KR20170037194A - Method for preparing polyolefin and polyolefin prepared therefrom - Google Patents
Method for preparing polyolefin and polyolefin prepared therefrom Download PDFInfo
- Publication number
- KR20170037194A KR20170037194A KR1020150136429A KR20150136429A KR20170037194A KR 20170037194 A KR20170037194 A KR 20170037194A KR 1020150136429 A KR1020150136429 A KR 1020150136429A KR 20150136429 A KR20150136429 A KR 20150136429A KR 20170037194 A KR20170037194 A KR 20170037194A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- alkyl
- aryl
- silyl
- cyclopentadienyl
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
Abstract
Description
The present invention relates to a process for producing polyolefins having a broad molecular weight distribution and to polyolefins prepared by such processes.
Polyolefins should have excellent mechanical properties such as toughness and strength in molding products for specific use. Such mechanical properties can be improved by increasing the molecular weight, but when the molecular weight is high, the processability of the polyolefin is deteriorated.
In order to solve this problem, various attempts have been made in the past to broaden the molecular weight distribution of polyolefins. Polyolefins having a broad molecular weight distribution are excellent in not only mechanical properties but also processability (particularly extrudability).
Methods for producing polyolefins (i.e., multimodal polyolefins) having a broad molecular weight distribution include post-reactor techniques or melt blending methods in which polymers having two or more different molecular weights are blended together before or during processing (See Patent Document 1 below). However, the polyolefin prepared by this method has a high gel content and thus has limitations in applying it to various products. In addition, since the polymer is physically blended, it is required to completely homogenize the polymer, which has a problem that the manufacturing cost is high.
On the other hand, another method of producing a polyolefin having a broad molecular weight distribution includes a method of polymerizing a catalyst mixture and monomers in a single reactor. Specifically, a catalyst composition in which two or more components are mixed in a single reactor is used to produce a polyolefin having a broad molecular weight distribution (see Patent Document 2 below). However, since this method uses a catalyst composition in which two or more components are mixed, it is difficult to ensure that a polyolefin having a uniform composition can be obtained. Since a polyolefin is produced in a single reactor, insertion of a comonomer into a high molecular weight portion is difficult, There was a limit in obtaining this excellent polyolefin.
It is an object of the present invention to provide a production method capable of producing a polyolefin having a broad molecular weight distribution and excellent mechanical properties in order to solve the above problems.
It is another object of the present invention to provide a polyolefin produced by the above production process.
In order to achieve the above-mentioned object, the present invention provides a process for producing a catalyst, comprising: a) injecting and polymerizing a catalyst comprising a catalyst compound and a cocatalyst compound, a first monomer and a second monomer into a first reactor and polymerizing to prepare a first polymer; And b) injecting and polymerizing the first polymer, the third monomer, the fourth monomer and hydrogen into a second reactor to produce a second polymer, wherein the temperature at which the first polymer is polymerized is greater than the temperature of the second Wherein the catalyst compound contains at least two of the compounds represented by the following general formulas (1) to (3), wherein the catalyst compound is at a temperature equal to or lower than the temperature at which the polymer is polymerized.
[Chemical Formula 1]
(2)
(3)
In the above Formulas 1 to 3,
M 1 to M 3 are the same or different and are each independently selected from the group consisting of Group 3 to Group 10 elements on the periodic table,
X 1 and X 2 are the same or different and are each independently selected from the group consisting of halogen, an amine group, (C 1 -C 20 ) alkyl group, (C 3 -C 20 ) cycloalkyl group, (C 1 -C 20 ) silyl (C 1 ~ C 20) alkyl, (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl (C 1 ~ C 20) alkyl, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20 aryl) silyl group, a silyl group (C 6 ~ C 20) aryl, (C 1 ~ C 20) alkoxy groups, (C 1 ~ C 20) alkyl siloxane group and a (C 6 to C 20 ) aryloxy groups,
n is an integer of 1 to 5,
Ar 1 to Ar 4 are the same or different and each independently a ligand having a cyclopentadienyl skeleton wherein the ligand is selected from the group consisting of halogen, (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl , (C 1 ~ C 20) alkyl silyl group, the silyl (C 1 ~ C 20) alkyl, halo (C 1 ~ C 20) alkyl, (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl (C 1 -C 20 ) alkyl group, (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group, (C 6 -C 20 ) arylsilyl group and a silyl (C 6 -C 20 ) , The substituent may be bonded to another adjacent substituent to form a ring,
B is selected from the group consisting of carbon (C), silicon (Si), germanium (Ge), nitrogen (N)
L is hydrogen, (C 1 ~ C 20) alkyl, (C 3 ~ C 20) cycloalkyl, (C 1 ~ C 20) alkyl silyl group, the silyl (C 1 ~ C 20) alkyl, (C 6 ~ C 20 ) aryl, (C 6 ~ C 20) aryl (C 1 ~ C 20) alkyl, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl silyl group, and Silyl (C 6 -C 20 ) aryl group,
m is an integer of 1 to 2,
Q 1 and Q 2 are the same or the different and are each independently of one another, halogen, (C 1 ~ C 20) alkyl, (C 2 ~ C 20) alkenyl, (C 2 ~ C 20) alkynyl, (C 6 ~ C 20) aryl, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl (C 1 ~ C 20) alkyl, (C 1 ~ C 20) alkyl Amido group, and (C 6 -C 20 ) arylamido group,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently hydrogen; A (C 1 -C 20 ) alkyl group with or without an acetal, ketal or ether group; A (C 2 -C 20 ) alkenyl group with or without an acetal, ketal or ether group; (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group, with or without an acetal, ketal or ether group; (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group, with or without an acetal, ketal or ether group; And a (C 1 -C 20 ) silyl group containing or not containing an acetal, ketal or ether group, R 1 and R 2 may be connected to each other to form a ring, and R 3 and R 4 May be connected to each other to form a ring, and R 5 to R 10 Two or more of them may be connected to each other to form a ring,
R 11 , R 12 and R 13 are each independently hydrogen; A (C 1 -C 20 ) alkyl group with or without an acetal, ketal or ether group; A (C 2 -C 20 ) alkenyl group with or without an acetal, ketal or ether group; (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group, with or without an acetal, ketal or ether group; (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group, with or without an acetal, ketal or ether group; A (C 1 -C 20 ) silyl group with or without an acetal, ketal or ether group; (C 1 -C 20 ) alkoxy group; And (C 6 ~ C 20) is selected from the group consisting aryloxy; R 11 and R 12 may be connected to each other to form a ring, and R 12 and R 13 may be connected to each other to form a ring.
The present invention also provides a polyolefin produced by the above process.
The present invention relates to a process for preparing a polyolefin by using a first reactor and a second reactor in which the polymerization conditions of the first reactor and the second reactor are controlled differently and the polymerization conditions in the first reactor include a catalyst component of a specific component A polyolefin having a broad molecular weight distribution and excellent mechanical properties can be provided.
1 is a reference diagram for explaining Experimental Example 2 of the present invention.
Hereinafter, the present invention will be described.
Conventionally, in order to produce a polyolefin having a broad molecular weight distribution, a catalyst composition in which two or more components are mixed in a polymerization reaction is applied, or a multi-stage reactor is applied. However, the catalyst composition in which two or more components are mixed has a limitation in controlling the molecular weight distribution of the polyolefin. When a multi-stage reactor is used, since the polymer having a low molecular weight is usually polymerized in the first reactor and the polymer having a high molecular weight is polymerized in the second reactor, the SCB content of the finally obtained polyolefin is not high, There was a difficulty in obtaining a polyolefin.
Accordingly, the present invention relates to a process for producing a polyolefin by using a first reactor and a second reactor, wherein the polymerization conditions in each reactor are specified, and at the same time, a catalyst comprising a catalyst compound in which two or more components are mixed, The catalyst compound is specifically applied to the polymerization reaction so that the catalyst exhibits high activity, which will be described in detail as follows.
One. Polyolefin Manufacturing method
a) Preparation of first polymer
A catalyst comprising a catalyst compound and a cocatalyst compound in a first reactor; The first monomer and the second monomer are injected and polymerized to produce the first polymer.
The catalyst compound included in the catalyst of the present invention includes two or more of the compounds represented by the following general formulas (1) to (3).
[Chemical Formula 1]
(2)
(3)
In the above Formulas 1 to 3,
M 1 to M 3 are the same or different and are each independently selected from the group consisting of Group 3 to Group 10 elements on the periodic table,
X 1 and X 2 are the same or different and are each independently selected from the group consisting of halogen, an amine group, (C 1 -C 20 ) alkyl group, (C 3 -C 20 ) cycloalkyl group, (C 1 -C 20 ) silyl (C 1 ~ C 20) alkyl, (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl (C 1 ~ C 20) alkyl, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20 aryl) silyl group, a silyl group (C 6 ~ C 20) aryl, (C 1 ~ C 20) alkoxy groups, (C 1 ~ C 20) alkyl siloxane group and a (C 6 to C 20 ) aryloxy groups,
n is an integer of 1 to 5,
Ar 1 to Ar 4 are the same or different and each independently a ligand having a cyclopentadienyl skeleton wherein the ligand is selected from the group consisting of halogen, (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl , (C 1 ~ C 20) alkyl silyl group, the silyl (C 1 ~ C 20) alkyl, halo (C 1 ~ C 20) alkyl, (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl (C 1 -C 20 ) alkyl group, (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group, (C 6 -C 20 ) arylsilyl group and a silyl (C 6 -C 20 ) , The substituent may be bonded to another adjacent substituent to form a ring,
B is selected from the group consisting of carbon (C), silicon (Si), germanium (Ge), nitrogen (N)
L is hydrogen, (C 1 ~ C 20) alkyl, (C 3 ~ C 20) cycloalkyl, (C 1 ~ C 20) alkyl silyl group, the silyl (C 1 ~ C 20) alkyl, (C 6 ~ C 20 ) aryl, (C 6 ~ C 20) aryl (C 1 ~ C 20) alkyl, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl silyl group, and Silyl (C 6 -C 20 ) aryl group,
m is an integer of 1 to 2,
Q 1 and Q 2 are the same or different, each independently from each other, halogen, (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, (C 6 -C 20) aryl, (C 1 -C 20) alkyl (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 1 -C 20) alkyl, (C 1 -C 20) alkyl (C 6 -C 20 ) arylamido groups, and the like.
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently hydrogen; A (C 1 -C 20 ) alkyl group with or without an acetal, ketal or ether group; A (C 2 -C 20 ) alkenyl group with or without an acetal, ketal or ether group; (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group, with or without an acetal, ketal or ether group; (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group, with or without an acetal, ketal or ether group; And a (C 1 -C 20 ) silyl group containing or not containing an acetal, ketal or ether group, R 1 and R 2 may be connected to each other to form a ring, and R 3 and R 4 May be connected to each other to form a ring, and R 5 to R 10 Two or more of them may be connected to each other to form a ring,
R 11 , R 12 and R 13 are each independently hydrogen; A (C 1 -C 20 ) alkyl group with or without an acetal, ketal or ether group; A (C 2 -C 20 ) alkenyl group with or without an acetal, ketal or ether group; (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group, with or without an acetal, ketal or ether group; (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group, with or without an acetal, ketal or ether group; A (C 1 -C 20 ) silyl group with or without an acetal, ketal or ether group; (C 1 -C 20 ) alkoxy group; And (C 6 -C 20) is selected from the group consisting aryloxy; R 11 and R 12 may be connected to each other to form a ring, and R 12 and R 13 may be connected to each other to form a ring.
Specific examples of the halogen represented by the definition of the compounds represented by the formulas (1) to (3) include a fluoro group, a chloro group, a bromo group, an iodo group, Can be; Specific examples of the amine group include a dimethylamine group, a diethylamine group, a dipropylamine group, a dibutylamine group, a diphenylamine group, a dibenzylamine group, (Dibenzylamine) group, and the like; Specific examples of the (C 1 -C 20 ) alkyl group, the (C 3 -C 20 ) cycloalkyl group, the (C 1 -C 20 ) alkylsilyl group, or the silyl (C 1 -C 20 ) An ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group Decyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a decahydronaphthalyl group, a methylsilyl group, A methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a propylsilyl group, a di A dipropylsilyl group, a tripropylsilyl group, a butylsilyl group, a dibutylsilyl group, a tributylsilyl group, a (methylsilyl) methyl group (dimethylsilyl) methyl group, (trimethylsilyl) methyl group, (ethylsilyl) methyl group, (diethylsilyl) methyl group, (Dimethylsilyl) methyl group, (triethylsilyl) methyl group, (methylsilyl) ethyl group, (dimethylsilyl) ethyl group, Trimethylsilyl) ethyl ((Trimethylsilyl) ethyl) group, and the like; (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl (C 1 ~ C 20) alkyl, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl silyl group, or a silyl group (C 6 ~ C 20) specific examples of the aryl group are phenyl (phenyl) group, biphenyl (biphenyl) group, a terphenyl (terphenyl) group, a naphthyl (naphtyl) group, a fluorenyl A benzyl group, a phenylethyl group, a phenylpropyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, A diethylphenyl group, a triethylphenyl group, a propylphenyl group, a dipropylphenyl group, a tripropylphenyl group, a phenylsilyl group, a methylphenylsilyl group, (Methylphenylsilyl) group, a dimethylphenylsilyl group, methyl (diphenyl) silyl, a triphenylsilyl group, an ethylphenylsilyl group, a methylphenylsilyl group, silyl) group, (ethylsilyl) phenyl group, (dimethylsilyl) phenyl ((dimethylsilyl) phenyl) silyl group, (trimethylsilyl) phenyl group, (trimethylsilyl) phenyl group, (ethylsilyl) phenyl group, (diethylsilyl) phenyl group, A trialkylsilyl phenyl group, a (propylsilyl) phenyl group, a dipropylsilyl phenyl group, a butylsilyl phenyl group, a dibutylsilyl phenyl group, ) phenyl group, and the like; Specific examples of the (C 1 -C 20 ) alkoxy group or the (C 1 -C 20 ) alkylsiloxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, A pentoxy group, a hexyloxy group, a methylsiloxy group, and a dimethylsiloxy group. A trimethylsiloxy group, an ethylsiloxy group, a diethylsiloxy group, and a triethylsiloxy group; and the like; Specific examples of the (C 6 -C 20 ) aryloxy group include a phenoxy group, a naphthoxy group, a methylphenoxy group, a dimethylphenoxy group, a trimethylphenoxy group, Ethylphenoxy group, diethylphenoxy group, triethylphenoxy group, propylphenoxy group, dipropylphenoxy group, tripropylphenoxy group, tripropylphenoxy group, tripropylphenoxy group, ) And the like.
In the compound represented by Formula 1, M 1 is preferably a Group 4 transition metal (specifically, zirconium (Zr), titanium (Ti), or hafnium (Hf)). Ar 1 and Ar 2 are each independently preferably a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, or a fluorenyl group. Specifically, the compound represented by the above formula (1) is preferably selected from the group consisting of bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) zirconium dichloride, bis (isopropylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (isobutylcyclopentadienyl) (Pentamethylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (1-butyl-3-methylcyclopentadienyl) zirconium dichloride, bis Zirconium dichloride, bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, or bis (n-butylcyclopentadienyl) hafnium dichloride Id can be.
In the compound represented by Formula 2, M 2 is preferably a Group 4 transition metal (specifically, zirconium (Zr), titanium (Ti), or hafnium (Hf)). Ar 3 and Ar 4 are each independently preferably a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, or a fluorenyl group. Specifically, the compound represented by the general formula (2) is preferably selected from the group consisting of rac-ethylene bis (1-indenyl) zirconium dichloride, rac-ethylene bis (1-indenyl) hafnium dichloride, rac- Zirconium dichloride, rac-ethylene bis (1-tetrahydroindenyl) hafnium dichloride, rac-dimethylsilanediylbis (2-methyl-tetrahydrobenzenylenyl) zirconium dichloride, rac-dimethylsilandiyl Diphenylsilanediylbis (2-methyl-tetrahydrobenzenylidene) zirconium dichloride, rac-diphenylsilandiylbis (2-methyltetrahydrobenzenylidene) hafnium dichloride, Dimethyl-silanediylbis (2-methyl-4,5-benzindenyl) zirconium dichloride, rac-dimethylsilanediylbis (2-methyl- 5-benzindenyl) hafnium dichloride, rac-diphenylsilane Zirconium dichloride, rac-diphenylsilandiylbis (2-methyl-4,5-benzindenyl) hafnium dichloride, rac-dimethylsilanediyl Cyclopentadienylindenyl) zirconium dichloride, rac-dimethylsilanediylbis (2-methyl-5,6-cyclopentadienylindenyl) hafnium dichloride, rac- Diphenylsilanediylbis (2-methyl-5,6-cyclopentadienylindenyl) zirconium dichloride, rac-diphenylsilandiylbis (2-methyl-5,6-cyclopentadienylindenyl) Hafnium dichloride, rac-dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylbis Diphenylsilylbis (2-methyl-4-phenylindenyl) hafnium dichloride, iso-propylidene (cyclopentadienyl) zirconium dichloride, Flu Zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) hafnium dichloride, diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenyl (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, iso-propylidene (3-methylcyclopentadienyl) Diphenylmethylidene (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (3-methylcyclopentadienyl) (Cyclopentadienyl) zirconium dichloride, diphenylsilyl (cyclopentadienyl) (9-fluorenyl) hafnium dichloride, diphenylsilyl (cyclopentadienyl) ) Hafnium dichloride, diphenylmethylidene (cyclopentadienyl) (2,7-ditertra (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (cyclopentadienyl) (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (2,1-di-tert-butylfluorene-9-yl) hafnium dichloride, diphenylmethylidene (3-tert- butyl- 5-methylcyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, 1,2,3,4-tetramethyldisiloxane (9-fluorenyl) zirconium dichloride, 1,2-ethylenebis (9-fluorenyl) hafnium dichloride, rac- [ - ethane] zirconium dichloride, rac- [1,2-bis (9-fluorenyl) (9-fluorenyl) -2- (5,6-cyclopenta-2-methyl-1-indenyl) -ethan] zirconium dichloride, [1- 2- (5,6-cyclopenta-2-methyl-1-indenyl) -ethan] hafnium dichloride, [4- (fluorenyl) -4,6,6- Phenyl-tetrahydropentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-phenyl-tetrahydropentrene] hafnium dichloride, iso- Cyclopentadienyl) hafnium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene Cyclopentadienyl) hafnium dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene Pentadienyl) (2,7-di-tert-butylfluoren-9-yl ) Zirconium dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluorene-9-yl) zirconium dichloride, diphenylmethylidene -9-yl) hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (p- tolyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl (9-tert-butylphenyl) -4,6,6-trimethyl-2- (p-tolyl) -tetrahydroperapentalene] hafnium dichloride, [isopropylidene- Fluorenyl)] zirconium dichloride, [isopropylidene- (2- (p-tolyl) -cyclopentadienyl) - (9-fluorenyl)] hafnium dichloride, [4- (fluorenyl) 4,6,6-trimethyl-2- (m-tolyl) -tetrahydropentrene] zirconium dichloride, [4- ( (M-tolyl) -cyclopentadienyl) - ((4-fluorophenyl) hafnium dichloride, Diphenylmethylidene (2- (m-tolyl) -cyclopentadienyl) - (9-fluorenyl)] hafnium dichloride, [diphenylmethylidene (2- cyclopentadienyl) - (9-fluorenyl)] zirconium dichloride, [diphenylmethylidene (2- (m-tolyl) -cyclopentadienyl) - (9- )] Hafnium dichloride, [isopropylidene (2- (m-tolyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [isopropylidene (2- (m-tolyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, diphenylmethylidene (2- (Cyclopentadienyl) (2,7-di-tert-butylfluorene-9-yl)] zirconium dichloride, [diphenylmethylidene (2- ) - cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [4- (fluorenyl) -4,6,6- -Tetrahydroperfluorene) zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (o-tolyl) -tetrahydropertentalene] hafnium dichloride, [isopropyl (9-fluorenyl) zirconium dichloride, [isopropylidene (2- (o-tolyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [(4- (fluorenyl) -4,6,6-trimethyl-2- (2,3-dimethylphenyl) -tetrahydropentrene] zirconium dichloride, [4- 2- (2,3-dimethylphenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- (2,4-dimethylphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,4- ) -Tetrahydropentrene] zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [isopropylidene Cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [isopropylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (9 (Diphenylmethylidene)] zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [diphenylmethylidene Cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [diphenylmethylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) ( (9-fluorenyl)) zirconium dichloride, [diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (2- (2,4-dimethylphenyl) -cyclopentadiene ) (9-fluorenyl)] hafnium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (2,7- )] Zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, Zirconium dichloride, [isopropylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (2,7- (2,4-dimethylphenyl) cyclopentadienyl) (2,7-di-tert-butylfluorene-9-yl)] hafnium dichloride, diphenylmethylidene (2- ) - cyclopentadienyl) (2,7-di-tert-butylfluorene-9-yl)] zirconium dichloride, [diphenylmethylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl Yl)] hafnium dichloride, [diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (2 (2,7-di-tert-butylfluorene-9-yl)] zirconium dichloride, [diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) -Butylfluorene-9-yl)] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (2,6- dimethylphenyl) -tetrahydro- pentalene] zirconium dichloride , [4- (fluorenyl) -4,6-trimethyl-2- (2,6-dimethylphenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) (6-trimethyl-2- (3,5-dimethylphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) Phenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-tetramethylphenyl-tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) ) -4,6,6-trimethyl-2-tetramethylphenyl-tetrahydropentene] hafnium dichloride, [4- (fluorenyl) -4, (2,4-dimethoxyphenyl) -tetrahydro-pentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (Dimethoxyphenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5- dimethoxyphenyl) -tetrahydropentrene] zirconium Tetramethylpentane] hafnium dichloride, [4- (fluorenyl) - (4-fluorophenyl) 4,6,6-trimethyl-2- (chlorophenyl) -tetrahydro (tetrahydrofuran) tetrakis (Fluorenyl) - 4,6,6-trimethyl-2- (fluorophenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) 4,6,6-trimethyl-2- (fluorophenyl) -tetrahydro-pentalene] hafnium dichloride, [4- 4- (trifluoromethyl) -4,6,6-trimethyl-2- (difluorophenyl) -tetrahydro-pentalene] zirconium dichloride, [4- (fluorenyl) (Fluorenyl) -4,6,6-trimethyl-2- (pentafluorophenyl) -tetrahydro-pentalene] zirconium dichloride, , [4- (fluorenyl) -4,6,6-trimethyl-2- (difluorophenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) -Trimethyl-2- (tert-butyl-phenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (3,5- (Trifluoromethyl) -phenyl) -tetrahydro-pentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- Hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5-di-tert- butylphenyl) tetra (4-fluorenyl) -4,6,6-trimethyl-2- (3,5-di-tert-butylphenyl) tetrahydropentene] hafnium dichloride, [4 - (fluorenyl) -4,6,6-trimethyl-2- (biphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) (Biphenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-naphthyltetrahydropentrene] zirconium dichloride, [4- Trimethyl-2-naphthyl-tetrahydropentane] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (3,5- Diphenyl-phenyl) -tetrahydro-pentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (3,5- Hafnium dichloride, isopropylidene (2-tetramethylphenyl-cyclopentadienyl) (9-fluorenyl) zirconium Zirconium dichloride, isopropylidene (2- (3,5-dimethylphenyl) - (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) Zirconium dichloride, isopropylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (9-fluorenyl) zirconium dichloride, isopropylidene (2- (dichlorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium di Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (fluorophenyl) -cyclopentadienyl) (9- Zirconium dichloride, isopropylidene (2- (pentafluorophenyl) - (cyclopentadienyl) zirconium dichloride, isopropylidene (2- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) , Isopropylidene (2- (tert-butylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (9-fluorenyl) zirconium dichloride, isopropylidene (2- (biphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2-naphthyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,6-dimethyl) zirconium dichloride, diphenylmethylidene (2-tetramethylphenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride , Diphenylmethylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5- dimethoxyphenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) Zirconium dichloride, diphenylmethylidene (2- (dichlorophenyl) cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, di Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (pentafluorophenyl) -cyclopentadienyl) (9 Zirconium dichloride, diphenylmethylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Diphenylmethylidene (2- (3,5-di-tert-butylphenyl) cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene ) -Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (biphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-naphthyl-cyclopentadienyl) (9-fluorenyl) (2,2-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5-dimethylphenyl) (2,7-di-tert-butylfluoro (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,4- dimethoxyphenyl) -cyclopentadienyl) Butenylfluorene-9-yl) hafnium dichloride, isopropylidene (2- (3,5-dimethoxyphenyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (chlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (dichlorophenyl) cyclopentadienyl) Chloride, isopropylidene (2- (trichlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoro -9-yl) hafnium dichloride, isopropylidene (2- (fluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (pentafluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene Phenyl) -cyclopentadienyl) ((2,6-di-tert-butylfluoren-9-yl) hafnium dichloride, (2,7-di-tert-butylfluorene-9-yl) hafnium dichloride, isopropylidene (2- (tert- butylphenyl) -cyclopentadienyl) -9-yl) hafnium dichloride, isopropylidene (2- (3,5-di-tert-butylphenyl) cyclopentadienyl) (2,7- Hafnium dichloride, isopropylidene (2- (biphenyl) -cyclopentadienyl) (2,7-di-tert- Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5-diphenyl- ) Hafnium dichloride, isopropylidene (2-naphthyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-tetramethylphenyl- Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,6- Cyclopentadienyl) (2,7-di-tert-butyl-triphenylphosphoryl) -9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5- Yl) hafnium dichloride, diphenylmethylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium Dichlorophenylmethylidene (2- (3,5-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylphenyl) Yl) hafnium dichloride, diphenylmethylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,6- dimethoxyphenyl) -cyclopentadienyl) (2- (dichlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,7-di-tert-butyl-9-yl) hafnium dichloride, diphenylmethylidene (2- (trichlorophenyl) -cyclopentadienyl) Yl) hafnium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, Diphenylmethylidene (2- (difluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluor (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (pentafluorophenyl) cyclopentadienyl) Diphenylmethylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5- Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (biphenyl) -cyclopentadienyl) ( Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (2-naphthyl-cyclopentadienyl) (2,7-di-tert-butyl) cyclopentadienyl Fluorene can be a 9-yl) hafnium dichloride.
In the compound represented by Formula 3, M 3 is preferably a Group 4 transition metal (specifically, zirconium (Zr), titanium (Ti), or hafnium (Hf)). In addition, the Q 1 and Q 2 are methyl or chlorine, each independently, R 1, R 2, R 3, R 4 and R 5 are each independently hydrogen or methyl (specifically, at least one of R 3 and R 4 Is methyl and R 5 is methyl, and R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are all hydrogen.
The catalyst of the present invention exhibits high activity because it contains a specific catalyst compound containing two or more of the compounds represented by the above general formulas (1) to (3). Here, considering further the activity of the catalyst of the present invention, the catalyst compound may be composed of the compounds represented by formulas (1) and (2), or the compounds represented by formulas (1) and (3)
Here, when the catalyst compound comprising the compound represented by formulas (1) and (2) is used, it is preferable to use the compound represented by formula (2) in an amount of 0.01 to 100 mol based on 1 mol of the compound represented by formula Do. When the catalyst compound comprising the compounds represented by formulas (1) and (3) is used, it is preferable to use the compound represented by the formula (3) in an amount of 0.01 to 100 mol based on 1 mol of the compound represented by the formula Do. When the catalyst compound consisting of all of the compounds represented by the formulas (1) to (3) is used, the amount of the catalyst compound used is preferably 0.01 to 100 mol based on 1 mol of the compound represented by the formula , Wherein the use ratio of the compounds represented by formulas (2) and (3) may be the same or different.
The promoter compound contained in the catalyst of the present invention activates the catalyst compound, and may be an aluminoxane compound, an organoaluminum compound, or a Bulky compound which activates a catalyst compound. Specifically, the promoter compound is preferably selected from the group consisting of compounds represented by the following formulas (4) to (6).
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
[CD]
In the above formulas 4 to 6,
Y 1 is a (C 1 -C 10 ) alkyl group,
q is an integer of 1 to 70,
Y 2 to Y 4 are the same or different, and each independently represents a (C 1 ~ C 10) alkyl, (C 1 ~ C 10) alkoxy group and is selected from the group consisting of halogen, just Y 2 to Y 4 in at least One is a (C 1 -C 10 ) alkyl group,
C is a hydrogen ion-binding cation of Lewis base, or a metal or non-metal compound having oxidizing power,
D is a compound of an organic substance and an element selected from the group consisting of elements of Groups 5 to 15 on the periodic table.
Specifically, the compound represented by Formula 4 may be selected from the group consisting of Methylaluminoxane, Ethylaluminoxane, Butylaluminoxane, Hexylaluminoxane, Octylaluminoxane, (Decylaluminoxane).
The compound represented by the formula (5) is specifically exemplified by trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, But are not limited to, tridecylaluminum, dimethylaluminum methoxide, diethylaluminum methoxide, dibutylaluminum methoxide, dimethylaluminum chloride, diethylaluminum chloride, But are not limited to, dibutylaluminum chloride, methylaluminum dimethoxide, ethylaluminum dimethoxide, butylaluminum dimethoxide, methylaluminum dichloride, It may be a butyl aluminum dichloride (Ethylaluminum dichloride), or butyl aluminum dichloride (Butylaluminum dichloride).
The compound represented by the above formula (6) is specifically exemplified by triphenylcarbenium tetrakis (pentafluorophenyl) borate, trimethylammonium tetraphenylborate, triethylammonium tetra Triethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, tri (Pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis Anilinium tetrakis (pentafluorophenyl) borate, anilinium tetraphenylborate, anilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium (N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate), pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate ), Ferrocenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) Tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, (2,3,4,5-tetrafluorophenyl) borane, tris (2,3,4,5-tetraphenylphenyl) borane, or tris Tris (3,4,5-trifluorophenyl) borane).
When the compound represented by Chemical Formula 4 or 5 is used as the cocatalyst compound, the ratio of the transition metal atom contained in the catalyst compound to the transition metal atom contained in the cocatalyst compound is in the range of 10: 1 to 100,000: 1 , And it is more preferable to use it in a ratio of 10: 1 to 100: 1. When the compound represented by the general formula (6) is used as the promoter compound, the transition metal atom contained in the catalyst compound and the transition metal atom contained in the promoter compound are used in a molar ratio of 1:10 to 10: 1 , More preferably from 1: 1 to 3: 1.
On the other hand, the catalyst of the present invention may further comprise a carrier for supporting the catalyst compound and the co-catalyst compound. The carrier is not particularly limited as long as it is a porous organic / inorganic compound having fine pores on the surface or inside thereof. Specifically, the carrier may be an organic compound such as starch, cyclodextrin, or synthetic polymer; Or an inorganic material selected from the group consisting of silica, alumina, magnesium chloride, calcium chloride, bauxite, zeolite, magnesium oxide, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide, thorium oxide, Compounds may be used. Examples of such complexes include a SiO 2 -MgO, SiO 2 -Al 2 O 3, SiO 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO2-MgO , etc. have.
The method of supporting the catalyst compound and the co-catalyst compound on such a carrier is not particularly limited, but a method of directly supporting the catalyst compound on the carrier from which moisture is removed; A method in which the carrier is pretreated with a promoter compound and then the catalyst compound is supported thereon; A method of post-treating a carrier with a catalyst compound and then treating with a promoter compound; A method in which a catalyst compound is reacted with a cocatalyst compound and then supported on a carrier. At this time, the two or more catalyst compounds may be carried on the carrier sequentially, or two or three kinds of catalyst compounds may be carried at a time.
The temperature at which the catalyst compound and the co-catalyst compound are supported on the support is not particularly limited. However, from the viewpoint of the efficiency of the supporting step, the temperature is preferably -20 ° C to 120 ° C, more preferably 0 ° C to 100 ° C.
In addition, a hydrocarbon solvent is used for carrying the catalyst compound and the co-catalyst compound on the carrier. The hydrocarbon solvent used is not particularly limited, but pentane, hexane, heptane, octane, , Nonane, decane, undecane, and dodecane; aliphatic hydrocarbons; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; and aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; Halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane, and trichloroethane; Or a mixture thereof.
The present invention relates to a process for preparing a first polymer by introducing a first monomer and a second monomer together with the above-described catalyst into a first reactor, wherein the temperature at which the first polymer is polymerized is a temperature at which the second polymer is polymerized Is equal to or lower than the threshold value. Here, the temperature at which the first polymer is polymerized is preferably lower than the temperature at which the second polymer is polymerized. Specifically, the temperature at which the first polymer is polymerized is preferably 40 to 150 캜, more preferably 60 to 90 캜.
The first monomer and the second monomer to be used for preparing the first polymer are not particularly limited, but ethylene, propylene, 1-butene, 1-pentene, (C 2 -C 20 ) -olefin (? -Olefin) such as 1-hexene (1-hexene); 1,3-butadiene, 1,4-pentadiene, and 2-methyl-1,3-butadiene. C 4 to C 20 ) diolefins; Such as C 3 to C 6 , such as cyclopentene, Cyclohexene, Cyclopentadiene, Cyclohexadiene, Norbonene, Methyl-2-Norbonene, ~ C 20) cycloolefin (cycloolefin); Cyclodiolefin; Styrene; Styrene may be substituted with a (C 1 -C 10 ) alkyl group, a (C 1 -C 10 ) alkoxy group, a halogen, an amine group, a silyl group, a halogenated alkyl group or the like to the benzene ring of styrene, And the second monomer are the same or different from each other. At this time, if the first monomer is a starting material, the second monomer may be a comonomer (first comonomer) of the first monomer.
If the second monomer is a comonomer in the production of the first polymer, the amount of the second monomer to be injected is preferably 0.1 to 3 mol% based on 100 mol% of the first monomer. The polymerization pressure during the production of the first polymer is preferably 10 to 60 kg / cm < 3 >.
On the other hand, the present invention may further inject hydrogen into the first reactor in the production of the first polymer. At this time, the amount of hydrogen to be injected is not particularly limited, but it is preferably 0.001 to 0.1 mol% based on 100 mol% of the first monomer.
b) Preparation of Second Polymer
The first polymer, the third monomer, the fourth monomer and hydrogen are injected into the second reactor and polymerized to prepare a second polymer. The temperature at which the second polymer is polymerized is not particularly limited, but is preferably 20 to 200 占 폚, more preferably 70 to 100 占 폚.
The third monomer and the fourth monomer to be added for preparing the second polymer are not particularly limited, but ethylene, propylene, 1-butene, 1-pentene, (C 2 -C 20 ) -olefin (? -Olefin) such as 1-hexene (1-hexene); 1,3-butadiene, 1,4-pentadiene, and 2-methyl-1,3-butadiene. C 4 to C 20 ) diolefins; Such as C 3 to C 6 , such as cyclopentene, Cyclohexene, Cyclopentadiene, Cyclohexadiene, Norbonene, Methyl-2-Norbonene, ~ C 20) cycloolefin (cycloolefin); Cyclodiolefin; Styrene; Styrene may be styrene substituted with a (C 1 -C 10 ) alkyl group, a (C 1 -C 10 ) alkoxy group, a halogen, an amine group, a silyl group, a halogenated alkyl group or the like to the benzene ring of styrene, And the fourth monomer are the same or different from each other. At this time, if the third monomer is a starting material, the fourth monomer may be a comonomer of the third monomer (second comonomer).
If the fourth monomer is a comonomer in the preparation of the second polymer, the amount of the fourth monomer to be injected is preferably 0.1 to 1.5 mol% based on 100 mol% of the third monomer. In addition, the amount of hydrogen injected during the production of the second polymer is preferably 0.001 to 0.2 mol% based on 100 mol% of the third monomer.
The polymerization pressure in the production of the second polymer is preferably 10 to 60 kg / cm 3.
As described above, in the production of polyolefins using a first reactor and a second reactor connected in series, a catalyst comprising two or more of the compounds represented by the general formulas (1) to (3) Since the polymerization conditions of the first reactor and the second reactor are controlled differently, a polyolefin having a broad molecular weight distribution and a high SCB content can be produced.
Specifically, the present invention relates to a method for producing a first polymer, which comprises injecting a comonomer into a first reactor at an injection amount higher than the injection amount of the comonomer injected into the second reactor and producing the first polymer at a temperature equal to or lower than the temperature of the second reactor, The polymer has a high incorporation rate of the comonomer to produce a first polymer having a high molecular weight and is injected into the second reactor so that a low molecular weight polymer can be prepared in preparing the second polymer by injecting it into the second reactor The injection amount of hydrogen is adjusted to be higher than the injection amount of hydrogen to be injected into the first reactor. As a result, it is possible to produce a second polymer in which a high molecular weight and a low molecular weight polymer are appropriately distributed.
In particular, since the second polymer according to the present invention has a higher SCB content in a polymer having a higher molecular weight than a polymer having a lower molecular weight, it is possible to provide a polyolefin having excellent mechanical properties when the final polyolefin is produced. That is, when the number of SCB (Short Chain Branch) originating from comonomer in the main chain of the polyolefin is large, the chain tends to be entangled to increase the resistance against the stress, so that the mechanical properties of the polyolefin become excellent. In the polyolefin of the present invention, The SCB content is high and the mechanical properties are excellent. When the SCB content of the polyolefin is the same, when the SCB content is high in a polymer having a higher molecular weight than in a polymer having a low molecular weight, the entanglement of the chain is increased and the mechanical properties are improved. It is possible to provide a polyolefin having a high SCB content in a polymer having a higher molecular weight than a polymer.
Meanwhile, the polymerization reaction for preparing the first polymer and the second polymer may be performed in a liquid phase, a gas phase, a bulk phase, and a slurry phase. Hydrocarbon solvents such as butane, isobutane, pentane, hexane, cyclohexane, and heptane may be used as the hydrocarbon solvent. , Aliphatic hydrocarbon solvents such as octane, nonane, decane, undecane, and dodecane; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; and aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; Halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane and trichloroethane, and the like.
2. Polyolefin
The present invention provides a polyolefin produced by the above process. The polyolefin of the present invention has a broad molecular weight distribution (Mw / Mn) and is excellent in workability, and has a high short chain branch (SCB) content and excellent mechanical properties. Specifically, the polyolefin of the present invention has a molecular weight distribution (Mw / Mn) of 3.0 to 30 (preferably 3.0 to 10) and an SCB content per 1000 carbon atoms of 2 to 50 (preferably 3 to 10) .
On the other hand, the weight average molecular weight of the polyolefin of the present invention is not particularly limited, but may be 500 to 3,000,000.
Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
[Supported Catalyst Synthesis]
All synthesis reactions proceeded in an inert atmosphere such as nitrogen or argon, using the standard Schlenk technique and the glove box technique.
Toluene was obtained by purchasing anhydrous grade from Sigma-Aldrich and then passing it through an activated molecular sieve (Molecular Sieve, 4A) or an activated alumina layer and drying it. MAO (methylaluminoxane) was purchased from Albemarle, Inc. in 10% toluene solution (HS-MAO-10%). The silica and the catalyst compound were used without further treatment (purification).
[Supported Catalyst Synthetic example One]
In a glove box, 1.0 g of silica was placed in a 100 ml round bottom flask, taken out of the glove box, and then 10 ml of toluene was added to prepare silica in a slurry state. 6.67 ml of MAO was slowly added to the prepared slurry silica, and the mixture was stirred at 70 ° C for 1 hour.
In a glove box, 100 μmol of bis (indenyl) zirconium dichloride and 100 μmol of [1,2,3,4-tetrahydro-2-methyl-8 - [(3a, 4,5,6,6a-η) 6-yl] quinolinato (2 -) -? N] titanium dichloride was taken out of the glove box and dissolved in 10 ml of toluene, Slowly added to the mixed slurry of silica and MAO. Then, the mixture was stirred at 50 DEG C for 1 hour, cooled to room temperature, and the toluene supernatant was separated and removed. Thereafter, the catalyst was washed with toluene and n-hexane, and vacuum dried to synthesize a supported catalyst in the form of a free flowing powder.
[Supported Catalyst Synthetic example 2]
6.67 ml of MAO, 100 umol of bis (indenyl) zirconium dichloride, 100 umol of [1,2,3,4-tetrahydro-2-methyl-8 - [(3a, 4,5,6,6a- Instead of 8.08 ml of MAO, 34 μmol of bis (indenyl) zirconium dichloride, 86 μmol of 2,4,5-trimethyl-6H-cyclopenta [b] thien-6-yl] quinolinato supported catalyst was synthesized in the same manner as in the supported catalyst Synthesis Example 1 except that rac-Ethylenebis (1-tetrahydro-indenyl) zirconium dichloride was used.
[ Example 1 and 2]
The synthesized supported catalyst was fed into two slurry loop continuous reactors to prepare polyethylene. At this time, isobutane was used as a solvent and 1-hexene was used as a comonomer. Polymerization conditions were as shown in Table 1 below.
[ Comparative Example One]
One slurry loop continuous reactor was used, and the polymerization conditions were as shown in Table 1 below to prepare polyethylene.
(Kg / cm2)
(Kg / hr)
(Kg / hr)
(g / hr)
[ Experimental Example 1] Property evaluation
The physical properties of the polyethylene prepared in Examples 1 and 2 and Comparative Example 1 were evaluated, and the results are shown in Table 2 below. Specifically, the number average molecular weight, the weight average molecular weight and the SCB content of the polyethylene were analyzed by gel permeation chromatography-FT-IR (GPC-FTIR), and the molecular weight distribution was determined by the ratio of the weight average molecular weight to the number average molecular weight.
Referring to Table 2, it can be seen that polyethylene having a high molecular weight distribution and a high SCB content was produced by controlling the polymerization conditions of the two slurry loop reactors, respectively, as in the present invention.
[ Experimental Example 2] SCB Distribution analysis
The SCB distribution of the polyethylene prepared in Examples 1 and 2 and Comparative Example 1 was analyzed by gel permeation chromatography-FT-IR (GPC-FTIR). The results are shown in FIG.
1, it can be confirmed that the polyethylene produced by the production method of the present invention has a higher SCB content in a polymer having a higher molecular weight than a polymer having a lower molecular weight.
Claims (9)
b) injecting and polymerizing said first polymer, said third monomer, said fourth monomer and hydrogen in a second reactor to produce a second polymer,
The temperature at which the first polymer is polymerized is equal to or lower than the temperature at which the second polymer is polymerized,
Wherein the catalyst compound comprises two or more of the compounds represented by the following general formulas (1) to (3).
[Chemical Formula 1]
(2)
(3)
In the above Formulas 1 to 3,
M 1 to M 3 are the same or different and are each independently selected from the group consisting of Group 3 to Group 10 elements on the periodic table,
X 1 and X 2 are the same or different and are each independently selected from the group consisting of halogen, an amine group, (C 1 -C 20 ) alkyl group, (C 3 -C 20 ) cycloalkyl group, (C 1 -C 20 ) silyl (C 1 ~ C 20) alkyl, (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl (C 1 ~ C 20) alkyl, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20 aryl) silyl group, a silyl group (C 6 ~ C 20) aryl, (C 1 ~ C 20) alkoxy groups, (C 1 ~ C 20) alkyl siloxane group and a (C 6 to C 20 ) aryloxy groups,
n is an integer of 1 to 5,
Ar 1 to Ar 4 are the same or different and each independently a ligand having a cyclopentadienyl skeleton wherein the ligand is selected from the group consisting of halogen, (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl , (C 1 ~ C 20) alkyl silyl group, the silyl (C 1 ~ C 20) alkyl, halo (C 1 ~ C 20) alkyl, (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl (C 1 -C 20 ) alkyl group, (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group, (C 6 -C 20 ) arylsilyl group and a silyl (C 6 -C 20 ) , The substituent may be bonded to another adjacent substituent to form a ring,
B is selected from the group consisting of carbon (C), silicon (Si), germanium (Ge), nitrogen (N)
L is hydrogen, (C 1 ~ C 20) alkyl, (C 3 ~ C 20) cycloalkyl, (C 1 ~ C 20) alkyl silyl group, the silyl (C 1 ~ C 20) alkyl, (C 6 ~ C 20 ) aryl, (C 6 ~ C 20) aryl (C 1 ~ C 20) alkyl, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl silyl group, and Silyl (C 6 -C 20 ) aryl group,
m is an integer of 1 to 2,
Q 1 and Q 2 are the same or the different and are each independently of one another, halogen, (C 1 ~ C 20) alkyl, (C 2 ~ C 20) alkenyl, (C 2 ~ C 20) alkynyl, (C 6 ~ C 20) aryl, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl (C 1 ~ C 20) alkyl, (C 1 ~ C 20) alkyl Amido group, and (C 6 -C 20 ) arylamido group,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently hydrogen; A (C 1 -C 20 ) alkyl group with or without an acetal, ketal or ether group; A (C 2 -C 20 ) alkenyl group with or without an acetal, ketal or ether group; (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group, with or without an acetal, ketal or ether group; (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group, with or without an acetal, ketal or ether group; And a (C 1 -C 20 ) silyl group containing or not containing an acetal, ketal or ether group, R 1 and R 2 may be connected to each other to form a ring, and R 3 and R 4 May be connected to each other to form a ring, and R 5 to R 10 Two or more of them may be connected to each other to form a ring,
R 11 , R 12 and R 13 are each independently hydrogen; A (C 1 -C 20 ) alkyl group with or without an acetal, ketal or ether group; A (C 2 -C 20 ) alkenyl group with or without an acetal, ketal or ether group; (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group, with or without an acetal, ketal or ether group; (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group, with or without an acetal, ketal or ether group; A (C 1 -C 20 ) silyl group with or without an acetal, ketal or ether group; (C 1 -C 20 ) alkoxy group; And (C 6 ~ C 20) is selected from the group consisting aryloxy; R 11 and R 12 may be connected to each other to form a ring, and R 12 and R 13 may be connected to each other to form a ring.
The temperature for polymerizing the first polymer is 40 to 150 캜,
And the temperature for polymerizing the second polymer is 20 to 200 占 폚.
Wherein the amount of the second monomer injected is 0.01 to 3 mol% based on 100 mol% of the first monomer.
Wherein hydrogen is further injected into the first reactor during production of the first polymer, and the amount of hydrogen injected is 0.001 to 0.1 mol% based on 100 mol% of the first monomer.
Wherein the catalyst compound comprises the compound represented by the formula (1) and the compound represented by the formula (2), or the compound represented by the formula (1) and the compound represented by the formula (3) ≪ / RTI >
Wherein the promoter compound is selected from the group consisting of compounds represented by the following formulas (4) to (6).
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
[CD]
In the above formulas 4 to 6,
Y 1 is a (C 1 -C 10 ) alkyl group,
q is an integer of 1 to 70,
Y 2 to Y 4 are the same or different, and each independently represents a (C 1 ~ C 10) alkyl, (C 1 ~ C 10) alkoxy group and is selected from the group consisting of halogen, just Y 2 to Y 4 in at least One is a (C 1 -C 10 ) alkyl group,
C is a hydrogen ion-binding cation of Lewis base, or a metal or non-metal compound having oxidizing power,
D is a compound of an organic substance and an element selected from the group consisting of elements of Groups 5 to 15 on the periodic table.
Wherein the catalyst further comprises a carrier carrying the catalyst compound and the co-catalyst compound.
A polyolefin having a molecular weight distribution (Mw / Mn) of 3.0 to 30 and an SCB (Short chain branch) content per 1000 carbon atoms of 2 to 50;
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150136429A KR101810740B1 (en) | 2015-09-25 | 2015-09-25 | Method for preparing polyolefin and polyolefin prepared therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150136429A KR101810740B1 (en) | 2015-09-25 | 2015-09-25 | Method for preparing polyolefin and polyolefin prepared therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170037194A true KR20170037194A (en) | 2017-04-04 |
| KR101810740B1 KR101810740B1 (en) | 2017-12-20 |
Family
ID=58588308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150136429A KR101810740B1 (en) | 2015-09-25 | 2015-09-25 | Method for preparing polyolefin and polyolefin prepared therefrom |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101810740B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200064562A (en) * | 2018-11-29 | 2020-06-08 | 롯데케미칼 주식회사 | Method for preparing polyolefin with advanced environmental stress crack resistance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4461873A (en) | 1982-06-22 | 1984-07-24 | Phillips Petroleum Company | Ethylene polymer blends |
| US4530914A (en) | 1983-06-06 | 1985-07-23 | Exxon Research & Engineering Co. | Process and catalyst for producing polyethylene having a broad molecular weight distribution |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1209179B1 (en) | 2000-03-31 | 2005-11-02 | Mitsui Chemicals, Inc. | Processes for producing polyolefin composition |
| JP2007197724A (en) * | 2005-12-28 | 2007-08-09 | Nippon Polyethylene Kk | Polyolefin-based composition |
-
2015
- 2015-09-25 KR KR1020150136429A patent/KR101810740B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4461873A (en) | 1982-06-22 | 1984-07-24 | Phillips Petroleum Company | Ethylene polymer blends |
| US4530914A (en) | 1983-06-06 | 1985-07-23 | Exxon Research & Engineering Co. | Process and catalyst for producing polyethylene having a broad molecular weight distribution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200064562A (en) * | 2018-11-29 | 2020-06-08 | 롯데케미칼 주식회사 | Method for preparing polyolefin with advanced environmental stress crack resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101810740B1 (en) | 2017-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101437509B1 (en) | Catalyst composition for preparing multimodal polyolefin resin having superior moldability and mechanical properties and polymerization method using the same | |
| JP5952870B2 (en) | Dual metallocene catalyst for film resin production with excellent machine direction (MD) Elmendorf tear strength | |
| KR101723774B1 (en) | High density ethylene polymer with excellent processability using supported hybrid metallocene catalyst and methods for producing the same | |
| KR101618460B1 (en) | Supported catalyst for olefin polymerization and process for preparing polyolefin using the same | |
| KR102372974B1 (en) | Mixed Catalytic Composition, Catalyst Comprising the Same, and Processes for Preparing the Same | |
| KR102032455B1 (en) | Supported hybrid catalyst and method for preparing olefin polymer using the same | |
| JP4813811B2 (en) | Catalyst composition for olefin polymerization and polymerization process using the same | |
| KR101810740B1 (en) | Method for preparing polyolefin and polyolefin prepared therefrom | |
| KR20210147290A (en) | Mixed Catalytic Composition, Catalyst Comprising the Same, and Processes for Preparing the Same | |
| KR101835993B1 (en) | Catalyst for olefin polymerization and method for preparing polyolefin using the same | |
| KR20210045201A (en) | Process for Preparing a Hybrid Catalyst for Polymerizing an Olefin, Hybrid Catalyst for Polymerizing an Olefin, and Polyolefin | |
| JP7202462B2 (en) | Method for preparing catalyst for olefin polymerization | |
| KR20110090462A (en) | Method for preparing supported metallocene catalyst for polymerizing olefin | |
| KR20190060317A (en) | A metallocene catalyst system for producing high density polyolefin with a wide molecular weight distribution and a method for producing polyolefin by using the same | |
| CN113166293A (en) | Process for preparing catalyst for polymerizing olefins | |
| KR101758572B1 (en) | Method for transition of incompatible catalysts in polymerization | |
| KR20210108665A (en) | Mixed Catalytic Composition, Catalyst Comprising the Same, and Processes for Preparing the Same | |
| KR101845626B1 (en) | Process for preparing polyolefin and polyolefin prepared thereby | |
| KR101845625B1 (en) | Method of producing polyolefin | |
| KR102169603B1 (en) | Catalyst for olefin polymerization, method for its preparation and use thereof | |
| KR102547232B1 (en) | Process for Preparing a Catalyst for Polymerizing an Olefin | |
| KR102474477B1 (en) | Polyolefin composition having imporoved stress resistance | |
| KR101181089B1 (en) | Supported catalysts for preparing polyolefin and preparation method of polyolefin using the same | |
| KR101696099B1 (en) | Catalyst composition for polyethylene polymerization and preparation method of controlled crosslinked polyethylene using the same | |
| KR20190063721A (en) | Method for preparing polyolefin with high productivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right |