KR101767317B1 - Method for preparing polyethylene and polyethylene prepared therefrom - Google Patents
Method for preparing polyethylene and polyethylene prepared therefrom Download PDFInfo
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- KR101767317B1 KR101767317B1 KR1020150135199A KR20150135199A KR101767317B1 KR 101767317 B1 KR101767317 B1 KR 101767317B1 KR 1020150135199 A KR1020150135199 A KR 1020150135199A KR 20150135199 A KR20150135199 A KR 20150135199A KR 101767317 B1 KR101767317 B1 KR 101767317B1
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- cyclopentadienyl
- silyl
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- 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
- C08F10/02—Ethene
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- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
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- 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
Abstract
The present invention provides polyethylene which exhibits very low density by controlling the polymerization conditions and applying the catalyst containing the catalyst compound consisting of the specific components to produce polyethylene.
Description
The present invention relates to a process for the production of polyethylene having an improved morphology and exhibiting ultra-low density and to the polyethylene produced therefrom.
Generally, a film made of a polymer compound is light in weight, has good barrier properties and transparency, and is relatively inexpensive and is used in various fields such as packaging materials, household goods, automobiles, electronic devices, and aircraft. Examples of the polymer compound used for producing such a film include polyethylene, polypropylene, polyvinyl chloride, and polyethylene terephthalate. Duplex polyethylene is classified into low density polyethylene, high density polyethylene and linear low density polyethylene depending on density, copolymerization and branching types.
Since the low-density polyethylene was synthesized in 1933 by ICI, attention was paid to excellent electrical properties, and the low-density polyethylene was used as an insulating material for military radar, and its use as various packaging materials has been expanded. In this case, a product having a melt index (MI) of 2 to 4 and a density of 0.920 to 0.925 is used as a general packaging material requiring transparency, and a product having a melt index (MI) of 1 to 2 , A product having a density of about 0.920 to 0.924 is used.
In addition, the linear low density polyethylene has a characteristic of general polyethylene and has high breaking strength and elongation, excellent tear strength and falling impact strength, and can be applied to a stretch film and an overlap film which are difficult to apply conventional low density polyethylene or high density polyethylene . The physical properties of such a linear low density polyethylene are influenced by the comonomer used in the production, and the tendency thereof is that the basic properties such as density, melt index and molecular weight distribution are equivalent, Are known to exhibit excellent physical properties in that order.
However, since linear low density polyethylene using 1-octene as a comonomer is produced in a single solution reactor, the molecular weight distribution is narrow, resulting in poor processability in molding. In addition, since linear low density polyethylene using 1-butene or 1-hexene as a comonomer is mostly produced in a single gas phase reactor or a single loop slurry reactor, the productivity is higher than that of using 1-octene, It is difficult to obtain a linear low density polyethylene having the required physical properties due to its limit.
SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing polyethylene improved in catalyst and process technology to solve the above problems.
It is another object of the present invention to provide polyethylene produced by the above production method.
In order to accomplish the above object, the present invention provides a process for preparing a prepolymer, comprising the steps of: a) injecting and polymerizing a catalyst comprising a catalyst compound and a promoter compound, an activator, and ethylene into a reactor to form a prepolymer; And b) injecting a comonomer, hydrogen, ethylene into the reactor in which the prepolymer is present and polymerizing to produce a polymer, wherein step a) is carried out in the absence of hydrogen, Wherein the compound is selected from the group consisting of compounds represented by the following formulas (1) and (2).
[Chemical Formula 1]
(2)
In the above Formulas 1 and 2,
M 1 and M 2 are the same or different from each other, and each independently selected from the group consisting of elements of Groups 3 to 10 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, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl silyl group, a silyl group (C 6 ~ C 20) the group consisting of an aryl group , 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)
R 1 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 a silyl (C 6 -C 20 ) aryl group,
m is an integer of 1 to 2;
The present invention also provides the polyethylene produced by the above-mentioned production method.
The present invention relates to a process for producing a prepolymer, wherein a preparation of a prepolymer is carried out in the absence (absence) of hydrogen, and a catalyst comprising a specific component of the catalyst compound (specifically, the compound represented by the above formula 1 or 2) It is possible to provide polyethylene having an improved morphology and exhibiting very low density.
Hereinafter, the present invention will be described.
The present invention relates to a process for preparing polyethylene by preparing (prepolymerizing) a prepolymer and then producing (polymerizing) a polymer, wherein a catalyst containing a catalyst compound composed of a specific component in the preparation of the prepolymer and a specific polymerization condition Which will be described in detail below.
1. Manufacturing method of polyethylene
a) Preparation of prepolymer
First, a catalyst, an activator, ethylene containing a catalyst compound and a promoter compound, ethylene is injected into the reactor and polymerized to prepare a prepolymer. The prepolymer is prepared in the absence (absence) of hydrogen. That is, the present invention is characterized in that no hydrogen is injected into the reactor during the preparation of the prepolymer.
Conventionally, hydrogen was injected in order to control the polymerization degree in the preparation of the prepolymer, but the effect of controlling the polymerization degree was not great and the density of the prepared prepolymer tended to be increased. Accordingly, the present invention provides a prepolymer having a low density while efficiently controlling the degree of polymerization of the prepolymer by controlling the amount of the catalyst, the amount of the activator, the polymerization temperature, and the polymerization pressure without injecting hydrogen in the preparation of the prepolymer will be.
The catalyst compound contained in the catalyst of the present invention is a specific component and is selected from the group consisting of compounds represented by the following general formulas (1) and (2). As described above, the present invention uses a catalyst comprising a specific catalyst compound represented by the following general formula (1) or (2), so that the polymerization activity of the prepolymer is excellent, and thus polyethylene having improved morphology can be provided.
[Chemical Formula 1]
(2)
In the above Formulas 1 and 2,
M 1 and M 2 are the same or different from each other, and each independently selected from the group consisting of elements of Groups 3 to 10 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, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl silyl group, a silyl group (C 6 ~ C 20) the group consisting of an aryl group , 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)
R 1 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 a silyl (C 6 -C 20 ) aryl group,
m is an integer of 1 to 2;
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. In consideration of the activity of the catalyst, at least one of Ar 1 and Ar 2 in the formula (1) is preferably substituted with at least one substituent selected from the group consisting of substituents represented by the following formulas (1-1) and (1-2) Do.
[Formula 1-1]
[Formula 1-2]
In the above formulas 1-1 and 1-2,
The hexagonal ring structure means a phenyl ring,
Z is selected from the group consisting of elements of group 15 or group 16 on the periodic table,
R 2 is hydrogen, (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 group, (C 6 -C 20 ) arylsilyl group and a silyl (C 6 -C 20 ) aryl group, wherein when R 2 is plural, a plurality of R 2 s are the same or different from each other,
a is an integer of 1 to 2,
p is an integer of 1 to 5,
The carbon in the phenyl ring which is not bonded to ZR 2 a is selected from the group consisting of hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl, (C 1 -C 20 ) alkylsilyl, 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, (C 1 ~ C 20) forms the combination with alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl silyl group and a silyl group (C 6 ~ C 20) substituents selected from the group consisting of an aryl group.
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, for example, non-limiting examples of rac-ethylene bis (1-indenyl) zirconium dichloride, rac- ethylene bis (1-indenyl) hafnium dichloride, rac- Tetrahydroindenyl) zirconium dichloride, rac-ethylene bis (1-tetrahydroindenyl) hafnium dichloride, rac-dimethylsilanediylbis (2-methyl-tetrahydrobenzenylenyl) zirconium dichloride, rac -Dimethylsilanediylbis (2-methyl-tetrahydrobenzenylenyl) hafnium dichloride, rac-diphenylsilandiylbis (2-methyl-tetrahydrobenzenylenyl) zirconium dichloride, rac- Dimethylsilandiylbis (2-methyl-4,5-benzindenyl) zirconium dichloride, rac-dimethylsilanediylbis (2-methyl-tetrahydrobenzenylidene) hafnium dichloride, Methyl-4,5-benzindenyl) hafnium dichloride (2-methyl-4,5-benzindenyl) zirconium dichloride, rac-diphenylsilandiylbis (2-methyl-4,5-benzindenyl) hafnium dichloride (2-methyl-5,6-cyclopentadienylindenyl) zirconium dichloride, rac-dimethylsilanediylbis (2-methyl-5,6-cyclopentadienylindenyl Diphenylsilanediylbis (2-methyl-5,6-cyclopentadienylindenyl) zirconium dichloride, rac-diphenylsilanediylbis (2-methyl- (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylbis (2-methyl-4-phenylindenyl) hafnium dichloride (2-methyl-4-phenylindenyl) zirconium dichloride, rac-diphenylsilylbis (2-methyl-4-phenylindenyl) hafnium dichloride, iso-propylidene (9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) hafnium dichloride, diphenylmethylidene (cyclopentadienyl) (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) hafnium dichloride, isopropylidene (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, (Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylsilyl (cyclopentadienyl) (9-fluorenyl) hafnium dichloride, diphenylsilyl Dienyl) (9-fluorenyl) hafnium dichloride, diphenylmethylidene (cyclo (2,7-di-tert-butylfluorene-9-yl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) (2,7-di-tert-butylfluorene-9-yl) zirconium dichloride, diphenylmethylidene (3-tert-butylcyclopentadienyl) Butylcyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (3-tert- butyl-5-methylcyclopentadienyl) Butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluorene-9-yl) zirconium dichloride, diphenylmethylidene (3-tert- (9-fluorenyl) zirconium dichloride, 1,2-ethylenebis (9-fluorenyl) hafnium dichloride, rac- [1,2-bis (9-fluorenyl) -1-phenyl-ethane] zirconium dichloride, rac- [ Ethane] hafnium dichloride, [1- (9-fluorenyl) -2- (5,6-cyclopenta-2-methyl-1-indenyl) ] Zirconium dichloride, [1- (9-fluorenyl) -2- (5,6-cyclopenta-2-methyl-1-indenyl) -ethan] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-phenyl-tetrahydropentene] zirconium dichloride, [4- (fluorenyl) (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, iso-propylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) hafnium di (2-phenyl-cyclopentadienyl) Chloride, isopropylidene (2-phenyl-cyclopentadienyl) (2,7-ditertra Zirconium dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethyl (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (2,7- Yl) hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (p- tolyl) -tetrahydropentrene] zirconium dichloride , [Isopropylidene- (2- (p-tolyl) -cyclopentenyl] hafnium dichloride, [4- (fluorenyl) (9-fluorenyl) zirconium dichloride, [isopropylidene- (2- (p-tolyl) -cyclopentadienyl) - (9-fluorenyl)] hafnium dichloride, 4- (fluorenyl) -4,6,6-trimethyl-2- (m-tolyl) -tetrahydropentrene] zirconium (M-tolyl) -tetrahydrofuran] hafnium dichloride, [isopropylidene (2- (m-tolyl) - Cyclopentadienyl) - (9-fluorenyl)] zirconium dichloride, [isopropylidene (2- (m-tolyl) -cyclopentadienyl) Cyclopentadienyl) - (9-fluorenyl)] zirconium dichloride, diphenylmethylidene (2- (m-tolyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [(isopropylidene) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [diphenylmethylidene (2 (m-tolyl) -cyclopentadienyl - (m-tolyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [di (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [4- (fluorenyl) -4, (O-tolyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (o- tolyl) -tetrahydro (O- tolyl) -cyclopentadienyl) zirconium dichloride, [isopropylidene (2- (o-tolyl) Cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (2,3-dimethylphenyl) -tetrahydropentrene] Zirconium dichloride, [4- (fluorenyl) - 4,6,6-trimethyl-2- (2,3-dimethylphenyl) -tetrahydropentrene] hafnium dichloride, (4,4-dimethylphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -4,6,6-tri (9-fluorenyl) zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl) ] Zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [isopropylidene (2- Cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) Zirconium dichloride, [diphenylmethylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, Cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) )] Zirconium dichloride, [diphenylmethylidene (2- (2,4-dimethyl Cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (2,7- Yl)] zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren- )] Zirconium dichloride, [isopropylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, Diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, (2,3-dimethylphenyl) cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, diphenylmethylidene (2- Phenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [diphenylmethylidene (2- (2,4- (Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [4- (fluorenyl) -4,6,6- Tetramethylpentane] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,6-dimethylphenyl) Fluorenyl) -4,6,6-trimethyl-2- (3,5-dimethylphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) Tetramethylphenyl] tetrahydropentalene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-tetramethylphenyl-tetrahydropentalene] zirconium dichloride , [4- (fluorenyl) -4,6,6-trimethyl-2-tetramethylphenyl-tetrahydropentrene] hafnium dichloride (Fluorenyl) -4,4,6,6-trimethyl-2- (2,4-dimethoxyphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) (3, 6-trimethyl-2- (2,4-dimethoxyphenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) Dimethoxyphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5- (Fluorenyl) -4,6,6-trimethyl-2- (chlorophenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) 2- (fluorophenyl) -tetrahydro-pentalene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (fluorophenyl) Zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (fluorophenyl) -tetrahydropentrene] hafnium (Fluorenyl) -4,6,6-trimethyl-2- (difluorophenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) (Trifluoromethyl) -2,6-trimethyl-2- (difluorophenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) (Fluorenyl) -4,6,6-trimethyl-2- (difluorophenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) ) -4,6,6-trimethyl-2- (tert-butyl-phenyl) -tetrahydro-pentalene] hafnium dichloride, [4- (fluorenyl) , 5-trifluoromethyl-phenyl) -tetrahydro-pentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- ) - tetrahydropentalene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5- (3,5-di-tert-butylphenyl) tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- (Fluorenyl) -4,6,6-trimethyl-2- (biphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) Tetramethylpiperene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-naphthyl-tetrahydropentalene] zirconium dichloride , [4- (fluorenyl) -4,6,6-trimethyl-2-naphthyl-tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) - (3,5-diphenyl-phenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- -Tetrahydropentrene] hafnium dichloride, isopropylidene (2-tetramethylphenyl-cyclopentadiene Zirconium dichloride, isopropylidene (2- (2,6-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) Dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,3-dimethoxyphenyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium di Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (dichlorophenyl) -cyclopentadienyl) (9- Cyclopentadienyl) zirconium dichloride, isopropylidene (2- (fluorophenyl) -cyclopentene) zirconium dichloride, isopropylidene (2- (trichlorophenyl) Dienyl) zirconium dichloride, isopropylidene (2- (difluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- Fluorophenyl) cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) Zirconium dichloride, isopropylidene (2- (3,5-di-tert-butylphenyl) -cyclopentadienyl) zirconium dichloride, isopropylidene (Butylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (biphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (3,5-diphenyl-phenyl) -cyclopentadienyl) Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-tetramethylphenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-dimethylphenyl) -cyclopentadienyl) (9 Zirconium dichloride, diphenylmethylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (9- Fluore ) Zirconium dichloride, diphenylmethylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium di Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (pentafluorophenyl) -cyclopentadienyl (cyclopentadienyl) ) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) Zirconium dichloride, diphenylmethylidene (2- (3,5-di-tert-butylphenyl) -cyclopentadienyl) Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (biphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-naphthyl-cyclopentadienyl) ( (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2-methylphenyl) (2,6-dimethylphenyl) cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5- - cyclopentadienyl) ( (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5- dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (2,6-dimethoxyphenyl) cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (chlorophenyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (dichlorophenyl) -cyclopentadienyl) Butylfluorene-9-yl) hafnium dichloride, isopropylidene (2- (trichlorophenyl) -cyclopentadienyl (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (fluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (difluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5-tributyldiphenyl-cyclopentadienyl) Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (tert- butylphenyl) -cyclopentadienyl (2,7-di-tert-butylfluorene-9-yl) hafnium dichloride, isopropylidene (2- (Di-tert-butylfluorene-9-yl) hafnium dichloride, isopropylidene (2- (biphenyl) Phenyl) -cyclopentadienyl) (2, 3-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2-naphthyl-cyclopentadienyl) Diphenylmethylidene (2-tetramethylphenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (Dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-dimethylphenyl) Yl) hafnium dichloride, diphenylmethylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) (2,7- di- Di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-dimethoxyphenyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,3- dimethoxyphenyl) -cyclopentadienyl) Di-tert-butylfluorene-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,6- dimethoxyphenyl) -cyclopentadienyl) -9-yl) hafnium dichloride, diphenylmethylidene (2- (chlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethyl Diphenylmethylidene (2- (trichlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9- (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) -Butylfluorene-9-yl) hafnium dichloride, diphenylmethylidene (2- (difluorophenyl) -cyclopentadienyl (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (pentafluorophenyl) -cyclopentadienyl) -Butylfluorene-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) (2,7- (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (tert- butylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (diphenylmethylidene) Diphenylmethylidene (2- (3,5-diphenyl-phenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9- -Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-naphthyl- Enyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride.
The promoter compound to be contained in the catalyst of the present invention is not particularly limited, but is preferably an aluminoxane compound or an aluminum (organoaluminum) compound. Specifically, the cocatalyst compound may be a compound represented by the following formula (3).
(3)
In Formula 3,
R 3 is a (C 1 -C 20 ) alkyl group, and q is an integer of 1 to 70.
The compound represented by Formula 3 may be selected from, but not limited to, methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, decylaluminate, And decylaluminoxane.
When the compound represented by Formula 3 is used as the co-catalyst compound, the ratio of the transition metal atom contained in the catalyst compound to the transition metal atom contained in the co-catalyst compound is 1: 1 to 1: 500 , And it is more preferable to use it so as to have a molar ratio of 1:10 to 1: 200.
The catalyst of the present invention is prepared by reacting the catalyst compound with the co-catalyst compound. The reaction conditions are not particularly limited, but the reaction temperature is 0 to 50 ° C (specifically, 0 to 30 ° C) Is preferably 30 minutes to 4 hours (specifically, 1 to 2 hours).
The catalyst of the present invention may further comprise a carrier for supporting the catalyst compound and the co-catalyst compound. Examples of the carrier include inorganic oxides; Inorganic materials such as inorganic chlorides; A resinous material such as a polymer; Or an organic material may be used. Specifically, the carrier of the periodic table Group 2, Group 3, Group 4, Group 5, Group 13 or Group 14 preferably a porous inorganic oxide obtained from a metal oxide, and examples thereof include silica (SiO 2), alumina (Al 2 O 3 ), silica-alumina (SiO 2 .Al 2 O 3 ), or mixtures thereof. When silica is used as the support, the surface area is 100 to 700 m 2 / g (specifically 200 to 500 m 2 / g) and the total pore volume is 0.1 to 5.0 cc / g (specifically 1.0 to 3.0 cc / g) (Specifically, 20 to 80 mu m) and an average pore size of 50 to 500 ANGSTROM (specifically, 80 to 400 ANGSTROM).
The method of supporting the catalyst compound and the co-catalyst compound on such a support is not particularly limited, but a method in which a reactant obtained by reacting a catalyst compound with a co-catalyst compound is injected into a carrier and carried thereon, followed by washing with a solvent. The temperature and time for carrying are not particularly limited, but the temperature is preferably 20 to 120 ° C (specifically, 50 to 100 ° C) and the time is preferably 30 minutes to 4 hours (specifically, 2 to 3 hours) . Also, the solvent used for washing the carrier carrying the reactant and the method thereof are not particularly limited, and examples thereof include benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, And then washed with an aromatic hydrocarbon solvent such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, It is preferable to carry out secondary washing with an aliphatic hydrocarbon-based solvent such as Dodecane.
The activator used for preparing the prepolymer of the present invention is not particularly limited, but is preferably a compound represented by the following formula (4).
[Chemical Formula 4]
In Formula 4,
R 4 to R 6 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, but at least one of R 4 to R 6 One is a (C 1 -C 10 ) alkyl group.
The compound represented by Formula 4 may be, but is not limited to, 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, Ethylaluminum dichloride, butylaluminum dichloride, and the like.
The amount of the activator to be injected is not particularly limited, but is preferably 50 to 500 moles, more preferably 100 to 300 moles, based on 1 mole of the catalyst, considering the activity of the catalyst, the degree of polymerization of the prepolymer, desirable.
The injection amount of ethylene injected in the preparation of the prepolymer of the present invention is not particularly limited, but is preferably 1 to 5 bar, more preferably 1 to 3 bar in view of the degree of polymerization and polymerization reactivity of the prepolymer.
In the present invention, the catalyst, the activator and the ethylene are injected into a reactor and polymerized to prepare a prepolymer. The polymerization temperature and the polymerization time are not particularly limited, but the activity of the catalyst, the polymerization degree of the prepolymer, In consideration of the reactivity and the like, the polymerization temperature is preferably -10 to 50 캜, more preferably 10 to 30 캜. The polymerization time is preferably 1 to 60 minutes, more preferably 5 to 30 minutes.
The preparation of the prepolymer of the present invention is carried out in the presence of an inert gas such as nitrogen or argon, and a solvent such as propane, isobutane, butane, isopentane, pentane, hexane and the like may be used.
b) Polymer preparation
Next, a comonomer, hydrogen and ethylene are injected into the reactor in which the prepolymer is present and polymerized to prepare a polymer.
The comonomer is not particularly limited, but examples thereof include propylene, 1-butene, 1-hexene, 1-octene and the like, preferably 1-hexene. The content ratio of the comonomer is not particularly limited, but is preferably 2 to 10 mol, more preferably 3 to 7 mol, based on 1 mol of ethylene in order to obtain a polymer having a desired density range.
The hydrogen is injected to control the molecular weight of the polymer. The amount of the hydrogen to be injected is not particularly limited, but is preferably 0.1 to 2 bar, more preferably 0.3 to 1 bar in view of the molecular weight of the polymer.
Also, the amount of ethylene injected is not particularly limited, but it is preferably 5 to 20 bar, more preferably 7 to 10 bar in view of the polymerization efficiency of the polymer.
The polymerization temperature in the production of the polymer of the present invention is not particularly limited. However, considering the polymerization efficiency and the melting temperature of the polymer, the polymerization temperature is preferably 30 to 100 캜, more preferably 40 to 80 캜.
2. Polyethylene
The present invention provides polyethylene produced by the above production method. The polyethylene of the present invention exhibits a very low density with a density of 0.910 g / ml or less. The polyethylene of the present invention can be used in various fields. It can be used as a sealant film, an easy peel film, a protective film, a sheet, a flexible hose, and the like which require low heat sealing start temperature, hot tack strength, And the like.
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.
[Catalyst compound Synthetic example ]
All synthesis reactions proceeded in an inert atmosphere such as nitrogen or argon, using the standard Schlenk technique and the glove box technique.
Tetrahydrofuran (Tetahydrofuran, THF), toluene (Toluene), normal hexane (n -Hexane), diethyl ether (Diethyl Ether), methylene chloride (Methylene Chloride, CH 2 Cl 2 ) is Sigma-Aldrich Corp. anhydrous grade (Anhydrous Grade) was purchased and then passed through an activated alumina column to remove water and then stored in an activated molecular sieve (Molecular Sieve 5A, Yakuri Pure Chemicals Co). The NMR structure analysis of the organometallic compound (Chloroform- d , CDCl 3 ) was purchased from Cambridge Isotope Laboratories and dried on activated molecular sieve (Molecular Sieve 5A, Yakuri Pure Chemicals Co.).
Ethanol (Ethanol), normal pentane (n -Pentane), ethyl acetate (Ethyl acetate), normal butyl lithium (n -Butyllithium (2.5 M Solution in n -Hexane)), methyl lithium (Methyllithium (1.6 M solution in Diethyl ether) ), 4-methoxyphenylmagnesium bromide (0.5 M solution in THF), 4-bromo-4'-methoxybiphenyl, 4-bromo- N, N-dimethylaniline (4-Bromo- N, N -dimethylaniline ), 4- bromo-thioanisole (4-Bromothioanisole), ammonium chloride (ammonium chloride), anhydrous magnesium sulfate (magnesium sulfate, anhydrous), para- toluenesulfonic acid monohydrate (para -Toluenesulfonic acid monohydrate (p -TsOH · H 2 O)) was used without purification purchased from Sigma-Aldrich Corporation, tetrachloro-bis (tetrahydrofuran) zirconium (Tetrachlorobis (tetrahydrofuran) zirconium, ZrCl 4 2C 4 H 8 O) was purchased from Strem and used without purification, 3,4-dimethylcyclopent-2-enone (3, 4-Dimethylcyclopent-2-enone, 3,4-Me 2 -C 5 H 4 O) were synthesized according to a known method.
1 H NMR and 13 C NMR were measured at room temperature using a Bruker Avance 400 Spectrometer and the chemical shifts of the NMR spectra were determined by chemical shifts ( 1 H NMR (CDCl 3 )) as indicated by deuterated chloroform 7.24 ppm in the case of 13 C NMR, and 77.0 ppm in 13 C NMR). All elemental analyzes were also performed using EA 1110-FISION (CE Instruments).
[ Synthetic example One] Bis -[One-( p - Dimethylaminophenyl ) -3,4- Dimethylcyclopentadienyl ] Zill Bronze Dichloride ( Bis -[One-( 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 of
<Step 1> 1- ( p - Dimethylaminophenyl ) -3,4-dimethylcyclopentadiene (1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadiene, ( p - Me 2 NC 6 H 4 ) -3,4- Me 2 C 5 H 3 )of synthesis castle
4-Bromo- N , N -dimethylaniline (4.00 g, 20 mmol) was dissolved in diethyl ether (50 mL), and 1 equivalent of n-butyl lithium (8.0 mL) was added at 0 ° C. After stirring at room temperature for 2 hours, 20 ml of a tetrahydrofuran solution in which 1 equivalent of 3,4-dimethylcyclopent-2-enone (2.20 g, 20 mmol) was dissolved at -78 ° C was added dropwise It was slowly raised to room temperature and stirred overnight. Then, an appropriate amount of a saturated aqueous solution of ammonium chloride was added to the obtained orange solution to terminate the reaction. Then, only the organic solution layer was extracted with diethyl ether (50 ml), collected, dried over anhydrous magnesium sulfate and filtered. The filtered solution was stripped of solvent in a rotary evaporator to give a yellow oil. The resulting 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 to obtain an ivory solid. Then, the solvent was evaporated with a rotary evaporator, and then precipitated with 30 ml of n-hexane and filtered using a glass filter. The filtered solid was rinsed with ethanol (30 ml), diethyl ether (30 ml) and n-pentane (30 ml), and dried under vacuum to obtain 1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadiene 63% yield.
1 H NMR results of the obtained 1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadiene are as follows.
1 H NMR (400.13 MHz, CDCl 3): δ 7.33 (d, 2H), 6.69 (d, 2H), 6.45 (s, 1H), 3.21 (s, 2H), 2.93 (s, 6H), 1.94 (s , ≪ / RTI > 3H), 1.86 (s, 3H).
<Step 2> bis [1- (p - dimethylaminophenyl)-3,4-dimethyl-cyclopentadienyl] zirconium dichloride (Bis - [1- (p - Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, Synthesis of [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) synthesized in the above Step 1 was dissolved in diethyl ether (30 ml), and a solution of 1 ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadiene N-butyllithium (2.4 ml) was added. Thereafter, the temperature of the reaction solution was raised to room temperature, and the mixture was stirred for 4 hours. All the solvent was evaporated to obtain a white lithium salt. The resulting white lithium salt was mixed with half as much tetrachlorobis (tetrahydrofuran) zirconium (1.132 g, 3 mmol) and dissolved in toluene (50 mL) at -78 ° C. Then, the mixed solution was slowly warmed to room temperature and stirred while heating to 60 ° C overnight. Then, the solution was filtered with Celite, and lithium chloride (LiCl) formed as a byproduct of the reaction was removed. Then, all of the solvent was evaporated, washed with normal hexane and dried to obtain 0.968 g of bis [1- ( p- dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride was obtained in a yield of 55%.
The 1 H of the obtained bis [1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The NMR results are as follows.
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
[ Synthetic example 2] Bis -[One-( p - Methoxyphenyl ) -3,4- Dimethylcyclopentadienyl ] Zirconium dichloride ( Bis -[One-( p - 메틸oxyphenyl ) -3,4- dimethylcyclopentadienyl ] zirconium dichloride, [1- ( p - Meoc 6 H 4 ) -3,4- Me 2 C 5 H 2 ] 2 ZrCl 2 ) Synthesis of
<Step 1> 1- ( p - Methoxyphenyl ) -3,4-dimethylcyclopentadiene (1- ( p - 메틸oxyphenyl ) -3,4-dimethylcyclopentadiene, ( p - Meoc 6 H 4 ) -3,4- Me 2 C 5 H 3 ) Synthesis of
After dissolving 3,4-dimethylcyclopenta-2-enone (2.20 g, 20 mmol) in tetrahydrofuran (20 mL), 1 equivalent of 4-methoxyphenylmagnesium bromide (20 mmol) He added. Thereafter, the temperature of the reaction solution was raised to room temperature and stirred overnight to obtain an orange solution. The reaction was terminated by adding an appropriate amount of a saturated ammonium chloride aqueous solution to the obtained orange solution. Then, the organic layer was extracted with diethyl ether (50 ml), collected, dried over anhydrous magnesium sulfate and filtered. Then, the solvent contained in the filtered solution was removed with a rotary evaporator to obtain an orange oil. The obtained oil was dissolved again in methylene chloride (30 ml), paratoluenesulfonic acid hydrate (ca. 0.1 g) was added, and the mixture was stirred at room temperature for one hour. Next, the solvent was removed again with a rotary evaporator, and the residue was dissolved in ethanol and recrystallized to obtain 2.20 g of 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene in 47% yield.
1 H NMR of the obtained 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene was as follows.
1 H NMR (400.13 MHz, CDCl 3): δ 7.36 (d, 2H), 6.81 (d, 2H), 6.50 (s, 1H), 3.79 (s, 3H), 3.22 (s, 2H), 1.95 (s , ≪ / RTI > 3H), 1.87 (s, 3H).
<Step 2> Bis -[One-( p - Methoxyphenyl ) -3,4- Dimethylcyclopentadienyl ] Zirconium dichloride ( Bis -[One-( p - 메틸oxyphenyl ) -3,4- dimethylcyclopentadienyl ] zirconium dichloride, [1- ( p - Meoc 6 H 4 ) -3,4- Me 2 C 5 H 2 ] 2 ZrCl 2 ) Synthesis of
( P -methoxyphenyl) -3,4-dimethylcyclopentadiene (1.202 g, 6.0 mmol) synthesized in the above Step 1 was used instead of 1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadiene. The reaction was carried out in the same manner as in [Step 2] of [Synthesis Example 1], except for using the bis- [1- ( p -methoxyphenyl) -3,4-dimethyl Cyclopentadienyl] zirconium dichloride was obtained in a yield of 53% (0.891 g).
The 1 H of the obtained bis- [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The NMR results are as follows.
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).
[ Synthetic example 3] Bis - [1- (p- Methoxybiphenyl ) -3,4- Dimethylcyclopentadienyl ] Zirconium dichloride ( Bis - [1- (p- 메틸oxybiphenyl ) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (p- MeO C 6 H 4 C 6 H 4 ) -3,4-Me 2 C 5 H 2 ] 2 ZrCl 2 ) Synthesis of
≪ Step 1 > 1- (p- Methoxyphenyl ) -3,4-dimethylcyclopentadiene (1- (p- 메틸oxyphenyl ) -3,4-dimethylcyclopentadiene, (p- Meoc 6 H 4 C 6 H 4 ) -3,4- Me 2 C 5 H 3 ) Synthesis of
4-Bromo-4'-methoxybiphenyl (2.631 g, 10 mmol) was dissolved in diethyl ether (50 mL), followed by the addition of 1 equivalent of n-butyllithium (4.0 mL) at 0 ° C. Thereafter, the temperature of the reaction solution was raised to room temperature, stirred for 2 hours, and then cooled to -78 ° C. Then, a tetrahydrofuran solution (20 ml) in which 1 equivalent of 3,4-dimethylcyclopenta-2-enone (1.10 g, 10 mmol) was dissolved was slowly added dropwise to the solution at room temperature and stirred overnight to obtain an orange solution. Then, an appropriate amount of a saturated aqueous solution of ammonium chloride was added to the obtained orange solution to terminate the reaction. Then, only the organic layer was extracted with diethyl ether (50 ml), and then dried with anhydrous magnesium sulfate and filtered. Then, the solvent contained in the filtered solution was removed with a rotary evaporator to obtain a yellow oil. The obtained oil was dissolved in methylene chloride (30 ml), paratoluene sulfonic acid hydrate (ca. 0.1 g) was added, and the mixture was stirred at room temperature for one hour. Next, the solvent was removed again with a rotary evaporator, ethanol (30 ml) was poured into the obtained solid, and filtered using a glass filter. Then, the resultant was washed with diethyl ether (10 ml) and n-pentane (1030 ml), and then dried under vacuum to obtain 1- (p-methoxybiphenyl) -3,4-dimethylcyclopentadiene in 55% yield .
1 H NMR of the obtained 1- (p-methoxybiphenyl) -3,4-dimethylcyclopentadiene was as follows.
1 H NMR (400.13 MHz, CDCl3 ): δ 7.52 (dd, 2H), 7.47 (s, 4H), 6.95 (dd, 2H), 6.68 (s, 1H), 3.83 (s, 3H), 3.29 (s, 2H), 1.98 (s, 3H), 1.90 (s, 3H).
<Step 2> Bis - [1- (p- Methoxybiphenyl ) -3,4- Dimethylcyclopentadienyl ] Zirconium dichloride ( Bis - [1- (p- 메틸oxybiphenyl ) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (p- Meoc 6 H 4 C 6 H 4 ) -3,4-Me 2 C 5 H 2 ] 2 ZrCl 2 ) Synthesis of
( P -methoxybiphenyl) -3,4-dimethylcyclopentadiene (0.829 g, 3.0 (b, d)) synthesized in the above Step 1 was used instead of 1- (p-dimethylaminophenyl) (p-methoxybiphenyl) -3,4-dimethylcyclohexylamino) propionate was obtained in the same manner as in [Step 2] of [Synthesis Example 1] Pentadienyl] zirconium dichloride was obtained in a yield of 60%.
1 H NMR results of the obtained bis- [1- (p-methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride are as follows.
1 H NMR (400.13 MHz, CDCl 3): δ 7.64 (d, 4H), 7.58 (d, 4H), 7.51 (d, 4H), 7.00 (d, 4H), 6.31 (s, 4H), 3.86 (s , ≪ / RTI > 6H), 1.80 (s, 12H).
[Supported Catalyst Synthetic example ]
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 purchased from Sigma-Aldrich and then passed through an activated molecular sieve ( Molecular Sieve, 4A) or an activated alumina layer, followed by further drying. MAO (Methylaluminoxane) was purchased from Albemarle Corporation using 10% toluene solution (HS-MAO-10%). Silica was purchased from Grace and used without purification. Also, racmic ethylene bis (1-tetrahydroindenyl) zirconium dichloride was purchased from Chemtura Organometallics GmbH, and dimethylsilylenebis (2-methyl-4- 2-methyl-4-phenylindenyl) zirconium dichloride was purchased from S-PCI and used without purification.
[Supported Catalyst Synthetic example One]
In a glove box, 0.059 g of the catalyst compound of Synthesis Example 1 and 1.0 g of Silica were taken out of the glove box in a 250 ml round bottom flask, and then 10 ml of toluene was added to the catalyst compound to completely dissolve the mixture. , MAO (9 mL) was added slowly to the catalyst compound solution and stirred for 1 hour. To the silica, 10 ml of toluene was added to obtain silica in a slurry state, the temperature was lowered to 0 占 폚, and the catalyst compound solution was slowly added. After stirring for 1 hour, the temperature was raised to 70 占 폚 and reaction was carried out for 3 hours. After the completion of the reaction, the stirring was stopped, and the toluene layer was separated and removed. Then, the solution was washed with n-hexane and then vacuumed to remove toluene to obtain a pale-brown free-flowing powder supported catalyst.
[Supported Catalyst Synthetic example 2]
Except that the catalyst compound (0.056 g) of [Synthesis Example 2] was used in place of the catalyst compound of [Synthesis Example 1], a supported catalyst was obtained.
[Supported Catalyst Synthetic example 3]
A supported catalyst was obtained in the same manner as in the supported catalyst Synthesis Example 1 except that the catalyst compound (0.082 g) of [Synthesis Example 3] was used in place of the catalyst compound of [Synthesis Example 1].
[Supported Catalyst Synthetic example 4]
Except that racmic ethylene bis (1-tetrahydro-indenyl) zirconium dichloride (0.046 g) was used instead of the catalyst compound of [Synthesis Example 1] Was carried out in the same manner as in Catalyst Synthesis Example 1 to obtain a supported catalyst.
[Supported Catalyst Synthetic example 5]
(Dimethylsilylene) bis (2-methyl-4-phenylindenyl) zirconium dichloride (0.063 g) was used instead of the catalyst compound of Synthesis Example 1 The supported catalyst was obtained in the same manner as in the supported catalyst Synthesis Example 1 except for using the catalyst.
[polymerization Example ]
1. Preparation of prepolymer (prepolymerization)
All the polymerization proceeded under constant ethylene pressure after injection of the required amount of solvent, catalyst, activator and ethylene in the autoclave completely blocked with outside air. Toluene, n-hexane used in Polymerization was passed and then, the activated molecular sieve (Molecular Sieve, 4A) or activated alumina (Alumina) layer purchase from the anhydrous grade (Anhydrous Grade) Sigma-Aldrich captive, further dried in The following was used, and 1.0 M triethylaluminum solution was purchased from Sigma-Aldrich and used without purification.
2. Polymer preparation ( Polymerization )
After the preparation of the prepolymer was completed, the temperature of the reactor was raised, and a required amount of comonomer, hydrogen and ethylene were injected to prepare a polymer.
[polymerization Example One]
After replacing the inside of the stainless steel reactor with nitrogen, 1 L of n-hexane was charged, 0.5 mmol of triethylaluminum was added, and 50 mg of the supported catalyst synthesized in [Supported Catalyst Synthesis Example 1] was injected. Next, ethylene gas was injected at a pressure of 3 bar, and a polymerization reaction was carried out for 5 minutes while maintaining the temperature of the reactor at 25 占 폚 to prepare a prepolymer.
Next, 40 ml of 1-hexene was injected in a nitrogen atmosphere, and then the temperature of the reactor was raised to 70 占 폚. Thereafter, ethylene gas was injected at a pressure of 7 bar, hydrogen was injected at a pressure of 0.5 bar, and polymerization was carried out for 1 hour. When the polymerization reaction was completed, the injection of ethylene gas was stopped, the temperature of the reactor was cooled to 20 DEG C, and unreacted ethylene gas was vented to the outside of the reactor. Finally, the reaction product was separated by filtration into a solid component and dried under vacuum at 80 캜 to produce polyethylene.
[polymerization Example 2]
Polyethylene was prepared in the same manner as in [Polymerization Example 1] except that the supported catalyst synthesized in [Supported Catalyst Synthesis Example 2] was used instead of the supported catalyst synthesized in [Supported Catalyst Synthesis Example 1].
[polymerization Example 3]
Polyethylene was prepared in the same manner as in [Polymerization Example 1], except that the supported catalyst synthesized in [Supported Catalyst Synthesis Example 3] was used instead of the supported catalyst synthesized in [Supported Catalyst Synthesis Example 1].
[polymerization Example 4]
[Polymerization Example 1] Except that the supported catalyst synthesized in [Supported Catalyst Synthesis Example 4] was used in place of the supported catalyst synthesized in [Supported Catalyst Synthesis Example 1], and ethylene gas was injected at 1 bar in the preparation of the prepolymer, To prepare polyethylene.
[polymerization Example 5]
Polyethylene was prepared in the same manner as in [Polymerization Example 1], except that the supported catalyst synthesized in [Supported Catalyst Synthesis Example 4] was used instead of the supported catalyst synthesized in [Supported Catalyst Synthesis Example 1].
[polymerization Example 6]
Except that the supported catalyst synthesized in [Supported Catalyst Synthesis Example 4] was used in place of the supported catalyst synthesized in [Supported Catalyst Synthesis Example 1], and 0.25 mmol of triethyl aluminum was added in the preparation of the prepolymer [Polymerization Example 1 ] To prepare polyethylene.
[polymerization Example 7]
Polyethylene was produced in the same manner as in [Polymerization Example 1] except that the supported catalyst synthesized in [Supported Catalyst Synthesis Example 5] was used instead of the supported catalyst synthesized in [Supported Catalyst Synthesis Example 1].
[polymerization Example 8]
Polyethylene was produced in the same manner as in [Polymerization Example 5], except that ethylene gas was injected at 6 bar in the preparation of the prepolymer.
[polymerization Example 9]
Polyethylene was prepared in the same manner as in [Polymerization Example 5], except that the polymerization reaction was conducted for 120 minutes in the preparation of the prepolymer.
[polymerization Example 10]
Polyethylene was prepared in the same manner as in [Polymerization Example 5], except that the temperature was maintained at 70 캜 in the preparation of the prepolymer.
[polymerization Example 11]
Polyethylene was produced in the same manner as in [Polymerization Example 5], except that 2 mmol of triethylaluminum was added in the preparation of the prepolymer.
[polymerization Comparative Example One]
The interior of the stainless steel reactor was purged with nitrogen, filled with 1 L of n-hexane, 0.5 mmol of triethylaluminum and 40 mL of 1-Hexene, 50 mg of catalyst was injected. Thereafter, when the temperature of the reactor was elevated to 70 캜, ethylene gas was injected at a pressure of 7 bar and polymerization was carried out for 1 hour. When the polymerization reaction was completed, the injection of ethylene gas was stopped, the temperature of the reactor was cooled to 20 DEG C, and unreacted ethylene gas was vented to the outside of the reactor. Finally, the reaction product was separated by filtration into a solid component and dried under vacuum at 80 캜 to produce polyethylene.
[polymerization Comparative Example 2]
Polyethylene was prepared in the same manner as in [Polymerization Comparative Example 1], except that the supported catalyst synthesized in [Supported Catalyst Synthesis Example 2] was used instead of the supported catalyst synthesized in [Supported Catalyst Synthesis Example 1].
[polymerization Comparative Example 3]
Polyethylene was prepared in the same manner as in [Polymerization Comparative Example 1], except that the supported catalyst synthesized in [Supported Catalyst Synthesis Example 3] was used instead of the supported catalyst synthesized in [Supported Catalyst Synthesis Example 1].
[polymerization Comparative Example 4]
Polyethylene was produced in the same manner as in [Polymerization Comparative Example 1] except that the supported catalyst synthesized in [Supported Catalyst Synthesis Example 4] was used instead of the supported catalyst synthesized in [Supported Catalyst Synthesis Example 1].
[polymerization Comparative Example 5]
Polyethylene was prepared in the same manner as in [Polymerization Comparative Example 1], except that the supported catalyst synthesized in [Supported Catalyst Synthesis Example 5] was used instead of the supported catalyst synthesized in [Supported Catalyst Synthesis Example 1].
[polymerization Comparative Example 6]
Polyethylene was prepared in the same manner as in [Polymerization Example 5], except that hydrogen was injected at 0.2 bar in the preparation of the prepolymer.
The polymerization conditions of Polymerization Examples 1 to 11 and Polymerization Comparative Examples 1 to 6 are summarized in Table 1 below.
(bar)
(min)
(° C)
Hydrogen input
(bar)
(mmol)
(Ml)
[ Experimental Example ] Property evaluation
The physical properties of the polyethylene prepared in Polymerization Examples 1 to 11 and Polymerization Comparative Examples 1 to 6 were evaluated as follows, and the results are shown in Table 2 below.
1. Catalytic activity: Calculated by dividing the amount of polyethylene obtained per g of the catalyst relative to the polymerization time (the amount (g) of polyethylene obtained after polymerization is measured and then divided by the polymerization time (h) and the amount of supported catalyst (g)
2. BD: Measure with Bulk Denstiy meter measuring instrument
3. Molecular weight: measured by Gel Permeation Chromatography (PL-GPC220) method
4. Melting point (Tm): Measured by DSC (Differential Scanning Calorimetry, TA Instruments) method
5. Density: measured by submerged displacement method
(gPE / gcat.h)
(g / mL)
(x 10 4 )
(° C)
(g / ml)
Referring to Table 2, it can be confirmed that the low density polyethylene is produced by preparing polyethylene according to the production method of the present invention.
Specifically, compared with the case of producing polyethylene through the process of producing a prepolymer (polymerization example 1) and producing polyethylene without the process of preparing a prepolymer (polymerization comparison example 1), the BD It can be confirmed that the value is improved. It is also confirmed that when hydrogen is used in the preparation of the prepolymer (Polymerization Comparative Example 6), polyethylene having a high density and a low molecular weight is produced.
Claims (9)
b) 2 to 10 moles of a comonomer, 0.1 to 2 bar of hydrogen, and 7 to 20 bar of ethylene per mole of ethylene are introduced into the reactor in which the prepolymer is present and polymerized at a temperature of 40 to 100 ° C to prepare a polymer ≪ / RTI >
Wherein the polyethylene has a bulk density of 0.25 g / mL or more, a molecular weight of 18 x 10 < 4 > or more, and a density of 0.91 g / mL or less.
[Chemical Formula 1]
(2)
(In the above formulas (1) and (2)
M 1 and M 2 are the same or different from each other, and each independently selected from the group consisting of elements of Groups 3 to 10 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, (C 1 ~ C 20) alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl silyl group, a silyl group (C 6 ~ C 20) the group consisting of an aryl group , 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)
R 1 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 a silyl (C 6 -C 20 ) aryl group,
and m is an integer of 1 to 2.)
Wherein the polymerization time in the step (a) is 1 to 60 minutes.
Wherein the amount of the activator is 50 to 500 moles based on 1 mole of the catalyst in the step a).
Wherein at least one of Ar 1 and Ar 2 in the formula (1) is substituted with at least one substituent selected from the group consisting of substituents represented by the following formulas (1-1) and (1-2).
[Formula 1-1]
[Formula 1-2]
(In the above formulas 1-1 and 1-2,
The hexagonal ring structure means a phenyl ring,
Z is selected from the group consisting of elements of group 15 or group 16 on the periodic table,
R 2 is hydrogen, (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 group, (C 6 -C 20 ) arylsilyl group and a silyl (C 6 -C 20 ) aryl group, wherein when R 2 is plural, a plurality of R 2 s are the same or different from each other,
a is an integer of 1 to 2,
p is an integer of 1 to 5,
The carbon in the phenyl ring which is not bonded to ZR 2 a is selected from the group consisting of hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl, (C 1 -C 20 ) alkylsilyl, 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, (C 1 ~ C 20) forms the combination with alkyl (C 6 ~ C 20) aryl, (C 6 ~ C 20) aryl silyl group and a silyl group (C 6 ~ C 20) substituents selected from the group consisting of an aryl group.)
Wherein the catalyst further comprises a carrier carrying the catalyst compound and the co-catalyst compound.
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