WO2018117403A1

WO2018117403A1 - Hybrid supported metallocene catalyst, and method for preparing polyolefin by using same

Info

Publication number: WO2018117403A1
Application number: PCT/KR2017/012420
Authority: WO
Inventors: 김선미; 최이영; 이기수; 홍복기; 이승민; 선순호; 박진영
Original assignee: 주식회사 엘지화학
Priority date: 2016-12-19
Filing date: 2017-11-03
Publication date: 2018-06-28

Abstract

The present invention relates to a hybrid supported metallocene catalyst, and a method for preparing a polyolefin by using the same. According to the present invention, a polyolefin having excellent environmental stress crack resistance while exhibiting a multimodal molecular weight distribution can be prepared when the hybrid supported metallocene catalyst is used.

Description

[Name of invention]

Metallocene catalyst and the ^polyolefin, using the same method for manufacturing a pin to heunseong supported _metal. Technical Field

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2016—0173802 dated December 19, 2016 and Korean Patent Application No. 10-2017-0145519 dated November 02, 2017. All content disclosed in the literature is included as part of this specification.

The present invention relates to a common supported metallocene catalyst and a method for preparing polyolefin using the same.

[Technique to become background of invention]

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics. Ziegler-Natta catalysts have been widely applied to the existing commercial processes since the invention in the 50s, but since the active site is a multi-site catalyst (mul-si te cata lyst) with multiple active sites, the broad molecular weight distribution of the polymer is Toxing, The composition distribution of comonomer is not uniform ^■ There is a problem that the limit to secure the desired physical properties.

Meanwhile, the metallocene catalyst is composed of a combination of a main catalyst composed mainly of transition metal compounds and a cocatalyst composed of an organometallic compound composed mainly of aluminum, and such a catalyst is a homogeneous complex catalyst. catalyst), which has a narrow molecular weight distribution according to the characteristics of a single active site and a homogeneous composition of the comonomer, and a stereoregularity, copolymerization characteristic, and molecular weight of the polymer according to the ligand structure modification and the change of polymerization conditions of the catalyst. , Has the property of changing the crystallinity and the like. ^■

U. S. Patent No. 5, 032, 562 describes a process for preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. This is supported by a single support of a titanium (Ti) -based Ziegler-Natta catalyst that produces high molecular weight and a zirconium (Zr) -based metallocene catalyst that produces low molecular weight. As a method of producing a bimodal di str ibut i on polymer, the supporting process is complicated and the morphology of the polymer is deteriorated due to the promoter. US Patent No. 5, 525, 678 describes a method of using a catalyst system for olefin polymerization in which a high molecular weight polymer and a low molecular weight polymer can be simultaneously polymerized by simultaneously supporting a metallocene compound and a nonmetallocene compound on a carrier. It is described. This has the disadvantage that the metallocene compound and the non-metallocene compound must be separately supported, and the carrier must be pretreated with various compounds for the supporting reaction.

U.S. Patent No. 5,914,289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount and time of preparation of the solvent used in preparing the supported catalyst This takes a lot, and the hassle of having to support the metallocene catalyst to be used on the carrier, respectively.

Korean Patent Application No. 2003-12308 discloses a method of controlling the molecular weight distribution by supporting a double-nucleated metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing a combination of catalysts in a reaction vessel. Doing. However, this method has a limitation in realizing the characteristics of each catalyst at the same time, and also has the disadvantage that the metallocene catalyst portion is released from the carrier component of the finished catalyst, causing fouling. .

Therefore, in order to solve the above disadvantages, there is a continuing need for a method of preparing an olefin-based polymer having desired physical properties by preparing a commonly supported common supported metallocene catalyst.

However, among all these attempts, only a few catalysts are actually applied in commercial plants, and there is still a need for catalysts that exhibit improved polymerization performance. [Content of invention]

Problem to be solved

The present invention is to provide a common supported metallocene catalyst capable of producing a polyolefin having excellent processability and showing a mul t imodal molecular weight distribution.

[Measures of problem] The present invention, the first metallocene compound represented by the formula (1); A second metallocene compound represented by Formula 2, wherein one of Formula 2 and C ₂ is Formula 3a; To be represented by the formula (2), in the formula (2) one of the C, and C ₂ to the metallocene compound of the third metal formula 3b; Cocatalyst compounds; And a common supported metallocene catalyst comprising a carrier.

The present invention also provides a method for producing polyolefin, comprising the step of polymerizing the olefin monomer in the presence of the common supported metallocene catalyst.

Hereinafter, a hybrid supported metallocene catalyst and a method for preparing polyolefin using the same according to specific embodiments of the present invention will be described in detail. According to one embodiment of the invention,

A first metallocene compound represented by Formula 1 below;

A second metallocene compound represented by Formula 2, wherein one of Formula 2 and C ₂ is Formula 3a;

A third methetallocene compound represented by Formula 2, wherein one of Formula 2 and C ₂ is Formula 3b; .

Cocatalyst compounds; And.

Common supported metallocene catalysts may be provided comprising a carrier:

[Formula 1]

In Chemical Formula 1, At least one of Ri to R ₈ is (CH ₂ ) _n -0R (wherein R is a straight or branched chain alkyl group having 1 to 6 carbon atoms, n is an integer of 2 to 10), and the others are the same as each other, or Different from each other independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

^ Is a Group 4 transition metal,

Xi and ¾ are the same as or different from each other, and each independently a halogen, or an alkyl group having 1 to 20 carbon atoms,

[

In Chemical Formula 2,

M ₂ is a Group 4 transition metal,

¾ and are the same as or different from each other, and are each independently a halogen or an alkyl group having 1 to 20 carbon atoms,

B is carbon, silicon or germanium

At least one of Qi and Q ₂ is — (C¾) _m — (where R 'is a straight or branched chain alkyl group having 1 to 6 carbon atoms and m is an integer from 2 to 10.), and the remainder is hydrogen A halogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, or an arylalkyl group of 7 to 20 carbon atoms,

And one of C ₂ is represented by the following Chemical Formula 3a or 3b, and the other is represented by the following Chemical Formula 3c,

[

[Formula 3b]

[

In Chemical Formulas 3a to 3c,

¾ to R ₂₇ are the same as or different from each other, and each independently, hydrogen, an alkyl group of C1 to C20, an alken.yl group of C2 to C20, an alkoxy group of C1 to C20, an alkylsilyl group of C1 to C20, and C1 to C20 A silylalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group. In the common supported metallocene catalyst according to the present invention, the substituents of Chemical Formulas 1, 2, 3a, 3b, and 3c will be described in more detail.

The alkyl group of <: Γ to C20 includes a linear or branched alkyl group, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nuclear group, hep And the like, but not limited thereto.

The alkenyl group of C2 to C20 includes a straight or branched alkenyl group, and specifically, may include an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like, but is not limited thereto. The C6 to C20 aryl group includes a monocyclic or condensed aryl group, and specifically includes a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but is not limited thereto.

Examples of the alkoxy group for C 1 to C 20 include a hydroxy group, an hydroxy group, a phenyloxy group, a cyclonuxyloxy group, and the like, but are not limited thereto.

Examples of the Group 4 transition metal include titanium, zirconium, hafnium, and the like, but are not limited thereto. The first metallocene compound represented by Formula 1 is-(C¾) n-0R in the substituent of cyclopentadiene (Cp), wherein R is a linear or branched alkyl group having 1 to 6 carbon atoms, and n is 2 to By introducing a substituent of J which is an integer of 10, a low molecular weight polyolefin can be produced when the polyolefin using the comonomer is produced, showing a lower conversion to the comonomer compared to other Cp-based catalysts not containing the substituent.

When the first metallocene compound of such a structure is supported on a carrier. The-(CH ₂ ) n-0R group in the substituent is stable because it can form a covalent bond through close interaction with the silanol group on the silica surface used as a support. Supported polymerization is possible.

In Formula 1, at least one of Ri and R ₅ is preferably-(CH ₂ ) _n -0R, and more preferably n is 2 to 4.

This may affect the co-synthesis of alpha -olefin comonomers such that-(CH ₂ ) _n — OR functionality is 1-butene, or 1-hexene. When n has a short alkyl chain of 4 or less, the copolymerization with respect to the alpha olepin comonomer is lowered while maintaining the overall polymerization activity, thereby making it possible to prepare a polyolefin having a controlled copolymerization without degrading other physical properties. Because there is.

Meanwhile, specific examples of the first metallocene compound represented by Chemical Formula 1 may include a compound represented by the following structural formulas, but the present invention is not limited thereto.

In addition, the second metallocene compound represented by Chemical Formula 2 and one of Chemical Formula ₂ and one of C ₂ is asymmetrical by the bridge between the indeno indol derivative and the indene derivative. And a non-covalent electron pair that can act as a Lewis base to the ligand structure, thus exhibiting high polymerization activity. Also, the electronically rich indenoindole derivatives have a beta-hydrogen of a polymer chain in which nitrogen atoms grow, By stabilizing by inhibiting beta-hydrogen el iminat i on it can polymerize a high molecular weight polyolefin compared to the first metallocene compound.

In addition, the second metallocene compound exhibits high copolymerization activity and low hydrogen reactivity as it contains indene derivatives having relatively little steric hindrance; greater than the molecular weight of polarulepine prepared using the first metallocene compound; The high molecular weight polyolefin which is smaller than the molecular weight of the polyolefin manufactured using the 3rd metallocene compound mentioned later can be superposed | polymerized.

And, in the second metallocene compound, R ₁₀ of Formula 3a is C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkoxy group, C1 to C20 alkylsilyl group, C1 to C20 silyl It is preferable that they are an alkyl group, C6-C20 aryl group, C7-C20 alkylaryl group, or C7-C20 arylalkyl group. As such, by introducing a substituent (R ₁₀ ) at a specific position of the indene derivative of formula (3a), the polymerization activity is higher than that of an unsubstituted indene compound or a metallocene compound containing an indene compound substituted at another position. Can have. In addition, in the second metallocene compound and the third metallocene compound to be described later, any one or more of R ₂₄ and _{7 in} the general formula (3c) is C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 Alkoxy group, C1 to C20 alkylsilyl group, C1 to C20 silylalkyl group, C6 to C20 aryl group, C7 to C20 It is preferable that it is an alkylaryl group or the C7-C20 arylalkyl group, A methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, tert- butyl group, a pentyl group, a nuclear group, a heptyl group, an octyl group phenyl group More preferably, a halogen group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, trimethylsilylmethyl group, methoxy group, or a special group. ^"Further, specific examples of the compound represented by Formula 3c, but a compound which is represented by one of the following structural formulas, but the invention is not limited thereto:

Meanwhile, specific examples of the second metallocene compound may include a compound represented by the following structural formulas, but the present invention is not limited thereto.

In addition, the third metallocene compound represented by Chemical Formula 2, and one of Chemical Formula 2 and C ₂ is Chemical Formula 3b, wherein the indeno indole derivative and the cyclopentadiene (Cp) derivative are asymmetric by the bridge. It forms a crosslinked structure, and exhibits high polymerization activity by having a lone pair of electrons which can act as a Lewis base in the ligand structure. In addition, the electronically rich indeno indole derivatives stabilize beta-hydrogen in the polymer chain in which nitrogen atoms are grown by hydrogen bonding, thereby inhibiting beta-hydrogen el iminat i on to polymerize high molecular weight polyolefins compared to the first metallocene compound. can do.

In addition, since the third metallocene compound includes cyclopentadiene (Cp) derivative # having less steric hindrance than the indene derivative, the third metallocene compound exhibits high copolymerization activity and low hydrogen reactivity, thereby using the first and second metallocene compounds. Higher molecular weight polyolefin can be polymerized with higher activity than the prepared polyolefin.

Meanwhile, specific examples of the third metallocene compound may include a compound represented by the following structural formula, but the present invention is not limited thereto.

As such, the common metallocene catalyst of the embodiment includes the first to third metallocene compounds, and exhibits a broad molecular weight distribution of mult imoda l, which is excellent in processability and particularly in physical properties. Polyolefin can be produced excellent in environmental stress cracking resistance.

In particular, the mixing molar ratio of the first metallocene compound, the second metallocene compound, and the third metallocene compound may be about 1: 0.1 to 5: 0.1 to 5, more preferably About _1: 0.2-5: 0.5-2. In addition, in the common supported metallocene catalyst of the embodiment, as a co-catalyst supported on a carrier for activating the metallocene compound, it is an organometallic compound containing a Group 13 metal, under a general metallocene catalyst It will not be specifically limited if it can be used when superposing | polymerizing an olefin. Specifically, the promoter compound is an aluminum-containing agent of the formula

It may include one or more of the cocatalyst, and a second borate-based cocatalyst of the formula (5).

[Formula 4]

[Al (R ₂₈ ) -0-] _k- . In Formula 4, ₈ is a halogen, halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more, [Formula 5]

T ⁺ [BG ₄ ] ^"

In formula (5), T + is a +1 polyvalent ion, B is boron in +3 oxidation state, G is independently a hydride group, a dialkyl amido group, and a halide group. Alkoxide group, aryl oxide group, hydrocarbyl group. It is selected from the group consisting of halocarbyl group and halo-substituted hydrocarbyl group, wherein G has 20 carbons or less, provided that G is a halaad group at a position below honey.

The first cocatalyst of Chemical Formula 4 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular, or reticular form. Specific examples of the first cocatalyst include methylaluminoxane (MA0) and ethylalumina. Noxic acid, isobutyl aluminoxane, or butyl aluminoxane etc. are mentioned.

In addition, the second cocatalyst of Formula 5 may be a borate-based compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt. Specific examples of such a second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate , Methyltetracyclooctadecylammonium tetraphenylborate, Ν, Ν—dimethylaninium tetraphenylborate, Ν, Ν-diethylaninynium tetraphenylborate, Ν, Ν-dimentyl (2,4,6-trimethylaniyl (Nium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, Methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium, tetrakis (pentafluorofonyl) borate,

Tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate, N ， N-dimethylaninium tetrakis (pentafluorophenyl) borate ， Ν, Ν-diethylaninium tetrakis (pentafluorophenyl) borate ， ^ dimethyl (2,4,6-trimethylaninynium) tetrakis ( Pentafulophenyl) borate.

Trimethylammonium tetrakis (2, 3, 4, 6-tetrafluorophenyl) borate,

Triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate. Tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (η-butyl) ammonium tetrakis (2,3.4,6-, tetrafluorophenyl) borate, dimethyl (t-butyl ) Ammonium Tetrakis (2,3,4,6-Tetrafluorophenyl) borate, N _: N dimethyl dimethylaninium tetrakis (2,3,4,6 ᅳ tetrafluorophenyl) borate, Ν, Ν- ^■ Diethylaninium tetrakis (2.3,4,6-tetrafluorophenyl) borate or Ν, Ν-dimethyl— (2,4,6 ᅳ trimethylaninynium) tetrakis- (2,3,4,6-tetra Borate compounds in the form of trisubstituted ammonium salts such as fluorophenyl) borate; dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclonucleoammonium tetra Beams in the form of dialkylammonium salts such as kiss (pentafluorophenyl) borate Latex compounds; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl And a borate compound in the form of a trisubstituted phosphonium salt such as) borate.

In the metallocene catalyst to the one embodiment the hybrid supported metal, the weight ratio of the total transition metal to the carrier included in the first metallocene compound, a metallocene compound and a metallocene compound with the third metal to second metal is from _1: 10 to _1: Can be 1,000. When the carrier and the metallocene compound are included in the mass ratio, an optimal shape can be exhibited. In addition, the mass ratio of the promoter compound to the carrier may be 1: 1 to 1: 100. When including the promoter and the carrier in the mass ratio, it is possible to optimize the active and polymer microstructure. In the mixed-supported metallocene catalyst of the embodiment, a carrier containing a hydroxy group on the surface may be used, and preferably, a highly reactive hydroxy group and a siloxane group which are dried to remove moisture on the surface The carrier which has is used.

For example, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, and these are typically oxides, carbonates, such as Na ₂ O, K ₂ C0 ₃ , BaS0 ₄ , and Mg (N0 ₃ ) ₂ . Sulfate, and nitrate components. The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, most preferably 300 to 40 CTC. Drying Temperature of the Carrier ^■ If it is less than 200 ^° C, the moisture and cocatalyst on the surface will react too much, and if it exceeds 800 ^° C, the pores on the surface of the carrier will merge and the surface area will decrease. It is not preferable because many hydroxyl groups are lost and only siloxane groups are left, resulting in a decrease in reaction space with the promoter.

The amount of hydroxy groups on the surface of the carrier is preferably from 0.1 to 10 mmol / g, more preferably from 0.5 to 5 mmol / g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxy group is less than 0.01 mmol / g, the reaction site with the promoter is small. If the amount of the hydroxyl group is more than 10 μL / g, the hydroxy group present on the surface of the carrier particle may be due to moisture. It is not desirable because there is.

The common supported metallocene catalyst of the above embodiment can be used by itself for the polymerization of olefinic monomers. In addition, the common supported metallocene catalyst may be prepared and used as a prepolymerized catalyst in contact with an olefinic monomer. For example, the catalyst may be separately used, such as ethylene, propylene, 1-butene, 1-nuxene, 1-octene, and the like. It can also be prepared and used as a prepolymerized catalyst by contacting with the pin monomer. On the other hand, the hybrid supported metallocene catalyst of the embodiment, the step of supporting the promoter on the carrier; Supporting the first to third metallocene compounds on the carrier on which the promoter is supported; It may be prepared by a manufacturing method comprising a. In this case, the first to third metallocene compounds may be supported one by one, or two or three may be supported together. At this time, the supporting order is not limited, but by first supporting the third metallocene catalyst having a relatively poor morphology, it is possible to improve the shape of the common supported metallocene catalyst, so as to the third metal After supporting the catalyst, the second metallocene catalyst and the first metallocene catalyst may be sequentially supported.

In the above method, the supporting conditions are not particularly limited and may be performed in a range well known to those skilled in the art. For example, it is possible to proceed by using a high temperature support and a low temperature support as appropriate, for example, the support temperature is possible in the range of 30 ^° C to 150 ^° C, preferably from room temperature to 100 ^° C, more preferably From room temperature to 80 ^° C. The supporting time is the metallocene 하고자 to be supported. It may be appropriately adjusted according to the amount of the compound. The supported catalyst can be used as it is by removing the solvent by distillation under reduced pressure by filtration or by distillation under reduced pressure.

And _; Preparation of a supported catalyst can be carried out in a solvent or in the absence ^of: A. When a solvent is used, available solvents include aliphatic hydrocarbon solvents such as nucleic acids or pentane, aromatic hydrocarbon solvents such as toluene or benzene, and hydrocarbon solvents substituted with chlorine atoms such as dichloromethane. And most organic solvents such as ether solvents such as diethyl ether or THF, acetone, ethyl acetate, and the like, and nucleic acid, heptane, toluene, or dichloromethane are preferred. On the other hand, according to another embodiment of the present invention, there may be provided a method for producing a polyolefin, including the step of polymerizing the olefin monomer in the presence of the common supported metallocene catalyst.

In turn, the olefin monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1- Dodecene, 1-tetradecene, 1—nuxadecene, 1-aitocene, norbornene, norbonadiene, ethylidene nobodene, phenyl nobodene, vinyl nobodene, dicyclopentadiene, 1, 4-butadiene ， 1 , 5-pentadiene. 1,6 ᅳ nucleodiene. Styrene, alpha-methylstyrene,. It may be at least one selected from the group consisting of divinylbenzene and 3—chloromethylstyrene. For the polymerization reaction of the olefin resin, a continuous solution polymerization process, bulk polymerization process, suspension polymerization process. Various polymerization processes known as polymerization reaction of olefin monomers, such as slurry polymerization process or emulsion polymerization process, may be employed. Such polymerization reaction may be carried out at a temperature of about 25 to 500 ^° C, or about 25 to 200 ^° C. or about 50 to 150 ^° C, and under a pressure of about 1 to 100 bar or about 10 to 80 bar.

In addition, in the polymerization reaction, the common supported metallocene catalyst may be used dissolved or diluted in a solvent such as pentane, nucleic acid, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like. At this time, by treating the solvent with a small amount of alkylaluminum or the like, a small amount of water or air which may adversely affect the catalyst can be removed in advance. In addition, the polyolefin prepared by the above production method may be a polyolefin having a multimodal molecular weight distribution.

And. The polyolefin prepared had a weight average molecular weight (Mw) of 100,000. To 300,000 g / mol. More preferably, the increase is. The average molecular weight is.

At least 120, 000 g / mol, at least 130, 000 g / mo 1, or. 140, 000 g / mo I or more, 250,000 g / mol or less, or 220,000 g / mol or less, or 200,000 g / mol or less.

In addition, the molecular weight distribution (PDI) of the prepared polyolefin may be 5 or more. More preferably, the molecular weight distribution is 8 or more, 9 or more, or 10 or more, 20 or less, 18 or less, or 17 or less.

The polyolefin may be an ethylene / alpha—lepin copolymer.

The ethylene / alpha-olefin copolymer has a density of 0.948 to 0.960 g / cm ³ , or 0.950 to 0.955 g / cm ³ . Density of Ethylene / Alpha-Lepin Copolymer

Lower than 0.948 g / cm ³ . When the bottle of carbonated beverage container is used as a bottle (cap.cap). Due to the pressure of the carbonated beverage, swelling may occur, and the ESCR characteristics may be deteriorated when the alpha-lefin content is decreased to increase the density. However, the ethylene / alpha -olefin copolymer is the appropriate While exhibiting high density in the range, ESCR has excellent properties.

In the ethylene / alpha-olefin copolymer, in the GPC curve graph in which the X axis is log Mw and the y axis is dw / dlogMw, the integral value of the region where log Mw is 5.0 to 5.5 is 10 to 20% of the total X-axis integral value. , Preferably 10 to 18%, more preferably 10 to 16%. In the above, Mw means weight average molecular weight, and w means weight fraction.

In the GPC curve graph, a log Mw of 5.0 to 5.5 is a region where physical properties and processability of the product provided by injection of the ethylene / alpha-olefin copolymer are confirmed.

In addition, the ratio which the integral value of the area | region whose log Mw is 5.0-5.5 with respect to the X-axis integral value is a numerical value which shows the tie molecular fraction of the high molecular weight in the said ethylene / alpha-olefin copolymer. Accordingly, when the ratio of the integral of the log Mw of 5.0 to 5.5 is less than 10% of the total integral value of the X axis, the ethylene / alpha-olefin copolymer has a relatively low level of environmental stress cracking resistance. (ESCR). In addition, when the ratio of the integral value of the region of the log Mw7} 5.0 to 5: 5 is greater than 20% with respect to the total X-axis integral value, the molecular weight distribution of the high molecular weight region according to the molecular weight distribution (MWD) Due to the excessive specific gravity, the processability of the ethylene / alpha-olepin copolymer may be greatly reduced.

In addition, the ethylene / alpha-lefin copolymer may have a spiral flow length (190 ° C, 90 bar) of 13 to 25 cm, more preferably 15 to 20 cm.

The spiral flow length (190 ° C, 90 bar) indicates the processability of the ethylene / alpha -olefin copolymer, the larger the value means that the processability is excellent. However, from the viewpoint of harmonization of mechanical properties and stability in addition to workability, a larger spiral flow length is not necessarily preferable, and there may be an appropriate range of spiral flow lengths depending on the application.

The spiral flow length is applied by applying a specific pressure and temperature to the spiral mold: how polymer is injected and thus melted and injected polymer It can be assessed by measuring if it is pushed out. As in the embodiment to be described later, in the present invention, using a mold having a thickness of 1.5 隱, an injection temperature of 190 ^° C, a mold temperature of 50 ^° C and the injection pressure can be measured by setting to 90 bar, the ethylene / The spiral flow length of the alpha-olefin co-polymer is 13-25 cm, indicating excellent processability.

In addition, the ethylene / alpha olefin copolymer is characterized by excellent environmental stress cracking resistance (ESCR, ^' envi ronmental st ress crack stance) in addition to the mechanical properties and processability as described above.

In general, the processability and environmental resistance crack resistance is a contrary physical properties, if the melt index is increased to increase the workability, the environmental resistance crack resistance is reduced, but the ethylene / of the above embodiment prepared using a specific hybrid supported metallocene catalyst The alpha-olefin copolymer can satisfy both good processability and environmental stress cracking resistance.

The ethylene / alpha-olefin copolymer may have an environmental stress crack resistance (ESCR) of 130 hours or more, 140 hours or more, or 150 hours or more, as measured according to ASTM D 1693. If the environmental stress cracking resistance (ESCR) is 130 hours or more, the performance can be stably maintained under the condition of the use of the bottle cap.The higher the environmental stress cracking resistance (ESCR) value is, the better, the upper limit is not limited. For example up to 1,000 hours, or up to 800 hours, or up to about 500 hours. Since the ethylene / alpha-olepin copolymer exhibits high performance of environmental stress cracking resistance, the ethylene / alpha-lepine copolymer can be molded into a food container product such as a borcap to maintain high stability even when used under high temperature and high pressure. . In addition, the ethylene / alpha -olefin copolymer may have a melt index (Ml, 190 ^° C, 2. 16 kg) of 0.7 g / 10 m in or less. More preferably the melt index is at least 0.05 g / 10 m in, at least 0.01 g / 10 m in, or at least 0.1 g / lOmin, at most 0.7 g / 10iiiin, at most 0.6 g / 10 m in, or at most 0.5 g /. It may be less than 10m in.

[Effects of the Invention】

When the common supported metallocene catalyst according to the present invention is used, it is excellent in workability and has a feature capable of producing a polyolefin having a mult imodal molecular weight distribution. [Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the present invention, the content of the present invention is not limited to the following examples. Preparation Example 1 Preparation of First Metallocene Compound

Preparation of 1-1 Ligand Compound

10.8 g (100 mmol) of chlorobutan was added to the dried 250 mL Schlenk flask, 10 g of molecular sieve and 100 mL of MTBE were added, and 20 g of sulfuric acid was added slowly over 30 minutes. The reaction mixture slowly turned pink over time and poured into saturated sodium bicarbonate solution cooled with ice after 16 hours. The mixture was extracted several times by adding ether (100 mL x 4), and the combined organic layers were dried over MgS0 ₄ , filtered, and the solvent was removed under vacuum pressure to give l- (tert butoxy) -4 as a yellow liquid. 10 g (60% yield) of -chlorobutane was obtained.

¹ H NMR (500 MHz, CDC1 ₃ ): 1.16 (9H, s), 1.67-1.76 (2H, m), 1.86-1.90 (2H, m), 1.94 (1 H, m), 3.36 (2H, m), 3.44 (1 H, m), 3.57 (3H, m)

4.5 g (25 mmol) of the synthetic l- (tert butoxy) -4-chlorobutane was added to the dried 250 mL Schlenk flask and dissolved in 40 mL of THF. 20 mL of sodium cyclopentadienylide THF solution was slowly added thereto, followed by stirring for one day. 50 mL of water was added to the reaction mixture, quenched, extracted with ether (50 mL x 3), and the combined organic layers were sufficiently washed with brine. Dry the remaining moisture with MgS0 ₄ , filter, and remove the solvent under reduced pressure under vacuum to quantify 2- (4- (tert-butoxy) butyl) cyclopenta-l, 3-diene as a dark brown viscous form. Obtained in yield.

¹ H NMR (500MHz, CDC1 ₃ ): 1.16 (9H, s), 1.54-1.60 (4H, m), 1.65 (1H, m), 1.82 (1H, m), 2.37-2.42 (2H, m), 2.87 , 2.92 (2H, s), 3.36 (2H, m), 5.99 (0.5H, s), 6.17 (0.5H, s), 6.25 (0.5H, s), 6.34 (0.5H, s), 6.42 (1H , s)

Preparation of 1-2 metallocene compound

4.3 g (23 μL) of the ligand compound synthesized in 1-1 was added to a dried 250 mL Schlenk flask and dissolved in 60 mL of THF. 11 mL of n-BuLi 2.0M hexane solution (28 mmol) was added thereto, and the mixture was stirred for one day. The solution was then added to a flask in which 3.83 g (10.3 μl) of ZrCl ₄ (THF) ₂ was dispersed in 50 mL of ether. Slowly added at 78 ^° C.

The reaction mixture changed from pale brown suspension to turbid yellow in suspension form when raised to room temperature. After stirring for one day, both the reaction mixture and the solvent were dried, 200 mL of nucleic acid was added thereto, and the sonic cat ion was allowed to settle. The nucleic acid solution in the upper layer was collected by decant at ion with cannula. This process. The nucleic acid solution obtained twice was dried under vacuum reduced pressure to give bis (3- (4— (tert-butoxy) butyl-2,4—dien-yl) zirconium (IV) chloride, a pale yellow solid. Confirmed- ᅳ

¹ H NMR (500MHz, CDC1 ₃ ): 0.84 (6H, m), 1.14 (18H, s), 1.55-1: 61 (8H, m), 2.61 (4H.ni), 3.38 (4H, m), 6.22 (3H, s). 6.28 (3H. S)

Preparation of 2-1 Ligand Compound ndole was added and 40 niL of ether was injected under argon. After the ether solution was cooled to 0 ^° C., 4.8 mL (12 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly raised to room temperature and stirred until the next day. Another 250 mL schlenk flask was charged with 20 mL of ether, and then 3.6 mL (30 mmol) of di ch 1 or ome t hy 1 (t er t bu t oxyhexy 1) si 1 ane were injected. After cooling the flask to -78 ^° C, a lithiated solution of Indenoindole was injected through cannula. After the injection, the mixture was slowly raised to room temperature, stirred for about 5 hours, stirred for one day, quenched with 50 ml of water in the Flask, and the organic layer was separated and dried over MgS0 ₄ . The ether used as solvent was removed under reduced pressure. This was confirmed by NMR and 10-((6- (tert-butoxy) hexyl) ehloro (methyl) silyl) -5,8-dimethyl-5, 10-di hydr oi ndeno [1, 2- with a purity of about 95% or more. b] i ndo 1 e was obtained.

After the synthesis of the indenoindole part is confirmed. 1.7 g (10 μl) of 3- (but-3-en-l-yl.)-LH-indene was injected into a dried 100 mL schlenk flask and dissolved in 40 mL of ether. Then 4.8 ml (12 隱 ol) of 2.5 M nBuLi hexane solution was slowly added dropwise at -78 ^° C and stirred for one day. 10-((6- (tert-butoxy) hexyl) chloro (methyl) si lyl) -5,8-dimethyl-5.10-di hydr oi ndeno [1, 2-b] indole synthesized previously in 40 mL of ether After melting, lithiated solution of buthylindene was added dropwise at ᅳ 78 ^° C. After about 20 hours, 50 mL of water was added to the flask, quenched, and the organic layer was separated and dried over MgS0 ₄ . The mixture obtained through filtration evaporated the solvent under vacuum reduced pressure conditions. As a result, 10- ((3- (but-3_en-l-yl) — lH—inden-1—yl) (6- (tert-butoxy) hexyl) (methyl) of 5.8 g (9.7 隱 ol, 97.) ) si lyl) -5,8-dimethyl-5,10-dihydroi ndeno [1,2-b] indole was obtained.

¾ 匪 R (500 MHz, CDC13): -0.71, -0.23 (3H, d), 0.82 (2H, s), 1.17

(9H, s), 1.23 1.39 (7H, m), 1.51 (1H, s), 2.26 (2H, m), 2.48 (2H, i), 2.61 (2H, m), 3.25 (2H. M), 3.50 (1H, s), 3.82 (1H, s), 4.09 (3H, m), 5.03 (2H, m), 5.89 (1H, m), 7.08 (1H, s), 7.15-7.75 (11H, m)

2-2 Preparation of Metallocene Compound

Place ligand in a dry 250 mL schlenk flask in Aubonn and dissolve in ether. 2.1 equivalents of nBuLi solution was added and lithiation was performed until the next day. One equivalent of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 ml schlenk flask to prepare a suspension containing ether or leuene. After the two flasks were cooled down to ᅳ 78 ^° C, ligand anion was slowly added to the Zr suspension. After the injection was over, the reaction mixture was slowly raised to room temperature. In this process, when the metallization was successful, it was confirmed that the index purple peculiar to the catalyst precursor appeared. After stirring for one day, toluene or ether in the mixture was removed by vacuum depressurization to about 1/5 volume and the volume of nucleic acid was added about 5 times the volume of the remaining solvent. The reason for adding the nucleic acid at this time is to promote crystallization because the synthesized catalyst precursor is insoluble in nucleic acid. This hexane slurry was filtered under argon, and after filtration, both the filtered solid and the filtrate were evaporated under vacuum reduced pressure. The remaining filter cake is weighed and sampled in the glove box for synthesis and yield. Purity was confirmed. Ether was used as the solvent for metallization, and 2.5 g (30.5%) of a purple solid was obtained from 5,8 g (9.7.% Ol) of ligand (purity (wt%) = 90% based on NMR. Mw = 762.06) ).

¾ NM (500 MHz.CDCI ₃ ): 0.81 (3H, m), 1.19 (10H, m), 1.55 1.78 (10H, m), 1.97 (2H, m), 2.26 (2H, m), 2.54 (3H. s.) 3.36 (2H, m), 3.94 (3H, s), 4.16 (1H, d), 4.85 (1H, ni), 5.64 (1H, s), 6.53 (IH, s), 6.97 (2H, m ), 7.10 to 7.45 (5H, m), 7.52 to 7.87 (4H, m)

Preparation of 3-1 Ligand Compound

3 g (10 μl) of I ndeno indole derivative was dissolved in 100 mL of Hexane, and 4.4 mL (ll μl) of 2.5M n-BuLi Hexane solution was added dropwise and stirred overnight at room temperature. Prepare another 250 niL schlenk flask, place it in a glove box, weigh 2.7 g (10 mmol) of (6-tert-butoxyhexy l) dichloro (methyl) si lane in the glove box, take it out, and dissolve in 50 mL of hexane. Was added dropwise. After completion of the injection, the mixture was slowly raised to room temperature, and then stirred overnight at 10 ° C by adding 10 mmol of sodium Cp salt in 100 mL of THF to the reaction mixture, which was stirred overnight. After removal of the residual moisture of the organic layer after extraction with banung MgS0 _4, the solvent was removed in vacuo to a reduced pressure condition was obtained as a ligand compound oilic a state, it was confirmed by NMR ¾.

^{'¾ NMR (500 MHz, CDC1} 3): 7.74 ~ 6.49 (7H, m), 5.87 (6H, s), 3.32 (2H, m), 3.49 (3H, s), 1.50 ~ 1.25 (8H, m), 1.15 (9H, s), 0.50 (2H, m), 0.17 (3H, d)

Preparation of 3-2 Metallocene Compound

7.9 mmol of the ligand compound synthesized in 3-1 was dissolved in 80 ml of toluene, and 6.6 mL (16.6 隱 ol) of 2.5M nBuLi hexane solution was added dropwise, followed by stirring at room temperature overnight. The 9 mmol of ZrCl ₄ (THF) ₂ was prepared as a slurry in 80 mL toluene was stirred to transfer the Ligand-Li solution.

After the reaction mixture was filtered to remove LiCl, filtrate was vacuum dried toluene to obtain 1.5 g of a liquid catalyst, yielding 23 mol%.

¾ NMR (500 MHz, CDC1 ₃ ): 7.66-7.20. (17 H _T m), ^J H NMR (500 MHz,

CDCI3): 7.89-6.53 (19H, m), 5.82 (4H, s), 3.19 (2H, s), 2.40 (3H, m), 1.35-1.21 (4H, m), 1.14 (9H, s), 0.97 0.9 (4H, m), —0.34 (3H, t)

Example 1

3 kg of toluene solution was added to a 20 L SUS reaction vessel, and the reaction temperature was maintained at 40 ^° C. 600 ^° silica was dehydrated by applying vacuum for 12 hours at a temperature of C (Grace davison manufactured, Sylopol 948) In 1 kg of the anti-unggi and then sufficiently dispersed silica key, ΐα wt methylaluminoxane (MA0) / a 3 kg of the luene solution was added thereto, followed by stirring at 40 ^° C. at 200 rpm for 12 hours. In addition, the metallocene compound of Preparation Example 3 was dissolved in toluene at a ratio of 0.1 mmol / gSi0 ₂ , and stirred and reacted at 40 ^° C. for 2 hours.

Next, the metallocene compound of Preparation Example 2 was added to the reaction vessel at a rate of 0.15 kPa ol / gSi¾, and then stirred at 40 ^° C. at 200 rpm for 2 hours. The metallocene metallocene compound of Preparation Example 1 was introduced into the reactor at a ratio of 0.15 kPa ol / gSi0 ₂ , and then stirred at 40 ^° C. at 200 rpm for 2 hours.

The nucleic acid slurry was transferred to a filter and the nucleic acid solution was filtered. 1 kg of the supported catalyst was prepared by drying under reduced pressure at 40 ^° C. for 4 hours. Example 2

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 1, except that 0.1 mmol / g Si0 _{2 was} added to the metallocene compound prepared in Preparation Example 1. Example 3

^'The metallocene compound as a metal prepared in Preparation Example 1, 0.1 mmol / g Si0 ₂ inputs, and a metallocene compound a metal prepared in Preparation Example 2, 0.1 mmol / g Si0 and is described in Example 1 except that the _second input Using the same method as in the above, the common immersion metallocene catalyst was prepared. Comparative Example 1

Polyethylene copolymer (ME1000, LG Chemical) made with Ziegler-Natta catalyst was used as Comparative Example 1. Comparative Example 2

0.1 mmol / g Si0 _{2 was} added to the metallocene compound prepared in Preparation Example 1, 0.2 mmol / g Si0 _{2 was} added to the metallocene compound prepared in Preparation Example 2, and the metal prepared in Preparation Example 3 was added. A common supported metallocene catalyst was prepared in the same manner as in Example 1 except that no rosene compound was added. Test Example: Preparation of Ethylene / 1-Butene Copolymer

Each of the common supported metallocene catalysts prepared in each of the above examples was introduced into a CSTR continuous polymerizer (reactor volume 50 L) to prepare an olefin polymer. As comonomer, 1-butene was used, and the reactor pressure was maintained at 10 bar and the deposition temperature was maintained at 90 ^° C.

The polymerization conditions using the common supported metallocene catalysts of Examples 1 to 2 and Comparative Examples 1 and 2 are collectively shown in Table 1 below.

Table 1

The physical properties of the polyolefins prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were measured by the following methods, and are shown in Table 2.

(1) Mn, Mw, PDI, GPC curve: Pre-treat the sample by dissolving it for 160 hours in 1,2,4-Trichlorobenzene containing 0.0125% of BHT using PL-SP260 for 10 hours, using PL-GPC220 The number average molecular weight and the weight average molecular weight were measured at a measurement temperature of 160 ° C. PDI was expressed as the ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight. Then, in a GPC curve graph where the X axis is log Mw and the y axis is dw / dlogMw, the integral value in the area where log Mw is 4.5-5.0, 5.0-5.5, or 5.5-6.0 is the ratio of the integral value of the X axis. The calculation is shown in Table 2.

(32) Density (g / cm ³ ): Measured according to ASTM 1505.

(3) Melt index (Ml, 2.16 kg): measured at a measurement temperature of 190 ° C according to ASTM 1238.

(4) ESCR: According to ASTM D 1693, using a 10% Igepal CO-630 Solution to measure the time to F50 (50% fracture) under 50 ° C silver.

(5). Spiral flow length: ENGEL 150 ton injection machine was used, mold thickness is 1.5 mm, injection temperature is 190 ° C, mold temperature is 50 ° C. The injection pressure was measured at 90 bar.

Table 2

As shown in Table 2, the ethylene / alpha -olefin copolymer of the embodiment exhibits a wide molecular weight distribution, as the ratio of the area of the log Mw of 5.0 to 5.5 meets a specific range, the environmental impact crack resistance 150 hours As described above, it can be seen that it exhibits a relatively high spiral flow length and shows excellent processability and significantly improved environmental stress cracking resistance.

Claims

[Patent Claims]

[Claim 11

A first metallocene compound represented by Formula 1 below;

A second pentalocene compound represented by Formula 2, wherein one of Formula 2 and C ₂ is the following Formula 3a;

To be represented by the formula (2), in the formula (2) one of the C, and C ₂ to the metallocene compound of the third metal formula 3b;

Cocatalyst compounds; And

Common supported metallocene catalysts comprising a carrier:

[Formula 1]

In Chemical Formula 1,

At least one of Ri to ¾ increase is-(CH ₂ ) _n -0R wherein R is a straight or branched chain alkyl group having 1 to 6 carbon atoms, n is an integer of 2 to 10, and J is the same or different from each other. And are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

^ Is a Group 4 transition metal,

¾ and ¾ are the same as or different from each other, and each independently a halogen or an alkyl group having 1 to 20 carbon atoms,

[Formula 2]

In Chemical Formula 2,

M ₂ is a Group 4 transition metal,

¾ and X ₄ are the same as or different from each other, and are each independently a halogen or an alkyl group having 1 to 20 carbon atoms,

B is carbon, silicon or germanium,

At least one of Qi and Q ₂ is — (C¾) _m −0R ′ wherein R ′ is a straight or branched chain alkyl group having 1 to 6 carbon atoms and ni is an integer of 2 to 10. A halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

[Formula 3b]

[Formula 3c]

In Chemical Formulas 3a to 3c,

R ₉ to R ₂₇ are the same as or different from each other, and each independently, hydrogen, C 1 to C 20 alkyl group, C 2 to C 20 alkenyl group, C 1 to C 20 alkoxy group, C 1 to C 20 alkylsilyl group, C 1 to C 20 siltyl An alkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group.

[Claim 2]

The method of claim 1,

At least one of Formula 1 and R ₅ is-(CH ₂ ) _n -0R (wherein R is a linear or branched alkyl group having 1 to 6 carbon atoms, n is an integer of 2 to 10) Hybrid supported metallocene catalyst to be used.

[Claim 3]

The method of claim 1,

R ₁₀ of Formula 3a is an alkyl group of C1 to C20, an alkenyl group of C2 to C20, and an alkoxy group of C1 to C20. C1 to C20 alkylsilyl group, C1 to C20 silylalkyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, characterized in that the common supported metallocene catalyst.

[Claim 4]

The method of claim 1,

At least one of R ₂₄ and R ₂₇ in Formula 3c may be a C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkoxy group, C1 to C20 alkylsilyl group, C1 to C20 silylalkyl group, C6 To C20 aryl group, C7 to It is a C20 alkylaryl group or C7-C20 arylalkyl group.

[Claim 5]

The method of claim 1,

The first supported metallocene catalyst is a compound represented by one of the following structural formulas,

[Claim 6]

The method of claim 1,

The second metallocene compound may be represented by the following structural formulas

Compound supported, commonly supported metallocene catalysts:

[Claim 8]

The method of claim 1,

The mixed molar ratio of the said 1st metallocene compound, the 2nd metallocene compound, and the 3rd metallocene compound is 1: 0.1-5: 0.1-5.

[Claim 9]

The method of claim 1,

The cocatalyst compound is a common supported metallocene catalyst comprising at least one selected from the group consisting of a first promoter of Formula 4, and a second promoter of Formula 5 below:

[Formula 4]

[Al (R ₂₈ ) -0-] _k -In Formula 4, R ₂₈ is each independently a halogen, a halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more, and 5]

T ⁺ [BG ₄ ] ^"

In formula (5), T + is a polyvalent silver atom of +1 value, B is boron in +3 oxidation state, G is independently a hydride group, a dialkylamido group, a halide group alkoxytide group, an aryl oxide group, hydro Selected from the group consisting of a carbyl group, a halocarbyl group and a halo-substituted hydrocarbyl group, wherein G has up to 20 carbons, but at less than one position G is a halide group. [Claim 10]

A process for producing a polyolefin comprising polymerizing reaction of an olefin monomer in the presence of the common supported metallocene catalyst of claim 1.

[Claim 11]

The method of claim 10, wherein the olefin resin is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1 -pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-ound Senes, 1-dodecene 1-tetradecene, 1—nuxadecene, 1-aitosen, norbornene, norbonadiene, ethylidene nobodene, phenyl nobodene, vinyl novophene, dicyclopentadiene, 1, 4- A method for producing a polyolefin comprising at least one member selected from the group consisting of butadiene, 1, 5-pentadiene, 1,6-nuxadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.