WO2016056744A1

WO2016056744A1 - Ligand compound, metallocene compound, and method for preparing olefin-based polymer by using same

Info

Publication number: WO2016056744A1
Application number: PCT/KR2015/008771
Authority: WO
Inventors: 홍복기; 이용호; 한창완; 최이영; 이기수
Original assignee: 주식회사 엘지화학
Priority date: 2014-10-06
Filing date: 2015-08-21
Publication date: 2016-04-14

Abstract

The present invention relates to a novel ligand compound, a metallocene compound, and a method for preparing an olefin-based compound by using the same. According to the present invention, the metallocene compound and a catalyst composition containing the same have excellent comonomer insertion capacity while having excellent polymerization activity, and thus have a wide molecular weight distribution. Therefore, an olefin-based compound having excellent processability can be prepared.

Description

【Specification】

[Name of invention]

Ligand compound, metallocene compound and method for producing olefin polymer using same

[Cross Citation with Related Application (s)]

This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0134342 dated October 6, 2014 and Korean Patent Application No. 10-2015-0117300 dated August 20, 2015. All content disclosed in the literature is included as part of this specification.

Technical Field

The present invention relates to a novel ligand compound, a metallocene compound, and a method for preparing an olefinic polymer using the same.

[Technique to become background of invention]

Dow announced in the early 'Me ² Si (Me ⁴ C ⁵ ) NtBu] TiCl ² (Constrained-Geometry Catalyst, hereinafter abbreviated as CGC) (US Pat. No. 5,064,802), ethylene and alpha- The superiority of CGC in the copolymerization reaction of olefins compared to the metallocene catalysts known to the prior art can be summarized into two main categories: (1) The production of high molecular weight polymers with high activity even at high polymerization temperatures. And (2) the copolymerization of alpha-olefins with large steric hindrances such as 1-nuxene and 1-octene is also excellent. In addition, various characteristics of CGC were gradually known in the case of addition reaction, and the derivatives thereof were actively synthesized in ^' academia' and 'industrial industry ^' to use as a polymerization catalyst.

A Group 4 metallocene compound having one or two cyclopentadienyl groups as a ligand can be activated as methylaluminoxane or boron compound to be used as a catalyst for leupin polymerization. Such catalysts exhibit unique properties that conventional Ziegler-Natta catalysts cannot realize. In other words, the polymer obtained using such a catalyst has a narrow molecular weight distribution, better response to a second monomer such as alpha olefin or cyclic olefin, and a uniform distribution of the second monomer of the polymer. In addition, by changing the substituent of the cyclopentadienyl ligand in the metallocene catalyst, it is possible to control the stereoselectivity of the polymer when polymerizing alpha lepin, and the degree of copolymerization, molecular weight, and crab monomer when copolymerizing ethylene and other olefins. Distribution and the like can be easily adjusted.

On the other hand, metallocene catalysts are expensive compared to conventional Ziegler-Natta catalysts, so they have good activity and are economically valuable. If the reaction properties to the second monomer are good, there is an advantage that a polymer containing a large amount of the second monomer can be obtained even with the addition of a small amount of the second monomer.

Several researchers have studied various catalysts and found that generally bridged catalysts have good reaction properties with respect to the second monomer. The bridged catalysts studied so far can be classified into three types depending on the type of bridge. One is a catalyst in which two cyclopentadienyl ligands are linked to an alkylenedibridge by reaction with an electrophile such as an alkyl halide and indene or fluorene, and the second is a silicon bridged catalyst connected by -SiR 2-and Methylene bridged catalysts obtained from reactions of fulven and indene, fluorene and the like.

However, among the above attempts, the catalysts actually applied in commercial plants are few, and there is still a need for the production of catalysts showing improved polymerization performance.

[Content of invention]

Problem to be solved

In order to solve the problems of the prior art, the present invention has a wide molecular weight distribution because of the excellent polymerization activity, and excellent comonomer insertion ability, and thus a metallocene compound capable of producing a leupine-based polymer having excellent processability. And, to provide a method for producing an olefin-based polymer using the same. [Measures of problem]

According to an aspect of the present invention to achieve the above object, it provides a ligand compound represented by the following formula (1):

One]

In Chemical Formula 1,

Ri to R ₁₆ are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, wherein R! Two or more adjacent to each other to R ₁₆ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, provided that R and R ₁₆ are all hydrogen;

L is a direct bond or an alkylene group having 1 to 10 carbon atoms;

R is a substituted or unsubstituted phenyl group, naphthyl group, a cycloalkyl group having 3 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms; Ql and Q ₂ are the same as or different from each other, and are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon atoms An alkylaryl group having 7 to 20 or an arylalkyl group having 7 to 20 carbon atoms.

In addition, the present invention provides a metallocene compound represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

M is a Group 4 transition metal;

Xi and ¾ are the same as or different from each other, and each independently halogen, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, nitro group, amido group, alkyl of 1 to 20 carbon atoms A silyl group, an alkoxy group having 1 to 20 carbon atoms, or a sulfonate group having 1 to 20 carbon atoms;

R) to R ₁₆ are the same as or different from each other, and each independently hydrogen, halogen, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, and cycloalkylalkyl group having 4 to 20 carbon atoms ， 1 carbon To 20 alkoxy group, an aryl group having 6 to 20 carbon atoms of the aryl group, having 5 to 20 heteroaryl group, a C7 to C20 alkylaryl group, or a carbon number of 7 to 20 of, adjacent to each other of the to R ₁₆ Two or more may be linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring, except where all of R to ₁₆ are hydrogen;

^. L is a direct bond or an alkylene group having 1 to 10 carbon atoms;

R is a substituted or unsubstituted phenyl group, naphthyl group, a cycloalkyl group having 3 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms;

Q _t and Q ₂ are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 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.

In addition, the present invention provides a method for producing an olefin-based polymer comprising the step of polymerizing a relefin-based monomer in the presence of a catalyst composition comprising the metallocene compound.

【Effects of the Invention】

The metallocene compound having the new ligand can easily control the electronic and three-dimensional environment around the metal by introducing various substituents to the ligand to which the indeno indole derivative and the fluorene derivative are linked, and ultimately, the structure of the polyolefin produced. The physical properties can be adjusted. The metallocene compound according to the present invention or the catalyst composition including the same can be used in the preparation of the olepin-based polymer, and especially exhibits high activity even in the co-polymerization using a comonomer, can improve the comonomer insertion ability, It is possible to manufacture an leupin-based polymer having a molecular weight distribution and excellent in processability.

[Specific contents to carry out invention]

In the present invention, terms such as first and second are used to describe various components, which terms constitute one component to another component. It is only used to distinguish it from the element. ,

In addition, the terminology used herein is for the purpose of describing example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "having" 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 a combination thereof. .

Also, in the present invention, when each layer or element is referred to as being formed "on" or "on" of each layer or element, it means that each layer or element is directly formed on each layer or element, or the other It is meant that a layer or element can additionally be formed between each layer, on the object, the substrate.

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 a particular disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in detail. Ligand compound according to the invention is characterized in that represented by the formula (1).

[Formula 1]

In Chemical Formula 1,

Rt to R ₁₆ are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms of the aryl group, having 5 to 20 heteroaryl group, a C7 to C20 alkylaryl group, or a carbon number of 7 to 20 of the, each of said through R ₁₆ Two or more adjacent groups may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, except that the above R ₁₆ are all hydrogen;

L is a direct bond or an alkylene group having 1 to 10 carbon atoms; ^'

Qi and Q ₂ are the same as or different from each other, and are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon atoms An alkylaryl group having 7 to 20 or an arylalkyl group having 7 to 20 carbon atoms. When described in more detail with respect to the main substituents in the formula (1).

The alkyl group having 1 to 20 carbon atoms 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, heptyl group And an octyl group etc. are mentioned, but it is not limited to this. The alkenyl group having 2 to 20 carbon atoms includes a straight or branched alkenyl group, and specifically includes an allyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and the like, but is not limited thereto. .

The aryl group having 6 to 20 carbon atoms 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.

The heteroaryl group having 5 to 20 carbon atoms includes a monocyclic or condensed heteroaryl group, and includes a carbazolyl group, a pyridyl group, a quinoline group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, a thiazolyl Groups, triazine groups, tetrahydropyranyl groups, tetrahydrofuranyl groups, and the like, but are not limited thereto.

Examples of the alkoxy group having 1 to 20 carbon atoms include mesophilic, ethoxy, phenyloxy, and cyclonucleooxy groups, but are not limited thereto.

The cycloalkyl group having 3 to 20 carbon atoms may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclonuxyl group, and the like, but is not limited thereto.

Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms include a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group _: a cyclopentylethyl group, a cyclonuxylmethyl group, and a cyclonuxylethyl group. It is not limited.

According to an embodiment of the present invention, R in Formula 1 is a phenyl group, a cyclopentyl group, a cyclonuxyl group, a fluorophenyl group, or a pentafluorophenyl group egg. Can be. The functional groups can be introduced into the fluorene derivative of the ligand compound of the embodiment to control the molecular weight and molecular weight distribution of the produced olefin polymer, in particular, using a phenyl group, cyclohexyl group, fluorophenyl group, pentafluorophenyl group, etc. In this case, since the acid group of the center metal can be increased to stabilize the ligand compound, there is an effect of improving the catalytic activity. In addition, the formula (1) can adjust the angle of the bite angle leading to the ligand, the central metal, and the ligand, depending on the substituent introduced into R, the above-described substituents to increase the bite angle of the compound of the chemical formula 1, comonomer It is easy to introduce and has the effect of improving copolymerizability.

In addition, R ₂ and R ₅ in Formula 1 may be the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

Specific examples of the compound represented by Formula 1 may be a compound represented by one of the following structural formulae, but the present invention is not limited thereto.

The compound represented by Chemical Formula 1 may be synthesized by the same method as in Scheme 1 below.

[Banungsik 1]

Banung in the formula R 1, to _6, and Q _2, the definition of L are the same and, Αι Α ₂ and defined as in the general formula (1) is halogen.

More specific examples are described in the following Examples, and those skilled in the art may prepare the compound of Formula 1 with reference to the contents described in the Examples.

In addition, the ligand compound of Formula 1 may prepare a metallocene compound described later through metallization with a transition metal. According to another aspect of the present invention, a metallocene compound represented by the following Chemical Formula 2 is provided.

[Formula 2]

In Chemical Formula 2,

M is a Group 4 transition metal;

X. and ¾ are the same as or different from each other, and each independently 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, a nitro group, an amido group, a carbon group having 1 to 20 carbon atoms An alkylsilyl group, an alkoxy group having 1 to 20 carbon atoms, or a sulfonate group having 1 to 20 carbon atoms;

Ri to R ₁₆ are the same as or different from each other, and each independently hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 1 to 20 carbon atoms, wherein Ri to R ₁₆ Two or more adjacent to each other may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, provided that R _! Except when R ₁₆ are all hydrogen;

L is a direct bond or an alkylene group having 1 to 10 carbon atoms;

R is a substituted or unsubstituted phenyl group, naphthyl group, 3 to 20 carbon atoms A cycloalkyl group or an alkoxy group having 1 to 20 carbon atoms;

Qi and Q ₂ are the same as or different from each other, and are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon atoms An alkylaryl group having 7 to 20 or an arylalkyl group having 7 to 20 carbon atoms.

Examples of the Group 4 transition metal include titanium, zirconium, and hafnium, but are not limited thereto.

According to an embodiment of the present invention, R in Formula 2 may be a phenyl group, a cyclopentyl group, a cyclonuxyl group, a fluorophenyl group, or a pentafluorophenyl group. The functional groups may be introduced into the fluorene derivative of the metallocene compound of the embodiment to control the molecular weight and molecular weight distribution of the olefin polymer to be produced, in particular, a phenyl group, a cyclonuclear group, a fluorophenyl group, a pentafluorophenyl group, or the like. In the case of using, since the acid group of the core metal can be raised to stabilize the ligand compound, there is an effect of improving the catalytic activity. In addition, the formula (1) can adjust the angle of the bite angle leading to the ligand, the central metal, and the ligand, depending on the substituents introduced into R, the above-mentioned substituents to increase the bite angle of the formula and the compound, It is easy to introduce | transduce, and there exists an effect which improves copolymerization by this.

In addition, R ₂ and R ₅ in Formula 2 may be the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

In addition, examples of the metallocene compound represented by Formula 2 include the following compounds, but are not limited thereto.

The metallocene compound of Chemical Formula 2 has an indeno indole derivative and a fluorene (fl _uorene ) derivative as a basic skeleton, and these two derivatives form asymmetrically crosslinked structure by a silicon bridge. In addition, by having a non-covalent electron pair capable of acting as a Lewis base in the ligand structure, it is supported on the surface having the Lewis acid characteristic of the carrier and shows high polymerization activity even when supported. In addition, the electronically rich indeno indole group and the fluorene group includes a high activity, due to the proper steric hindrance and the electronic effect of the ligand is not only low hydrogen response, but also maintains high activity in the presence of hydrogen. In addition, the beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno indole derivative is grown is stabilized by hydrogen bonding, thereby inhibiting beta-hydrogen elimination, thereby polymerizing ultra high molecular weight olepin-based polymer. In addition, the metallocene compound of the embodiment may introduce various substituents to the fluorene group, thereby controlling the molecular weight and molecular weight distribution of the leupine copolymer prepared according to the type and bulky degree of the introduced substituents. According to an embodiment of the present invention, R in Formula 2 is a substituted or unsubstituted phenyl group, naphthyl group, a C3-C20 cycloalkyl group, or C1-C1 When the alkoxy group of 20 is used, copolymerization ability can be improved and the comonomer insertion ability can be improved, thereby producing an olefinic polymer having a wide molecular weight distribution and a high molecular weight.

As described above, the metallocene compound of the present invention can realize excellent activity and high copolymerizability, and can prepare a polyolefin having a high molecular weight and a wide molecular weight distribution, thereby ultimately controlling the structure and physical properties of the resulting polyolefin. It is possible. .

The metallocene compound of Chemical Formula 2 according to the present invention may be used as a catalyst for polymerization of olefin monomers. ᅳ

The metallocene compound represented by Chemical Formula 2 may be prepared by reacting the ligand compound represented by Chemical Formula 1 with a metal source according to the following reaction formula 2 and metallization thereof.

Scheme 2

In Formula 2, the definitions of R, R, to R ₁₆ , Q, and Q ₂ , L, X ₍ and X ₂ ) are the same as those defined in Chemical Formula 2.

More specific examples are described in the following Examples, and those skilled in the art may prepare the metallocene compound of Formula 2 with reference to the contents described in the Examples. According to another aspect of the present invention, in the presence of a catalyst composition comprising a metallocene compound of Formula 2, it provides a method for producing an olefinic polymer comprising the step of polymerizing the olefinic monomers / The catalyst composition may further include at least one cocatalyst compound selected from the group consisting of a compound of Formula ₃ , a compound of Formula 4, and a compound of Formula 5, in addition to the metallocene compound of Formula 2.

[Formula 3]

-[Al (R ₁₇ ) -0] n- In Formula 3, R ₁₇ 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, η is 2 Is an integer greater than or equal to

[Formula 4]

D ( ₁₈ ) ₃

In Chemical Formula 4,

D is aluminum or boron, R ₁₈ is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

[Formula 5]

[LH] ⁺ [ZE ₄ ] -or [L] ⁺ [ZE ₄ ] ᅳ

In Chemical Formula 5,

L is a neutral or divalent Lewis base, Ή 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, a 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.

Among the promoter compounds, the compound of Formula 3 and the compound of Formula 4 may alternatively be represented by an alkylating agent, and the compound of Formula 5 may be represented by an activator.

The compound represented by Chemical Formula 3 is not particularly limited as long as it is an alkyl aluminoxane, but preferred examples thereof include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and preferably methyl aluminoxane.

The alkyl metal compound represented by Formula 4 is not particularly limited. However, preferred examples include trimethylaluminum, triethylaluminum triisobutylaluminum, tripropylaluminum, tributylaluminum dimethylchloroaluminum, triisopropylaluminum, tri-S-butylaluminium tricyclopentylaluminum, tripentylaluminum and triiso Pentyl aluminum trinuclear aluminum, trioctyl aluminum, ethyl dimethyl aluminum methyl diethyl aluminum, triphenyl aluminum, tri-P-allyl aluminum dimethyl aluminum mesoxide, dimethyl aluminum ethoxy i, trimethyl boron triethyl boron, triisobutyl boron, Tripropyl boron tributyl boron, and the like, and preferably trimethyl aluminum, triethyl aluminum, triisobutyl aluminum and the like can be used.

Examples of the compound represented by Formula 5 include triethylammonium tetra (phenyl) boron, tributyl ammonium tetra (phenyl) boron, trimethyl ammonium tetra (phenyl) boron, tripropyl ammonium tetra (phenyl) boron, trimethyl Ammonium Tetra (P-lryl) boron, Trimethylammonium Tetra (ο, ρ-dimethylphenyl) boron, Tributylammonium Tetra (Ρ-trifluoromethylphenyl) boron, Trimethylammonium Tetra (Ρ-trifluoromethylphenyl )

Tributylammonium tetra (pentafluorophenyl) boron, Ν, Ν-diethylamyldium tetra (phenyl) boron, Ν, Ν-diethylanilidedium tetra (phenyl) boron, _Ν , _Ν _diethylaniyl Liniumtetra (pentafluorophenyl) boron,

Diethylammonium tetra (pentafluorophenyl) boron,

Triphenylphosphonium tetra (phenyl) boron, trimethyl phosphonium tetra (phenyl) boron, triethylammonium tetra (phenyl) aluminum,

Tributylammonium tetra (phenyl) aluminum ，

Trimethylammonium tetra (phenyl) aluminum ，

Tripropyl Ammonium Tetra (phenyl) Aluminum, Trimethyl Ammonium Tetra (Ρ-rylryl) Aluminum, Tripropyl Ammonium Tetra (Ρ-rylryl) Aluminum, Triethyl Ammonium Tetra (ο, ρ-dimethylphenyl) Aluminum, Tributyl Ammonium tetra (Ρ-trifluoromethylphenyl) aluminum, trimethylammonium tetra (Ρ-trifluoromethylphenyl) aluminum,

Tributylammonium tetra (pentafluorophenyl) aluminum, Ν, Ν- Diethylanilinium tetra (phenyl) aluminum, Ν, Ν-diethylanilinium tetra (phenyl) aluminum, Ν, Ν-diethylanilinium tetra (pentafluorophenyl) aluminum,

Diethylammonium tetra (pentafluorophenyl) aluminum,

Triphenylphosphoniumtetra (phenyl) aluminum, -trimethylphosphoniumtetra (phenyl) aluminum,

Triethylammonium tetra (phenyl) aluminum,

Tributyl Ammonium Tetra (phenyl) aluminum, Trimethyl Ammonium Tetra (phenyl) boron, Tripropyl Ammonium Tetra (phenyl) boron, Trimethyl Ammonium Tetra (Ρ-rylryl) boron, Tripropyl Ammonium Tetra (Ρ-ryl) Boron,

Triethylammonium tetra (ο, ρ-dimethylphenyl) boron, trimethylammonium tetra (ο, ρ-dimethylphenyl) boron, tributylammonium tetra (Ρ-trifluoromethylphenyl) boron, trimethylammoniumtetra (Ρ -Trifluoromethylphenyl) boron,

Tributylammonium tetra (pentafluorophenyl) boron, Ν, Ν- diethylanilinium tetra (phenyl) boron, Ν, Ν-daethylanilinium tetra (phenyl) boron, Ν, Ν-diethylaniyl Liniumtetra (pentafluorophenyl) boron,

Diethylammonium tetra (pentafluorophenyl) borone ，

Triphenyl phosphonium tetra (phenyl) boron, triphenyl carbonium tetra (Ρ- tripulomethylphenyl) boron, triphenyl carbonium tetra (pentapolourophenyl) boron, trityl tetra (pentafluorophenyl) Boron, etc., but is not limited thereto.

In addition, the catalyst composition may be used for olefin homopolymerization or copolymerization.

On the other hand, as a method for producing the catalyst composition according to the present invention, for example, the following method can be used.

First contacting the metallocene compound of Formula 2 with the compound of Formula 3 and / or the compound of Formula 4 to obtain a mixture; And adding a compound of Chemical Formula 5 to the mixture.

Second, the metallocene compound of Formula 2 and the above formula A method of preparing the catalyst composition by contacting the compound of 3 may be used. In addition, a method of preparing a catalyst composition by contacting the metallocene compound of Formula 2 and the compound of Formula 5 may be used.

In the first method of preparing the catalyst composition, the molar ratio of the compound of Formula 3 and the compound of Formula 4 to the metallocene compound of Formula 2 may be 1: 2 to 1: 5,000, preferably Preferably 1:10 to 1: 1,000, more preferably 1:20 to 1: 500. In addition, the molar ratio of the metallocene compound of Formula 2 to the compound of Formula 5 may be 1: 1 to 1:25, preferably 1: 1 to 1:10, and more preferably 1: 2 to 1: 5.

When the amount of the compound of Formula 3 and the compound of Formula 4 is less than 2 moles relative to 1 mole of the metallocene compound of Formula 2, the amount of the alkylating agent is very small so that alkylation of the metal compound may not proceed completely. ᅳ Also, when the amount of the compound of Formula 3 and the compound of Formula 4 is more than 5,000 moles relative to 1 mole of the metallocene compound of Formula 2, alkylation of the metal compound is performed, but the remaining alkylating agent There is a problem that the activation of the alkylated metal compound is not fully achieved due to side reactions between the activators of the formula (5). Also, the amount of the compound of the formula (5) to 1 mole of the metallocene compound of the formula (2) may be less than 1 mole. In this case, the amount of the activator is relatively small, resulting in incomplete activation of the metal compound. If the activity of the catalyst composition is inferior, and the amount of the compound of Formula 5 is more than 25 moles with respect to 1 mole of the metallocene compound of Formula 2, the activation of the metal compound is completely performed, There is a problem that the cost of the catalyst composition as an activator is not economical or the purity of the resulting polymer is poor.

In the second method of preparing the catalyst composition, the molar ratio of the metallocene compound of Formula 2 to the compound of Formula 3 may be 1:10 to 1: 10,000, preferably 1: 100 to 1: 5,000, more preferably 1: 500 to 1: 2,000. When the amount of the compound of Formula 3 is less than 10 moles with respect to 1 mole of the metallocene compound of Formula 2, Since the amount of the activator is relatively small, there is a problem in that the activity of the catalyst composition generated due to the incomplete activation of the metal compound is insufficient. If the molar excess exceeds the activation of the metal compound, there is a problem that the cost of the catalyst composition is not economically reduced or the purity of the resulting polymer is reduced due to the excess activator remaining.

In the third method of preparing the catalyst composition, the molar ratio of the metallocene compound of Chemical Formula 2 to the compound of Chemical Formula 5 may be 1: 1 to 1:25, and preferably 1: 1 to 1 : 10, More preferably, it is 1: 2-1: 5.

In the preparation of the catalyst composition, a hydrocarbon solvent such as pentane, nucleic acid, heptane, or an aromatic solvent such as benzene, toluene, or the like may be used as the reaction solvent, but the solvent is not necessarily limited thereto. Can be used.

The process of the olefinic polymer according to the invention can be carried out by contacting the catalyst composition with a monomer. According to the method for producing the olefin polymer of the present invention, an olefin homopolymer or an olefin copolymer can be provided.

The polymerization method of the present invention may be carried out by a solution polymerization process, a slurry process or a gas phase process. ᅳ

In the production method of the polymer according to the present invention, the catalyst composition eulre pin polymerization process having a carbon number of 5-12 aliphatic hydrocarbon solvents suitable for, for example, pentane, hexane, heptane, nonane, decane, and _the, the and isomers thereof Aromatic hydrocarbon solvents such as luene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene may be dissolved or diluted and injected. 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.

Examples of the olefin monomer that can be polymerized using the metallocene compounds and the cocatalyst include ethylene, alpha-olefin, cyclic olefin, and the like. The diene olefin monomer or triene olefin monomer etc. which have two or more bonds can also superpose | polymerize. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-nuxadecene, 1-aitocene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc., These monomers may be mixed and copolymerized two or more kinds. When the olefin polymer is a copolymer of ethylene and other comonomers, the monomer constituting the copolymer is selected from the group consisting of propylene, 1-butene, 1-nuxene, and 4-methyl-1-pentene, and 1-octene It is preferred that it is at least one comonomer selected.

In particular, in the method for producing an ellepin polymer according to the present invention, the catalyst composition is also capable of copolymerization reaction of ethylene and monomers having high steric hindrance, such as 1-nuxene or 1-octene, and various substituents on the basic skeleton of the fluorene derivative. By introducing the E, it is possible to easily control the electronic and three-dimensional environment around the metal and ultimately to control the structure and physical properties of the resulting polyolefin.

According to one embodiment of the present invention, the weight average molecular weight (Mw) of the olefinic polymer may be about 100,000 to 1,000,000 g / mol. The weight average molecular weight of the olepin-based polymer may vary depending on whether the metallocene compound used or the catalyst composition comprising the same is supported and polymerization conditions. For example, the olephine-based polymer prepared using the supported catalyst may be 800,000. It may have a very high weight average molecular weight of at least g / mol, preferably at least 850,000 g / mol.

In addition, the molecular weight distribution (PDI) of the olefin polymer may be about 1 to 20, preferably about 1 to 10.

Hereinafter, the polymerization process of the olefin polymer is exemplified, but this is only for the purpose of illustrating the present invention, and the scope of the present invention is not intended to be limited by the following contents.

The reaction group used in the process for producing the polymer according to the invention is continuous It is preferred that it is a stirred reactor (CSTR) or a continuous flow reactor (PFR). The reactor is preferably arranged in two or more in series or in parallel. In addition, the production method preferably further includes a separator for continuously separating the solvent and the unfung monomer from the reaction mixture.

When the method of preparing the polymer according to the present invention is carried out in a continuous solution polymerization process, it may be composed of a catalytic process, a polymerization process, a solvent separation process, a rare water process step, more specifically as follows.

a) catalytic process

The catalyst composition according to the present invention may be injected by dissolving or diluting an aliphatic or aromatic solvent having 5 to 12 carbon atoms or unsubstituted with a halogen suitable for an olefin polymerization process. For example, aliphatic hydrocarbon solvents such as pentane, nucleic acid, heptane, nonane, decane, and isomers thereof, aromatic hydrocarbon solvents such as toluene, xylene, benzene, and hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, chlorobenzene And the like can be used. The solvent used here is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating with a small amount of alkylaluminum or the like, and can also be carried out using an excessive amount of a promoter.

b) polymerization process

The polymerization process is carried out by introduction of at least one olefin monomer and a catalyst composition comprising the organometallic compound of Formula 2 and a promoter in a reactor. In the case of solution phase and slurry phase polymerization, a solvent is injected onto the reactor. In the case of solution polymerization, a mixture of a solvent, a catalyst composition, and a monomer is present in the reaction vessel.

The molar ratio of monomer to solvent suitable for the reaction should be a ratio suitable for dissolving the raw material before the reaction and the polymer produced after the reaction. _{Specifically:} a 20: a molar ratio of monomer to solvent is 10: 1 to 1: 10,000, preferably from 5: 1 to 1: 100, more preferably _{ι: 1} to 1. When the molar ratio of the solvent is less than 10: 1, the amount of the solvent is too small to increase the viscosity of the fluid, which causes a problem in transferring the produced polymer. When the molar ratio of the solvent exceeds 1: 10,000, Since the amount is more than necessary, the equipment increase according to the recirculation of solvent purification and There are problems such as increased energy costs.

The solvent is preferably introduced into the reactor at a temperature of -40 to 150 ^° C using a heater or a pulsator, whereby the polymerization reaction is started with the monomer and the catalyst composition. If the temperature of the solvent is -4 (less than C, there will be some differences depending on the reaction amount, but in general, the temperature of the solvent is too low, so the reaction temperature is also difficult to drop, and the temperature control is difficult, exceeding 150 ^° C. In this case, the solvent temperature is too high, there is a problem that the heat removal of the reaction semi-heat due to reaction.

A high capacity pump raises the pressure above 50 bar to supply the feeds (solvent, monomer, catalyst composition, etc.), thereby providing a mixture of the feeds without additional pumping between the reaction vessel, pressure drop device and separator. Can be passed.

The internal temperature of the reaction vessel suitable for the present invention, ie the polymerization reaction temperature, is -15 to 300 ^° C, preferably 30 to 200 ^° C, more preferably 70 to 200 ^° C. If the internal temperature is less than -151, there is a problem that the productivity is low because the reaction rate is low, and if it exceeds 300 ^° C, problems such as discoloration, such as generation of impurities and carbonization of the polymer due to side reactions may occur. .

The internal pressure of the reactor suitable in the present invention is 1 to 300 bar, preferably 10 to 200 bar, more preferably about 30 to 100 bar. If the internal pressure is less than lbar, the reaction rate is low to lower productivity _: there is a problem due to evaporation of the solvent used, and if it exceeds 300 bar, there is a problem of an increase in equipment costs such as device cost according to high pressure.

The polymer produced in the reaction vessel is maintained at a concentration of less than 20 wt% in the solvent and is preferably transferred to the first solvent separation process for solvent removal after a short residence time. The residence time in the reaction mixture of the resulting polymer is 1 minute to 10 hours, preferably 3 minutes to 1 hour, more preferably ₅ minutes to 30 minutes. If the residence time is less than 3 minutes, there is a problem such as productivity loss and catalyst loss due to a short residence time, and increase in the manufacturing cost accordingly, if more than 1 hour, depending on the reaction over the appropriate active period of the catalyst, The reaction period increases and equipment costs increase accordingly there is a problem.

C) Solvent Separation Process

The solvent separation process is performed by varying the solution temperature and pressure to remove the solvent present with the polymer exiting the reactor. For example, the polymer solution transferred from the reactor is heated up to about 200 to 230 ^° C through a heater and then the pressure is lowered through a pressure drop device to vaporize the raw materials and solvent in the first separator.

At this time, the pressure in the separator is suitably 1 to 30 bar, preferably 1 to 10 bar, more preferably 3 to 8 bar. The temperature in the separator is suitably 150 to 250 ^° C., preferably 170 to 230 ^° C., more preferably 180 to 230 ^° C.

If the pressure in the separator is less than 1 bar, the content of the polymer is increased, there is a problem in the transfer, if it exceeds 30 bar there is a problem that the separation of the solvent used in the polymerization process is difficult. When the temperature in the separator is less than 150 ^° C., the viscosity of the copolymer and its mixture is increased, and there is a problem in transporting. When the temperature is less than 250 ^° C., there is a problem of discoloration due to carbonization of the polymer due to high temperature.

The solvent vaporized in the separator can be recycled to the reaction counter condensed in the overhead system. The first step of solvent separation yields a polymer solution concentrated up to 65%, which is transferred to the second separator by a transfer pump through a heater, where the separation of residual solvent occurs. In order to prevent the deformation of the polymer due to high temperature while passing through the heater, a heat stabilizer is added and a reaction inhibitor is injected into the heater together with the heat stabilizer to suppress reaction of the polymer due to the residual activity of the activator present in the polymer solution. The residual solvent in the polymer solution injected into the second separator is finally completely removed by a vacuum pump, and the granular polymer can be obtained by passing through the angle and the cutter. The solvent and other unreacted monomers vaporized in the second separation process can be sent to a recovery process for purification and reuse.

d) recovery process The organic solvent added with the raw material to the polymerization process may be recycled to the polymerization process together with the non-banung raw material in the primary solvent separation process. But,

The solvent recovered in the secondary solvent separation process contains a large amount of water that acts as a catalyst poison in the solvent due to contamination by the reaction of an anti-inhibitor to stop the catalytic activity and steam supply from the vacuum pump, and is reused after purification in the recovery process. It is preferable.

The present invention will be explained in more detail based on the following examples. However, these Examples are only for illustrating the present invention, and the scope of the present invention is not limited thereby.

The term "overnight" means approximately 12 to 16 hours and "room temperature" or "phase" refers to a temperature of 20 to 25 ^° C. Synthesis of all metal compounds and preparation of experiments were carried out under dry argon (Ar) atmosphere using dry box technology or using dry glass apparatus. All solvents used are anhydrous grade and dried before use.

Preparation Example 1

(1) Preparation of Ligand Compound:

2.56 g of 2-Benzyl-9H-fluorene (BnFlu) and 10 mm were dissolved in 100 ml of Hexane and 4.17 ml (3.5eq) of MTBE, and 4.6 ml and 11.5 mm of n-BuLi 2.5M hexane solution were added dropwise in a dryice / acetone bath. And, after reacting all night at room temperature, yellow A slurry was obtained. 2.98g, 11mm of Si-tether bridge compound was prepared in the glove box to make Hexane 100ml solution, and BnFlu-Li solution was dropwise fed in a dryice / acetone bath. It was confirmed that the solution turned purple by stirring at room temperature overnight (BnFlu-Si-tether).

2.33 g, 10 mm of indenoindole (Inln) was dissolved in 50 ml of THF, and 4.6 ml of n-BuLi 2.5M hexane solution and 11.5 mmol were added dropwise in a dryice / acetone bath. Then, after reaction overnight at room temperature, a red slurry was obtained. Inln-Li in the prepared BnFlu-Si-tether slurry _. The solution was dropwise fed in a dryice / acetone bath. It was confirmed that the solution turned dark brown by stirring at room temperature overnight. Then, 6.5 g of sticky oil was obtained after water / ether work-up (yield: 94.5%).

1 H NMR (500 MHz, CDC1 ₃ ): -0.35--0.13 (3H, m), 0.23-1.57 (19H, m), 2.35-2.45 (3H, m), 3.21-3.27 (2H, m), 3.92- 4.01 (2H, m), 4.03-4.11 (5H, m), 7.05-7.83 (19H, m)

(2) Preparation of Metallocene Compounds:

4.82 g (7 mmol) of the ligand compound synthesized in the above (1) was dissolved in 100 mL of toluene, and 6.2 mL of 2.5 M n-BuLi hexane solution was added to a solution in which 3.3 mL of MTBE and 4.0 eq. It was added dropwise in the bath, stirred at room temperature overnight to obtain a reddish slurry. 2.64 g, 7 mmol of ZrCl ₄ (THF) ₂ was prepared in a glove box to prepare a 100 mL solution of toluene, and the ligand-Li solution was dropwise fed in a dry ice / acetone bath. Then, it was confirmed that the solution turned purple by stirring at room temperature overnight. Toluene was vacuum dried about 80%, recrystallized with hexane, and the slurry was filtered to obtain 3.62 g of a filtered dark purple metallocene compound (yield: 61%).

1 H NMR (500 MHz, CDC1 ₃ ): 0.80-2.28 (22H, m), 2.43 (3H, d), 3.28 1 3.32 (2H, m), 3.78-3.84 (3H, d), 3.90 (3H, s) 6.62 ° 7.90 (19H, m) Preparation Example 2

(1) Preparation of Ligand Compound:

2- (cyclo exylmethyl) -9H-fluorene (CyhexmeFlu) 1.84 g, 7 mm, dissolved in 100 ml of Hexane, 2.92 ml (3.5 eq) of MTBE, n-BuLi 2.5 M hexane solution 3.2 ml, 8. lmm, dropwise in a dryice / acetone bath It was. Then, after reaction at room temperature overnight, an orange slurry was obtained. Hexane 100ml solution was prepared by comparing Si-tether bridge compound 2.09g and 7.7mn l in the glove box, and CyhexmeFlu-Li solution was dropwise fed in a dryice / acetone bath. In ^phase, it was confirmed that the change to purple, as by stirring overnight (CyhexmeFlu-Si-tether).

1.63 g of Indenoindole (Mn), 7 mm or less, was dissolved in 50 ml of THF, and 3.2 ml of n-BuLi 2.5M hexane solution and 8.1 mmol were added dropwise in a dryice / acetone bath. And, after reacting overnight at room temperature, a burgundy slurry was obtained. Inln-Li solution was dropwise fed to a prepared CyhexmeFlu-Si-etherether slurry in a dryice / acetone bath. It was confirmed that the solution turned dark brown by stirring at room temperature overnight. Then, 4.86 g of sticky oil was obtained after water / ether work-up (yield: 100%).

NMR (500 MHz, CDC1 ₃ ): -0.36--0.23 (3H, m), 0.15-1.70 (29H, m), 1.98-2.06 (1H, m), 2.39-2.42 (3H, m), 2.55- 2.60 (2H, m), 3.19-3.23 (2H, m), 3.96 (1H, d), 4.08-4.09 (3H, m), 4.11-4.13 (1H, m), 7.05-7.83 (14H, m)

(2) Preparation of Metallocene Compounds:

4.76 g (7 mmol) of the ligand compound synthesized in the above (1) was dissolved in 100 mL of toluene, and 6.2 mL of 2.5 M n-BuLi hexane solution was added to a solution injected with 3.3 mL of MTBE and 4.0 eq., Dry ice / acetone. It was added dropwise in the bath, stirred at room temperature overnight to obtain a reddish slurry. Prepare 2.64g, 7mmol of ZrCl ₄ (THF) ₂ in the glove box to make a 100 mL solution of toluene, and add the ligand-Li solution to 4ry Dropwise feeding was performed in an ice / acetone bath. And it was confirmed that the phase turned dark purple by stirring overnight. The toluene was vacuum dried about 80% and then recrystallized with hexane. The slurry was filtered to obtain 2.89 g of a purple metallocene compound (yield: 49.1%).

1 H NMR (500 MHz, CDC1 ₃ ): 0.84-2.20 (32H, m), 2.58 (3H, d), 3.37-3.41 (2H, m), 3.92 (3H, s), 6.63-7.94 (14H, m)

(1) Preparation of Ligand Compound:

2- (2-Fluorobenzyl) -PH-fluorene (2-FBnFlu) 2.74g, 10mm in Hexane 100ml, MTBE 4.17ml (3.5eq) dissolved in n-BuLi 2.5M hexane solution 4.6ml, 11.5mm in dryice / acetone bath Dropped at Then, after reacting all night in Sangeun, a burgundy slurry was obtained. 2.98g, l hnm of Si-tether bridge compound was prepared in the glove box to make Hexane 100ml solution, and 2-FBnFlu-Li solution was dropwise fed in a dryice / acetone bath. It was confirmed that the phase turned purple by stirring overnight at (2-FBnFlu-Si-tether).

2.33 g, 10 mm of indenoindole (Inln) was dissolved in 50 ml of THF, and 4.6 ml of n-BuLi 2.5M hexane solution and 11.5 mmol were added dropwise in a dryice / acetone bath. And then after an overnight reaction at Sangeun, I got a burgundy slurry. Inln-Li solution was dropwise fed to a prepared 2-FBnFlu-Si-etherether slurry in a dryice / acetone bath. It was confirmed that the phase turned purple with stirring overnight. Then, 6.75 g of sticky oil was obtained after water / ether work-up (yield: 95.6%)

NMR (500 MHz, CDC1 ₃ ): -0.39--0.19 (3H, m), 0.16-1.54 (19H, m), 2.35 -2.44 (3H, m), 3.20-3.25 (2H, m), 3.93-4.01 (3H, m), 4.02-4.08 (4H, m), 6.96-7.81 (18H, m)

(2) Preparation of Metallocene Compounds:

6.75 g (9.6 mm0l) of the ligand compound synthesized in (1) above was dissolved in 100 mL of toluene, and 8.4 ml of 2.5 M hexane solution, 2.2 eq. It was added dropwise in an acetone bath and stirred at room temperature overnight to obtain a bluish slurry. 3.61 g of ZrCl ₄ (THF) ₂ was prepared in a glove box to prepare 9.6 mmol of toluene, and a ligand-Li solution was dropwise fed in a dry ice / acetone bath. And, it was confirmed that the solution turned dark red by stirring at room temperature overnight. The toluene was vacuum dried about 80%, recrystallized with hexane, and the slurry was filtered to obtain 5.45 g of a filtered reddish brown metallocene compound (yield: 64.3%).

1 H NMR (500 MHz, CDCl ₃ ): 1.17-1.20 (12H, m), 1.47-2.35 (10H, m), 2.45-2.57 (3H, m), 3.35-3.40 (2H, m), 3.74-4.00 ( 5H, m), 6.82-7.93 (18H, m) Comparative Example 1

(1) Preparation of Ligand Compound:

2,7-Bis (l, 1 -dimethylethyl) -9H-fluorene (tBuFlu) 1.95g, 7mm dissolved in 100ml Hexane, 2.92ml (3.5eq.) MTBE, n-BuLi 2.5M hexane solution 3.2ml, 8.1mm Add dropwise in dryice / acetone bath. And after reaction overnight at room temperature _{: an} ocher slurry was obtained. 2.09g Si-tether bridge compound in glove box, Hexane 100ml solution was prepared by preparing 7.7mn l, and tBuFlu-Li solution was dropwise fed in a dryice / acetone bath. It was confirmed that the phase turned purple by stirring overnight at (tBuFlu-Si-tether).

1.63 g of Indenoindole (Inln) was dissolved in 50 ml of THF, and 3.2 ml of n-BuLi 2.5M hexane solution and 8.1 mmol were added dropwise in a dryice / acetone bath. Then, after reacting overnight at room temperature, a burgundy slurry was obtained. Inln-Li solution was dropwise fed to a prepared tBuFlu-Si-tether slurry in a dryice / acetone bath. The phase was turned purple by stirring overnight. Then, 4.86 g of sticky oil was obtained after water / ether work-up (yield: 100%).

NMR (500 MHz, d6-benzene): -0.30--0.18 (3H, d), 0.40 (2H, m), 0.65-

1.45 (8H, m), 1.12 (9H, d), 1.29-1.31 (18H, d), 2.36-2.40 (3H, d), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17- 4.21 (1H, d), 4.34-4.38 (1H, d), 6.90-7.80 (13H, m)

(2) Preparation of Metallocene Compounds:

4.97 g (7 mmol) of the ligand compound synthesized in (1) was dissolved in 100 mL of toluene, and 6.2 mL of 2.5 M n-BuLi hexane solution was added to a solution injected with 3.3 mL of MTBE and 4.0 eq. Of dry ice / acetone. It was added dropwise in the bath, stirred at room temperature overnight to obtain a reddish slurry. 2.64 g, 7 mmol of ZrCl ₄ (THF) ₂ was prepared in a glove box to prepare a 100 mL solution of toluene, and the ligand-Li solution was dropwise fed in a dry ice / acetone bath. And, it was confirmed that the solution turned dark purple by stirring overnight at room temperature. The toluene was vacuum dried about 80% and then recrystallized with hexane. The slurry was filtered to obtain 5.22 g of a purple metallocene compound (yield: 85.7%).

1 H NMR (500 MHz, CDC1 ₃ ): 0.96-1.22 (18H, d), 1.19 (9H, d), 1.71 (3H, d), 1.50-1.70 (4H, m), 1.79 (2H, m), 1.98 2.19 (4H, m), 2.58 (3H, s), 3.38 (2H, m), 3.91 (3H, d), 6.66-7.88 (13H, m) Preparation Comparative Example 2

(1) Preparation of Ligand Compound:

5.5 ml of 2.5M n-BuLi hexane solution, prepared by dissolving 2 g of fluorene in 5 ml MTBE and 100 ml of hexane, was added dropwise in a dry ice / acetone bath and stirred overnight in silver. Then, 3.6 g of (6- (tert-butoxy) hexyl) dichloro (methyl) silane was dissolved in 50 ml of nucleic acid (hexane), and the fluorene-Li slurry was transferred for 30 minutes under a dry ice / acetone bath, followed by stirring overnight at phase silver. At the same time, 5.5 ml of 2.5M n-BuLi hexane solution prepared by dissolving 5,8-dimethyl-5,10-dihydroindeno [1, 2-b] indole (12 mmol, 2.8 g) in THF 60 ml and dry ice / acetone It was added dropwise in the bath and stirred overnight at room temperature.

After NMR sampling the reaction solution of fluorene and (6- (tert-butoxy) hexyl) dichloro (methyl) silane to confirm reaction completion, 5,8-dimethyl-5,10-dihydroindeno [l, 2-b] indole Li solution was transferred under dry ice / acetone bath. The phase was stirred overnight, and the reaction was followed by extraction with ether / water to remove residual moisture of the organic layer with MgS0 ₄ to obtain a ligand compound (Mw 597.90, 12 mmol), and two isomers were generated in 1H-NMR. Confirmed.

1 H NMR (500 MHz, d6-benzene): -0.30--0.18 (3H, d), 0.40 (2H, m), 0.65-1.45 (8H, m), 1.12 (9H, d), 2.36-2.40 (3H , d), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21 (1H, d), 4.34-4.38 (1H, d), 6.90-7.80 (15H, m)

(2) Preparation of Metallocene Compounds:

7.2 g (12 mmol) of the ligand compound synthesized in (1) was added dropwise to 11.5 mL of 2.5M n-BuLi hexane solution prepared in 50 mL of diethylether in a dry ice / acetone bath, and the mixture was stirred overnight at brown. color sticky oil Got it. This was dissolved in toluene to prepare a slurry. And, in a ZrCl ₄ (THF) ₂ put in a 50 mL toluene was transfer to a ZrCl ₄ (THF) ₂ a prepared toluene slurry, and ZrCl ₄ (THF) ₂ in 50mL of toluene slurry dry ice / acetone bath. And, it was confirmed that the solution turned purple by stirring overnight at room temperature. After reaction, the reaction solution was filtered to remove LiCl, the toluene of the filtrate was removed by vacuum drying, and the nucleic acid was added and sonicated for 1 hour. The slurry was filtered to give 6 g (Mw 758.02, 7.92 mmol, yield 66 mol%) of a dark violet metallocene compound as a filtered solid, resulting in the formation of two isomers. Confirmed by NMR.

1 H NMR (500 MHz, CDC1 ₃ ): 1.19 (9H, d), 1.71 (3H, d), 1.50-1.70 (4H, m),

1.79 (2H, m), 1.98-2.19 (4H, m), 2.58 (3H, s), 3.38 (2H, m), 3.91 (3H, d), 6.66-7.88 (15H, m) Preparation Example 4: Preparation of Supported Catalysts

Silica (SYLOPOL 948, manufactured by Grace Davison) was dehydrated under vacuum at 400 ^° C. for 12 hours to prepare a silica carrier.

100 mL of a toluene solution was added to a glass reaction chamber at room temperature, 10 g of the silica carrier prepared above was added thereto, and the reaction mixture was stirred while stirring at 40 ^° C. After the silica was dispersed well, 60.6 mL of a 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, the temperature was raised to 80 ^° C., and the mixture was stirred at 200 rpm for 16 hours. After lowering the temperature again to 40 ^° C and washed with a sufficient amount of toluene to remove the unreacted aluminum compound. Again 100 mL of toluene was charged and 5 mm of the metallocene compound prepared in Preparation Example 1 was added thereto, followed by stirring for 2 hours. After the reaction was completed, the stirring was stopped, the toluene layer was separated and removed, and then the reduced pressure was removed at 40 ^° C. to remove the remaining toluene to prepare a supported catalyst. Preparation Example 5 Preparation of Supported Catalyst

The supported catalyst was prepared in the same manner as in Preparation Example 4, except that the metallocene compound prepared in Preparation Example 2 (5. 5 mmd) was used. Prepared. Preparation Example 6 Preparation of Supported Catalyst

The supported catalyst was prepared in the same manner as in Preparation Example 4, except that 0.5 mmd of the metallocene compound prepared in Preparation Example 3 was used. Preparation Comparative Example 3: Preparation of Supported Catalyst

The supported catalyst was prepared in the same manner as in Preparation Example 4, except that 0.5 mm of the metallocene compound prepared in Preparation Comparative Example 1 was used. Preparation Comparative Example 4: Preparation of Supported Catalyst

The supported catalyst was prepared in the same manner as in Preparation Example 4, except that 0.5 mm of the metallocene compound prepared in Preparation Comparative Example 2 was used.

<Ethylene-1-Nexene Copolymerization Example>

Example 1: Solution Polymerization

A 100 mL Andrew bottle was prepared, assembled with an impeller part, and replaced with argon in a glove box. 70 mL of toluene containing a small amount of TMA was added into the Andrew bottle, and 10 mL of MAO (10 wt% in toluene) solution was added thereto. The metallocene compound catalyst of Preparation Example 1, 5 mL (5 μπιοΐ of catalyst) of 1 mM catalyst / luene solution dissolved in toluene was injected into an Andrew bottle. The Andrew bottle was immersed in an oil bath heated to 90 ^° C and the top of the bottle was fixed to the mechanical stirrer and stirred for 5 minutes until the reaction solution reached 90 ^° C. 5 mL of comonomer 1-hexen was injected, and the inside of the bottle was purged three times with ethylene gas, and then the ethylene valve was opened and slowly pressurized. The mechanical stirrer is operated for 30 minutes at 500 rpm while maintaining the pressure by continuously supplying ethylene as much as the consumed ethylene. I responded. After the reaction was completed, the temperature was lowered to room temperature, the ethylene valve was closed, the stirring was stopped, and the pressure in the reactor was slowly vented. The reaction was poured into 400 mL of ethanol / HC1 aqueous solution mixture, stirred for about 1 hour, and the polymer obtained by filtration was dried in a vacuum oven at 60 ^° C for 20 hours. The obtained polymer was weighed to calculate the activity of the catalyst from which the 10 mg sample was taken and used for GPC analysis. Example 2: Solution Polymerization

The olefin copolymerization was carried out in the same manner as in Example 1 except that the metallocene compound 5 μηt) 1 of Preparation Example 2 was used. Example 3: Solution Polymerization

Copolymerization of olefins was carried out in the same manner as in Example 1, except that 5 μηιοΐ of the metallocene compound of Preparation Example 3 was used. Example 4 Supported Catalyst Consolidation

30 mg of the supported catalyst prepared in Preparation Example 4 was quantified in a dry box, and each was placed in a 50 mL glass bottle, sealed with a rubber diaphragm, and taken out of the dry box to prepare a catalyst to be injected. The polymerization was carried out in a 2 L metal alloy reactor, which was equipped with a mechanical stirrer and used at high pressure.

1.2 L of nucleic acid containing 1.0 mmol triethylaluminum was introduced into the reactor, the supported catalyst was introduced without reaction into the reactor, and gas ethylene monomer was continuously heated at a pressure of 40 bar at 80 ^° C. The polymerization was carried out for 1 hour while adding. Termination of the polymerization was completed by first stopping stirring and then evacuating and removing ethylene. The polymer obtained therefrom was filtered to remove most of the polymerization solvent and then dried in an 80 ^° C. vacuum oven for 12 hours. Example 5: Supported Catalytic Polymerization Except that the metallocene compound catalyst of Preparation Example 5 was used, ethylene-1-nuxene copolymerization was performed in the same manner as in Example 4, and the obtained polymer was analyzed. Example 6: Supported Catalytic Polymerization

Except that the metallocene compound catalyst of Preparation Example 6 was used, ethylene-1-nuxene copolymerization was performed in the same manner as in Example 4, and the obtained polymer was analyzed. Comparative Example 1: Solution Polymerization

The olefin copolymerization was carried out in the same manner as in Example 1, except that 5 μηι of the metallocene compound of Preparation Comparative Example 1 was used. Comparative Example 2: Solution Polymerization

The olefin copolymerization was carried out in the same manner as in Example 1, except that 5 μηι of the metallocene compound of Preparation Comparative Example 2 was used. Comparative Example 3: Supported Catalyst Polymerization

The olefin copolymerization was carried out in the same manner as in Example 4, except that 5 μπιοΐ of the metallocene compound of Preparation Comparative Example 1 was used. Comparative Example 4: Supported Catalyst Polymerization

The olefin copolymerization was carried out in the same manner as in Example 4, except that 5 μπιοΐ of the metallocene compound of Preparation Comparative Example 2 was used.

Experimental Example

(1) The catalytic activity of Examples 1 to 6 and Comparative Examples 1 to 4 is determined by the ratio of the weight of the polymer produced per mass of catalyst used per unit time (h) and the content of metallocene compound in the catalyst. Calculated as the ratio of the weight of the resulting polymer. (2) And, the weight average molecular weight and molecular weight distribution of the polymers of Examples 1 to 6 and Comparative Examples 1 to 4 were measured by using a solid silver GPC apparatus, and the results are shown in Table 1 below.

(2) The content of 1-nuxene of the ethylene-1-nuxene copolymers prepared in Examples 1 to 6 and Comparative Examples 1 to 4 was measured using 1 H NMR, and the results are shown in Table 1 below.

Table 1

As shown in Table 1, the metallocene compound of the Preparation Example or the catalyst composition comprising the same shows high activity in copolymerization using a comonomer, and can improve the comonomer insertion ability. It is possible to prepare a polyolefin copolymer having a high molecular weight while having a high content of nucleene.

Claims

【Patent Claims】【Claim 1】 A ligand compound represented by the following formula (1):

[ One]

In Formula 1,

Ri to R ₁₆ are the same or different from each other, and are each independently hydrogen, halogen, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, a cycloalkylalkyl group with 4 to 20 carbon atoms, An alkoxy group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, a heteroaryl group with 5 to 20 carbon atoms, an alkylaryl group with 7 to 20 carbon atoms, or an arylalkyl group with 7 to 20 carbon atoms, among the above to R ₁₆ Two or more adjacent ones may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, except for the case where all of the above to R ₁₆ are hydrogen;

L is a direct bond or an alkylene group having 1 to 10 carbon atoms;

R is a substituted or unsubstituted phenyl group, a naphthyl group, a cycloalkyl group with 3 to 20 carbon atoms, or an alkoxy group with 1 to 20 carbon atoms; Ql and Q ₂ are the same or different from each other, and are each independently hydrogen, halogen, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, and a carbon number It is an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

【Claim 2】

The ligand compound according to claim 1, wherein R in Formula 1 is a phenyl group, cyclopentyl group, cyclohexyl group, fluorophenyl group, or pentafluorophenyl group.

【Claim 3】

The ligand compound according to claim 1, wherein R ₂ and R ₅ of Formula 1 are the same as or different from each other, and are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

【Claim 4】

The method of claim 1, wherein the compound represented by Formula 1 is a ligand compound of one of the following structural formulas:

【Claim 5】

Metallocene compound represented by the following Chemical Formula 2: [Formula 2]

In general formula 2,

M is a group 4 transition metal;

Xi and are the same or different from each other, and are each independently halogen, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, a nitro group, an amido group, and an alkylsilyl group with 1 to 20 carbon atoms. group, an alkoxy group having 1 to 20 carbon atoms, or a sulfonate group having 1 to 20 carbon atoms;

Ri to R ₁₆ are the same or different from each other, and are each independently hydrogen, halogen, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, a cycloalkylalkyl group with 4 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, a heteroaryl group with 5 to 20 carbon atoms, an alkylaryl group with 7 to 20 carbon atoms, or an arylalkyl group with 7 to 20 carbon atoms, and each of the above to R ₁₆ Two or more adjacent rings may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, except for the case where all of the above to R ₁₆ are hydrogen;

L is a direct bond or an alkylene group having 1 to 10 carbon atoms;

R is a substituted or unsubstituted phenyl group, naphthyl group, and having 3 to 20 carbon atoms. It is a cycloalkyl group or an alkoxy group having 1 to 20 carbon atoms;

Qi and Q ₂ are the same or different from each other, and are each independently hydrogen, halogen, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, and a carbon number It is an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

【Claim 6】

The metallocene compound of claim 5, wherein R in Formula 2 is a phenyl group, cyclopentyl group, cyclohexyl group, fluorophenyl group, or pentafluorophenyl group.

【Claim 7】

The metallocene compound according to claim 5, wherein R2 and _R5 of Formula 2 are the same as or different from each other, and are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

【Claim 8】

According to item 5, the compound represented by Formula 2 is a metallocene compound of the following structural formulas:

【Claim 9】

A method for producing an olefin-based polymer comprising the step of polymerizing an olefin-based monomer in the presence of a catalyst composition comprising the metallocene compound of claim 5.

【Claim 10】

The method of claim 9, wherein the catalyst composition is an olefin-based polymer comprising at least one cocatalyst compound selected from the group consisting of a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5). Manufacturing method:

[Formula 3]

-[Al(R ₁₇ )-0]n- In Formula 3, R ₁₇ 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 η is 2. Ideal and integer,

[Formula 4] In Formula 4 above,

D is aluminum or boron, 11 ₁₈ is a hydrocarbyl having 1 to 20 carbon atoms or a hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

[Formula 5]

[LH] ⁺ [ZE ₄ ]- or [L] ⁺ [ZE ₄ ] ^"

In Formula 5 above,

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

【Claim 11】

The method of claim 9, wherein the polymerization is performed by a solution polymerization process, a slurry process, or a gas phase process.

【Claim 12】

The method of claim 9, wherein the olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undene. A method for producing at least one olefinic polymer selected from the group consisting of methylene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-itocene.