KR100834889B1 - Transition metal compound, catalyst for polymerization of propylene and preparation method of propylene polymer - Google Patents

Abstract

The present invention is a transition metal compound, Provided are a catalyst for propylene polymerization, and a method for producing a propylene polymer using the catalyst.

When using the catalyst according to the present invention, it is possible to control the stereoregularity through the interaction of the catalyst and the cocatalyst without using a catalyst having a complicated structure, and to obtain a propylene polymer having high molecular weight and high stereoregularity.

Propylene * Transition Metal * Catalyst * Stereogram

Description

Transition metal compound, catalyst for polymerization of propylene and preparation method of propylene polymer

1 is a molecular structure measured through X-ray of bis- [1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride obtained in Synthesis Example 1 of the present invention,

2 is a DSC graph of Polymerization Example 2 (P2), Polymerization Example 7 (P7), Polymerization Example 11 (P11), Polymerization Comparative Example 1 (CP1), and Polymerization Comparative Example 2 (CP2),

3 is a DSC graph of Polymerization Example 18 (P18), Polymerization Example 21 (P21), Polymerization Comparative Example 3 (CP3), Polymerization Comparative Example 4 (CP4), and Polymerization Comparative Example 5 (CP5).

The present invention relates to a transition metal compound, a catalyst for propylene polymerization, and a method for producing a propylene polymer using the catalyst. Specifically, a novel transition metal compound is used as a main catalyst and a conventional aluminum compound is used as a promoter. The present invention relates to a catalyst capable of controlling stereoregularity of a propylene polymer, and a method for preparing a propylene polymer using the same.

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, metallocene i PP and s PP have been commercialized by petrochemical companies and applied to film, fiber, injection molding, etc. A complex metallocene catalyst compound was needed.

In order to synthesize such a complex metallocene catalyst compound, a complex synthesis process and expensive equipment are required in several stages. Therefore, metallocene PP is a major factor in increasing the manufacturing cost of PP using a metallocene catalyst. It has been an obstacle to expanding.

    Therefore, the manufacturing method of metallocene PP catalyst with high stereoregularity at low cost has been a major concern of all research groups and companies around the world, and this research group has actively researched and developed this field. The invention was completed.

An object of the present invention is to provide a novel transition metal compound useful as a component of a metallocene catalyst for propylene polymerization.

Another object of the present invention to provide a catalyst for propylene polymerization containing the transition metal compound.

A further object of the present invention is to provide a method for producing a propylene polymer using the catalyst.

Hereinafter, the present invention will be described in detail.

The present invention relates to a novel transition metal compound, a catalyst for propylene polymerization, and a polymerization method of propylene using the same.

In the present invention, a transition metal compound is used as a main catalyst which is one of the components of the catalyst for propylene polymerization, which will be described in detail below.

1. Transition Metal Compound

 The transition metal compound of the present invention is represented by the following formula (1).

Wherein M ¹ and M ² are the same as or different from each other, and are selected from the group consisting of Group 3 to 10 elements of the periodic table,

Cp ¹ and Cp ² , Cp ³ and Cp ⁴ , which are the same as or different from each other, are ligands having a cyclopentadienyl skeleton including at least one substituent containing a hetero atom,

X and Y are the same as or different from each other, 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, C6-C20 arylalkyl group, C6-C20 alkylaryl group, C6-C20 arylsilyl group, C6-C20 silylaryl group, C1-C20 alkoxy group, C1-C20 alkylsiloxane It is time, C6-C20 aryloxy group, a halogen group, an amine group, or a tetrahydroborate group,

a and b are integers from 1 to 5,

p is 0 or 1,

B ¹ is a bridge connecting the Cp ¹ and Cp ² , and is a compound represented by the following Chemical Formula 2,

In Formula 2, B ³ is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an alkylsilylene group having 1 to 20 carbon atoms, a silylalkylene group having 1 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms At least one member selected from the group consisting of an arylalkylene group having 6 to 20 carbon atoms, an alkylarylene group having 6 to 20 carbon atoms, an arylsilylene group having 6 to 20 carbon atoms, and a silyl arylene group having 6 to 20 carbon atoms,

Q ³ and Q ⁴ are the same as or different from each other, and are selected from compounds represented by the following Chemical Formulas 3 to 5,

In Chemical Formula 3, R is a hydrogen atom 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, and an aryl group having 6 to 20 carbon atoms , An arylalkyl group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and a silylaryl group having 6 to 20 carbon atoms,

In Formula 4, R ¹ is a hydrogen atom or a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C1-C20 alkylsilyl group, a C1-C20 silylalkyl group, a C6-C20 aryl Group, a C6-C20 arylalkyl group, a C6-C20 alkylaryl group, a C6-C20 arylsilyl group, and a C6-C20 silylaryl group,

In Formula 5, Ary is an arylene group.

The respective chemical formulas will be described in detail as follows.

M ¹ and M ^{2, which} are the central metals of Formula 1, are selected from the group consisting of elements of Groups 3 to 10 of the periodic table, and specific examples thereof include scandium (Sc), yttrium (Y), titanium (Ti), and zirconium ( Zr), hafnium (Hf), vanadium (V), iron (Fe), nickel (Ni), palladium (Pd), and the like, preferably zirconium (Zr), titanium (Ti), and hafnium (Hf). Group 4 element selected from the group consisting of.

In addition, Cp ¹ to Cp ⁴ of the general formula (1) is a ligand having a cyclopentadienyl skeleton containing at least one substituent containing a hetero atom, the ligand having a cyclopentadienyl skeleton is cyclopentadienyl (Cyclopentadienyl ) Group, Indenyl group, and fluorenyl group, but is not limited thereto.

In addition, the substituent containing a hetero atom included in the ligand having a cyclopentadienyl skeleton is a compound represented by the following formula (6).

In Formula 6, B ² is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an alkylsilylene group having 1 to 20 carbon atoms, a silylalkylene group having 1 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms , An arylalkylene group having 6 to 20 carbon atoms, an alkylarylene group having 6 to 20 carbon atoms, an arylsilylene group having 6 to 20 carbon atoms, and a silyl arylene group having 6 to 20 carbon atoms,

c is an integer from 0 to 4,

Z is a hetero atom of group 15 or 16 of the periodic table,

R ² is a hydrogen atom 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, an aryl group having 6 to 20 carbon atoms, and 6 to 6 carbon atoms Selected from the group consisting of 20 arylalkyl groups, 6 to 20 alkylaryl groups, 6 to 20 arylsilyl groups, and 6 to 20 silylaryl groups,

m is 1 or 2.

In Chemical Formula 6, B ² is a carbon compound functional group (Hydrocarbyl Radicals) connecting a ligand having a cyclopentadienyl skeleton and a hetero atom, specifically, an alkylene group having 1 to 20 carbon atoms and a cycloalkylene group having 3 to 20 carbon atoms , C1-C20 alkylsilylene group, C1-C20 silylalkylene group, C6-C20 arylene group, C6-C20 arylalkylene group, C6-C20 alkylarylene group, C6-C20 An arylsilylene group, and a silyl arylene group having 6 to 20 carbon atoms,

Alkylene group having 1 to 20 carbon atoms in the carbon compound functional group is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dimethylmethylene Group, 1,2-dimethylethylene group, 1,1,2,2-tetramethylethylene group, 1,2,3-tetramethylpropylene group, 1,1,2,2,3,3-hexamethylpropylene group , 1,2,3,4-tetramethylbutylene group, diethylmethylene group, 1,2-diethylethylene group, 1,1,2,2-tetraethylethylene group, 1,2,3-triethylpropylene Group, and 1,2,3,4-tetraethylbutylene group,

The C3-C20 cycloalkylene group is selected from the group consisting of a cyclohexylene group, a cyclooctylene group, and a decahydronaphthalylene group,

The C1-C20 alkylsilylene group is a methylsilylene group, dimethylsilylene group, dimethylsilylene group, ethylsilylene group, diethylsilylene group, propylsilylene ( Selected from the group consisting of a propylsilylene group, a dipropylsilylene group, a butylsilylene group, and a dibutylsilylene group,

The C1-C20 silylalkylene group includes (methylsilyl) methylene ((Methylsilyl) methylene) group, (dimethylsilyl) methylene ((Dimethylsilyl) methylene) group, (trimethylsilyl) methylene ), (Ethylsilyl) methylene ((Ethylsilyl) methylene) group, (diethylsilyl) methylene ((Diethylsilyl) methylene) group, (triethylsilyl) methylene ((Triethylsilyl) methylene) group, (methylsilyl) ethylene ( (Methylsilyl) ethylene), (dimethylsilyl) ethylene ((Dimethylsilyl) ethylene) group, and (trimethylsilyl) ethylene ((Trimethylsilyl) ethylene) group selected from the group consisting of

The arylene group having 6 to 20 carbon atoms has a phenylene group, a biphenylene group, a terphenylene group, a naphtylene group, and a fluorenylene group. Selected from the group consisting of

The C6-C20 arylalkylene group is selected from the group consisting of a phenylmethylene group, a phenylethylene group, and a phenylpropylene group,

The alkylarylene group having 6 to 20 carbon atoms has a methylphenylene group, a dimethylphenylene group, a trimethylphenylene group, an ethylphenylene group, and a diethylphenylene group. ) Group, triethylphenylene group, propylphenylene group, dipropylphenylene group, and tripropylphenylene group,

The arylsilylene group having 6 to 20 carbon atoms has a phenylsilylene group, a methylphenylsilylene group, a diphenylsilylene group, an ethylphenylsilylene group, and a (methylphenyl) silylene group. ((Methylphenyl) silylene) group, (ethylphenyl) silylene ((Ethylphenyl) silylene) group, and (trifluoromethylphenyl) silylene ((Trifluoromethylphenyl) silylene) group, and

The C 6-20 silyl arylene (Silylarylene) group is a (methylsilyl) phenylene ((Methylsilyl) phenylene group, (dimethylsilyl) phenylene ((Dimethylsilyl) phenylene group, (trimethylsilyl) phenylene ((Trimethylsilyl) ) phenylene), (ethylsilyl) phenylene ((Ethylsilyl) phenylene) group (diethylsilyl) phenylene ((Diethylsilyl) phenylene) group, (triethylsilyl) phenylene ((Triethylsilyl) phenylene) group, (propyl (Silyl) phenylene ((Propylsilyl) phenylene) group, (dipropylsilyl) phenylene ((Dipropylsilyl) phenylene group, (butylsilyl) phenylene ((Butylsilyl) phenylene) group, and (dibutylsilyl) phenylene ( (Dibutylsilyl) phenylene) group selected from the group consisting of, but is not limited thereto.

In Formula 6, B ² is preferably an arylene group having 6 to 20 carbon atoms, an alkyl arylene group having 6 to 20 carbon atoms, and a silyl arylene group having 6 to 20 carbon atoms. It is selected from the group.

In Chemical Formula 6, Z is a hetero atom of group 15 or 16 of the periodic table, preferably nitrogen (Nitrogen, N), phosphorus (Phosphorus, P), arsenic (Arsenic, As), oxygen (Oxygen, O), Sulfur (S), selenium (Selenium, Se), and the like, but is not limited thereto.

In the formula (6), in the definition of R ² , a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C1-C20 alkylsilyl group, a C1-C20 silylalkyl group, a C6-C20 aryl group And it is selected from the group consisting of a C6-C20 arylalkyl group, a C6-C20 alkylaryl group, a C6-C20 arylsilyl group, and a C6-C20 silylaryl group, Specifically, it is as follows.

The alkyl group having 1 to 20 carbon atoms is selected from the group consisting of methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group,

The cycloalkyl group having 3 to 20 carbon atoms is selected from the group consisting of a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a decahydronaphthalyl group,

The C1-C20 alkylsilyl group is methylsilyl group, dimethylsilyl (dimethylsilyl) group, trimethylsilyl (Trimethylsilyl) group, ethylsilyl (Ethylsilyl) group, diethylsilyl (Diethylsilyl) group, triethylsilyl (Triethylsilyl) group, Selected from the group consisting of a propylsilyl group, a dipropylsilyl group, a tripropylsilyl group, a tripropylsilyl group, a butylsilyl group, a dibutylsilyl group, and a tributylsilyl group Will,

The C1-C20 silylalkyl group is a (methylsilyl) methyl ((Methylsilyl) methyl) group, (dimethylsilyl) methyl ((Dimethylsilyl) methyl) group, (trimethylsilyl) methyl ((Trimethylsilyl) methyl) group, (ethyl (Sylyl) methyl ((Ethylsilyl) methyl) group, (diethylsilyl) methyl ((Dethylsilyl) methyl) group, (triethylsilyl) methyl ((Triethylsilyl) methyl) group, (methylsilyl) ethyl ((Methylsilyl) ethyl) Group, (dimethylsilyl) ethyl ((Dimethylsilyl) ethyl) group, (trimethylsilyl) ethyl ((Trimethylsilyl) ethyl) group,

The aryl group having 6 to 20 carbon atoms is selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group, a naphtyl group, and a fluorenyl group,

The arylalkyl group having 6 to 20 carbon atoms is selected from the group consisting of benzyl, phenylethyl, and phenylpropyl groups,

The alkyl aryl group having 6 to 20 carbon atoms is methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, and triethylphenyl group. ) Group, a propylphenyl group, a dipropylphenyl group, and a tripropylphenyl group,

The arylsilyl group having 6 to 20 carbon atoms is a phenylsilyl group, a methylphenylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, a triphenylsilyl group, and a triphenylsilyl group. An ethylphenylsilyl group, (methylphenyl) silyl ((Methylphenyl) silyl), (ethylphenyl) silyl ((Ethylphenyl) silyl) group, and trifluoromethylphenylsilyl (Trifluoromethylphenylsilyl) group, and

The C6-C20 silylaryl group is a (methylsilyl) phenyl ((Methylsilyl) phenyl) group, (dimethylsilyl) phenyl ((Dimethylsilyl) phenyl) group, (trimethylsilyl) phenyl ((Trimethylsilyl) phenyl) group, (ethyl Silyl) phenyl ((Ethylsilyl) phenyl) group (diethylsilyl) phenyl ((Diethylsilyl) phenyl) group, (triethylsilyl) phenyl ((Triethylsilyl) phenyl) group, (propylsilyl) phenyl ((Propylsilyl) phenyl) group , (Dipropylsilyl) phenyl ((Dipropylsilyl) phenyl) group, (butylsilyl) phenyl ((Butylsilyl) phenyl) group, (dibutylsilyl) phenyl ((Dibutylsilyl) phenyl) group selected from the group consisting of, but the present invention This is not limited to this.

In addition, Cp ¹ and Cp ² , which are ligands having a cyclopentadienyl skeleton of Chemical Formula 1, may include C 1-20 alkyl groups, C 3-20 cycloalkyl groups, C 1-20 alkyl, in addition to the substituent containing the hetero atom. Silyl group, C1-C20 silylalkyl group, C6-C20 aryl group, C6-C20 arylalkyl group, C6-C20 alkylaryl group, C6-C20 arylsilyl group, C6-C20 It may be bonded with a silylaryl group or a halogen (Halogen) group, may form a ring by a bond between these substituents, and when p is 1, the number of substituents except for substituents including hetero atoms is 0 to 3 If the value is satisfied and p is 0, the number of substituents excluding the substituent including a hetero atom satisfies the value of 0 to 4.

In addition, Cp ³ and Cp ⁴ , which are ligands having a cyclopentadienyl skeleton represented by Chemical Formula 1, may include a C 1-20 alkyl group, a C 3-20 cycloalkyl group, a C 1-20 alkyl, in addition to a substituent including the hetero atom. Silyl group, C1-C20 silylalkyl group, C6-C20 aryl group, C6-C20 arylalkyl group, C6-C20 alkylaryl group, C6-C20 arylsilyl group, C6-C20 It may be bonded with a silylaryl group or a halogen group, and a bond between these substituents may form a ring, and the number of substituents except for substituents including hetero atoms may be 0 to 4 regardless of the value of p. Satisfies the value of.

In addition, the alkyl group having 1 to 20 carbon atoms as a substituent bonded to Cp ¹ and Cp ² , Cp ³ and Cp ⁴ of Formula 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octa One selected from the group consisting of a tilyl group, a nonyl group, and a decyl group,

The cycloalkyl group having 3 to 20 carbon atoms is selected from the group consisting of a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a decahydronaphthalyl group,

The C1-C20 alkylsilyl group is methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, propylsilyl group, dipropylsilyl group, tripropylsilyl group, butyl Selected from the group consisting of silyl group, dibutylsilyl group, and tributylsilyl group,

The C1-C20 silylalkyl group is a (methylsilyl) methyl group, (dimethylsilyl) methyl group, (trimethylsilyl) methyl group, (ethylsilyl) methyl group, (diethylsilyl) methyl group, (triethylsilyl) methyl group, (methylsilyl ) Ethyl group, (dimethylsilyl) ethyl group, and (trimethylsilyl) ethyl group,

The aryl group having 6 to 20 carbon atoms is selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, and a fluorenyl group,

The arylalkyl group having 6 to 20 carbon atoms is selected from the group consisting of benzyl, phenylethyl, and phenylpropyl groups,

The alkylaryl group having 6 to 20 carbon atoms is selected from the group consisting of methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, propylphenyl group, dipropylphenyl group, and tripropylphenyl group,

The arylsilyl group having 6 to 20 carbon atoms is a phenylsilyl group, methylphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, triphenylsilyl group, ethylphenylsilyl group, (methylphenyl) silyl group, (ethylphenyl) silyl group , And trifluoromethylphenylsilyl group,

The C6-C20 silylaryl group is a (methylsilyl) phenyl group, (dimethylsilyl) phenyl group, (trimethylsilyl) phenyl group, (ethylsilyl) phenyl group, (diethylsilyl) phenyl group, (triethylsilyl) phenyl group, (propylsilyl A phenyl group, a (dipropylsilyl) phenyl group, a (butylsilyl) phenyl group, and a (dibutylsilyl) phenyl group are selected from the group consisting of, but the present invention is not limited thereto.

Of the substituents of X and Y of Formula 1, the alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, silylalkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms Specific examples of the aryl group, an arylalkyl group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and a silylaryl group having 6 to 20 carbon atoms may include Cp ¹ and Cp ² of Formula 1 , As defined in the substituents bonded to Cp ³ and Cp ⁴ , in addition to alkoxy groups having 1 to 20 carbon atoms are selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexyloxy groups Will,

The alkylsiloxy group having 1 to 20 carbon atoms is selected from the group consisting of methylsiloxy group, dimethylsiloxy, trimethylsiloxy group, ethylsiloxy group, diethylsiloxy group, and triethylsiloxy group,

Aryloxy groups having 6 to 20 carbon atoms are phenoxy, naphthoxy, methylphenoxy, dimethylphenoxy, trimethylphenoxy, ethylphenoxy, diethylphenoxy, triethylphenoxy, propylphenoxy, dipropylphenoxy, Selected from the group consisting of tripropylphenoxy,

The halogen group is selected from the group consisting of a fluoro group, a chloro group, a bromo group, and an iodo group,

 The amine group is selected from the group consisting of dimethylamine group, diethylamine group, dipropylamine group, dibutylamine, diphenylamine group, and dibenzylamine group, but the present invention is not limited to these compounds.

In addition, X and Y of the formula 1 is a methyl group, ethyl group, propyl group, phenoxy group, naphthoxy group, methyl phenoxy group, dimethyl phenoxy group, trimethyl phenoxy group, ethyl phenoxy group, diethyl phenoxy group, triethyl phenoxy group, Propylphenoxy, dipropylphenoxy, tripropylphenoxy, chloro, bromo, dimethylamine, diethylamine, dipropylamine, dibutylamine, diphenylamine, dibenzylamine, or Tetrahydroborate groups are preferred.

In addition, in Chemical Formula 2, B ³ is as defined in B ² of Chemical Formula 6, and preferably, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, and nonyl And a group consisting of a lene group and a decylene group.

In addition, specific examples of the arylene group represented by Formula 5 include a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a binaphthylene group, a fluorenylene group, an anthylene group, a pyridylene group, and a bipyridyl It is selected from the group consisting of a benzene group, a terpyridylene group, a quinolylene, a pyridazylene group, a pyrimidylene group, a pyrazilylene group, and a quinoxalylene group.

The transition metal compound represented by Chemical Formula 1 of the present invention is preferably a compound represented by the following Chemical Formula 9.

In Formula 9, M ³ is selected from the group consisting of Group 3 to 10 elements of the periodic table,

Cp ⁵ and Cp ⁶ are the same as or different from each other, and are ligands having a cyclopentadienyl skeleton including at least one substituent containing a hetero atom,

X ¹ 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 6 to 20 carbon atoms, C6-C20 alkylaryl group, C6-C20 arylsilyl group, C6-C20 silylaryl group, C1-C20 alkoxy group, alkylsiloxy group, C6-C20 aryloxy group, halogen group , An amine group, or a tetrahydroborate group,

d is an integer of 1-5.

Specific examples of M ³ , Cp ⁵ and Cp ⁶ , and X ¹ , defined in Formula 9, are the same as defined in M ¹ , Cp ³ and Cp ⁴ , and X of Formula 1, respectively.

In the polymerization catalyst of the present invention, the transition metal compound represented by the formula (1) has a structure of the formula (9), wherein B ² of the formula (6) is an arylene group having 6 to 20 carbon atoms, or an alkyl arylene group desirable.

2. Catalyst for Propylene Polymerization

The catalyst system for producing a propylene polymer of the present invention includes a cocatalyst compound wherein the transition metal compound is a main catalyst and the main catalyst has a polymerization catalyst activity.

The main metal transition metal compound is as described in detail in the above (1), and the promoter includes an aluminoxane compound represented by the following formula (7) or an organoaluminum compound represented by the following formula (8), which are the main catalysts It reacts with transition metal compounds to control the stereoregularity of polypropylene.

In Formula 7, R ³ is an alkyl group having 1 to 10 carbon atoms,

n is an integer of 1-70.

In the case of the aluminoxane compound of Formula 7, it has a linear or cyclic or network structure, specifically, methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, hexyl aluminoxane, octyl aluminoxane, And decyl aluminoxane.

In Formula 8, R ⁴ , R ⁵ , and R ⁶ are the same as or different from each other, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group, and at least one of R ⁴ , R ⁵ , and R ⁶ is an alkyl group. to be.

Also, the The organoaluminum compound represented by the formula (8) is selected from the group consisting of trialkylaluminum, dialkylaluminum alkoxide, dialkylaluminum halide, alkylaluminum dialkoxide, and alkylaluminum dihalide.

The trialkylaluminum is at least one selected from the group consisting of trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum,

The dialkyl aluminum alkoxide is one or more selected from the group consisting of dimethyl aluminum methoxide, diethyl aluminum methoxide, and dibutyl aluminum methoxide,

The dialkylaluminum halide is at least one selected from the group consisting of dimethylaluminum chloride, diethylaluminum chloride, and dibutylaluminum chloride,

The alkylaluminum dialkoxide is at least one selected from the group consisting of methylaluminum dimethoxide, ethylaluminum dimethoxide, and butylaluminum dimethoxide,

The alkylaluminum dihalide is one or more selected from the group consisting of methylaluminum dichloride, ethylaluminum dichloride, and butylaluminum dichloride, but is not limited thereto.

The promoter represented by the formula (7) or (8) may be used alone or in combination of two or more during polymerization.

In the present invention, a catalyst composed of the transition metal compound as the main catalyst and the aluminum compound as the cocatalyst may be directly used for propylene polymerization, or a supported catalyst supported on an inorganic or organic compound may be used.

3. Process for producing propylene polymer

In the present invention, it can be used in the method for producing a propylene polymer including polymerizing the propylene polymer using the catalyst structure as described above.

When propylene is polymerized using the polymerization catalyst of the present invention, the polymerization may be performed in a slurry phase, a liquid phase, a gas phase, a bulk phase.

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

Solvents used for the polymerization are, for example, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, 1,2- Dichloroethane, chlorobenzene, and the like, and these solvents may be mixed and used at a constant ratio.

When the polymerization is carried out through the slurry phase, the liquid phase, the gas phase, or the bulk process of the present invention, the amount of the transition metal compound used is not particularly limited, but the concentration is 10 ^-8 mol / in the central metal concentration in the reaction system used for the polymerization. Liter to 1 mol / liter is suitable, preferably 10 ^-7 mol / liter to 10 ^-2 mol / liter.

Also, the amount of co-catalyst is an aluminoxane compound or organoaluminum compound used for polymerization of the present invention is not particularly limited, but the tank 10 1/1 ^6/1, preferably in a molar ratio of catalyst / main catalyst used in the reaction system it is preferably used as the 1/1 ~ 5x10 ^4/1.

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, and is batch type, semi-continuous type or continuous type. The polymerization is carried out in a continuous type, and the polymerization pressure is usually 1.0 to 3000 atm, preferably 1 to 500 atm.

When preparing a polypropylene polymer using the catalyst according to the present invention as described above, it is possible to obtain a polypropylene having high molecular weight and high melting point and high stereoregularity through the interaction of the main catalyst and the promoter. Moreover, the stereoregularity of polypropylene can also be adjusted according to the structure of a catalyst and polymerization conditions.

   This effect is caused by having a hetero atom in the catalyst that can interact with the promoter, and specifically, a hetero atom bonded to the cyclopentadienyl ligand in the catalyst reacts with the promoter to effect steric control around the active site of the catalyst. This is because the stereoregularity is controlled by determining the direction of propylene insertion with respect to the catalytic active point by inducing the (Stereocontrol Effect).

In addition to this polypropylene homopolymer, the catalyst of the present invention can also be used for the preparation of copolymers with other olefins or other monomers.

   Available olefins or other monomers include ethylene for copolymerization, including ethylene (Ethylene), and 1-butene (1-Butene), 1-pentene (1-Pentene) and 1-hexene (1-Hexene). Alpha-olefin of 20; 1,3-butadiene, 1,4-pentadiene, and 2-methyl-1,3-butadiene Diolefin having 4 to 20 carbon atoms selected from the group; Group consisting of Cyclopentene, Cyclohexene, Cyclopentadiene, Cyclohexadiene, Norbonene, and Methyl-2-Norbonene Cycloolefin having 3 to 20 carbon atoms selected from; Or substituted styrene in which a cycloalkylene, styrene or benzene ring of 1 to 10 carbon atoms, alkoxy group, halogen group, amine group, silyl group, haloalkyl group, etc. (Substituted Styrene) and the like.

The weight average molecular weight of the polypropylene polymer obtained according to the present invention is 500 to 1,500,000, preferably 1,000 to 500,000, and molecular weight distribution is 1.5 to 20.

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

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

Synthetic solvents such as tetrahydrofuran (THF), toluene, normal hexane ( n- Hexane), diethyl ether, and methylene chloride (CH ₂ Cl ₂ ) were activated by purchasing an anhydrous grade from Sigma-Aldrich. After drying on a molecular sieve (Molecular Sieve 4A), the double-substituted chloroform (CDCl ₃ ) used for the NMR structure analysis of organometallic compounds was purchased from Cambridge Isotope Laboratories and then activated molecular sieve (Molecular Sieve, Dried over 4A).

Ethanol, normalpentane, normalbutyllithium (2.5M Solution in n- Hexane), methyllithium (1.6M solution in Diethyl ether), 4-methoxyphenylmagnesium bromide (0.5M Solution in THF), ammonium chloride ( Ammonium chloride), anhydrous magnesium sulfate (magnesium sulfate, anhydrous), para-toluenesulfonic acid hydrate (para -Toluenesulfonic acid, monohydrate (p -TsOH (H 2 O)), 4- bromo-N, N-dimethylaniline (4 -Bromo- N , N -dimethylaniline) and 4-bromothioanisole were purchased from Sigma-Aldrich and used without purification, and tetrachlorobis (tetrahydrofuran) zirconium, ZrCl ₄ ㅇ 2C ₄ H ₈ O) was purchased from Strem and used without purification. 3,4-dimethylcycloglota-2-enone (3,4-Dimethylcyclopent-2-enone) was listed in the literature. Synthesis was carried out according to the method.

¹ H NMR and ¹³ C NMR were measured using a Bruker Avance 400 Spectrometer at room temperature. Elemental analysis was performed using EA 1110-FISION (CE Instruments). X-ray molecular structure analysis was performed using Enrarf-Nonius CAD4TSB Diffractometer. After the measurement, it was analyzed by calculation on the Silicon Graphics Indigo2XZ Workstation.

Synthesis Example 1 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 1-1

: 1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadiene (1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadiene, ( p -Me ₂ NC ₆ H ₄ ) -3,4-Me Synthesis of ₂ C ₅ H ₃ )

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. The oil was dissolved in methylene chloride (30 ml), para-toluenesulfonic 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 1- (p - dimethylaminophenyl) The results of 3,4-dimethyl cyclopentadiene ¹ H- NMR and ¹³ C ^{1 H} NMR confirmed the synthesis of the next.

¹ H NMR (400.13 MHz, CDCl ₃ ): 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 ): 142.8, 135.4, 133.7, 128.3, 125.5, 112.9, 45.2, 40.8, 13.4, 12.6.

[Synthesis Example 1-2]: Bis [1- (p - dimethylaminophenyl) -3,4-dimethyl-cyclopentadienyl] 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 )

1.280 g (6.0 mmol) of 1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadiene synthesized in Synthesis Example 1-1 was dissolved in 30 ml diethyl ether, and then equivalent to normal butyl at -78 ° C. 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-NMR and ¹³ C { ¹ H} NMR confirming the synthesis of the bis- [1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride and elemental analysis thereof Is shown below.

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

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): 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 1-3 Dimethylbis- [1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium (Dimethylbis- [1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl ] zirconium, Synthesis of [1- ( p -Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ Zr (CH ₃ ) ₂ )

Bis- [1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (1.174 g, 2.0 mmol) synthesized in Synthesis Example 1-2 was dissolved in 30 ml of diethyl ether. Thereafter, two equivalents of methyllithium (2.5 ml) were added at -78 ° C. The reactor was slowly raised to room temperature and stirred for 4 hours to remove solvent. Again dissolved in 30 ml of methylene chloride and filtered through Celite to give a solution. The solvent was again removed in vacuo from the solution, followed by recrystallization at −20 ° C. with methylene chloride / normal hexane solution to 0.852 g of dimethylbis- [1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl ] Zirconium was obtained in 78% yield.

The dimethyl bis - [1- (p - dimethylaminophenyl) -3,4-dimethyl-cyclopentadienyl] The ¹ H- NMR and ¹³ C ^{1 H} NMR results and the results of its elemental analysis confirmed the synthesis of the zirconium It is shown next.

¹ H NMR (400.13 MHz, CDCl ₃ ): 7.09 (d, 4H), 6.70 (d, 4H), 5.56 (s, 4H), 2.95 (s, 12H), 1.81 (s, 12H), -0.51 (s , 6H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): 149.1, 125.3, 123.8, 121.6, 121.5, 112.7, 108.0, 40.7, 29.8, 12.9.

Anal. Calcd for C ₃₂ H ₄₂ N ₂ Zr: C, 70.40; H, 7.75; N, 5.13.

Found: C, 70.68; H, 7.93; N, 5.66.

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

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. The solvent was properly removed by the rotary evaporator, and then recrystallized with ethanol at 20 ° C. to obtain 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene (2.20 g, 47% yield).

The 1- (p - methoxyphenyl) -3,4-dimethyl-The results of cyclopentadiene ¹ H- NMR and ¹³ C ^{1 H} NMR confirmed the synthesis of the next.

¹ H NMR (400.13 MHz, CDCl ₃ ): 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 ): 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 2-2 Bis [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium Synthesis of dichloride, [1- ( p -MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ )

The same method as in Synthesis Example 1-2, except that 1.202 g (6.0 mmol) of 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene synthesized in Synthesis Example 2-1 was used. The reaction was carried out to give bis- [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride as yellowish fine crystals. 0.891 g (53% yield) was obtained.

¹ H-NMR and ¹³ C { ¹ H} NMR confirming the synthesis of the bis- [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride and elemental analysis thereof Is shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): 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 ): 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 3 Bis [1- ( p -Methylthiophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis [1- ( p -methylthiophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -MeSC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 3-1

1- ( p -methylthiophenyl) -3,4-dimethylcyclopentadiene (1- ( p -Methylthiophenyl) -3,4-dimethylcyclopentadiene, ( p -MeSC ₆ H ₄ ) -3,4-Me ₂ C ₅ Synthesis of H ₃ )

Used in Synthesis Example 1-1 Under the same conditions, except that 4-bromothioanisole (4.33 g, 20 mmol) was used instead of 4-bromo- N, N -dimethylaniline, the reaction proceeded under 1.69 g of a pale yellow solid, 1- ( p -methylthiophenyl) -3,4-dimethylcyclopentadiene was obtained in 39% yield.

The 1- (p - methylthiophenyl) -3,4-dimethyl-The results of cyclopentadiene ¹ H- NMR and ¹³ C ^{1 H} NMR confirmed the synthesis of the next.

¹ H NMR (400.13 MHz, CDCl ₃ ): 7.34 (d, 2H), 7.17 (d, 2H), 6.61 (s, 1H), 3.22 (s, 2H), 2.46 (s, 3H), 1.96 (s, 3H), 1.87 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): 141.9, 135.7, 135.55, 135.50, 133.6, 131.4, 127.1, 124.9, 45.2, 16.2, 13.4, 12.6.

Synthesis Example 3-2 Bis [1- ( p -methylthiophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis [1- ( p -methylthiophenyl) -3,4-dimethylcyclopentadienyl] zirconium Synthesis of dichloride, [1- ( p -MeSC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ )

1- ( p -methylthiophenyl) -3,4-dimethylcyclopentadiene 1.298 g (6.0 mmol) synthesized in Synthesis Example 3-1 was reacted under the same conditions as in Synthesis Example 1-2. Bis [1- ( p -methylthiophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (0.907 g, 51% yield) was obtained as a yellow solid.

The bis [1- (p - methylthiophenyl) -3,4-dimethyl-cyclopentadienyl] The ¹ H- NMR and ¹³ C ^{1 H} NMR results and the results of its elemental analysis confirmed the synthesis of the zirconium dichloride It is shown next.

¹ H NMR (400.13 MHz, CDCl ₃ ): 7.35 (d, 4H), 7.30 (d, 4H), 6.20 (s, 4H), 2.51 (s, 6H), 1.79 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): 137.8, 130.1, 128.2, 126.9, 125.6, 122.0, 115.7, 15.8, 13.2.

Anal. Calcd for C ₂₈ H ₃₀ Cl ₂ S ₂ Zr: C, 56.73; H, 5.10.

Found: C, 56.21; H, 5.36.

The synthesis process applied to the synthesis examples 1 to 3 is briefly shown in the following scheme 1.

In Scheme 1, 1-1 is the product of Synthesis Example 1-1, 2-1 is the product of Synthesis Example 2-1, 3-1 is the product of Synthesis Example 3-1, and 1-2 is The result is the synthesis example 1-2, 1-3 is the result of the synthesis example 1-3, 2-2 is the result of the said synthesis example 2-2, and 3-2 shows the result of the said synthesis example 3-2.

In addition, FIG. 1 shows a molecular structure measured through X-ray of bis- [1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride obtained in Synthesis Example 1. It was.

Hereinafter, the present invention will be described in more detail with reference to specific examples for preparing a propylene polymer using the obtained transition metal compound, but the present invention is not limited to these examples.

All polymerization proceeded with constant propylene pressure after injection of the required amount of solvents, catalysts, promoters, propylene, etc. in a reactor (Flask or Autoclave) completely isolated from outside air. Solvents such as toluene and normal hexane used in the polymerization are purchased from Sigma-Alsrich, Anhydrous Grade, and then further dried by passing through an activated molecular sieve (4A) or activated alumina layer. Methylaluminoxane was purchased from Witco's 10% toluene solution (EURECEN AL5100 / 10T) and then dried to a solid state.

Triisobutylaluminum is obtained from Sigma-Alsrich, Inc., trityl (tetrapentafluorophenyl) borate (trityl (pentafluorophenyl) borate) and 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. Bisdendenylzirconium dichloride (Ind ₂ ZrCl ₂ ) was synthesized by referring to the literature. Was used.

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, mmmmPentad II) dissolves polypropylene in trichlorobenzene and benzene- d ₆ (Benzene- d ₆ , C ₆ D ₆ ) and then uses ¹³ C NMR (Bruker, Avance 400 Spectrometer) method at 100 ° C. Measured by.

Polymerization Example 1

To a 250 ml glass flask in which the inside was replaced with nitrogen in a glove box, 0.29 g of methylaluminoxane (5 mmol based on Al) was measured and 48 ml of toluene was added at room temperature, and the temperature of the reactor was adjusted to 0 ° C. While stirring for 30 minutes, the propylene gas was saturated to 1 bar. Subsequently, toluene solution (2.0 ml, 5.0 μmol of Zr) in which the catalyst of Synthesis Example 1-2 was dissolved was added by syringe to initiate polymerization.

After maintaining the bar at 0 ° C. for 2 hours, 5 ml of 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 finally dried by heating at 80 ° C. for at least 15 hours using a vacuum oven to finally obtain polypropylene.

Polymerization Examples 2-4

Propylene was polymerized according to the same method as in Polymerization Example 1, except that the reaction temperature was performed at 25 ° C, 50 ° C, and 70 ° C, respectively.

Polymerization Example 5

Propylene was polymerized in the same manner as in Polymerization Example 1, except that the catalyst prepared in Synthesis Example 1-3 was reacted at a reaction temperature of 25 ° C.

Polymerization Example 6

Propylene was polymerized in the same manner as in Polymerization Example 1, except that the catalyst prepared in Synthesis Example 2-2 was reacted for 1 hour.

Polymerization Examples 7-9

Propylene was prepared in the same manner as in Polymerization Example 1, except that the catalyst prepared in Synthesis Example 2-2 was reacted for 1 hour at a reaction temperature of 25 ° C., 50 ° C., and 70 ° C., respectively. Was polymerized.

Polymerization Example 10

Propylene was polymerized in the same manner as in Polymerization Example 1, except that the catalyst prepared in Synthesis Example 3-2 was used.

Polymerization Examples 11-13

Propylene was prepared in the same manner as in Polymerization Example 1, except that the catalyst prepared in Synthesis Example 3-2 was reacted at a reaction temperature of 25 ° C., 50 ° C., and 70 ° C. for 1 hour, respectively. Was polymerized.

Polymerization Comparative Example 1

Using the catalyst of Synthesis Example [1-3], 5 μmol of trityl (tetrapentafluorophenyl) borate instead of methylaluminoxane, 1 mmol of triisobutylaluminum was injected to remove impurities in the polymerization solvent at 25 ° C. Except for reacting at, propylene was polymerized in the same manner as in Polymerization Example 1.

Polymerization Comparative Example 2

Propylene according to the same method as in Polymerization Example 1, except that the reaction was carried out at 25 ° C. for 25 minutes using a racemic-ethylene (bisindenyl) zirconium dichloride catalyst instead of the catalyst of Synthesis Example 1-2. Was polymerized.

The reaction conditions and polymerization results of Polymerization Examples 1 to 13 and Polymerization Comparative Examples 1 and 2 were summarized in the following Table 1, and the physical properties of the obtained polypropylene were summarized in Table 2 below.

In Table 2 above ^a ES (Ether Soluble) is the ratio of atactic polypropylene with low stereoregularity in polypropylene obtained after polymerization, using Soxhlet Extractor using diethyl ether as a solvent. ^b no means no melting point was found.

As shown in the results of Table 2, in the case of the polypropylene prepared using the catalyst of the present invention, the weight average molecular weight is higher than that of the conventional catalyst, and the stereoregularity is variously adjusted to a desired level by controlling the reaction conditions. Can be.

The polymerization method from the polymerization example 1 to the polymerization comparative example 2 was performed by slurry polymerization, and a separate polymerization solvent was added to carry out the polymerization reaction at normal pressure.

In the following examples, the propylene polymer was polymerized under a high pressure using the catalyst of the present invention. The polymerization solvent was not used separately, but was used only when the catalyst and the promoter were used. This is because liquid propylene acts as a solvent for polymerization and as a reaction monomer, and this polymerization method is referred to as bulk polymerization. In the case of the bulk polymerization, since the process of removing the polymerization solvent after the polymerization is not necessary, the cost of the polypropylene can be lowered, so most polypropylene plants use this method.

Polymerization Example 14

The interior of the stainless steel autoclave with an internal volume of 2 L 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, 5.0 μmol) in which the catalyst obtained in Synthesis Example 1-2 was dissolved. of Zr) was added. Thereafter, 500 g of propylene was added, and polymerization was carried out at 0 ° C for 1 hour.

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 thus obtained was dried for at least 15 hours while heating to 80 ° C. in a vacuum oven to finally obtain polypropylene.

Polymerization Examples 15-18

    In polypropylene polymerization, the polypropylene was polymerized according to the same method as in Polymerization Example 14, except that the reaction temperature was performed at 30 ° C, 40 ° C, 60 ° C, and 70 ° C, respectively.

Polymerization Examples 19-21

The polypropylene was polymerized according to the same method as the polymerization example 14 except that the catalyst prepared in Synthesis Example 2-2 was reacted at a reaction temperature of 30 ° C., 60 ° C., and 70 ° C., respectively. It was.

Polymerization Comparative Example 3

Propylene polymerization was carried out in the same manner as in Polymerization Example 14, but the catalyst of [Synthesis Example 1-3] was used at 70 ° C., and 7.5 μmol of trityl (tetrapentafluorophenyl) borate was used instead of MAO, and impurities in the polymerization solvent were used. For the removal, 1 mmol of triisobutylaluminum was injected and polymerized.

Polymerization Comparative Examples 4 to 5

Polymerization Example 14 except that the reaction was carried out at 70 ° C. using a racemic-ethylene (bisindenyl) zirconium dichloride catalyst and a bisdenyl zirconium dichloride catalyst instead of the catalyst of Synthesis Example 1-2. Polypropylene was polymerized according to the same method as.

The reaction conditions of the polymerization example 14 to the polymerization example 21, and the polymerization comparative example 3 to the polymerization comparative example 5 are summarized in the following Table 3, and the physical properties of the obtained polypropylene are summarized in Table 4.

In Table 4, ^a XS (Xylene Soluble) is a ratio of atactic polypropylene having a low stereoregularity in the polypropylene obtained after polymerization, and used Soxhlet Extractor as a styrene solvent, ^b no means that no melting point was found. do.

As shown in Table 4 above, when propylene polymerization was carried out using the catalyst system of the present invention, the catalyst and the cocatalyst were not used without using a catalyst having a complicated structure as in [Comparative Comparative Example 2] and [Comparative Comparative Example 4]. Through the interaction of the polypropylene with a high molecular weight, high melting point, high stereoregularity can be obtained. Moreover, the stereoregularity of polypropylene can also be adjusted according to the structure of a catalyst and polymerization conditions.

This effect is caused by having a hetero atom in the transition metal compound, which is the main catalyst of the present invention, which interacts with the promoter, and [Polymerization Example 2], [Comparative Polymerization Example 1], [Polymerization Example 18] and It is demonstrated by comparing [polymerization comparative example 3] and [polymerization comparative example 5] directly.

DSC graphs of the polypropylene obtained in the above Polymerization Example 2, Polymerization Example 7, Polymerization Example 11, and Polymerization Comparative Example 1 and Polymerization Comparative Example 2 are summarized in FIG. In Example 7, when the transition metal compound of the present invention is used as the main catalyst and MAO as the promoter, the stereoregularity diagram having a melting point of 150 ° C. or higher without using the catalyst of the conventional complex structure used in Comparative Example 2 is shown. Shows that the isotactic polypropylene is highly polymerized. In polymerization example 11, the stereoregularity can be controlled by changing the type of hetero atoms in the transition metal compound under the same conditions. Using a transition metal compound as a main catalyst and a borate compound that does not react with heteroatoms in the transition metal compound of the present invention as a promoter In this case, the atactic polypropylene with no melting point was shown to have a low stereoregularity.

In addition, the DSC graphs of the polypropylene obtained in Polymerization Example 18, Polymerization Example 21, and Polymerization Comparative Example 3, Polymerization Comparative Example 4, and Polymerization Comparative Example 5 were collectively shown in the following FIG. In the polymerization Example 21, when the transition metal compound of the present invention was used as the main catalyst and MAO as the promoter, the solid having a melting point of 150 ° C. or higher without using the catalyst of the conventional complex structure used in Comparative Example 4 The results show that the isotactic polypropylene having a high degree of regularity was polymerized. In Comparative Example 3, a borate compound which does not react with heteroatoms in the transition metal compound of the present invention is prepared using the transition metal compound of the present invention as a main catalyst. When used as a catalyst, atactic polypropylene without melting point was polymerized due to low stereoregularity. Case of using the catalyst and the MAO not having a hetero atom in a compound with a co-catalyst and the stereoregularity degree and the results are shown to be low melting point of the atactic polypropylene polymerization no.

In addition, when using the catalyst containing the transition metal compound of the present invention from the above embodiment it is possible to effectively polymerize the isotactic polypropylene under both slurry polymerization and bulk polymerization conditions.

As described above, by using the transition metal compound according to the present invention as the main catalyst of the propylene polymer, it is possible to control the stereoregularity of propylene, and through the interaction of the catalyst and the promoter without the use of a complex catalyst, It is useful for the polymerization of propylene polymers with high melting points and high stereoregularity.

Claims (25)

delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete (1) the transition metal compound represented by the following formula (1); And Formula 1

In Formula 1, M ¹ is selected from Group 4 elements of the periodic table, Cp ¹ and Cp ³ are the same as or different from each other, and are ligands having a cyclopentadienyl skeleton including at least one substituent including a hetero atom represented by Formula 6 below, Formula 6

In Formula 6, B ² is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an alkylsilylene group having 1 to 20 carbon atoms, a silylalkylene group having 1 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms , An arylalkylene group having 6 to 20 carbon atoms, an alkylarylene group having 6 to 20 carbon atoms, an arylsilylene group having 6 to 20 carbon atoms, and a silyl arylene group having 6 to 20 carbon atoms, Z is a hetero atom selected from the group consisting of N, P, As, O, S and Se, R ² is a hydrogen atom 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, an aryl group having 6 to 20 carbon atoms, and 6 to carbon atoms Selected from the group consisting of 20 arylalkyl groups, 6 to 20 alkylaryl groups, 6 to 20 arylsilyl groups, and 6 to 20 silylaryl groups, m is 1 or 2. 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 6 to 20 carbon atoms, C6-C20 alkylaryl group, C6-C20 arylsilyl group, C6-C20 silylaryl group, C1-C20 alkoxy group, C1-C20 alkylsiloxy group, C6-C20 aryl An oxy group, a halogen group, an amine group, or a tetrahydroborate group, a is an integer of 1-5. (2) polymerizing propylene in the presence of a catalyst for propylene polymerization comprising an aluminoxane compound represented by the following formula (7) or an organoaluminum compound represented by the following formula (8), Pressure during polymerization is a method for producing a propylene polymer, characterized in that 2 to 50 bar. Formula 7

In Formula 7, R ³ is an alkyl group having 1 to 10 carbon atoms, n is an integer of 1-70. Formula 8

In Formula 8, R ⁴ , R ⁵ , and R ⁶ are the same as or different from each other, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group, and at least one of R ⁴ , R ⁵ , and R ⁶ is an alkyl group. to be. The method for preparing a propylene polymer according to claim 20, wherein the transition metal compound represented by Chemical Formula 1 in the catalyst is 10 ^-8 mol / liter-1 mol / liter at a central metal concentration. The method of claim 20 wherein the catalyst is a method for producing a propylene polymer, characterized in that the molar ratio of co-catalyst / catalyst week of 1/1 to 10 ^6/1. The method of claim 20, wherein the propylene polymer is prepared in a liquid phase, a gas phase, a bulk phase, or a slurry phase. 21. The method of claim 20, wherein the polymerization temperature is -50 ° C to 200 ° C. delete

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