KR20120087706A - Metallocene compounds and olefin based polymer prepared by using the same - Google Patents

Abstract

PURPOSE: A metallocene compound and an olefin based polymer manufactured by using the same is provided to enhance polymerization properties and to be used for manufacturing of olefin based polymers. CONSTITUTION: A metallocene compound is represented by chemical formula 1. Here, R^1 - R^17 are respectively and independently indicate hydrogen, halogen, C1-20 alkyl group, C2-20 alkenyl, C2-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl or C7-20 arylalkyl, or forms C2-20 cycloalkyl radical, C6-20 aryl, C7-20 alkylaryl group or C7-20 arylalkyl group by mutually being united. One or more of R^1-R^17 are substituent other than hydrogen and halogen. L indicates C1-10 linear or branched alkylene group.

Description

Metallocene compound and olefin polymer manufactured using the same {METALLOCENE COMPOUNDS AND OLEFIN BASED POLYMER PREPARED BY USING THE SAME}

The present invention relates to a novel metallocene compound, and more particularly, to a metallocene compound which is excellent in copolymerizability and can effectively prepare a high molecular weight olefin polymer.

Dow announced [Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (Constrained-Geometry Catalyst, hereinafter abbreviated as CGC) in the early 1990s (US Pat. No. 5,064,802). The advantages of CGC in the copolymerization of -olefins compared to the metallocene catalysts known to the prior art can be summarized into two main categories: (1) high molecular weight polymers with high activity even at high polymerization temperatures. And (2) copolymerization of alpha-olefins with high steric hindrances such as 1-hexene and 1-octene is also very good. In addition, during the polymerization reaction, various characteristics of CGC are gradually known, and efforts to synthesize derivatives thereof and use them as polymerization catalysts have been actively conducted in academia and industry.

A Group 4 transition metal compound having one or two cyclopentadienyl groups as a ligand can be used as a catalyst for olefin polymerization by activating with methylaluminoxane or boron compound. Such catalysts exhibit unique properties that conventional Ziegler-Natta catalysts cannot achieve.

That is, the polymer obtained using such a catalyst has a narrow molecular weight distribution, has a better reactivity with a second monomer such as an alpha olefin or a cyclic olefin, and the second monomer distribution of the polymer is also uniform. 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 the alpha olefin, the degree of copolymerization, molecular weight, and the second monomer when copolymerizing ethylene and other olefins Distribution and the like can be easily adjusted.

On the other hand, since the metallocene catalyst is more expensive than the conventional Ziegler-Natta catalyst, it is economically valuable when the activity is good. If the reactivity with the second monomer is 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 bridged catalysts generally have good reactivity with 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 of an electrophile such as an alkyl halide with indene or fluorene, the second is a silicon bridged catalyst connected by -SiR _2- , and the third is Is a methylene bridged catalyst obtained from the reaction of fulven with indene or fluorene.

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 that show improved polymerization performance.

The present invention is to provide a metallocene compound that can effectively produce a high molecular weight olefin polymer.

The present invention also provides a catalyst composition comprising the same and an olefin polymer prepared using the same.

The present invention provides a metallocene compound represented by the following formula (1).

[Formula 1]

Wherein,

R ¹ to R ¹⁷ are the same as or different from each other; R ¹ to R ¹⁷ are each independently hydrogen, halogen, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, cycloalkyl group of 2 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, alkyl of 7 to 20 carbon atoms. An aryl group or an arylalkyl group having 7 to 20 carbon atoms; Or R ¹ to R ¹⁷ combine with each other to form a cycloalkyl 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; ^At least one of R ¹ to R ¹⁷ is a substituent other than hydrogen and halogen in the substituents,

L is a linear or branched alkylene group having 1 to 10 carbon atoms,

D is -O-, -S-, -N (R ¹⁸ )-or -Si (R ¹⁹ ) (R ²⁰ )-, wherein R ¹⁸ to R ²⁰ 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, or an aryl group having 6 to 20 carbon atoms,

A 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, an arylalkyl group of 7 to 20 carbon atoms, or 1 to 20 carbon atoms An alkoxy group, a C2-C20 alkoxyalkyl group, a C2-C20 heterocycloalkyl group, or a C5-C20 heteroaryl group,

M is a Group 4 transition metal,

X ¹ and X ² are the same as or different from each other, and are 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, and 1 to 20 carbon atoms. Alkylsilyl group, alkoxy group having 1 to 20 carbon atoms, or a sulfonate group having 1 to 20 carbon atoms.

The present invention also provides a catalyst composition comprising the metallocene compound.

The present invention also provides an olefinic polymer prepared in the presence of the catalyst composition.

Hereinafter, a metallocene compound according to a specific embodiment of the present invention, a catalyst composition comprising the same, and an olefin polymer prepared using the same will be described in detail. However, this is presented as an example of the invention, whereby the scope of the invention is not limited, it is apparent to those skilled in the art that various modifications to the embodiments are possible within the scope of the invention.

Unless specifically stated throughout this specification, "comprising" or "containing" means including any component (or component) without particular limitation, and excludes the addition of other components (or components). Cannot be interpreted as.

According to one embodiment of the invention, the metallocene compound of the present invention is characterized by represented by the following formula (1).

[Formula 1]

Wherein,

R ¹ to R ¹⁷ are the same as or different from each other; R ¹ to R ¹⁷ are each independently hydrogen, halogen, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, cycloalkyl group of 2 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, alkyl of 7 to 20 carbon atoms. An aryl group or an arylalkyl group having 7 to 20 carbon atoms; Or R ¹ to R ¹⁷ combine with each other to form a cycloalkyl 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; ^At least one of R ¹ to R ¹⁷ is a substituent other than hydrogen and halogen in the substituents,

L is a linear or branched alkylene group having 1 to 10 carbon atoms,

D is -O-, -S-, -N (R ¹⁸ )-or -Si (R ¹⁹ ) (R ²⁰ )-, wherein R ¹⁸ to R ²⁰ 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, or an aryl group having 6 to 20 carbon atoms,

A 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, an arylalkyl group of 7 to 20 carbon atoms, or 1 to 20 carbon atoms An alkoxy group, a C2-C20 alkoxyalkyl group, a C2-C20 heterocycloalkyl group, or a C5-C20 heteroaryl group,

M is a Group 4 transition metal,

X ¹ and X ² are the same as or different from each other, and are 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, and 1 to 20 carbon atoms. Alkylsilyl group, alkoxy group having 1 to 20 carbon atoms, or a sulfonate group having 1 to 20 carbon atoms.

In the metallocene compound according to the present invention, the substituents of Chemical Formula 1 will be described in more detail below.

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, hexyl group, hep And the like, but are not limited thereto.

The alkenyl group having 1 to 20 carbon atoms includes a linear or branched alkenyl group, and specifically includes an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like, but is not limited thereto. .

The aryl group having 6 to 20 carbon atoms includes an aryl group having a monocyclic or condensed ring, 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 a methoxy group, an ethoxy group, a phenyloxy group, a cyclohexyloxy group, and the like, but are not limited thereto.

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

In the metallocene compound according to the present invention, R ¹ to R ¹⁷ in Formula 1 are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group (n-Bu), tert-butyl It may be a group (t-Bu), a pentyl group, a hexyl group, a heptyl group, an octyl group, or a phenyl group. Among them, isopropyl group, tert-butyl group (t-Bu), phenyl group and the like may be preferable in terms of solubility and copolymerization characteristics, but is not limited thereto.

In addition, R ¹ to R ¹⁷ in Chemical Formula 1 may be each one of two or more to form a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a phenyl group, or the like instead of forming an individual substituent. Among them, a cyclohexyl group, a phenyl group, etc. may be preferable in view of improving solubility and copolymerization characteristics, but are not limited thereto.

In particular, in the substituent of Formula 1, one or more, preferably two or more of R ¹ to R ¹⁷ may be a substituent other than hydrogen and halogen in the substituent. Accordingly, at least one of R ¹ to R ¹⁷ is each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms. 20 may be an alkylaryl group or an arylalkyl group having 7 to 20 carbon atoms, and two or more of the substituents R ¹ to R ¹⁷ may be bonded to each other to form a cycloalkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon atoms. An alkylaryl group of 7 to 20 or an arylalkyl group of 7 to 20 carbon atoms may be formed. In this case, substituents other than hydrogen or halogen may be substituted at positions 2, 3, 6, 7, etc. of the fluorene ligand in Chemical Formula 1.

As described above, the metallocene compound of the present invention can significantly improve the solubility in toluene, which is a solvent when applied as a catalyst, by introducing one or more specific substituents other than hydrogen or halogen into the fluorene ligand. Thereby, the fall of activity or the nonuniformity of a polymerization reaction, etc. which may arise by agglomeration without dissolving a catalyst at the time of a polymerization reaction can be prevented. In addition, by introducing such specific substituents, it is possible to optimize the angle and structural shielding properties of the bridges in the metallocene compound structure and to promote the incorporation of alpha olefins in the copolymerization of ethylene / alpha olefins and the like. By optimizing, it is possible to effectively produce a high molecular weight olefin polymer having excellent processability and the like.

In the metallocene compound according to the present invention, L in Chemical Formula 1 is more preferably a linear or branched alkylene group having 4 to 8 carbon atoms, but is not limited thereto. In addition, the alkylene group may be unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Among these, an alkyl group having 4 to 10 carbon atoms may be preferable in view of improving synthesis efficiency and improving polymerization characteristics.

In the metallocene compound according to the present invention, A in Formula 1 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert-butoxymethyl group, The 1-ethoxyethyl group, 1-methyl-1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group is more preferable, but is not limited thereto.

Specific examples of the metallocene compound represented by Chemical Formula 1 may include a compound represented by the following Chemical Formula 2 or Chemical Formula 3, but are not limited thereto.

[Formula 2]

(3)

The method for producing a metallocene compound according to the present invention is described in detail in the following examples.

On the other hand, according to another embodiment of the invention, there is provided a catalyst composition comprising a metallocene compound as described above.

The catalyst composition according to the present invention may further include at least one separate promoter in addition to the metallocene compound. The promoter may be an aluminum compound represented by Formula 4 below.

[Formula 4]

-[Al (R ²¹ ) -O] _n-

In Chemical Formula 4,

R ²¹ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

n is an integer of 2 or more.

Examples of the compound represented by the formula (4) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like, and more preferred compound is methyl aluminoxane.

In addition, the promoter may be a compound represented by the following Chemical Formula 5.

[Chemical Formula 5]

D ¹ (R ²² ) ₃

In Formula 5,

R ²² may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

D ¹ is aluminum or boron.

Examples of the compound represented by Formula 5 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

In addition, the promoter may be a compound represented by the following formula (6) or (7).

[Formula 6]

[L ¹ ] ⁺ [Z ¹ A ¹ ₄ ] ^-

In Formula 6,

L ¹ is a neutral or cationic Lewis acid;

Z ¹ is a Group 13 element;

A ¹ is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, wherein the at least one hydrogen atom is unsubstituted or substituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy;

[Formula 7]

[L ² -H] ⁺ [Z ² A ² ₄ ] ^-

In Chemical Formula 7,

L ² is a neutral or cationic Lewis acid;

H is a hydrogen atom;

Z ² is a Group 13 element;

A ² is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, wherein the at least one hydrogen atom is unsubstituted or substituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy.

Examples of the compound represented by the formula (6) or (7) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p -Tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributyl Ammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, tri Phenylphosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetrape Aluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributyl Ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum , N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra (p- Tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (P- methylphenyl to triple) turned boron, triphenyl car and the like with phenylboronic Titanium tetra-penta flow.

The catalyst composition according to the present invention comprises the steps of 1) contacting a metallocene compound represented by Formula 1 with a compound represented by Formula 4 or Formula 5 to obtain a mixture; And 2) adding the compound represented by Chemical Formula 6 or Chemical Formula 7 to the mixture.

In addition, the catalyst composition according to the present invention may be prepared by contacting the metallocene compound represented by Chemical Formula 1 with the compound represented by Chemical Formula 4 as a second method.

In the first method of preparing the catalyst composition, the molar ratio of the metallocene compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 4 or Chemical Formula 5 is preferably 1 / 5,000 to 1/2, More preferably, it is 1 / 1,000-1/10, Most preferably, it is 1/500-1/20. When the molar ratio of the metallocene compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 4 or Chemical Formula 5 is more than 1/2, the amount of alkylating agent is so small that the alkylation of the metal compound does not proceed completely. In the case where the molar ratio is less than 1 / 5,000, alkylation of the metal compound is performed, but the activation of the alkylated metal compound is not completely performed due to a side reaction between the remaining excess alkylating agent and the activator of Formula 6 or Formula 7. There is. In addition, the molar ratio of the metallocene compound represented by Formula 1 to the compound represented by Formula 6 or Formula 7 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably Is 1/5 to 1. When the molar ratio of the metallocene compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 6 or Chemical Formula 7 is greater than 1, the amount of the activator is relatively small, resulting in incomplete activation of the metal compound. If there is a problem that the activity of the catalyst composition is inferior, and the molar ratio is less than 1/25, the metal compound is fully activated, but the excess amount of the activator does not allow the cost of the catalyst composition to be economical or to reduce the purity of the resulting polymer. there is a problem.

In the second method of the method for preparing the catalyst composition, the molar ratio of the metallocene compound represented by Chemical Formula 1 / Compound 4 is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000-1/100, most preferably 1 / 3,000-1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not fully performed, resulting in a decrease in the activity of the resulting catalyst composition. Although the activation is complete, there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the excess activator remaining.

In preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used. The metallocene compound and the cocatalyst compound can also be used in the form of silica or alumina.

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

In the method for producing an olefin polymer according to the present invention, specific examples of the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1 -Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aitocene, and the like, and these may be mixed and copolymerized.

The olefin polymer is more preferably an ethylene / alpha olefin copolymer, but is not limited thereto.

In the case where the olefin polymer is an ethylene / alpha olefin copolymer, the content of the alpha olefin which is the comonomer is not particularly limited and may be appropriately selected according to the use, purpose, and the like of the olefin polymer. More specifically, it may be more than 0 and 99 mol% or less.

The ethylene / alphaolefin copolymer may be a multiblock copolymer containing two or more segments or blocks having different chemical or physical properties.

In order to prepare the multi-block copolymer, a method of using two different transition metal catalysts and a chain shuttling agent is conventionally known. However, this is complicated in the process of preparing a multi-block copolymer, because two different transition metal catalysts and chain compound of a specific compound must be used, and the molecular weight distribution (Mw / Mn) of the multi-block copolymer produced is weak. Since it was very narrow as 2.0, there was a problem inferior in workability.

However, the present invention uses a single metallocene compound as a polymerization catalyst without using the chain reciprocating agent, and thus has a feature that a block olefin polymer can be easily produced. In addition, the olefin polymer to be prepared may have a wide molecular weight distribution (M _w / M _n ), and thus has excellent characteristics in workability.

Meanwhile, according to another embodiment of the present invention, an olefin polymer prepared in the presence of the catalyst composition as described above is provided.

In addition, the olefin block copolymer of the present invention may be prepared by the above-described method. The olefinic block copolymer may be an olefinic block copolymer having a melting point (T _m ) of 95 ° C. or higher, preferably 100 ° C. or higher, in particular, an ethylene / alpha olefin block copolymer.

In the present invention, the molecular weight distribution (Mw / Mn) of the olefin polymer is preferably 2 or more, more preferably 2.5 or more, but is not limited thereto.

In the present invention, the weight average molecular weight (Mw) of the olefin polymer may be 135,000 to 3,000,000, more preferably 140,000 to 2,500,000 or 150,000 to 2,500,000, but is not limited thereto.

The density of the olefin polymer is preferably 0.85 g / cm ³ to 0.92 g / cm ³ , and more preferably 0.85 g / cm ³ to 0.90 g / cm ³ .

The olefinic polymer according to the present invention has a single or multiple crystalline melting point relative to the density of the polymer when the melting point (T _m ) is measured by DSC. The melting point (T _m ) of the olefin polymer may be 95 ° C. or more, regardless of the density of the polymer, preferably 100 ° C. or more, and more preferably 105 ° C. to 135 ° C., but is not limited thereto.

In general, in the case of the ethylene / alpha olefin copolymer, the higher the comonomer content in the copolymer, the lower the density of the copolymer and the lower the melting point. However, the olefin copolymer according to the present invention may exhibit a melting point of 95 ° C. or higher, preferably 100 ° C. or higher even when the content of the comonomer is increased, and thus has excellent mechanical strength as well as heat resistance.

Therefore, the olefin polymer according to the present invention is excellent in heat resistance, mechanical strength, processability, and the like, and can be variously applied according to the use thereof of the olefin polymer.

In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

The metallocene compound and the catalyst composition including the same according to the present invention can be used in the preparation of the olefin polymer, have excellent copolymerizability, and can prepare a high molecular weight olefin polymer.

In particular, when the metallocene compound according to the present invention is used, a block copolymer having excellent heat resistance can be prepared, and an olefin polymer having a high melting point (Tm) can be prepared even when the content of the comonomer is increased during the preparation of the olefin polymer. It can manufacture.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Example  One

One) Ligand  Preparation of compounds

1.0 mole of a Grignard reagent tert-Bu-O- (CH ₂ ) ₆ MgCl solution was obtained from the reaction between the tert-Bu-O- (CH ₂ ) ₆ Cl compound and Mg (0) in THF solvent. The Grignard compound prepared above was added to a flask containing MeSiCl ₃ compound (176.1 mL, 1.5 mol) and THF (2.0 mL) at −30 ° C., and stirred at room temperature for 8 hours or more, and the filtered solution was vacuumed. Drying afforded a compound of tert-Bu-O- (CH ₂ ) ₆ SiMeCl ₂ (yield 92%).

Under argon atmosphere, 5.48 g (20 mmol) of 2,7-di (tert-butyl) fluorene was dissolved in 100 mL of THF (Tetrahyrafuran) in a reactor, followed by 9 mL of n-BuLi (2.5 M in Hexane, 22.5 mmol). Was slowly added dropwise at room temperature and then stirred overnight at room temperature to obtain a lithium salt solution of 2,7-di (tert-butyl) fluorene. After dissolving the lithium salt solution in 100 mL of hexane, the temperature was lowered to -78 ° C, 5.47 g (25 mmol) of tert-Bu-O- (CH ₂ ) ₆ SiMeCl ₂ was added dropwise, followed by stirring at room temperature overnight. After the reaction, the solvent was removed through a vacuum filter to obtain a (tert-Bu-O- (CH ₂ ) ₆ ) MeSiCl (2,7-di (tert-Bu) -C ₁₃ H ₇ ) compound in a brown liquid phase. .

Further, under an argon atmosphere, fluorene (fluorene) 1.27 g (7.6 mmol ) of diethyl ether (Et ₂ O, diethylether) of n-BuLi (2.5M in Hexane, 8 mmol) in 3.2 mL dissolved in 30 mL at room temperature After dropwise addition, the mixture was stirred at room temperature overnight to obtain a lithium salt solution of fluorene.

3.92 g (7.6 mmol) of (tert-Bu-O- (CH ₂ ) ₆ ) MeSiCl (2.7-t-butyl-C ₁₃ H ₇ ) prepared as described above was dissolved in 40 mL of THF / TMEDA = 10/1. After dissolving in a mixed solvent, the fluorene lithium salt solution (7.6 mmol) was slowly added dropwise to this solution. After the reaction solution was stirred at 40 ° C. overnight, the reaction was stopped by addition of a saturated aqueous solution of ammonium chloride and the resulting ligand compound was extracted using ethyl acetate solvent. The extracted solution was dried using MgSO ₄ , filtered and the solvent was removed under reduced pressure and recrystallized from hexane to give a white solid (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (C ₁₃ H ₉ ) (2 , 7-di (tert-Bu) -C ₁₃ H ₇ ) was obtained (2.41 g, yield 49%). The structure of the resulting ligand compound was confirmed by 1 H-NMR:

1 H NMR (400 MHz, C ₆ D ₆ ): -0.20 (SiMe, s, 3H), 0.65 (CH ₂ , m, 2H), 0.86 (CH ₂ , t, 2H), 0.98 (CH ₂ , m, 2H ), 1.11 (tert-BuO, s, 9H), 1.20 (CH ₂ , m, 2H), 1.33 (Flu-t-Bu, s, 9H), 1.35 (Flu-t-Bu, s, 9H), 1.37 (CH ₂ , m, 2H), 3.17 (OCH ₂ , t, 2H), 3.91 (Flu-9H, s, 1H), 3.97 (Flu-9H, s, 1H), 7.20 (Flu-H, m, 4H ), 7.37 (Flu-H, m, 4H), 7.54 (Flu-H, d, 2H), 7.71 (Flu-H, d, 2H), 7.75 (Flu-H, d, 2H).

2) Metallocene  Preparation of compounds

Under argon atmosphere, the ligand compound (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (C ₁₃ H ₉ ) (2,7-di (tert-Bu)-in 10 mL of MTBE (methyl tert-butyl ether)- C ₁₃ H ₇ ) 2.41 g (3.7 mmol) was dissolved to prepare a solution of the ligand compound, and then 1.8 mL of n-BuLi (2.5 M in Hexane, 4.5 mmol) was slowly added dropwise to the ligand compound solution at room temperature. . After all of n-BuLi was added dropwise, the mixture was stirred at room temperature overnight to obtain dilithium salts of the ligand compounds.

In addition, 1.54 g (4.1 mmol) of ZrCl ₄ (THF) ₂ was dispersed in 10 mL of hexane, and the temperature was lowered to −20 ° C., followed by the slow addition of dilithium salts solution prepared as described above overnight at room temperature. The reaction was stirred. After the reaction, the resulting complex was filtered using a glass filter and washed several times with hexane to remove impurities. The obtained complex compound was dissolved in toluene at 50 ° C., and then the insoluble byproduct LiCl salt and the like were removed with a filter, and the solvent was removed under reduced pressure (tert-Bu-O- (CH ₂ ) ₆ ) represented by the following Chemical Formula 2 in a purple solid form. MeSi (C ₁₃ H ₈ ) (2,7-di (tert-Bu) -C ₁₃ H ₆ ) ZrCl ₂ compound was obtained (2.7 g, yield 92%). The structure of the resulting metallocene compound was confirmed to be represented by the following Chemical Formula 2 through 1H-NMR:

[Formula 2]

Example  2

One) Ligand  Preparation of compounds

1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octane instead of 2,7-di (tert-butyl) fluorene Except for using 6.96 g (10 mmol) of hydro-1H-dibenzo [b, h] fluorene, (tert-Bu-O- (CH ₂ )) ₆ ) MeSi (C ₁₃ H ₉ ) (C ₂₉ H ₃₇ ) ligand compound was obtained (5.3 g, yield 62%). The structure of the resulting ligand compound was confirmed to be represented by the following Chemical Formula 8 through 1H-NMR.

[Formula 8]

2) Metallocene  Preparation of compounds

Example 1, except that (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (C ₁₃ H ₉ ) (C ₂₉ H ₃₇ ) ligand compound represented by Chemical Formula 8 prepared as described above was used. (Tert-Bu-O- (CH ₂ ) ₆ ) MeSi (C ₁₃ H ₈ ) (C ₂₉ H ₃₆ ) ZrCl ₂ metallocene compound represented by the following Chemical Formula 3 in the form of a purple solid was obtained: g, yield 89%). The structure of the resulting metallocene compound was confirmed to be represented by the following Chemical Formula 3 through 1H-NMR.

(3)

Comparative example  One

One) Ligand  Preparation of compounds

1.0 mole of a Grignard reagent tert-Bu-O- (CH ₂ ) ₆ MgCl solution was obtained from the reaction between the tert-Bu-O- (CH ₂ ) ₆ Cl compound and Mg (0) in THF solvent. The Grignard compound prepared above was added to a flask containing MeSiCl ₃ compound (176.1 mL, 1.5 mol) and THF (2.0 mL) at −30 ° C., and stirred at room temperature for 8 hours or more, and the filtered solution was vacuumed. Drying afforded a compound of tert-Bu-O- (CH ₂ ) ₆ SiMeCl ₂ (yield 92%).

Fluorene (3.33 g, 20 mmol), hexane (100 mL) and MTBE (methyl tert-butyl ether, 1.2 mL, 10 mmol) were added to the reactor at -20 ° C. 8 mL of n-BuLi (2.5M in Hexane) was added. ) Was added slowly and stirred at room temperature for 6 hours. After stirring was terminated, the reactor temperature was cooled to -30 ° C and in tert-Bu-O- (CH ₂ ) ₆ SiMeCl ₂ (2.7 g, 10 mmol) solution dissolved in hexane (100 mL) at -30 ° C. The prepared fluorenyl lithium solution was slowly added over 1 hour. After stirring for 8 hours or longer at room temperature, water was added, followed by extraction and evaporation to obtain (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₉ ) ₂ compound (5.3 g , Yield 100%). The structure of the ligand was confirmed by 1 H-NMR.

1 H NMR (500 MHz, CDCl ₃ ): -0.35 (MeSi, 3H, s), 0.26 (Si-CH ₂ , 2H, m), 0.58 (CH ₂ , 2H, m), 0.95 (CH ₂ , 4H, m) , 1.17 (tert-BuO, 9H, s), 1.29 (CH ₂ , 2H, m), 3.21 (tert-BuO-CH ₂ , 2H, t), 4.10 (Flu-9H, 2H, s), 7.25 (Flu) -H, 4H, m), 7.35 (Flu-H, 4H, m), 7.40 (Flu-H, 4H, m), 7.85 (Flu-H, 4H, d).

2) Preparation of Metallocene Compounds

4.8 mL of n-BuLi (2.5M) in (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₉ ) ₂ (3.18 g, 6 mmol) / MTBE (20 mL) solution at -20 ° C. in Hexane) was added slowly and reacted for at least 8 hours while raising the temperature to room temperature, and then the dilithium salts slurry solution prepared above at -20 ° C was ZrCl ₄ (THF) ₂ (2.26 g, 6 mmol) / hexane ( 20 mL) was slowly added to the slurry solution, and further reacted at room temperature for 8 hours. The precipitate was filtered and washed several times with hexane to give (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₈ ) ₂ ZrCl ₂ compound as a red solid (4.3 g, yield 94.5%). ).

1 H NMR (500 MHz, C6D6): 1.15 (tert-BuO, 9H, s), 1.26 (MeSi, 3H, s), 1.58 (Si-CH2, 2H, m), 1.66 (CH2, 4H, m), 1.91 (CH2, 4H, m), 3.32 (tert-BuO-CH2, 2H, t), 6.86 (Flu-H, 2H, t), 6.90 (Flu-H, 2H, t), 7.15 (Flu-H, 4H , m), 7.60 (Flu-H, 4H, dd), 7.64 (Flu-H, 2H, d), 7.77 (Flu-H, 2H, d)

Manufacturing example  One

The metallocene compound prepared according to Example 1 (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (C ₁₃ H ₈ ) (2,7-di ( An olefinic polymer was prepared using tert-Bu) -C ₁₃ H ₆ ) ZrCl ₂ .

First, 235 mL of toluene was added to a 500 mL glass reactor, 5 mL of 1-hexene was added, and 10 mL of 10 wt% toluene solution of MAO was added thereto, followed by Example 1 1 mM toluene of metallocene compound (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (C ₁₃ H ₈ ) (2,7-di (tert-Bu) -C ₁₃ H ₆ ) ZrCl ₂ prepared in After adding 5 mL (5 μmol) of solution, 50 psig of ethylene was added to the reactor to initiate polymerization. Stir for 0.5 h, vent, and pour the reaction into ethanol / hydrochloric acid solution. After stirring and filtering the resulting polymer, it was washed with ethanol and the solvent was evaporated to obtain an olefinic polymer.

Catalytic amount Reaction temperature Reaction time [Al] / [M] MAO Ethylene 5 μmol 90 ℃ 30 min 3000 10 mL 50 psig

Manufacturing example  2

Except that the compound (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (C ₁₃ H ₈ ) (C ₂₉ H ₃₆ ) ZrCl ₂ prepared in Example 2 was added as the metallocene compound. An olefin polymer was prepared in the same manner as in Example 1.

compare Manufacturing example  One

As a metallocene compound, except that the compound (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₈ ) ₂ ZrCl ₂ prepared in Comparative Example 1 was added thereto, In the same manner, an olefinic polymer was prepared.

compare Manufacturing example  2

An olefin polymer was prepared in the same manner as in Preparation Example 1, except that an existing metallocene catalyst represented by Chemical Formula 9 was used as the metallocene compound.

[Chemical Formula 9]

Physical property evaluation results for the olefin polymers prepared according to Production Examples 1 and 2 and Comparative Production Examples 1 and 2 are as shown in Table 1 below.

division 1-Hx
(mL) Polymer yield
(g) Activity
(Ton / mol.hr) Comonomer
(mol%) Tm
(℃) Mw PDI Preparation Example 1 5 8.3 3.3 6.5 96 183,071 3.6 Production Example 2 5 7.1 2.8 4.1 101 288,355 2.3 Comparative Preparation Example 1 5 4 1.6 6.6 121 119,184 2.9 Comparative Production Example 2 5 7.3 2.92 9.9 99 107,700 3.56

As shown in Table 2, the olefin polymer of Preparation Examples 1-2 using the metallocene compound of Examples 1-2 according to the present invention as a catalyst was higher than that of Comparative Preparation Examples 1-2 using the conventional catalyst. It confirmed that it shows molecular weight. Particularly, according to Preparation Examples 1 to 2, the weight average molecular weight (Mw) is 183,071 to 288,355, and at the same time, the molecular weight distribution index (PDI) is 2.3 to 3.6, and the melting point (Tm) is 96 to 101 ° C. It can be seen that the polymer can be prepared.

On the other hand, as shown in the experimental results for Comparative Preparation Examples 1 and 2, when a specific substituent is not introduced to the fluorene ligand, it can be seen that the characteristics of the high molecular weight as in the present invention cannot be secured. In particular, in Comparative Preparation Example 1 using the catalyst of Comparative Example 1 containing a fluorene ligand without introducing a substituent and Comparative Preparation Example 2 using the existing metallocene catalyst, the molecular weight of the resulting olefin-based polymer was 119,184, respectively. And 107,700.

Claims (11)

A metallocene compound represented by Formula 1 below:
[Formula 1]

Wherein,
R ¹ to R ¹⁷ are the same as or different from each other; R ¹ to R ¹⁷ are each independently hydrogen, halogen, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, cycloalkyl group of 2 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, alkyl of 7 to 20 carbon atoms. An aryl group or an arylalkyl group having 7 to 20 carbon atoms; Or R ¹ to R ¹⁷ combine with each other to form a cycloalkyl 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; ^At least one of R ¹ to R ¹⁷ is a substituent other than hydrogen and halogen in the substituents,
L is a linear or branched alkylene group having 1 to 10 carbon atoms,
D is -O-, -S-, -N (R ¹⁸ )-or -Si (R ¹⁹ ) (R ²⁰ )-, wherein R ¹⁸ to R ²⁰ 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, or an aryl group having 6 to 20 carbon atoms,
A 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, an arylalkyl group of 7 to 20 carbon atoms, or 1 to 20 carbon atoms An alkoxy group, a C2-C20 alkoxyalkyl group, a C2-C20 heterocycloalkyl group, or a C5-C20 heteroaryl group,
M is a Group 4 transition metal,
X ¹ and X ² are the same as or different from each other, and are 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, and 1 to 20 carbon atoms. Alkylsilyl group, alkoxy group having 1 to 20 carbon atoms, or a sulfonate group having 1 to 20 carbon atoms. The method of claim 1,
R ¹ to R ¹⁷ are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, or phenyl; Sen compound. The method of claim 1,
The R ¹ to R ¹⁷ are bonded to each other to form a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a phenyl group. The method of claim 1,
Wherein L is a metallocene compound of 4 to 8 carbon atoms linear or branched alkylene group. The method of claim 1,
A is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert-butoxymethyl group, 1-ethoxyethyl group, 1-methyl-1-methoxy Metallocene compound which is an ethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group. The method of claim 1,
Metallocene compound represented by the following formula (2).
(2)

The method of claim 1,
Metallocene compound represented by the following formula (3).
(3)

A catalyst composition comprising the metallocene compound according to any one of claims 1 to 7. The method of claim 8,
A catalyst composition further comprising at least one of the promoter compounds represented by the following formula (4), (5), (6), or (7):
[Chemical Formula 4]
-[Al (R ²¹ ) -O] _n-
[Chemical Formula 5]
D ¹ (R ²² ) ₃
[Chemical Formula 6]
[L ¹ ] ⁺ [Z ¹ A ¹ ₄ ] ^-
(7)
[L ² -H] ⁺ [Z ² A ² ₄ ] ^-
Wherein,
R ²¹ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
n is an integer of 2 or more;
R ²² may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
D ¹ is aluminum or boron;
L ¹ and L ² are each independently neutral or cationic Lewis acid;
Z ¹ and Z ² are each independently a Group 13 element;
A ¹ and A ² are each independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, wherein the aryl group or alkyl group has one or more hydrogen atoms substituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy Or unsubstituted;
H is a hydrogen atom. An olefinic polymer prepared in the presence of a catalyst composition according to claim 8. The method of claim 10,
The polymer is an ethylene / alpha olefin polymer having a density of 0.85 to 0.92 g / cm ³ and a melting point (T _m ) of 95 ° C. or more.