KR101648553B1 - Catalyst composition and method for preparing olefin-based polymer thereby - Google Patents

Abstract

The present invention relates to an improved catalyst composition exhibiting high activity as a polymerization catalyst in the polymerization of olefins and a process for preparing olefinic polymers using the same.
The use of the catalyst composition according to the invention not only makes it possible to produce polymers of high molecular weight and low density of olefinic polymers, for example propylene polymers or propylene-alpha olefin copolymers, Can be obtained.

Description

TECHNICAL FIELD [0001] The present invention relates to a catalyst composition, and more particularly, to a catalyst composition and a process for producing olefin polymer using the catalyst composition. [0002] CATALYST COMPOSITION AND METHOD FOR PREPARING OLEFIN- BASED POLYMER THEREBY [

The present invention relates to a catalyst composition and a process for producing an olefin polymer using the same. More particularly, the present invention relates to an improved transition metal catalyst composition exhibiting high activity as a polymerization catalyst in the polymerization of olefins, and a process for producing an olefin polymer using the same.

Dow has produced a class of catalysts known as constrained geometry catalysts. European Patent Application No. 416,815 discloses a catalyst composition comprising a CGC catalyst in the presence of an active cosolvent such as alkylaluminoxane, aluminum alkyl, aluminum halide, aluminum alkyl halide.

In addition, European Patent Application No. 418,044 (corresponding to U.S. Patent No. 5,064,802) discloses certain cationic constrained geometric metal catalysts formed by reacting a metal catalyst with a salt of a Bronsted acid containing a compatible non-coordinating anion . This document discloses that such catalyst compositions are commonly used in olefin polymerization. In addition, European Patent Application No. 520,732 (corresponding to U.S. Patent No. 5,721,185) discloses another technique for preparing a cationic constrained geometry catalyst by anion removal using a Lewis acid, a borane compound.

In U.S. Patent Application No. 5,399,635, a cationic catalyst was prepared by contacting a transition metal catalyst with a carbonium salt of a compatible non-coordinating anion and used for olefin polymerization. In addition, U.S. Patent Application (No. 5,453,410) provides a cationic catalyst composition having improved resistance to catalyst toxicity using aluminoxane with a cationic constraining geometric complex prepared by contacting a Lewis acid with a transition metal catalyst, Can be improved. In particular, this patent shows in the examples that trialkyl aluminum can not substantially replace aluminoxane.

Despite the above-described catalyst development, there is a need in the art to develop an olefin polymerization method using such a catalyst, as well as an improved method which enables more effective production of the catalyst.

It is an object of the present invention to provide a novel transition metal catalyst composition for use in olefin polymerization and a process for producing the catalyst composition.

It is also an object of the present invention to provide a process for producing an olefin polymer using the catalyst composition.

According to an aspect of the present invention, there is provided a transition metal compound represented by Chemical Formula 1, A compound represented by the following formula (2); And a compound represented by the following general formula (3).

[Chemical Formula 1]

In Formula 1,

n is an integer of 1 to 2,

R ₁ to R ₁₆ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a heterocyclic group having 5 to 20 carbon atoms, or a silyl group, and R ₁ to R ₁₆ At least two adjacent to each other may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring;

R ₁₇ is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms;

Q is carbon or silicon;

M is a Group 4 transition metal;

X ₁ and X ₂ are the same or different and each independently represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An aryloxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;

(2)

Al (R _{18) 3}

In the above formula (2), R < ₁₈ > is each independently a halogen or a hydrocarbyl substituted or unsubstituted with halogen having 1 to 20 carbon atoms;

(3)

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Formula 3, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is each independently an aryl or alkyl having 6 to 20 carbon atoms in which at least one hydrogen atom is substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy.

A second aspect of the present invention provides a process for preparing the catalyst composition.

A third aspect of the present invention provides a process for preparing an olefin polymer using the catalyst composition.

The catalyst composition according to the present invention shows improved activity. The use of the catalyst composition according to the present invention makes it possible to produce an olefin polymer having a high molecular weight and a low density. In particular, olefinic polymers such as propylene polymers, propylene-ethylene copolymers or propylene-alpha olefin copolymers can be produced with high activity.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, integers, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the present invention will be described in detail.

One aspect of the present invention relates to a transition metal compound represented by the following general formula (1): A compound represented by the following formula (2); And a compound represented by the following general formula (3).

[Chemical Formula 1]

In Formula 1,

n is an integer of 1 to 2,

R ₁ to R ₁₆ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a heterocyclic group having 5 to 20 carbon atoms, or a silyl group, and R ₁ to R ₁₆ At least two adjacent to each other may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring;

R ₁₇ is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms;

Q is carbon or silicon;

M is a Group 4 transition metal;

X ₁ and X ₂ are the same or different and each independently represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An aryloxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;

(2)

Al (R _{18) 3}

In the above formula (2), R < ₁₈ > is each independently a halogen or a hydrocarbyl substituted or unsubstituted with halogen having 1 to 20 carbon atoms;

(3)

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Formula 3, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is each independently an aryl or alkyl having 6 to 20 carbon atoms in which at least one hydrogen atom is substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy.

Each of the substituents defined in Formula 1 will be described in detail as follows.

The alkyl group includes a linear or branched alkyl group.

The alkenyl group includes a linear or branched alkenyl group.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like, no.

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group means an alkyl group substituted by the aryl group.

The halogen group means a fluorine group, a chlorine group, a bromine group or an iodine group.

The silyl group includes trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris (trimethylsilyl) , But are not limited to these examples.

The aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.

The heterocyclic group means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 carbon atoms and containing at least one heteroatom, and may be a single ring or a condensed ring of two or more rings. The heterocyclic group may be substituted or unsubstituted with an alkyl group. Examples thereof include indoline, tetrahydroquinoline and the like, but the present invention is not limited thereto.

According to one embodiment of the present invention, R ₁ to R ₁₆ are each independently hydrogen, an alkyl 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, an alkylaryl group having 7 to 20 carbon atoms An arylalkyl group, or a heterocyclic group having 5 to 20 carbon atoms, and R ₁₇ may be an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

According to one embodiment of the present invention, the transition metal of Group 4 corresponding to M may be Ti, Zr, or Hf, but is not limited thereto.

According to an embodiment of the present invention, the transition metal compound represented by Formula 1 may be represented by one of the following structural formulas, but is not limited thereto.

In the above structural formula, Me represents a methyl group and Ph represents a phenyl group.

The transition metal compound represented by the formula (1) can be synthesized, for example, by the following reaction schemes 1 and 2, but is not limited thereto.

[Reaction Scheme 1]

[Reaction Scheme 2]

The transition metal compound represented by the formula (1) has a structure in which a bisindenyl group is bridged by carbon or silicon, and an indoline group or a tetrahydroquinoline group is connected to one indenyl group, thereby exhibiting an asymmetric cross-linking structure .

According to one embodiment of the present invention, in the catalyst composition, the non-coordinating anion [ZA ₄ ] ^- constituting the salt compound of the second catalyst represented by the general formula (3) is B [C ₆ F ₅ ] ^4- desirable.

In the catalyst composition, the ratio of the number of moles of transition metal of the compound represented by Formula 1 to the number of moles of aluminum represented by Formula 2 may be 1: 1 to 1: 1,000, preferably 1: 5 to 1: 1: 250, and most preferably from 1: 5 to 1:50. The ratio of the number of moles of transition metal of the compound represented by Formula 1 to the moles of the Group 13 element of the compound represented by Formula 3 may be 1: 1 to 1:10, and 1: 1 to 1: 5 .

The compound represented by the above-mentioned general formula (2) is not particularly limited, but trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, Aluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethyl Aluminum ethoxide, and the like. Particularly preferred compounds may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

Examples of the compound represented by the formula (3) include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) (pentafluorophenyl) borate, tri (2-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis -Butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (triisopropylsilyl) -2,3,5,6-tetrafluoro Phenyl) borate, N, N-dimethylanilinium pentafluorophenoxy (Pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis Borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2 (3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t- butyl) ammonium tetrakis , 3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis 2,3,4,6-tetrafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, decyldimethyl Ammo (Pentafluorophenyl) borate, dodecyldimethylammonium tetrakis (pentafluorophenyl) borate, tetradecyldimethylammonium tetrakis (pentafluorophenyl) borate, hexadecyldimethylammonium tetrakis (pentafluorophenyl) ) Octadecyldimethylammonium tetrakis (pentafluorophenyl) borate, eicosyldimethylammonium tetrakis (pentafluorophenyl) borate, methyldidecylammonium tetrakis (pentafluorophenyl) borate, methylidodecylammonium tetra (Pentafluorophenyl) borate, methyldiotetradecylammonium tetrakis (pentafluorophenyl) borate, methyldihexadecylammonium tetrakis (pentafluorophenyl) borate, methyl dioctadecylammonium tetrakis Phenyl) borate, methyldiacosylammonium tetrakis (pentafluorophenyl) borate, (Pentafluorophenyl) borate, tridecylammonium tetrakis (pentafluorophenyl) borate, trityl tetradecylammonium tetrakis (pentafluorophenyl) borate, trihexadecylammonium tetrakis (Pentafluorophenyl) borate, tetradecane (pentafluorophenyl) borate, decyldodecylammonium tetrakis (pentafluorophenyl) borate, trieocosylammonium tetrakis (Pentafluorophenyl) borate, N, N-didodecyl anilinium tetrakis (penta) amido tetrakis (pentafluorophenyl) borate, octadecyl (Pentafluorophenyl) borate, methyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecyl anilinium tetrakis Sites such examples can be cited; Examples of compounds having a dialkylammonium salt bonded thereto include di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, and the like; Examples of compounds having a carbonium salt bond include tropylium tetrakis (pentafluorophenyl) borate, triphenylmethylium tetrakis (pentafluorophenyl) borate, benzene (diazonium) tetrakis (pentafluorophenyl) Borate, and the like.

Particularly preferred compounds include N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, di (octadecyl) methylammonium tetrakis (pentafluorophenyl) Borate, di (octadecyl) (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylmethylium tetrakis (pentafluorophenyl) borate, tropylium tetrakis For example.

According to a second aspect of the present invention, there is provided a method for preparing a catalyst, comprising: preparing a mixture by contacting a transition metal compound represented by Formula 1 with a first promoter represented by Formula 2; And

And contacting the mixture of the transition metal compound and the first co-catalyst to a second co-catalyst represented by the formula (3).

In the first step of the method for producing the catalyst composition, the ratio of the number of moles of the transition metal of the transition metal compound represented by the formula (1) to the number of moles of aluminum of the first cocatalyst represented by the formula (2) : 1,000, preferably from 1: 5 to 1: 250, and most preferably from 1: 5 to 1: 50. When the ratio of the transition metal to aluminum is within the above range, the effect is sufficient, but the excessive amount of alkyl acts as a catalyst poison rather than causing a side reaction and a problem that a large amount of aluminum remains in the polymer substantially does not occur.

In the second step, the ratio of the number of moles of the transition metal compound to the number of moles of the Group 13 element of the second co-catalyst may be 1: 1 to 1:10, more preferably 1: 1 to 1: 5 desirable. In the case where the ratio of the transition metal and the Group 13 element is in the above range, the amount of the second catalyst is relatively small and the activation of the metal compound is not completely achieved, And the unit cost of the catalyst composition is appropriate.

In general, the catalyst composition can be prepared by mixing the components in a suitable solvent at a temperature ranging from -100 to 300 ° C, preferably from 25 to 75 ° C. As a solvent suitable for the preparation of the catalyst composition, hydrocarbon solvents such as pentane, hexane, heptane and the like, or aromatic solvents such as benzene, toluene and the like can be used.

The catalyst composition may be prepared separately using the compounds of Formulas 1 to 3 before the use of the catalyst composition described above or may be prepared in situ by sequentially contacting the components of the catalyst composition in the presence of the monomer to be polymerized . Preferably, the catalyst composition is formed in a separate step in a suitable solvent before addition to the polymerization reactor. When the respective components are added in different orders, it is difficult to obtain a catalyst composition exhibiting excellent activity. Since the catalyst composition is sensitive to moisture and oxygen, it is preferable to treat the catalyst composition in an inert atmosphere such as nitrogen or argon.

A third aspect of the invention relates to a process for preparing an olefinic polymer comprising contacting the catalyst composition with a monomer.

The most preferred polymerization process using the catalyst composition of the present invention is a solution process. Also, when such a composition is used together with an inorganic carrier such as silica, it is applicable to a slurry or a vapor phase process.

The catalyst composition of the present invention can be produced by reacting an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, such as pentane, hexane, heptane, nonane, decane and isomers thereof and an aromatic hydrocarbon solvent such as toluene, benzene, A hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene, or the like. The solvent used herein is preferably treated with a small amount of alkylaluminum to remove a small amount of water or air acting as a catalyst poison.

Suitable solvents for polymerization are inert liquids. Inert liquids include hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof; And aromatic compounds such as benzene and toluene. It is also possible to use liquid olefins which may also serve as monomers or comonomers, for example ethylene, propylene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentene, , Styrene, ethylenedenorbornene, and the like. Mixtures of these compounds may also be included.

Examples of the polymerizable olefin-based monomer using the catalyst composition include ethylene, alpha-olefin, cyclic olefin, and the like. Diene olefin-based monomers or triene olefin-based monomers having two or more double bonds can also be polymerized. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Butene, dicyclopentadiene, 1,4-butadiene, 1,4-butadiene, 1,3-butadiene, 1,3-butadiene, Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. These two or more monomers may be mixed and copolymerized.

Most of the polymerization reaction can be carried out at a temperature ranging from atmospheric pressure to 1,000 psi, preferably from 15 psi to 700 psi, at a temperature of 0 to 200 DEG C, preferably 25 to 160 DEG C, using the monomer. The amount of the catalyst to be used is preferably 10 ^-12 to 10 ^-1 mol, more preferably 10 ^-9 to 10 ^-5 mol per mol of the monomer.

More specifically, the monomers constituting the copolymer may be at least one selected from the group consisting of ethylene and propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, 1-octene, styrene and ethylidene norbornene Alpha-olefin monomers. In particular, according to one embodiment of the present invention, the catalyst composition may be used in the production of propylene polymers such as propylene polymers, propylene-ethylene copolymers, or propylene-alpha olefin copolymers, Can be used in the production of olefinic polymers.

Hereinafter, the present invention will be described more specifically based on the following examples. These examples are provided to aid understanding of the present invention and the scope of the present invention is not limited thereto.

< Example >

In the following examples, the term " overnight "or" overnight "means approximately 12 to 16 hours and" normal temperature "refers to a temperature of 20 to 30 ° C. The organic reagents and solvents used were purchased from Aldrich and Merck and purified by standard methods. At every stage of the synthesis, the contact between air and moisture was blocked to improve the reproducibility of the experiment. Spectra were obtained using a 500 MHz nuclear magnetic resonance (NMR) system to demonstrate the structure of the resulting compound.

Ligand  Synthesis of compounds and transition metal compounds

Manufacturing example  One

(4- (3,4- dihydroquinoline -1 (2 H ) - yl )-2- methyl -One H - inden -One- yl )(4- phenyl -2- methyl -1H- inden -1-yl) dimethyl silane Synthesis of

Into the 1- (2-methyl-1 H -inden-4-yl) -1,2,3,4-tetrahydroquinole (2.2g, 8.42mmol) in 100mL of Schenk flask was added dry diethyl ether was dissolved 40mL of the starting material , N-BuLi (2.5M in n-Hx) (3.7mL) was added at -78 ° C, and the mixture was stirred at room temperature overnight. Then, it was filtered using glass frit (G4). The solid remaining in the glass frit was vacuum dried to give a lithiated product (2.2 g, 98% yield) of a white solid. The lithiated product (2.2 g, 8.03 mmol), chloro (2-methyl-4-phenyl-1H-inden-1-yl) dimethyl silane (2.40 g, 8.03 mmol), copper cyanide (0.026 g, 0.29 mmol ) Was placed in a 250 mL Schlenk flask, and 80 mL of dry diethyl ether was added thereto at -78 ° C., and the mixture was stirred at room temperature overnight. After completion of the reaction, 100 mL of aqueous NH ₄ Cl and 100 mL of deionized water were added to terminate the reaction.

The organic layer was separated from the water layer, dried over MgSO ₄ , filtered, and vacuum dried to obtain a pale yellow solid ligand compound (4.20 g, quantitative yield relative to lithiated product, 99% yield based on starting material). ¹ H-NMR analysis showed that the ratio of rac: meso was about 1: 1.

_{^{1 H-NMR (CDCl 3)}} : δ 7.55-7.12 (m, 22H in rac - and meso -isomers), 7.04 (dd, 2H in rac - and meso -isomers), 6.85-6.80 (m, 4H in rac - and meso -isomers), 6.63 (td , 2H in rac - and meso -isomers), 6.47 (s, 2H in rac - and meso -isomers), 6.29 (d, 2H in rac - and meso -isomers), 3.81 ( s, 2H in rac -isomer), 3.80 (s, 2H in meso -isomer), 3.70-3.59 (m, 4H in rac - and meso -isomers), 2.94 (t, 4H in rac - and meso -isomers), 2.27 (d, 2H in rac and meso- isomers), 2.20 (d, 6H in meso- isomer), 2.18 (d, 6H in rac- isomer), 2.13-2.08 (m, 8H in rac- and meso- isomers ), -0.22 (s, 3H in meso -isomer), 0.23 (d, 6H in rac -isomer), -0.25 (s, 3H in meso -isomer)

rac - dimethylsilylene - (4- (3,4- dihydroquinoline -1 (2 H ) - yl )-2- methyl -One H - inden -One- yl ) (4-phenyl-2-methyl-1H-inden-1-yl) zircoium dichloride  synthesis

In 100mL of Schenk flask (4- (3,4-dihydroquinolin -1 (2 H) -yl) -2-methyl-1 H -inden-1-yl) (4-phenyl-2-methyl-1H-inden- 1-yl) dimethyl silane (2.67 mmol, rac: meso = 1: 1) and 30 mL of dry diethyl ether was added to dissolve the starting material. Then, n-BuLi (2.5 M in Hx) 2.4 mL, and the mixture was stirred at room temperature overnight. Then, it was filtered using glass frit (G4). The solid remaining in the glass frit was vacuum dried to obtain a lithiated product of white solid. The lithiated product, ZrCl ₄ (0.69 g, 2.94 mmol), was placed in a 100 mL Schenk flask in a glove box, and then 15 mL of dry hexane and 15 mL of diethyl ether were added at -78 ° C., and the mixture was stirred at room temperature overnight. After completion of the reaction, the mixture was filtered with a glass frit (G4) containing celite. Solids remaining in the glass frit were dissolved in dichloromethane (DCM). The DCM filtrate was vacuum dried to give a red solid. ¹ H-NMR analysis showed that both solids were Zr complexes with rac: meso = 1: 1. The crude product was collected and recrystallized in dry toluene and hexane for 3 days in a -30 ° C freezer. The resulting red solid was filtered with glass frit (G4), washed twice with 10 mL of dry n-hexane, and dried in vacuo to yield 0.2 g (11% yield) of the racemic product.

¹ H-NMR (CDCl ₃ ):? 7.61-7.30 (m, 8H), 7.14 (d, IH), 7.07-6.99 (m, 3H), 6.88 , 6.63 (t, IH), 6.57 (s, IH), 6.29 (d, IH), 3.79-3.75 (m, 2H), 2.83-2.78 , 3H), 2.05-1. 94 (m, 2H), 1.29 (s, 6H)

Manufacturing example  2

rac - dimethylsilylene - (4- (3,4- dihydroquinoline -1 (2 H ) - yl )-2- methyl -One H - inden -One- yl ) (4-phenyl-2-methyl-1H-inden-1-yl) hafnium dichloride  synthesis

Prepared in Preparation Example 1 in 100mL of Schenk flask (4- (3,4-dihydroquinolin -1 (2 H) -yl) -2-methyl-1 H -inden-1-yl) (4-phenyl-2 (3.05 mmol, rac: meso = 1: 1) and 40 mL of dry diethyl ether was added to dissolve the starting material. Then, n-BuLi (2.5 M in n-Hx) was added thereto, and the mixture was stirred at room temperature overnight. Then, it was filtered using glass frit (G4). The solid remaining in the glass frit was vacuum dried to obtain a lithiated product of white solid. The lithiated product, HfCl ₄ (1.1 g, 3.36 mmol), was placed in a 100 mL Schenk flask in a glove box, 20 mL of dry hexane and 20 mL of diethyl ether were added at -78 ° C, and the mixture was stirred at room temperature overnight. After completion of the reaction, the mixture was filtered with a glass frit (G4) containing celite. Solids remaining in the glass frit were dissolved in dichloromethane (DCM). The DCM filtrate was vacuum dried to give a red solid. ^{As a} result of ¹ H-NMR analysis, both solids were Hf complexes of rac: meso = 1: 1. The crude product was collected and placed in an oil bath at 45 ° C and dissolved in 30 mL of dry toluene while stirring. This was stored in a -30 ° C freezer for 3 days and recrystallized. The resulting red solid was filtered with glass frit (G4), washed twice with 10 mL of dry n-hexane and dried in vacuo to give the racemic final product, 0.4 g (17% yield).

_{^{1 H-NMR (CDCl 3)}} : δ 7.64 (td, 1H), 7.57-7.55 (m, 2H), 7.41-7.38 (m, 3H), 7.32-7.27 (m, 3H), 7.15-7.09 (m, 2H), 2.82-2.78 (m, 2H), 7.04-6.97 (m, 3H), 6.80 (t, , 2.31 (s, 3H), 2.27 (s, 3H), 2.06-1.91 (m, 2H), 1.28

compare Manufacturing example  One

rac -1,1'- dimethytylsilylene - bis ( indenyl ) hafnium dichloride

The rac-1,1'-dimethytylsilylene-bis (indenyl) hafnium dichloride compound is disclosed in U.S. Pat. 5,905,162, which is incorporated herein by reference.

Preparation of Propylene Polymer

Example  One

A toluene solvent (0.2 L) was added to a 250 mL minicable reactor, and the temperature of the reactor was preheated to 70 캜. 0.2 ml of a dimethylanilinium tetrakis (pentafluorophenyl) borate co-catalyst of 5 x 10 ^-6 M was introduced into the reactor through a syringe, and the transition metal compound (1 x 10 ^-6 M, 0.1 mL) was charged to the reactor. Polymerization was carried out by injecting 5 bar of propylene for 10 minutes. After the polymerization reaction was carried out for 10 minutes, the remaining gas was removed and the polymer solution was cooled by adding excess ethanol to induce precipitation. The obtained polymer was washed with ethanol and acetone two to three times, respectively, and dried in a vacuum oven at 80 캜 for 12 hours or more, and then the physical properties thereof were measured.

Example  2

An olefin polymer was prepared in the same manner as in Example 1 except that the transition metal compound of Production Example 2 was used.

Comparative Example  One

5 x 10 ^-6 M of dimethylanilinium tetrakis (penta flow-phenyl) borate cocatalyst in 1.0mL use, and a transition metal compound of the above Comparative Production Example 1, treated with triisobutylaluminum compound (1x10 ^-6 M , 0.5 mL) was used as a polymerization initiator, to prepare an olefin-based polymer.

The melting point (Tm) of the polymer was measured using Q100 from TA. The measurements were obtained through a second melting step, which was ramped to 10 ° C per minute to eliminate the thermal history of the polymer.

The properties of Examples 1 and 2 and Comparative Example 1 were measured in the same manner as described above, and the results are shown in Table 1 below.

Catalytic activity
(Unit: kg / mmol hr) Polymer weight
(Unit: g) Melting point
(Unit: ℃) Example 1 474 7.9 147.8 Example 2 432 7.2 148.4 Comparative Example 1 151 12.6 122.5

Referring to Table 1 above, the propylene polymer produced by Examples 1 and 2 exhibited a higher melting point (Tm) than the polymer of Comparative Example 1. That is, it was confirmed that when the transition metal compound of the present invention is used as a catalyst, olefin polymer having high catalytic activity and high isotacticity is obtained.

Preparation of Propylene-Ethylene Copolymer

Example  3

A toluene solvent (0.8 L), propylene (250 g) and ethylene (70 psi) were added to the 2 L autoclave reactor, the pressure was adjusted to 500 psi under high pressure argon pressure, and the reactor temperature was preheated to 70 캜. 0.2 ml of a 5-x 10 ^-6 M dimethylanilinium tetrakis (pentafluorophenyl) borate co-catalyst was charged into a reactor under a high-pressure argon pressure, and the transition metal compound of Preparation Example 1 1 x 10 ^-6 M, 0.1 mL) was placed in a catalyst storage tank, and a high-pressure argon pressure was added to the reactor. The polymerization reaction was carried out for 10 minutes. The reaction heat was removed through a cooling coil inside the reactor to keep the polymerization temperature at a maximum. After the polymerization reaction was carried out for 10 minutes, the remaining gas was taken out, the polymer solution was discharged to the lower part of the reactor, and excessive ethanol was added to cool the solution to induce precipitation. The obtained polymer was washed with ethanol and acetone two to three times, respectively, and dried in a vacuum oven at 80 캜 for 12 hours or more, and then the physical properties thereof were measured.

Comparative Example  2

5 x 10 ^-6 M of dimethylanilinium tetrakis (penta flow-phenyl) borate cocatalyst in 1.0mL use, and a transition metal compound of the above Comparative Production Example 1, treated with triisobutylaluminum compound (1x10 ^-6 M , 0.5 mL) was used as a polymerization initiator, to prepare an olefin-based polymer.

The melt flow rate (MFR) of the polymer was measured by ASTM D-1238 (condition E, 230 ° C, 2.16 kg load). The melting point (Tm) was measured using Q100 from TA. The measurements were obtained through a second melting step, which was ramped to 10 ° C per minute to eliminate the thermal history of the polymer.

The properties of Example 3 and Comparative Example 2 were measured in the same manner as described above, and the results are shown in Table 2 below.

Catalytic activity
(Unit: kg / mmol hr) Polymer weight
(Unit: g) density
(Unit: g / cc) Melting point
(Unit: ℃) Melt Index
(Unit: g / 10 min) Example 3 6546 109 0.870 - 28 Comparative Example 2 1040 86.6 0.856 - 13

Referring to Table 2, the propylene-ethylene polymer prepared in Example 3 exhibited excellent effects such as high catalytic activity and melt index as compared with Comparative Example 2.

Claims (13)

A transition metal compound represented by the following formula (1); A compound represented by the following formula (2); And a compound represented by the following general formula (3):
[Chemical Formula 1]

In Formula 1,
n is an integer of 1 to 2,
R ₁ to R ₁₆ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a heterocyclic group having 5 to 20 carbon atoms, or a silyl group, and R ₁ to R ₁₆ At least two adjacent to each other may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring;
R ₁₇ is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms;
Q is carbon or silicon;
M is a Group 4 transition metal;
X ₁ and X ₂ are the same or different and each independently represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An aryloxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;
(2)
Al (R _{18) 3}
In the above formula (2), R &lt; ₁₈ &gt; is each independently a halogen or a hydrocarbyl substituted or unsubstituted with halogen having 1 to 20 carbon atoms;
(3)
[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-
In Formula 3, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is each independently an aryl or alkyl having 6 to 20 carbon atoms in which at least one hydrogen atom is substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy. The compound according to claim 1, wherein R ₁ to R ₁₆ in Formula 1 are each independently selected from the group consisting of hydrogen, an alkyl 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 a heterocyclic group having 5 to 20 carbon atoms, and R &lt; ₁₇ &gt; is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The catalyst composition according to claim 1, wherein M in Formula 1 is a transition metal selected from the group consisting of Ti, Zr, and Hf. The catalyst composition according to claim 1, wherein the transition metal compound represented by Formula 1 has a structure selected from the group consisting of:

The method of claim 1, wherein the ratio of the number of moles of transition metal represented by Formula 1 to the number of moles of aluminum represented by Formula 2 is 1: 1 to 1: 1,000, Wherein the ratio of the number of moles of transition metal to the number of moles of the Group 13 element of the compound represented by Formula 3 is 1: 1 to 1:10. 2. The method of claim 1, wherein the compound represented by Formula 2 is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- Triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, and dimethylaluminum in the presence of a catalyst such as a catalyst, Lt; RTI ID = 0.0 &gt; of: &lt; / RTI &gt; The catalyst composition according to claim 1, wherein the non-coordinating anion [ZA ₄ ] ^- of the compound represented by the general formula (3) is B [C ₆ F ₅ ] ^4- . Contacting a transition metal compound represented by the following formula (1) with a first co-catalyst represented by the following formula (2) to prepare a mixture; And
Contacting the mixture of the transition metal compound and the first cocatalyst with a second cocatalyst represented by the following formula 3:
[Chemical Formula 1]

In Formula 1,
n is an integer of 1 to 2,
R ₁ to R ₁₆ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a heterocyclic group having 5 to 20 carbon atoms, or a silyl group, and R ₁ to R ₁₆ At least two adjacent to each other may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring;
R ₁₇ is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms;
Q is carbon or silicon;
M is a Group 4 transition metal;
X ₁ and X ₂ are the same or different and each independently represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An aryloxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;
(2)
Al (R _{18) 3}
In the above formula (2), R &lt; ₁₈ &gt; is each independently a halogen or a hydrocarbyl substituted or unsubstituted with halogen having 1 to 20 carbon atoms;
(3)
[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-
In Formula 3, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is each independently an aryl or alkyl having 6 to 20 carbon atoms in which at least one hydrogen atom is substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy. The method of claim 8, wherein the transition metal compound represented by Formula 1 has a structure selected from the group consisting of:

The method of claim 8, wherein the ratio of the number of moles of transition metal of the compound represented by Formula 1 to the number of moles of aluminum represented by Formula 2 is 1: 1 to 1: 1,000, Wherein the ratio of the number of moles to the number of moles of the Group 13 element of the compound represented by Formula (3) is 1: 1 to 1:10. 10. A process for producing an olefin-based polymer comprising the step of contacting a monomer composition according to any one of claims 1 to 7 with a monomer. 12. The process for producing an olefinic polymer according to claim 11, wherein the monomer comprises at least one member selected from the group consisting of ethylene, alpha-olefin, cyclic olefin, diene olefin and triene olefin. 12. The composition of claim 11, wherein the monomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, And at least one selected from the group consisting of 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene.