KR100961079B1 - Catalyst for polymerization of olefin and polymerization process of olefin using the same - Google Patents

Abstract

The present invention is a novel metallocene compound useful as a component of a catalyst for olefin polymerization; An olefin polymerization catalyst including the metallocene compound as a main catalyst and an aluminoxane compound and / or an aluminum compound as a promoter; A supported catalyst for olefin polymerization in which the catalyst for olefin polymerization is supported on a carrier; A polymerization method of olefins using the olefin polymerization catalyst and / or the supported catalyst for olefin polymerization; And it relates to an olefin polymer prepared according to the polymerization method. When the catalyst for olefin polymerization and / or the supported catalyst for olefin polymerization according to the present invention is used, the interaction between the metallocene compound as the main catalyst and the aluminoxane compound and / or the organoaluminum compound as the main catalyst can be achieved without using a catalyst having a complicated structure. Through the action, an olefin polymer, particularly a propylene polymer, having high molecular weight and melting point and high stereoregularity can be obtained.

Description

Catalyst for olefin polymerization and polymerization method of olefin using same {Catalyst for polymerization of olefin and polymerization process of olefin using the same}

The present invention is a novel metallocene compound useful as a component of a catalyst for olefin polymerization; An olefin polymerization catalyst including the metallocene compound as a main catalyst and an aluminoxane compound and / or an aluminum compound as a promoter; A supported catalyst for olefin polymerization in which the catalyst for olefin polymerization is supported on a carrier; A polymerization method of olefins using the olefin polymerization catalyst and / or the supported catalyst for olefin polymerization; And it relates to an olefin polymer prepared according to the polymerization method.

Polypropylene can be classified into isotactic polypropylene ( i PP), syndiotactic polypropylene ( s PP) and atactic polypropylene ( a PP) according to the structural rules of the structure. There is a metallocene catalyst, all three types of polypropylene can be prepared.

Among i PP and s PP has good mechanical properties and are picked research and development target of many research groups around the world due to thermal characteristics, W. Kaminsky and H. Brintzinger is the first time such rules also have a three-dimensional i PP for producing high metal world Sen catalysts were synthesized ( Angew. Chem. Int. Ed. Engl. , 1985 , 24 , 507), and JA Ewen et al. Synthesized the world's first metallocene catalysts for the production of s PP having high stereoregularity ( J. Am. Chem. Soc., 1988, 110 , 6255).

Since then, i PP and s PP have been commercialized by petrochemical companies and applied to film, fiber, injection molding, etc. Metallocene catalyst compounds were needed.

In order to synthesize such a complex metallocene catalyst compound, a complicated synthesis process and expensive equipment are required at various stages. Therefore, the development of the metallocene catalyst is a major factor in increasing the production cost of PP and expanding the PP market. Has been an obstacle. Thus, the production of high stereoregular PP at low cost has become a major concern for all research groups and companies around the world.

It is an object of the present invention to provide novel transition metal compounds useful as components of a catalyst for olefin polymerization.

Another object of the present invention is to provide a catalyst for olefin polymerization containing the novel transition metal compound and a supported catalyst for olefin polymerization in which the catalyst for olefin polymerization is supported on a carrier.

Still another object of the present invention is to provide a polymerization method of olefin using the catalyst for olefin polymerization and / or the supported catalyst for olefin polymerization, and an olefin polymer prepared according to the above method.

The present invention provides a metallocene compound of Formula 1 below.

[Formula 1]

In Formula 1, M is selected from the group consisting of Group 3 to 10 elements on the periodic table;

X is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, C7-20 alkylaryl group, C6-C20 arylsilyl group, C6-C20 silylaryl group, C1-C20 alkoxy group, C1-C20 alkylsiloxy group, C6-C20 aryl It is selected from the group consisting of an oxy group, a halogen group, an amine group and a tetrahydroborate group,

n is an integer from 1 to 5;

Cp ¹ and Cp ² are the same as or different from each other, and each independently a ligand having a cyclopentadienyl skeleton,

The ligand having a cyclopentadienyl skeleton is hydrogen, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C1-C20 alkylsilyl group, a C1-C20 silylalkyl group, a C1-C20 halo Alkyl group, C6-C20 aryl group, C7-C20 arylalkyl group, C7-C20 alkylaryl group, C6-C20 arylsilyl group, C6-C20 silylaryl group, a halogen group, a following formula A substituent of 2 and one or more substituents selected from the group consisting of substituents of the following general formula (3),

In this case, the ligand having a cyclopentadienyl skeleton has at least one substituent of Formula 2 or a substituent of Formula 3 below,

Substituents substituted for the ligand having the cyclopentadienyl skeleton does not bind to each other to form a ring or to each other;

[Formula 2]

(3)

In Chemical Formulas 2 and 3,

Z is an element of group 15 or 16 of the periodic table;

R is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl having 7 to 20 carbon atoms An alkyl group, a C7-20 alkylaryl group, a C6-C20 arylsilyl group, and a C6-C20 silylaryl group;

m is an integer of 1 to 2; p is an integer from 1 to 5;

Carbon atoms in the phenyl ring not bonded with ZR _m may be bonded to hydrogen, or have 1 to 20 alkyl groups, 3 to 20 cycloalkyl groups, 1 to 20 alkylsilyl groups, 1 to 20 carbonyl silyl groups, A C1-C20 haloalkyl group, a C6-C20 aryl group, a C7-C20 arylalkyl group, a C7-C20 alkylaryl group, a C6-C20 arylsilyl group, a C6-C20 silylaryl group And it combines with a substituent selected from the group consisting of halogen groups.

In Formulas 2 and 3, when p is 1, the substituent ZR _m is preferably substituted at the ortho-position or meta-position of the phenyl ring. More preferably, when p is an integer of 1 to 4, the substituent ZR _m may be substituted at the ortho-position, or meta-position, or ortho-position and meta-position of the phenyl ring.

In addition, the present invention (a) the metallocene compound of Formula 1; And

(b) a compound selected from the group consisting of an aluminoxane compound of Formula 4 and an organoaluminum compound of Formula 5;

[Formula 4]

In Formula 4, R ¹ is an alkyl group having 1 to 10 carbon atoms,

q is an integer from 1 to 70;

[Chemical Formula 5]

In Chemical Formula 5, R ² , R ³ and R ⁴ are the same as or different from each other, and are selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and halogen groups, respectively, and R ² , R ³ and At least one of R ⁴ is an alkyl group having 1 to 10 carbon atoms.

The present invention also provides a supported catalyst for olefin polymerization in which the catalyst for olefin polymerization is supported on a carrier. In this case, the carrier is an inorganic compound and / or an organic compound.

Preferably, in the present invention, the olefin is propylene, and the catalyst of the present invention is a catalyst for propylene polymerization and a supported catalyst for propylene polymerization.

The present invention also provides a polymerization method of olefins, characterized in that the olefins are polymerized using a catalyst selected from the group consisting of the catalyst for olefin polymerization and the supported catalyst for olefin polymerization.

The present invention also provides an olefin polymer which is produced according to the polymerization method, wherein the olefin polymer includes the catalyst for olefin polymerization and / or the supported catalyst for olefin polymerization in the olefin polymer. Preferably the olefin polymer is a homopolymer or copolymer of olefins, more preferably polypropylene or propylene copolymer.

When the catalyst for olefin polymerization and / or the supported catalyst for olefin polymerization according to the present invention is used, the metallocene compound of the formula (1) as the main catalyst and the aluminoxane compound of the formula (4) as the promoter and / or without using a complex structure catalyst and / Alternatively, an olefin polymer, particularly a propylene polymer, having high molecular weight and high melting point and high stereoregularity may be obtained through the interaction between the organoaluminum compounds of the formula (5). In addition, in the catalyst for olefin polymerization and / or the supported catalyst for olefin polymerization according to the present invention, the stereoregularity of the olefin polymer, especially the propylene polymer, can also be adjusted by appropriately adjusting the catalyst structure and polymerization conditions.

The present invention will be described in more detail below, but the content of the present invention is not limited to the following.

<Metallocene Compound of Formula 1>

In the present invention, the metallocene compound of Chemical Formula 1 may be used as a main catalyst which is one of the components of the catalyst for olefin polymerization according to the present invention, and is a transition metal compound.

In Formula 1, M is selected from the group consisting of Group 3 to 10 elements on the periodic table. Non-limiting examples thereof include scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), and hafnium. (Hf), vanadium (V), iron (Fe), nickel (Ni), palladium (Pd) and the like. In Formula 1, M is preferably a Group 4 element on the periodic table, more preferably zirconium (Zr), titanium (Ti), or hafnium (Hf).

In addition, in Formula 1, Cp ¹ and Cp ² are the same as or different from each other, and each independently represent a ligand having a cyclopentadienyl skeleton, and include at least one substituent of Formula 2 or the following Formula 3. In this case, the ligand having a cyclopentadienyl skeleton may be selected from the group consisting of a cyclopentadienyl group, an indenyl group, and a fluorenyl group, but is not limited thereto.

[Formula 2]

(3)

In Chemical Formulas 2 and 3, Z is an element of Group 15 or Group 16 on the periodic table, preferably nitrogen (Nitrogen, N), phosphorus (Phosphorus, P), arsenic (Arsenic, As), oxygen (Oxygen, O ), Sulfur (Sulfur, S), or selenium (Selenium, Se).

In addition, in Chemical Formulas 2 and 3, R is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. Aryl groups, a C7-20 arylalkyl group, a C7-20 alkylaryl group, a C6-C20 arylsilyl group, and a C6-C20 silylaryl group; m is an integer of 1 to 2; p is an integer of 1-5.

In addition, in Formulas 2 and 3, when p is 1, the substituent ZR _m is preferably substituted at the ortho-position or meta-position of the phenyl ring. More preferably, when p is an integer of 1 to 4, the substituent ZR _m may be substituted at the ortho-position, or meta-position, or ortho-position and meta-position of the phenyl ring.

In addition, in Formulas 2 and 3, the carbon atom in the phenyl ring not bonded to ZR _m is bonded to hydrogen; Or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms And a substituent selected from the group consisting of 7 to 20 arylalkyl groups, 7 to 20 alkylaryl groups, 6 to 20 carbon atoms, arylsilyl groups, 6 to 20 carbon atoms, and halogen groups. In addition, a ring may be formed by a bond between substituents.

In Chemical Formula 1 according to the present invention, in addition to the substituents of Chemical Formulas 2 and 3, the substituents bonded to Cp ¹ and Cp ² include hydrogen, including C 1-20 alkyl groups, C 3-20 cycloalkyl groups, and C 1 -C 20 alkylsilyl groups, C1-20 silylalkyl groups, C1-20 haloalkyl groups, C6-20 aryl groups, C7-20 arylalkyl groups, C7-20 alkylaryl groups, C6-6 It is 20 aryl silyl group, a C6-C20 silyl aryl group, a halogen group, etc. It can also form a ring by the bond between substituents.

In addition, in Chemical Formula 1, X is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms 7-20 arylalkyl groups, C7-20 alkylaryl groups, C6-C20 arylsilyl groups, C6-C20 silylaryl groups, C1-C20 alkoxy groups, C1-C20 alkylsiloxy groups , An aryloxy group having 6 to 20 carbon atoms, a halogen group, an amine group, and a tetrahydroborate group.

Preferably, in Formula 1, X represents a methyl group, an ethyl group, a propyl group, a phenoxy group, a naphthoxy group, a methylphenoxy group, a dimethylphenoxy group, a trimethylphenoxy group, an ethylphenoxy group, a diethylphenoxy group, a triethylphenoxy group, Propylphenoxy, dipropylphenoxy, tripropylphenoxy, chloro, bromo, dimethylamine, diethylamine, dipropylamine, dibutylamine, diphenylamine, dibenzylamine, and Selected from the group consisting of tetrahydroborate groups.

In addition, in Chemical Formula 1, n is an integer of 1 to 5 and varies depending on the oxidation number of the central metal.

In addition, in Chemical Formulas 1 to 3 according to the present invention, the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group having 3 to 20 carbon atoms, the alkylsilyl group having 1 to 20 carbon atoms, and carbon atoms Non-limiting examples of 1 to 20 silylalkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. ) Group, heptyl group, octyl group, nonyl group, nonyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclobutyl group, cyclopentyl group, cyclohexyl (Cyclohexyl) group, cyclooctyl group, decahydronaphthalyl group, methylsilyl group, dimethylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, dithylsilyl group, dithylsilyl group Diethylsilyl group, Triethylsilyl group, Propylsilyl group, Dipropylsilyl group, Tripropylsilyl (Tri propylsilyl group, butylsilyl group, dibutylsilyl group, tributylsilyl group, tributylsilyl group, (methylsilyl) methyl ((Methylsilyl) methyl group, (dimethylsilyl) methyl ((Dimethylsilyl) methyl ), (Trimethylsilyl) methyl ((Trimethylsilyl) methyl) group, (ethylsilyl) methyl ((Ethylsilyl) methyl) group, (diethylsilyl) methyl ((Dethylsilyl) methyl) group, (triethylsilyl) methyl ( (Triethylsilyl) methyl), (methylsilyl) ethyl ((Methylsilyl) ethyl) group, (dimethylsilyl) ethyl ((Dimethylsilyl) ethyl) group, (trimethylsilyl) ethyl ((Trimethylsilyl) ethyl) group, and the like;

The C6-C20 aryl (Aryl) group, C7-C20 arylalkyl (Arylalkyl), C7-C20 alkylaryl (Alkylaryl), C6-C20 arylsilyl (Arylsilyl), C6 Non-limiting examples of ˜20 silylaryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphtyl, and fluorenyl groups. , Benzyl group, Phenylethyl group, Phenylpropyl group, Methylphenyl group, Dimethylphenyl group, Trimethylphenyl group, Ethylphenyl group, Diethyl Diphenylphenyl group, Triethylphenyl group, Propylphenyl group, Dipropylphenyl group, Tripropylphenyl group, Phenylsilyl group, Methylphenylsilyl group , Dimethylphenylsilyl group, methyldiphenylsilyl group, triphenylsilyl (Tripheny lsilyl group, ethylphenylsilyl group, (methylphenyl) silyl ((Methylphenyl) silyl group, (ethylphenyl) silyl ((Ethylphenyl) silyl group, trifluoromethylphenylsilyl) group, (methylsilyl (Phenyl) ((Methylsilyl) phenyl) group, (dimethylsilyl) phenyl ((Dimethylsilyl) phenyl) group, (trimethylsilyl) phenyl ((Trimethylsilyl) phenyl) group, (ethylsilyl) phenyl ((Ethylsilyl) phenyl) group, ( Diethylsilyl) phenyl ((Diethylsilyl) phenyl) group, (triethylsilyl) phenyl ((Triethylsilyl) phenyl) group, (propylsilyl) phenyl ((Propylsilyl) phenyl) group, (dipropylsilyl) phenyl ((Dipropylsilyl) phenyl), (butylsilyl) phenyl ((Butylsilyl) phenyl) group, (dibutylsilyl) phenyl ((Dibutylsilyl) phenyl) group and the like;

Non-limiting examples of the haloalkyl group having 1 to 20 carbon atoms include a trifluoromethyl group, a trichloromethyl group, and the like;

Non-limiting examples of the halogen group include a fluoro group, a chloro group, a bromo group, an iodo group, and the like;

Non-limiting examples of the C1-20 alkoxy (alkoxy), C1-20 alkylsiloxy (Alkylsiloxy) groups are methoxy (Methoxy), ethoxy (Ethoxy), propoxy (Propoxy) group , Butoxy group, Pentoxy group, Hexyloxy group, Methylsiloxy group, Dimethylsiloxy group. Trimethylsiloxy group, ethylsiloxy group, diethylsiloxy group, triethylsiloxy group and the like;

Non-limiting examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a naphtoxy group, a methylphenoxy group, a dimethylphenoxy group, and a trimethylphenoxy group. Trimethylphenoxy group, Ethylphenoxy group, Diethylphenoxy group, Triethylphenoxy group, Propylphenoxy group, Dipropylphenoxy group, Tree Propylphenoxy group;

Non-limiting examples of the amine group include a dimethylamine group, a diethylamine group, a dipropylamine group, a dibutylamine group, a dibutylamine group, and a diphenylamine group. And dibenzylamine groups.

<Catalyst for Olefin Polymerization and Supported Catalyst for Olefin Polymerization >

The catalyst for olefin polymerization of the present invention

(a) the metallocene compound of Formula 1; And

(b) a compound selected from the group consisting of an aluminoxane compound of Formula 4 and an organoaluminum compound of Formula 5; and a catalyst system for preparing an olefin polymer.

In the supported catalyst for olefin polymerization of the present invention, the catalyst for olefin polymerization is supported on a carrier. In this case, the carrier is an inorganic compound and / or an organic compound.

Specifically, the supported catalyst for olefin polymerization of the present invention

(i) (a) a metallocene compound of Formula 1; And (b) a compound selected from the group consisting of an aluminoxane compound of Formula 4 and an organoaluminum compound of Formula 5; And

(ii) A catalyst system for producing an olefin polymer, comprising a carrier supporting the catalyst for olefin polymerization of (i).

Preferably, in the present invention, the olefin is propylene, and the catalyst of the present invention is a catalyst for propylene polymerization and a supported catalyst for propylene polymerization.

In the catalyst of the present invention, that is, the catalyst for olefin polymerization and the supported catalyst for olefin polymerization, (a) the metallocene compound of Formula 1 is included as a main catalyst, and (b) the aluminoxane compound of Formula 4 and the Compounds selected from the group consisting of organoaluminum compounds of formula (5) are included as cocatalysts for the metallocene compound of formula (1) to have a polymerization catalytic activity.

In addition, in the catalyst of the present invention, (a) the metallocene compound of Formula 1 is reacted with a compound selected from the group consisting of the aluminoxane compound of Formula 4 and the organoaluminum compound of Formula 5 to form an olefin polymer. It is characterized by adjusting the stereoregularity.

Specifically, the substituent of Formula 2 and / or the substituent of Formula 3 in the metallocene compound of Formula 1 reacts with the aluminoxane compound of Formula 4 and / or the organoaluminum compound of Formula 5 to activate the active site of the catalyst. The stereoregularity of the olefin (preferably propylene) polymer can be controlled by determining the direction of insertion of the olefin (preferably propylene) relative to the catalytic active site by inducing a stereocontrol effect around the periphery.

In addition, in the catalyst of the present invention, (b) the aluminoxane compound of formula (4) and / or the organoaluminum compound of formula (5) is a cocatalyst for (a) the metallocene compound of formula (1) to have a polymerization catalyst activity Of the olefin polymer (preferably propylene polymer) by reaction with the metallocene compound of formula 1 (particularly the substituent of formula 2 and / or the substituent of formula 3 in the metallocene compound of formula 1) together with the role of It can play a role in controlling stereograms.

In the present invention, in the case of the aluminoxane compound of Formula 4, it may have a linear (linear) or cyclic (Cyclic) or network (Network) structure, non-limiting examples of methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane , Hexyl aluminoxane, octyl aluminoxane, and decyl aluminoxane.

In addition, The organoaluminum compound of formula 5 may be selected from the group consisting of trialkylaluminum, dialkylaluminum alkoxide, dialkylaluminum halide, alkylaluminum dialkoxide, and alkylaluminum dihalide.

remind Non-limiting examples of the organoaluminum compound of Formula 5 include Trimethylaluminum, Triethylaluminum, Tributylaluminum, Trihexylaluminum, Trioctylaluminum, Tridecylaluminum Trialkylaluminum such as Tricylaluminum;

Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum methoxide, and dibutylaluminum methoxide;

Dialkylaluminum alkoxides such as dimethylaluminum chloride, diethylaluminum chloride, and dibutylaluminum chloride;

Alkyl aluminum dialkoxides such as methylaluminum dimethoxide, ethylaluminum dimethoxide, and butylaluminum dimethoxide; or

Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, butylaluminum dichloride, and the like, but are not limited thereto.

The aluminoxane compound of Formula 4 and / or the organoaluminum compound of Formula 5 may be used alone or in combination of two or more thereof.

Meanwhile, in the supported catalyst for olefin polymerization of the present invention, the main catalyst (a) the metallocene compound of Formula 1 and the cocatalyst (b) the aluminoxane compound of Formula 4 and / or the organoaluminum compound of Formula 5 The support supporting the catalyst for olefin polymerization including the above may be an inorganic compound and / or an organic compound.

The inorganic compound usable as the carrier is not limited to a specific material but may be used without limitation as long as the surface has a fine pore and a large surface area.

Examples of the inorganic compound include silica, alumina, bauxite, zeolite, MgCl ₂ , CaCl ₂ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or mixtures thereof may be used, but is not limited thereto. In addition, examples of the mixture of the inorganic compounds include SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -CrO ₂ O ₃ , SiO ₂ -TiO ₂ -MgO and the like, but is not limited thereto. In addition, the inorganic compound or a mixture thereof may include a small amount of carbonate, sulfate, and / or nitrate.

In addition, examples of the organic compound that can be used as the carrier include, but are not limited to, Starch, Cyclodextrin, or synthetic polymer.

In addition, the inorganic compound and / or organic compound which can be used as the said carrier can be used individually or in mixture of 2 or more types.

On the other hand, in the supported catalyst for olefin polymerization of the present invention, (a) for the olefin polymerization containing a metallocene compound of formula (1) and (b) an aluminoxane compound of formula (4) and / or an organoaluminum compound of formula (5) The method of supporting the catalyst on the carrier of the inorganic compound and / or the organic compound is not particularly limited.

As a non-limiting example, a method of directly supporting (a) a metallocene compound synthesized on a dehydrated carrier; Or (b) pretreating the carrier with the organoaluminoxane compound and / or the organoaluminum compound, and then (a) supporting the metallocene compound; Or (a) supporting the synthesized metallocene compound on the carrier and then (b) treating the organoaluminoxane compound and / or the organoaluminum compound; Or a method of reacting (a) the metallocene compound with (b) the organoaluminoxane compound and / or the organoaluminum compound and then with the carrier.

A solvent can be used when supporting the catalyst for olefin polymerization of this invention on a support | carrier. Examples of solvents that may be used include pentane, hexane, heptane, octane, nonane, decane, decane, undecane, and dodecane. Aliphatic hydrocarbon solvents such as these; Or aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; Or halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane, trichloroethane, and the like, but are not limited thereto. It can mix and use the above.

In the catalyst for olefin polymerization of the present invention, the main catalyst is selected from the group consisting of (a) a metallocene compound of Formula 1 and a promoter (b) an aluminoxane compound of Formula 4 and an organoaluminum compound of Formula 5 the amount of the compound of between not particularly limited, but the co-catalyst / catalyst state ((b) / (a) ) is 1/1 to 10 ^6/1 in molar ratio, preferably 1/1 ~ 5 × 10 ⁴ / It can be a ratio of 1.

In addition, in the supported catalyst for olefin polymerization of the present invention, the main catalyst (a) is composed of a metallocene compound of Formula 1 and a promoter (b) an aluminoxane compound of Formula 4 and an organoaluminum compound of Formula 5 the amount of the compound is selected from among the group of particularly limited, but the co-catalyst / catalyst state ((b) / (a) ) is 1/1 to 10 ^4/1 in molar ratio, preferably from 1/1 - 2 × 10 ^3/1 may be a ratio. In addition, the amount between the catalyst for olefin polymerization of (i) containing the main catalyst and the cocatalyst and the carrier is not particularly limited and may be appropriately adjusted according to the polymerization reaction system.

The temperature maintained when the catalyst for olefin polymerization of (i) of the present invention is supported on a carrier is -50 ° C to 150 ° C, preferably -20 ° C to 100 ° C.

<Olefin polymer and preparation method thereof>

The present invention provides a polymerization method of olefins, characterized in that the olefins are polymerized using the catalyst for olefin polymerization and / or the supported catalyst for olefin polymerization according to the present invention.

In addition, the present invention provides an olefin polymer, characterized in that it comprises an olefin polymer catalyst and / or a supported catalyst for olefin polymerization according to the present invention as an olefin polymer prepared according to the polymerization method.

The catalyst of the present invention can be used for the production of copolymers with other olefins or other monomers, in addition to the homopolymers of olefins. Therefore, in the present invention, the olefin polymer is preferably a homopolymer or copolymer of olefins.

Non-limiting examples of the olefin in the present invention, the C2-C20 α-Olefin, C4-C20 Diolefin, C3-C20 Cycloolefin, C4-C4 20 cyclodiolefin, styrene, or styrene derivatives, but is not limited thereto. The styrene derivative has at least one functional group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen group, an amine group, a silyl group, and a haloalkyl group having 1 to 10 carbon atoms, and a benzene ring of styrene. (phenyl ring) may be substituted.

Preferably, the olefin is propylene in the present invention and the olefin polymer of the present invention is polypropylene or propylene copolymer.

In addition, in the present invention, other olefins or other monomers usable in the preparation of the copolymer of propylene may be those excluding propylene from the above-described olefins, and these may be used alone or in combination of two or more thereof.

In the case of homopolymerization or copolymerization of propylene using the catalyst of the present invention, the polymerization may be carried out in a slurry phase, a liquid phase, a gas phase, or a bulk phase.

When the polymerization is carried out in a slurry, liquid or mass, a solvent or olefin itself may be used as the medium, and the olefins used for the polymerization may be used alone or in combination of two or more kinds thereof.

Non-limiting examples of the solvent used in the polymerization of the present invention, butane (Butane), isobutane (Isobutane), pentane (Hexane), heptane (Octane), Nonane (Nonane) Aliphatic hydrocarbon solvents such as decane, undecane, undecane, dodecane, cyclopentane, methylcyclopentane and cyclohexane;

Or aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene and chlorobenzene;

Or halogenated dichloromethane, trichloromethane, chloroethane, dichloroethane, dichloroethane, trichloroethane, 1,2-dichloroethane, etc. Aliphatic hydrocarbon solvents, but are not limited to these. In addition, these solvents can be used individually or in mixture of 2 types at the time of a polymerization reaction.

In the present invention, when the polymerization is carried out through a slurry phase, a liquid phase, a gaseous phase, or a bulk process, the amount of the olefin polymerization catalyst and / or the supported catalyst for olefin polymerization according to the present invention is not particularly limited. The concentration of the central metal of the metallocene compound of Chemical Formula 1 in the reaction system is 10 ^-10 mol / liter-1 mol / liter, preferably 10 ^-8 mol / liter-10 ^-2 mol / liter.

In the polymerization according to the present invention, the polymerization temperature is not particularly limited, but is -50 to 200 ° C, preferably 0 to 150 ° C; Polymerization can be carried out in a batch type, semi-continuous type or continuous type; The polymerization pressure is usually 1 to 3,000 bar, preferably 1 to 500 bar, and more preferably 2 to 100 bar. If the pressure is less than 2bar, XS (the ratio of Atactic Polypropylene having low stereoregularity among polypropylenes obtained after polymerization) increases (see Table 4 below) .The higher the pressure, the better. .

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and polymerization examples, but the scope of the present invention is not limited to the following contents.

[Synthesis Example of Metallocene Compound]

All synthesis reactions were carried out in an Inert Atmosphere such as Nitrogen or Argon, using standard Schlenk technology and Glove Box technology.

The solvent for synthesis such as tetrahydrofuran (THF), n - hexane, diethyl ether, methylene chloride (Methylene Chloride, CH ₂ Cl ₂ ), etc. is activated alumina layer. After removing water by passing through (Activated Alumina Column), it was used while storing on activated molecular sieves (Molecular Sieve 5A, Yakuri Pure Chemicals Co), and used for the NMR structure analysis of organometallic compounds. d , CDCl ₃ ) was purchased from Cambridge Isotope Laboratories and dried on an activated molecular sieve (Molecular Sieve 5A, Yakuri Pure Chemicals Co).

Ethanol, ethylacetate, acetonitrile, sodium cyanoborohydride, n - butyllithium (2.5 M solution in n- hexane), methyllithium (1.6 M solution in Diethyl ether)), 2-Methoxyphenylmagnesium bromide (1.0 M solution in THF), 3-Methoxyphenylmagnesium bromide (1.0 M solution in THF) ), 2-bromo - N, N- dimethylaniline (2-Bromo- N, N- dimethylaniline ), 3- bromo - N, N- dimethylaniline (3-Bromo- N, N- dimethylaniline ), 1- bromo-3,5-dimethoxybenzene (1-bromo-3,5-dimethoxybenzene ), ammonium chloride (ammonium chloride), anhydrous magnesium sulfate (magnesium sulfate, anhydrous), para-toluenesulfonic acid hydrate (para- toluenesulfonic acid monohydrate ( p- TsOH.H ₂ O)) was purchased from Sigma-Aldrich and used without purification. Trahydrofuran) zirconium (Tetrachlorobis (tetrahydrofuran) zirconium, ZrCl ₄ 2C ₄ H ₈ O) was purchased from Strem and used without purification.

¹ H NMR and ¹³ C NMR were measured using a Bruker Avance 400 Spectrometer at room temperature, and the chemical shift of the NMR spectrum was determined by the chemical shift ( ¹ H NMR) indicated by deuterated chloroform (CDCl ₃ ). In the case of δ = 7.24 ppm, and ¹³ C NMR, δ = 77.0 ppm). All elemental analyzes were measured using EA 1110-FISION (CE Instruments), and X-ray molecular structure analysis was measured by Enrarf-Nonius CAD4TSB Diffractometer and calculated by calculation on Silicon Graphics Indigo2XZ Workstation.

Synthesis Example 1 Bis- [1- ( o- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( o- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( o- Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 1-1 1- ( o- Dimethylaminophenyl) -3,4-dimethylcyclopentadiene (1- ( o- Dimethylaminophenyl) -3,4-dimethylcyclopentadiene, ( o- Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

2-Bromo- N , N- dimethylaniline (4.00 g, 20 mmol) was dissolved in 50 mL of diethyl ether, and then 1 equivalent of normal butyllithium (8.0 mL) was added at 0 ° C. After stirring for 2 hours at room temperature, the temperature was lowered to -78 ° C and 20 mL of tetrahydrofuran solution in which 1 equivalent of 3,4-dimethylcyclopenta-2-enone (2.20 g, 20 mmol) was added dropwise, followed by room temperature. Slowly put up and stir overnight. Then, distilled water (10 mL) was added to the obtained brown solution, and 20 mL of HCl solution was added thereto. Then, only the aqueous layer was extracted and collected and washed with 50 mL of diethyl ether. The combined aqueous layer was neutralized again with 10% NaOH aqueous solution, and then the organic layer was extracted with diethyl ether (2 × 50 mL), collected, dried over anhydrous magnesium sulfate, and filtered. The solvent was evaporated with a rotary evaporator. The yellow oil obtained was purified by column chromatography (silica gel, ethyl acetate / normal hexane = 1/10) to give 1- ( o- dimethylaminophenyl) -3,4- as a pale yellow oil. Dimethylcyclopentadiene was obtained in 32% yield.

The results of ¹ H NMR and ¹³ C { ¹ H} NMR confirming the synthesis of 1- ( o- dimethylaminophenyl) -3,4-dimethylcyclopentadiene are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.27 (d, 1H), 7.12 (t, 1H), 7.01 (d, 1H), 6.93 (t, 1H), 6.71 (s, 1H), 3.36 (s , 2H), 2.65 (s, 6H), 1.96 (s, 3H), 1.89 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 151.3, 142.3, 135.5, 135.2, 134.5, 131.0, 129.2, 126.8, 122.1, 118.4, 46.7, 43.8, 13.3, 12.6.

Synthesis Example 1-2 Bis- [1- ( o- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( o- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( o- Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

1- ( o- dimethylaminophenyl) -3,4-dimethylcyclopentadiene (0.853 g, 4.0 mmol) synthesized in Synthesis Example 1-1 was dissolved in 20 mL diethyl ether, and then dried at -78 ° C. One equivalent of normal butyllithium (1.6 mL) was added. The reactor was raised to room temperature and stirred for 4 hours. The solvent was evaporated and the white lithium salt obtained was mixed with half equivalent of tetrachlorobis (tetrahydrofuran) zirconium (0.755 g, 2 mmol), and then dissolved in 30 mL of toluene at -78 ° C. The mixed solution was slowly raised to room temperature and stirred while heating to 60 ° C. overnight. Next, lithium chloride (LiCl) formed as a by-product of the reaction was removed by Celite filtration, and the solvent was evaporated. Then, the solvent was washed with normal hexane and dried to obtain 0.616 g of bis [1- ( o- dimethylaminophenyl) -3, 4-dimethylcyclopentadienyl] zirconium dichloride was obtained in 52% yield. In addition, the resultant was recrystallized in methylene chloride / normal hexane solution at -20 ℃ to give a yellow crystalline solid.

¹ H confirming the synthesis of the bis [1- ( o- dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.45 (d, 2H), 7.18-7.02 (m, 4H), 7.00 (t, 2H), 6.68 (s, 4H), 2.62 (s, 12H), 1.71 (s, 12H).

¹³ C {1H} NMR (100.62 MHz, CDCl ₃ ): δ 151.4, 130.0, 127.8, 127.6, 126.6, 122.9, 121.7, 119.0, 118.6, 44.5, 13.2.

Anal. Calcd for C ₃₀ H ₃₆ Cl ₂ N ₂ Zr: C, 61.41; H, 6.18 .; N, 4.77.

Found: C, 60.46; H, 6. 23; N, 4.70.

Synthesis Example 2 Bis- [1- ( m- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( m- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( m- Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 2-1 1- ( m- Dimethylaminophenyl) -3,4-dimethylcyclopentadiene (1- ( m- Dimethylaminophenyl) -3,4-dimethylcyclopentadiene, 1- ( m- Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

[Synthesis] except that 3-bromo- N , N- dimethylaniline (4.00 g, 20 mmol) was used instead of 2-bromo- N , N- dimethylaniline used in [Synthesis Example 1-1]. When the reaction was carried out under the same conditions as in Example 1-1], 1.27 g of 1- ( m- dimethylaminophenyl) -3,4 - dimethylcyclopentadiene as a pale yellow solid was obtained in 30% yield.

The 1- (m- dimethylaminophenyl) ¹ H confirming the synthesis of 3,4-dimethyl cyclopentadiene NMR and ¹³ C { ¹ H} NMR results are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.17 (t, 1H), 6.86-6.83 (m, 2H), 6.64 (s, 1H), 6.59 (dd, 1H), 3.28 (s, 2H), 2.96 (s, 6H), 1.98 (s, 3H), 1.90 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 150.9, 143.3, 137.1, 135.5, 135.4, 131.4, 129.1, 113.7, 111.0, 108.9, 45.4, 40.7, 13.4, 12.6.

Synthesis Example 2-2 Bis- [1- ( m- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( m- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( m- Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 1-2, except that 1- ( m- dimethylaminophenyl) -3,4-dimethylcyclopentadiene (0.853 g, 4.0 mmol) synthesized in Synthesis Example 2-1 was used. ], 0.567 g (48% yield) of bis- [1- ( m- dimethylaminominophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride as a light yellow crystalline solid. Got.

¹ H confirming the synthesis of the bis- [1- ( m- dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.29 (t, 2H), 6.81 (d, 2H), 6.77 (s, 2H), 6.66 (d, 2H), 6.21 (s, 4H), 3.00 (s , 12H), 1.82 (s, 12H).

¹³ C {1H} NMR (100.62 MHz, CDCl ₃ ): δ 151.1, 134.3, 129.7, 128.0, 123.5, 116.6, 113.5, 111.6, 109.6, 40.6, 13.3.

Anal. Calcd for C ₃₀ H ₃₆ Cl ₂ N ₂ Zr: C, 61.41; H, 6.18 .; N, 4.77.

Found: C, 62.04; H, 6. 37; N, 4.77.

Synthesis Example 3 Bis- [1- (3,5- N, N, N ', N'- Tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (3,5- N, N, N ', N'- tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (3,5- (Me ₂ N) ₂ C ₆ H ₃ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 3-1 1-Bromo-3,5- N, N, N ', N'- Tetramethyldiaminobenzene (1-Brmo-3,5- N, N, N ', N'- tetramethyldiaminobenzene, 1-Br-3,5- (Me ₂ N) ₂ C ₆ H ₃ ) Synthesis

1-Bromo-3,5-diaminobenzene (2.80 g, 15 mmol) was dissolved in acetonitrile and p- formaldehyde (1.80 g, 60 mmol) was added at 0 ° C. After stirring at room temperature for 3 minutes, sodium cyanoborohydride (3.00 g total, 48 mmol) was divided into four portions over 40 minutes, followed by further stirring for 25 minutes. Glacial acetic acid was added until the solution was neutralized, and stirring was continued for 45 minutes. Then, all solvents were removed and a 2 normal KOH aqueous solution was added until the pH was 9. Only the organic layer was extracted with ethyl acetate (3 × 50 mL), collected, dried over anhydrous magnesium sulfate, and filtered. The oil thus obtained was purified by column chromatography (silica gel, ethyl acetate / normal hexane = 1/9) to obtain 0.40 g of an off-white solid, 1-bromo-3,5- N, N, N ', N'- tetramethyl. Diaminobenzene was obtained in 11% yield.

¹ H NMR, ¹³ C { ¹ H} NMR confirming the synthesis of 1-bromo-3,5- N, N, N ', N'- tetramethyldiaminobenzene, and the results of mass spectrometry are as follows. It was.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 6.26 (d, 2H), 5.88 (s, 1H), 2.90 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 152.3, 124.0, 104.9, 95.4, 40.6.

Synthesis Example 3-2 1- (3,5- N, N, N ', N'- Tetramethyldiaminophenyl) -3,4-dimethylcyclopentadiene (1- (3,5- N, N, N ', N'- tetramethyldiaminophenyl) -3,4-dimethylcyclopentadiene, 1- ((3,5-Me ₂ N) ₂ C ₆ H ₃ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

1-bromo-3,5- N, N, N ', N'- tetramethyldiaminobenzene (1.21 g) instead of 2-bromo- N, N- dimethylaniline used in [Synthesis Example 1-1] , 5 mmol) was used under the same conditions as in [Synthesis Example 1-1] to give 0.53 g of a pale yellow solid, 1- (3,5- N, N, N ', N'- Tetramethyldiaminophenyl) -3,4-dimethylcyclopentadiene can be obtained in 41% yield.

The 1- (3,5- N, N, N ', N'- tetramethyl-diamino-phenyl) ¹ H confirming the synthesis of 3,4-dimethyl cyclopentadiene NMR and ¹³ C { ¹ H} NMR results are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 6.62 (s, 1H), 6.33 (d, 2H), 6.01 (s, 1H), 3.28 (s, 2H), 2.95 (d, 12H), 1.97 (s , 3H), 1.90 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 151.8, 144.1, 137.5, 135.2, 131.1, 99.9, 96.9, 45.6, 41.0, 13.4, 12.6.

Synthesis Example 3-3 Bis- [1- (3,5- N, N, N ', N'- Tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (3,5- N, N, N ', N'- tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (3,5- (Me ₂ N) ₂ C ₆ H ₃ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

1- (3,5- N, N, N ', N'- tetramethyldiaminophenyl) -3,4-dimethylcyclopentadiene (0.513 g, 2.0 mmol) synthesized in Synthesis Example 3-2 above Except that tetrachlorobis (tetrahydrofuran) zirconium (0.377 g, 1 mmol) was used, and the reaction was carried out in the same manner as in [Synthesis Example 1-2] to give a bis- [1- ( 0.321 g (48% yield) of 3,5- N, N, N ', N'- tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride was obtained.

¹ H confirming the synthesis of the bis- [1- (3,5- N, N, N ', N'- tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 6.26 (s, 4H), 6.25 (d, 4H), 6.00 (s, 2H), 2.98 (s, 24H), 1.85 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 152.1, 134.8, 127.7, 124.5, 116.9, 100.0, 96.6, 40.8, 13.4.

Anal. Calcd for C ₃₄ H ₄₆ Cl ₂ N ₄ Zr: C, 60.69; H, 6.89; N, 8.33.

Found: C, 60.45; H, 6. 80; N, 8.66.

Synthesis Example 4 Bis- [1- ( o- Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( o- methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( o- MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 4-1 1- ( o- Methoxyphenyl) -3,4-dimethylcyclopentadiene (1- ( o- methoxyphenyl) -3,4-dimethylcyclopentadiene, ( o- MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

Dissolve 3,4-dimethylcyclopenta-2-enone (2.20 g, 20 mmol) in 20 mL of tetrahydrofuran, and slowly add 1 equivalent of 2-methoxyphenylmagnesium bromide (20 mmol) at -78 ° C. gave. The reaction solution was raised to room temperature and stirred overnight. The reaction was terminated by adding an appropriate amount of saturated aqueous ammonium chloride solution to the orange solution. Then, the organic layer was extracted with diethyl ether (50 mL), collected, dried over anhydrous magnesium sulfate, and filtered. The filtered solution was removed from the solvent in a rotary evaporator to give a pale orange oil. The oil was dissolved in methylene chloride (30 mL) again, and then paratoluenesulfonic acid hydrate (approximately 0.1 g) was added and stirred at room temperature for 1 hour. The solvent was removed using a rotary evaporator, and the resulting yellow oil was purified by column chromatography (silica gel, ethyl acetate / normal hexane = 1/10) to yield 1.20 g of an off-white solid 1- ( o -methoxyphenyl). -3,4-dimethylcyclopentadiene was obtained in 30% yield.

The results of ¹ H NMR and ¹³ C { ¹ H} NMR confirming the synthesis of 1- ( o -methoxyphenyl) -3,4-dimethylcyclopentadiene are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.38 (d, 1H), 7.12 (t, 1H), 6.92-6.87 (m, 3H), 3.88 (s, 3H), 3.35 (s, 2H), 1.97 (s, 3 H), 1.90 (s, 3 H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 156.7, 139.0, 135.8, 135.6, 135.5, 127.6, 126.7, 125.6, 120.5, 111.0, 55.2, 47.4, 13.3, 12.6.

Synthesis Example 4-2 Bis- [1- ( o- Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( o- methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( o- MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 1-2, except that 1- ( o -methoxyphenyl) -3,4-dimethylcyclopentadiene (0.801 g, 4.0 mmol) synthesized in Synthesis Example 4-1 was used. ], The reaction was carried out in the same manner to obtain 0.504 g (45% yield) of bis- [1- ( o -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride as a light yellow solid.

¹ H confirming the synthesis of the bis- [1- ( o -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.36 (dd, 2H), 7.26 (d, 2H), 7.01-6.97 (m, 4H), 6.40 (s, 4H), 3.91 (s, 6H), 1.83 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 155.7, 128.4, 128.3, 127.8, 122.4, 120.8, 119.8, 118.1, 111.3, 55.1, 13.2.

Anal. Calcd for C ₂₈ H ₃₀ Cl ₂ O ₂ Zr: C, 59.98; H, 5.39.

Found: C, 59.97; H, 5.64.

Synthesis Example 5 Bis- [1- ( m- Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( m- methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( m- MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 5-1 1- ( m- Methoxyphenyl) -3,4-dimethylcyclopentadiene (1- ( m- methoxyphenyl) -3,4-dimethylcyclopentadiene, 1- ( m- MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

The reaction was carried out under the same conditions as in [Synthesis Example 4-1], except that 3-methoxyphenylmagnesium bromide (20 mmol) was used instead of 2-methoxyphenylmagnesium bromide used in Synthesis Example 4-1. Proceeding, 1.00 g of pale yellow oil, 1- ( m -methoxyphenyl) -3,4-dimethylcyclopentadiene, was obtained in 25% yield.

The 1- (m- methoxyphenyl) ¹ H confirming the synthesis of 3,4-dimethyl cyclopentadiene NMR and ¹³ C { ¹ H} NMR results are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.18 (t, 1H), 7.03 (d, 1H), 6.96 (t, 1H), 6.69 (dd, 1H), 6.64 (s, 1H), 3.80 (s , 3H), 3.24 (s, 2H), 1.96 (s, 3H), 1.88 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 159.8, 142.3, 137.8, 136.1, 135.5, 132.1, 129.4, 117.3, 111.4, 110.2, 55.2, 45.3, 13.4, 12.6.

Synthesis Example 5-2 Bis- [1- ( m- Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( m- methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( m- MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 1-2, except that 1- ( m -methoxyphenyl) -3,4-dimethylcyclopentadiene (0.801 g, 4.0 mmol) synthesized in Synthesis Example 5-1 was used. ], The reaction was carried out in the same manner as to obtain 0.519 g (46% yield) of bis- [1- ( m -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride as a light yellow solid.

¹ H confirming the synthesis of the bis [1- ( m -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.35 (t, 2H), 7.05 (d, 2H), 6.98 (t, 2H), 6.82 (dd, 2H), 6.22 (s, 4H), 3.85 (s , 6H), 1.79 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 160.2, 134.8, 130.2, 128.3, 122.1, 117.6, 116.4, 113.0, 110.8, 55.3, 13.2.

Anal. Calcd for C ₂₈ H ₃₀ Cl ₂ O ₂ Zr: C, 59.98; H, 5.39.

Found: C, 60.59; H, 5.62.

Synthesis Example 6 Bis- [1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (3,5-dimethoxyphenyl) -3,4 -dimethylcyclopentadienyl] zirconium dichloride, [1- (3,5- (MeO) ₂ C ₆ H ₃ ) -3,4- Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 6-1 1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadiene (1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadiene, 1- (3,5 -(MeO) ₂ C ₆ H ₃ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

1-bromo-3,5-dimethoxybenzene (4.34 g, 20 mmol) was dissolved in 20 mL of diethyl ether and then 1 equivalent of normal butyllithium (8.0 mL) was added at 0 ° C. After stirring for 2 hours at room temperature, the temperature was lowered to -78 ° C and 20 mL of tetrahydrofuran solution in which 1 equivalent of 3,4-dimethylcyclopenta-2-enone (2.20 g, 20 mmol) was added dropwise, followed by room temperature. Slowly put up and stir overnight. Next, the reaction was carried out in the same manner as in [Synthesis Example 4-1], and the obtained yellow oil was dissolved in ethanol and recrystallized at -20 ° C to give 1.31 g of a light off-white solid, 1- (3,5). -Dimethoxyphenyl) -3,4-dimethylcyclopentadiene was obtained in 33% yield.

¹ H confirming the synthesis of 1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadiene NMR and ¹³ C { ¹ H} NMR results are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 6.64 (s, 1H), 6.59 (d, 2H), 6.28 (t, 1H), 3.79 (s, 6H), 3.23 (s, 2H), 1.96 (s , 3H), 1.88 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 160.9, 142.3, 138.3, 136.2, 135.4, 132.4, 102.8, 98.3, 55.3, 45.4, 13.4, 12.6.

Synthesis Example 6-2 Bis- [1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (3,5-dimethoxyphenyl) -3 , 4-dimethylcyclopentadienyl] zirconium dichloride, [1- (3,5- (MeO) ₂ C ₆ H ₃ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

[Synthesis example 1], except that 1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadiene (0.921 g, 4.0 mmol) synthesized in Synthesis Example 6-1 was used. 0.42 g (36% yield) of bis- [1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride as a yellow solid Got.

¹ H confirming the synthesis of the bis [1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 6.59 (d, 4H), 6.39 (d, 2H), 6.19 (s, 4H), 3.83 (s, 12H), 1.85 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 161.4, 135.5, 128.3, 122.3, 116.7, 103.5, 99.4, 55.4, 13.3.

Anal. Calcd for C ₃₀ H ₃₄ Cl ₂ O ₄ Zr: C, 58.05; H, 5.52.

Found: C, 58.61; H, 5.66.

Synthesis Example 7 Bis- [1- ( p- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p- Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 7-1 1- ( p- Dimethylaminophenyl) -3,4-dimethylcyclopentadiene (1- ( p- Dimethylaminophenyl) -3,4-dimethylcyclopentadiene, ( p- Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

4-bromo- N, N- dimethylaniline (4.00 g, 20 mmol) was dissolved in 50 ml of diethyl ether, and then 1 equivalent of normal butyllithium (8.0 ml) was added at 0 ° C. After stirring for 2 hours at room temperature, the lithium salt obtained by evaporating all the solvent was washed twice with normal hexane, and then dried in vacuo. The lithium salt was dissolved in 40 ml of tetrahydrofuran again at -78 ° C, and a 20 ml solution of an equivalent amount of 3,4-dimethylsiglopenta-2-enone (2.20 g, 20 mmol) was dissolved in cannula. After dropping through, slowly raised to room temperature and stirred overnight. Then, an appropriate amount of saturated aqueous ammonium chloride solution was added to the orange solution to terminate the reaction.

Then, only the organic layer was extracted with diethyl ether (50 ml), collected, dried over anhydrous magnesium sulfate, and filtered. The filtered solution was removed solvent in a rotary evaporator to give a yellow oil. This oil was dissolved in methylene chloride (30 ml), para-toluenesulfone acid hydrate (ca. 0.1 g) was added thereto, and stirred at room temperature for 1 hour to obtain an ivory-colored solid. The solvent was evaporated with a rotary evaporator, precipitated with 30 ml of normal hexane, and filtered using a glass filter. The filtered solid was washed with ethanol (30 ml), diethyl ether (30 ml) and normal-pentane (30 ml) and dried in vacuo to give 63% of 1- ( p- dimethylaminophenyl) -3,4-dimethylcyclopentadiene. Obtained in yield.

The results of ¹ H NMR and ¹³ C { ¹ H} NMR confirming the synthesis of 1- ( p- dimethylaminophenyl) -3,4-dimethylcyclopentadiene are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.33 (d, 2H), 6.69 (d, 2H), 6.45 (s, 1H), 3.21 (s, 2H), 2.93 (s, 6H), 1.94 (s , 3H), 1.86 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 142.8, 135.4, 133.7, 128.3, 125.5, 112.9, 45.2, 40.8, 13.4, 12.6.

Synthesis Example 7-2 Bis [1- ( p- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis [1- ( p- Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p- Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

1.280 g (6.0 mmol) of 1- ( p- dimethylaminophenyl) -3,4 - dimethylcyclopentadiene synthesized in [Synthesis Example 7-1] was dissolved in 30 ml diethyl ether, followed by 1 equivalent at -78 ° C. Normal butyl lithium (2.4 mL) was added. The reactor was raised to room temperature and stirred for 4 hours. The solvent was evaporated and the white lithium salt obtained was mixed with half equivalent of tetrachlorobis (tetrahydrofuran) zirconium (3.0 mmol, 1.132 g), and then dissolved in toluene (50 ml) at -78 ° C. The mixed solution was slowly raised to room temperature and stirred while heating to 50 ° C. overnight. Next, lithium chloride (LiCl) formed as a by-product of the reaction was removed by Celite filtration, and the solvent was evaporated to 0.968 g of bis- [1- ( p- dimethylaminophenyl) -3,4-dimethylcyclopentadie. Nil] zirconium dichloride Obtained in 55% yield. In addition, the resultant was recrystallized in methylene chloride / normal hexane solution at -20 ℃ to give a red crystalline solid.

¹ H confirming the synthesis of the bis- [1- ( p- dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.34 (d, 4H), 6.77 (d, 4H), 6.14 (s, 4H), 2.99 (s, 12H), 1.77 (s, 12H).

¹³ C {1H} NMR (100.62 MHz, CDCl ₃ ): δ 149.7, 127.1, 126.2, 123.9, 121.7, 114.6, 112.6, 40.5, 13.1.

Anal. Calcd for C ₃₀ H ₃₆ Cl ₂ N ₂ Zr: C, 61.41; H, 6.18; N, 4.77.

Found: C, 61.60; H, 6.25; N, 4.99.

Synthesis Example 8 Bis [1- ( p- Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p- methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p- MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 8-1 1- ( p- Methoxyphenyl) -3,4-dimethylcyclopentadiene (1- ( p- methoxyphenyl) -3,4-dimethylcyclopentadiene, ( p- MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

40 ml of 4-methoxyphenylmagnesium bromide (20 mmol) was slowly added to a 3,4-dimethylsiglopenta-2-enone (2.20 g, 20 mmol) / 20 ml tetrahydrofuran solution at -78 ° C. The reaction solution was raised to room temperature and stirred overnight. The reaction was terminated by adding an appropriate amount of saturated aqueous ammonium chloride solution to the orange solution. Then, the organic layer was extracted with diethyl ether (50 ml), collected, dried over anhydrous magnesium sulfate, and filtered. The filtered solution was removed by solvent in a rotary evaporator to give an orange oil. The oil was dissolved in methylene chloride (30 ml), para-toluenesulfonic acid hydrate (ca. 0.1 g) was added thereto, and the mixture was stirred at room temperature for one hour. After the solvent was properly removed by the rotary evaporator, the solution was recrystallized with ethanol at 20 ° C. to obtain 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene (2.20 g, 47% yield).

¹ H confirming the synthesis of 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene NMR and ¹³ C { ¹ H} NMR results are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.36 (d, 2H), 6.81 (d, 2H), 6.50 (s, 1H), 3.79 (s, 3H), 3.22 (s, 2H), 1.95 (s , 3H), 1.87 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 158.1, 142.2, 135.4, 134.7, 129.8, 129.6, 125.7, 113.9, 55.3, 45.3, 13.4, 12.6.

Synthesis Example 8-2 Bis [1- ( p- Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p- methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p- MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

[Synthesis Example 7-2], except that 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene (0.801 g, 4.0 mmol) synthesized in Synthesis Example 8-1 was used. ] The reaction was carried out in the same manner as in] to obtain a yellowish yellow crystal, bis- [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride 0.891 g (53% yield) was obtained.

¹ H confirming the synthesis of the bis [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.38 (d, 4H), 6.96 (d, 4H), 6.16 (s, 4H), 3.85 (s, 6H), 1.78 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 159.0, 127.7, 126.5, 126.1, 122.7, 115.4, 114.5, 55.4, 13.2.

Anal. Calcd for C ₂₈ H ₃₀ Cl ₂ O ₂ Zr: C, 59.98; H, 5.39.

Found: C, 59.63; H, 5.64.

[Synthesis example of supported catalyst for olefin polymerization]

All synthesis reactions were carried out in an Inert Atmosphere such as Nitrogen or Argon, using standard Schlenk technology and Glove Box technology.

Toluene was purchased from Sigma-Aldrich and then further dried by passing through an activated molecular sieve (4A) or activated alumina layer, followed by MAO (methylalumina). Noxic acid, Methylaluminoxane) was purchased from Albemarle's 10% toluene solution (HS-MAO-10%) and dried to a solid state.

Silica used in the supported catalyst synthesis used Grace XPO2412 without further treatment.

[Supported Catalyst Synthesis Example 1]

The metallocene compound (0.027 g, 40 μmol), MAO (0.348 g, 6 mmol) and Silica (0.4 g) synthesized in Synthetic Example 3-3 in the Glove Box were respectively 250 ml RBf (round bottom flask), 100 ml RBf, 250ml RBf was taken out of the Glove Box, and then 5ml toluene and 10ml toluene were completely dissolved in the metallocene compound and MAO, and toluene was added to Silica so that Silica was submerged. The MAO solution was slowly added to the metallocene compound solution at room temperature, stirred for 1 hour, and then the metallocene compound / MAO reaction solution was slowly added to Silica in a slurry state at 0 ° C. Thereafter, the reaction mixture was heated to room temperature overnight, and then vacuumed to remove all toluene, thereby obtaining a supported catalyst of free flowing powder (0.713 g).

[Supported Catalyst Synthesis Example 2]

[Supported Catalyst Synthesis Example 1] and the method except that the metallocene compound (0.025 g, 40 μmol) synthesized in [Synthesis Example 6-2] was used instead of the metallocene compound synthesized in [Synthesis Example 3-3] In the same manner, the supported catalyst was synthesized.

[Example of Polymerization of Propylene Using Catalyst for Olefin Polymerization (Unsupported Catalyst)]

All the polymerizations were carried out while maintaining a constant propylene pressure after injecting the required amount of solvent, main catalyst, promoter, propylene, etc. in a reactor (Autoclave) completely isolated from outside air. Solvents such as toluene and normal hexane used in the polymerization can be purchased by purchasing anhydrous grade from Sigma-Aldrich, and then passing it through an activated molecular sieve (4A) or activated alumina layer. After drying, MAO (methylaluminoxane, Methylaluminoxane) was purchased from Albemarle's 10% toluene solution (HS-MAO-10%) and then dried to a solid state. The racemic-ethylene (bisindenyl) zirconium dichloride ( rac- Ethylene (bisindenyl) zirconium dichloride, rac- C ₂ H ₄ (Ind) ₂ ZrCl ₂ )) catalyst was purchased from Strem and used without further purification. Bisindenyl zirconium dichloride (Ind ₂ ZrCl ₂ ) was synthesized using the literature.

The molecular weight and molecular weight distribution of polypropylene produced after polymerization were measured by GPC (Gel Permeation Chromatography, PL-GPC220) method, and melting point was measured by DSC (Differential Scanning Calorimetry, TA Instruments) method. (Isotactisity, mmmm Pentad II) dissolve polypropylene in trichlorobenzene and benzene- d ₆ (Benzene- d ₆ , C ₆ D ₆ ), and then ¹³ C NMR (Bruker, Avance 400 Spectrometer) method was used.

[Polymerization Example 1]

The interior of a stainless steel autoclave with an internal volume of 2L was completely replaced with nitrogen. While maintaining nitrogen purging, 0.58 g of methylaluminoxane (10 mmol based on Al) was added to 20 ml toluene at room temperature, followed by toluene solution (2.0 ml) in which the metallocene compound synthesized in Synthesis Example 1-2 was dissolved. , 5.0 μmol of Zr) was added.

Thereafter, 500 g of propylene was added, the temperature was raised to 70 ° C, and polymerization was carried out for 1 hour. The pressure at the time of polymerization was 30 bar. After the completion of polymerization, the mixture was kept at room temperature, and excess propylene was removed through a discharge line to obtain a white powdery solid. The white solid powder obtained was dried for at least 15 hours while heating to 80 ° C. in a vacuum oven to finally obtain polypropylene.

[Polymerization Example 2]

Propylene polymerization was carried out in the same manner as in [Polymerization Example 1], except that the metallocene compound synthesized in [Synthesis Example 2-2] was used instead of the metallocene compound synthesized in [Synthesis Example 1-2]. Polypropylene was obtained.

[Polymerization Example 3]

Propylene polymerization was carried out in the same manner as in [Polymerization Example 1], except that the metallocene compound synthesized in [Synthesis Example 3-3] was used instead of the metallocene compound synthesized in [Synthesis Example 1-2]. Polypropylene was obtained.

[Polymerization Example 4]

Propylene polymerization was carried out in the same manner as in [Polymerization Example 1], except that the metallocene compound synthesized in [Synthesis Example 4-2] was used instead of the metallocene compound synthesized in [Synthesis Example 1-2]. Polypropylene was obtained.

[Polymerization Example 5]

Propylene polymerization was carried out in the same manner as in [Polymerization Example 1], except that the metallocene compound synthesized in [Synthesis Example 5-2] was used instead of the metallocene compound synthesized in [Synthesis Example 1-2]. Polypropylene was obtained.

[Polymerization Example 6]

Propylene polymerization was carried out in the same manner as in [Polymerization Example 1], except that the metallocene compound synthesized in [Synthesis Example 6-2] was used instead of the metallocene compound synthesized in [Synthesis Example 1-2]. Polypropylene was obtained.

[Polymerization Example 7]

Propylene polymerization was carried out in the same manner as in [Polymerization Example 1], except that the metallocene compound synthesized in [Synthesis Example 7-2] was used instead of the metallocene compound synthesized in [Synthesis Example 1-2]. Polypropylene was obtained.

[Polymerization Example 8]

Propylene polymerization was carried out in the same manner as in [Polymerization Example 1], except that the metallocene compound synthesized in [Synthesis Example 8-2] was used instead of the metallocene compound synthesized in [Synthesis Example 1-2]. Polypropylene was obtained.

[Polymerization Comparative Example 1]

Propylene polymerization was carried out in the same manner as in [Polymerization Example 1], except that 3.0 μmol of racemic-ethylene (bisindenyl) zirconium dichloride and 6 mmol of MAO were used instead of the metallocene compound synthesized in Synthesis Example 1-2. Was carried out to obtain polypropylene.

[Polymerization Comparative Example 2]

Polypropylene was prepared in the same manner as in [Polymerization Example 1], except that 3.0 μmol of bisindenyl zirconium dichloride and 6 mmol of MAO were used instead of the metallocene compound synthesized in Synthesis Example 1-2. Got it.

The results from [Polymerization Example 1] to [Polymerization Example 8] and the results of [Polymerization Comparative Example 1] and [Polymerization Comparative Example 2] are summarized in Table 1 below. It summarized in 2 and recorded.

Metallocene compound Yield (g) Active ^b Polymerization Example 1 1-2 0.33 70 Polymerization Example 2 2-2 16.5 3,300 Polymerization Example 3 3-3 7.6 1,520 Polymerization Example 4 4-2 0.20 40 Polymerization Example 5 5-2 18.7 3,740 Polymerization Example 6 6-2 8.0 1,600 Polymerization Example 7 7-2 102.0 20,400 Polymerization Example 8 8-2 54.0 10,800 Polymerization Comparative Example 1 EBIZr ^c 80.0 26,700 Polymerization Comparative Example 2 BIZr ^d 40.0 13,300

^a polymerization condition: Propylene, 500 g; [Al] / [Zr], 2,000; Polymerization temperature 70 ° C., ^b unit: (kg of PP) / ((mol of Zr) hr), ^c rac- (C ₂ H ₄ ) (Ind) ₂ ZrCl ₂ , ^d Ind ₂ ZrCl _2.

Molecular Weight (M _w )
(× 10 ^-3 ) Molecular weight distribution
(MwD, M _w / M _n ) Melting point
(℃) XS ^a
(%) II
(%, mmmm) Polymerization Example 1 101 6.81 153.9 23 65 Polymerization Example 2 141 8.92 156.7 22 67 Polymerization Example 3 205 7.06 154.7 8 87 Polymerization Example 4 98 7.25 154.7 26 63 Polymerization Example 5 119 6.96 155.8 25 67 Polymerization Example 6 202 7.83 158.0 9 87 Polymerization Example 7 128 12.20 157.1 22 74 Polymerization Example 8 180 9.39 149.7 19 73 Polymerization Comparative Example 1 30 2.63 130.6 12 78 Polymerization Comparative Example 2 5 2.65 no ^b 100 7

^a XS: Xylene Soluble (the ratio of Atactic Polypropylene with low stereoregularity among polypropylenes obtained after polymerization), Soxhlet Extractor as Xylene solvent.

[Example of Polymerization of Propylene Using Supported Catalyst for Olefin Polymerization]

[Polymerization Example 9]

The interior of a stainless steel autoclave with an internal volume of 2L was completely replaced with nitrogen. While maintaining nitrogen purging, 10 ml of normal hexane and 0.12 g of MAO (2 mmol of Al, 4 ml toluene solution) were added sequentially, and then 0.2 g of the catalyst of [Supported Catalyst Synthesis Example 1] was slurried in 5 ml normal hexane. Was added to the reactor.

Thereafter, 500 g of propylene was added, followed by polymerization at 70 ° C. for 1 hour. The pressure at the time of polymerization was 30 bar. After completion of the polymerization, the reactor was cooled to room temperature, and excess propylene was removed through the discharge line to obtain a white powder solid. The white solid powder thus obtained was dried for at least 15 hours while heating to 80 ° C. in a vacuum oven to finally obtain polypropylene. The supported catalyst activity was 10 (g of PP) / (g-cat. · Hr), and the obtained polypropylene characteristics are listed in Table 3 below.

[Polymerization Example 10]

Polypropylene was obtained by carrying out propylene polymerization in the same manner as in [Supported Catalyst Polymerization Example 1], except that the catalyst of [Supported Catalyst Synthesis Example 2] was used instead of the catalyst of [Supported Catalyst Synthesis Example 1]. The supported catalyst activity was 10.5 (g of PP) / (g-cat.hr), and the obtained polypropylene characteristics are listed in Table 3 below.

Polymerization using supported catalyst Molecular Weight (M _w )
(× 10 ^-3 ) Molecular weight distribution
(MwD, M _w / M _n ) Melting point
(℃) XS ^a
(%) II
(%, mmmm) Polymerization Example 9 221 8.51 153.6 9 85 Polymerization Example 10 218 8.81 157.3 10 86

^a XS: Xylene Soluble (the ratio of Atactic Polypropylene with low stereoregularity among polypropylenes obtained after polymerization), Soxhlet Extractor as Xylene solvent.

[Changes in Physical Properties of Polypropylene with Changes in Polymerization Pressure]

[Polymerization Comparative Example 3]

In a 250 ml glass flask in which the inside was replaced with nitrogen in a glove box, 0.29 g of MAO (5 mmol) was added, and toluene (48 ml) was added at room temperature, followed by adjusting to 70 ° C. While stirring for 30 minutes, the propylene gas was saturated to 1 bar. Next, toluene solution (2.0 ml, 5.0 μmol of Zr) in which the catalyst of [Synthesis Example 5-2] was dissolved was added to the polymerization by a syringe. After maintaining the bar at 70 ° C. for 2 hours, 5 ml of a 10% HCl ethanol mixed solution was added to the polymerization reaction to terminate the polymerization. Additional 200mL of ethanol was added to precipitate the polymer, stirred for about an hour and filtered. The filtered polypropylene was dried for at least 15 hours while heating to 80 ° C. in a vacuum oven to finally obtain polypropylene.

[Polymerization Comparative Example 4]

Polymerization was carried out in the same manner as in Comparative Example 3, but polymerization was carried out using the catalyst of Synthesis Example 6-2.

In order to show the influence of the polymerization pressure on the polypropylene physical properties obtained from the present invention, the results of polymerization comparative examples 3 to 4 and polymerization examples 5 to 6 are listed in Table 4 below.

Metallocene
compound Polymerization pressure
(bar) Active ^a Molecular Weight (M _w )
(× 10 ^-3 ) Molecular weight distribution
(MwD, M _w / M _n ) Melting point
(℃) XS ^b
(%) Polymerization Comparative Example 3 5-2 1.0 104 195 4.15 129.3 47 Polymerization Comparative Example 4 6-2 1.0 117 14 4.75 134.6 26 Polymerization Example 5 5-2 30 3,740 119 6.96 155.8 25 Polymerization Example 6 6-2 30 1,600 202 7.83 158.0 9

^a unit: (kg of PP) / ((mol of Zr) hr

^b XS: Xylene Soluble (The ratio of Atactic Polypropylene with low stereoregularity among Polypropylene obtained after polymerization), Soxhlet Extractor as Xylene solvent

As can be seen from Tables 1 to 4 prepared on the basis of the above [Polymerization Example] and [Comparative Polymerization Example], when propylene polymerization is performed using the catalyst of the present invention, it is complicated as in Comparative Examples 1 and 2 High molecular weight, high melting point, and high stereoregular polypropylene can be obtained through the interaction between the main catalyst (metallocene compound) and the cocatalyst (aluminoacid compound and / or organoaluminum compound) without using a catalyst having a structure. have.

In addition, by adjusting the position and number of hetero atoms in the substituent of the formula (2) or (3) in the metallocene compound of the present invention can also adjust the stereoregularity of the polypropylene, can obtain a stereoregularity up to 87% have.

In addition, it is possible to improve the activity of the catalyst and the physical properties of the polypropylene through the propylene pressure rise during the polymerization. In particular, polypropylene having a low melting point and a high XS is obtained at 1 bar polymerization, whereas a polypropylene having a high melting point and a low XS (high stereoregularity) is obtained at a high pressure polymerization.

 This effect is caused by having a hetero atom in the metallocene compound of the present invention that can interact with a promoter, which is demonstrated by directly comparing the polymerization example with the polymerization comparative example.

1 is an X-ray molecular structure of a metallocene compound synthesized in Synthesis Example 2-2 of the present invention;

2 is an X-ray molecular structure of the metallocene compound synthesized in Synthesis Example 6-2 of the present invention.

Claims (19)

A metallocene compound of Formula 1 [Formula 1]

In Formula 1, M is selected from the group consisting of Group 3 to 10 elements on the periodic table; X is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, C7-20 alkylaryl group, C6-C20 arylsilyl group, C6-C20 silylaryl group, C1-C20 alkoxy group, C1-C20 alkylsiloxy group, C6-C20 aryl Oxy group, halogen group, amine group and tetrahydroborate group; n is an integer from 1 to 5; Cp ¹ and Cp ² are the same as or different from each other, and each independently a ligand having a cyclopentadienyl skeleton, The ligand having a cyclopentadienyl skeleton is hydrogen, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C1-C20 alkylsilyl group, a C1-C20 silylalkyl group, a C1-C20 halo Alkyl group, C6-C20 aryl group, C7-C20 arylalkyl group, C7-C20 alkylaryl group, C6-C20 arylsilyl group, C6-C20 silylaryl group, a halogen group, a following formula A substituent of 2 and one or more substituents selected from the group consisting of substituents of the following general formula (3), In this case, the ligand having a cyclopentadienyl skeleton has at least one substituent of Formula 2 or a substituent of Formula 3 below, Substituents substituted for the ligand having the cyclopentadienyl skeleton does not bind to each other to form a ring or to each other; [Formula 2]

(3)

In Chemical Formulas 2 and 3, Z is an element of group 15 or 16 of the periodic table; R is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl having 7 to 20 carbon atoms An alkyl group, a C7-20 alkylaryl group, a C6-C20 arylsilyl group, and a C6-C20 silylaryl group; m is an integer of 1 to 2; p is an integer from 1 to 4; Carbon atoms in the phenyl ring not bonded with ZR _m may be bonded to hydrogen, or have 1 to 20 alkyl groups, 3 to 20 cycloalkyl groups, 1 to 20 alkylsilyl groups, 1 to 20 carbonyl silyl groups, A C1-C20 haloalkyl group, a C6-C20 aryl group, a C7-C20 arylalkyl group, a C7-C20 alkylaryl group, a C6-C20 arylsilyl group, a C6-C20 silylaryl group And a substituent selected from the group consisting of halogen groups; The ZR _m is substituted at the ortho- or meta-position of the phenyl ring, or at the ortho- and meta-positions. delete The metallocene compound of claim 1, wherein M in Formula 1 is a Group 4 element on the periodic table. According to claim 1, wherein the ligand having a cyclopentadienyl skeleton of Cp ¹ and Cp ² in the formula 1 is characterized in that each independently selected from the group consisting of cyclopentadienyl group, indenyl group, and fluorenyl group Metallocene compound of formula (1). (a) a metallocene compound of Formula 1; And (b) a catalyst for olefin polymerization comprising: a compound selected from the group consisting of an aluminoxane compound of formula 4 and an organoaluminum compound of formula 5: [Formula 1]

In Formula 1, M is selected from the group consisting of Group 3 to 10 elements on the periodic table; X is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, C7-20 alkylaryl group, C6-C20 arylsilyl group, C6-C20 silylaryl group, C1-C20 alkoxy group, C1-C20 alkylsiloxy group, C6-C20 aryl Oxy group, halogen group, amine group and tetrahydroborate group; n is an integer from 1 to 5; Cp ¹ and Cp ² are the same as or different from each other, and each independently a ligand having a cyclopentadienyl skeleton, The ligand having a cyclopentadienyl skeleton is hydrogen, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C1-C20 alkylsilyl group, a C1-C20 silylalkyl group, a C1-C20 halo Alkyl group, C6-C20 aryl group, C7-C20 arylalkyl group, C7-C20 alkylaryl group, C6-C20 arylsilyl group, C6-C20 silylaryl group, a halogen group, a following formula A substituent of 2 and one or more substituents selected from the group consisting of substituents of the following general formula (3), In this case, the ligand having a cyclopentadienyl skeleton has at least one substituent of Formula 2 or a substituent of Formula 3 below, Substituents substituted for the ligand having the cyclopentadienyl skeleton does not bind to each other to form a ring or to each other; [Formula 2]

(3)

In Chemical Formulas 2 and 3, Z is an element of group 15 or 16 of the periodic table; R is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl having 7 to 20 carbon atoms An alkyl group, a C7-20 alkylaryl group, a C6-C20 arylsilyl group, and a C6-C20 silylaryl group; m is an integer of 1 to 2; p is an integer from 1 to 4; Carbon atoms in the phenyl ring not bonded with ZR _m may be bonded to hydrogen, or have 1 to 20 alkyl groups, 3 to 20 cycloalkyl groups, 1 to 20 alkylsilyl groups, 1 to 20 carbonyl silyl groups, A C1-C20 haloalkyl group, a C6-C20 aryl group, a C7-C20 arylalkyl group, a C7-C20 alkylaryl group, a C6-C20 arylsilyl group, a C6-C20 silylaryl group And a substituent selected from the group consisting of halogen groups; The ZR _m is substituted at the ortho-, meta-, or ortho- and meta-position of the phenyl ring; [Formula 4]

In Formula 4, R ¹ is an alkyl group having 1 to 10 carbon atoms, q is an integer from 1 to 70; [Chemical Formula 5]

In Chemical Formula 5, R ² , R ³ and R ⁴ are the same as or different from each other, and are selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and halogen groups, respectively, and R ² , R ³ and At least one of R ⁴ is an alkyl group having 1 to 10 carbon atoms. delete According to claim 5, (b) wherein the aluminoxane compound of formula (4) and the organoaluminum compound of formula (5) is a cocatalyst for (a) the metallocene compound of formula (1) having a polymerization catalytic activity and the formula (1) A catalyst for olefin polymerization, characterized by controlling the stereoregularity of the olefin polymer by reacting with a metallocene compound. The catalyst for olefin polymerization according to claim 5, wherein M in Formula 1 is a Group 4 element on the periodic table. 6. The ligand according to claim 5, wherein the ligands having the cyclopentadienyl skeleton of Cp ¹ and Cp ² in Formula 1 are each independently selected from the group consisting of a cyclopentadienyl group, an indenyl group, and a fluorenyl group Catalyst for olefin polymerization. The catalyst for olefin polymerization according to claim 5, wherein the aluminoxane compound of Chemical Formula 4 is selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, hexyl aluminoxane, octyl aluminoxane and decyl aluminoxane. . The catalyst for olefin polymerization according to claim 5, wherein the organoaluminum compound of the formula (5) is selected from the group consisting of trialkylaluminum, dialkylaluminum alkoxide, dialkylaluminum halide, alkylaluminum dialkoxide and alkylaluminum dihalide. . A supported catalyst for olefin polymerization, wherein the catalyst for olefin polymerization according to claim 5 is supported on a carrier. The method of claim 12, wherein the carrier comprises silica, alumina, bauxite, zeolite, MgCl ₂ , CaCl ₂ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -CrO ₂ O ₃ , SiO ₂ -TiO _2- Supported catalyst for olefin polymerization, characterized in that at least one member selected from the group consisting of MgO, Starch, Cyclodextrin and synthetic polymer. Using a catalyst selected from the group consisting of a catalyst for olefin polymerization according to any one of claims 5 and 7 to 11 and a supported catalyst for polymerization of an olefin according to any one of claims 12 to 13. Polymerization method of an olefin characterized by superposing | polymerizing an olefin. 15. The method of claim 14, wherein the polymerization is carried out under a pressure of 2 ~ 100 bar. The method of claim 14, wherein the polymerization is performed in a phase selected from the group consisting of a liquid phase, a gas phase, a bulk phase, and a slurry phase. Polymerization Method of Olefin. 15. The method of claim 14, wherein said olefin is propylene. An olefin polymer prepared according to the polymerization method according to claim 14, wherein the olefin polymer comprises the catalyst for olefin polymerization or the supported catalyst for olefin polymerization in the olefin polymer. 19. The olefin polymer of claim 18 wherein the olefin polymer is a polypropylene or propylene copolymer.

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