form an aliphatic or aromatic ring;

Ml is a group 4 transition metal;

Q1 and Q2 may be the same or different from each other, and are each independently halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkyl amido having 1 to 20 carbon atoms; Aryl amido having 6 to 20 carbon atoms; or alkylidene having 1 to 20 carbon atoms;

[

、 In Formula 2 above,

. M2 is a group 4 transition metal;

Q3 and Q4 may be the same or different from each other, and each independently represents a halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; 5 aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkyl amido having 1 to 20 carbon atoms; Aryl amido having 6 to 20 carbon atoms; or it may be an alkylidene having 1 to 20 carbon atoms;

R4 to R10 may be the same or different from each other, and are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; 0 alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; or alkylaryl having 7 to 20 carbon atoms; It is arylalkyl having 7 to 20 carbon atoms;

B is carbon, silicon, or germanium, and is a bridge that binds the cyclopentadienyl series ligand and JRIO _z ᅳ _y by a covalent bond;

5 J is a group 15 or 16 element of the periodic table;

z is the oxidation number of element J; y is the bond number of the J element;

n is an integer from 0 to 10.

【Claim 6】

The polyolefin of claim 5, wherein the common metallocene catalyst contains the second metallocene compound in an amount of more than 0 md% to less than 50 mol% based on the total amount of the first and second metallocene compounds. .

【Claim 7】

6. A polyolefin according to claim 5, wherein the polymerization of ethylene and alpha olefin comonomer is carried out in a continuous solution polymerization process.

【Claim 8】

The polyolefin according to claim 5, wherein the common metallocene catalyst further comprises one or more cocatalysts selected from compounds represented by the following formulas 5 to 7:

[Formula 5]

-[Al(R13)-0]c- In Formula 5, R13 is a halogen radical, a hydrocarbyl radical with 1 to 20 carbon atoms, or a hydrocarbyl radical with 1 to 20 carbon atoms substituted with halogen, and c is an integer of 2 or more. and

[Formula 6]

D(R14) ₃

In Formula 6 above,

D is aluminum or boron, R14 is a hydrocarbyl with 1 to 20 carbon atoms or a hydrocarbyl with 1 to 20 carbon atoms substituted with halogen,

[Formula 7]

[LH] ⁺ [ZE ₄ ]- or [L] ⁺ [ZE ₄ ] ^"

In Formula 7 above,

L is a neutral or amphiphilic Lewis base, H is a hydrogen atom, and Z is It is a group 13 element, and E may be the same or different from each other, and each independently represents an aryl group with 6 to 20 carbon atoms or 1 carbon atom in which one or more hydrogen atoms are substituted or unsubstituted with halogen, hydrocarbon with 1 to 20 carbon atoms, alkoxy, or phenoxy. It is an alkyl group of 20 to 20.

【Claim 9】

The polyolefin according to claim 5, wherein the polymerization of ethylene and alpha olefin comonomer is carried out at 130 to 250 ^° C.

[Claim 10]

The method of claim 5, wherein the alpha olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undene. A polyolefin that is at least one selected from the group consisting of sene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene.