KR101845625B1 - Method of producing polyolefin - Google Patents

Abstract

As a catalyst system which is easy to control the activity by using an antistatic agent, disclosed is a method for stably controlling the activity of a highly active catalyst while maintaining physical properties such as conventional molecular weight, molecular weight distribution, melting point and the like. The present invention discloses a method for regulating the activity of the catalyst system depending on treated component amount, in which a metallocene catalyst system for olefin polymerization containing: (A) a metallocene compound represented by the chemical formula (1) or (2); (B) a cocatalyst compound which reacts with the metallocene compound to have catalytic activity; and (C) a carrier carrying the metallocene compound and the cocatalyst compound is treated with the antistatic agent in which an antistatic composition containing an organic compound of hydrocarbyl group having 6 to 30 carbons is contained.

Description

METHOD OF PRODUCING POLYOLEFIN [0001]

More particularly, the present invention relates to a metallocene catalyst system which is easy to control its activity, and a process for producing a polyolefin using the metallocene catalyst system.

Methods for producing polyolefins include a solution polymerization process, a slurry polymerization process, and a gas phase polymerization process. The gas phase polymerization process is performed at a temperature lower than the melting point of the produced polyolefin, and when the temperature of the polymer increases above the critical temperature of the produced polymer, the polymer particles soften and aggregate or stick to the reaction apparatus. Therefore, in the vapor phase polymerization process, polymer aggregation occurs due to a fouling phenomenon in which the polymer adheres to the inner wall surface of the circulation gas line, the heat exchanger, the inner wall of the cooler, and the resultant aggregation near the softening point of the resulting polyolefin. This phenomenon is affected by the polymerization medium, molecular weight, comonomer concentration, etc. The higher the concentration of the particles, the smaller the particle size, the deeper the heat transfer and heat removal in the reactor, and the normal polyolefin transport is disturbed, Which makes it impossible to smoothly control the reaction and to operate for a long time, and also to lower the production efficiency. Several attempts have been made to eliminate fouling and bunching phenomena, one of which is the treatment of antistatic agents.

The antistatic agent includes an antistatic compound having an acid group or an ester group, an amine group or an amide group or a polar functional group such as a hydroxyl group or an ether group. Such an antistatic agent can be treated in a gas phase polymerization process to prevent fouling. When a small amount of the antistatic agent is added, fouling and polymer phenomenon due to the generation of static electricity can not be sufficiently prevented. When an excessive amount of the antistatic agent is treated, Of the polyolefin.

[Prior Patent Literature]

- Japanese Laid-Open Patent No. 1995-247308 (September 26, 1995)

- Japanese Patent No. 5562636 (Jun. 20, 2014)

- Korean Patent No. 0470842 (Jan. 31, 2005)

- U.S. Patent No. 6,201,076 (Mar. 13, 2001)

The present invention provides a catalyst system which is easily controlled in activity by using an antistatic agent, and is intended to provide a method for stably controlling the activity of a highly active catalyst while maintaining physical properties such as molecular weight, molecular weight distribution and melting point.

And also to provide a method for preparing an olefin polymer using a catalyst system which is easy to control its activity.

In order to solve the above problems, the present invention relates to a metallocene catalyst system for olefin polymerization comprising the following components (A) to (C): (D) Lt; / RTI > activity.

(A) A metallocene compound represented by the following formula (1) or (2):

[Chemical Formula 1]

(2)

(In the formulas (1) and (2), M is selected from Group 3 to Group 10 elements in the periodic table, Ar ¹ and Ar ² are each independently a ligand having a cyclopentadienyl skeleton and the ligand has 1 to 20 carbon atoms An alkyl group, an alkyl group, an alkylsilyl group, a silylalkyl group, a haloalkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylalkyl group, an alkylaryl group, an arylsilyl group, a silylaryl group or a halogen group may be used as a substituent and a ring may be formed by a bond between the substituents And X is an alkyl group having 1 to 20 carbon atoms, an alkyl group, a cycloalkyl group, an alkylsilyl group, a silylalkyl group, an aryl group having 6 to 20 carbon atoms, An alkylaryl group, an arylsilyl group, a silylaryl group, an alkoxy group having 1 to 20 carbon atoms, (C), silicon (Si), germanium (Ge), silicon (Si), and silicon (Si) ), Nitrogen (N) or phosphorus (P), and R represents hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkylsilyl group, a silylalkyl group, An arylalkyl group, an alkylaryl group, an arylsilyl group, or a silylaryl group, n is an integer of 1 to 5, and m is an integer of from 1 to 5, 1 or 2.)

(B) a cocatalyst compound which reacts with the metallocene compound to have catalytic activity.

(C) a carrier carrying the metallocene compound (A) and the co-catalyst compound (B).

(D) An antistatic agent comprising an antistatic functional composition comprising an organic acid compound of a hydrocarbyl group having 6 to 30 carbon atoms.

And the component (D) is treated in an amount of 0.1 to 20% by weight to adjust the catalytic activity to -80 to 30% relative to the untreated component (D).

(D) is within ± 100,000, the variation range of the molecular weight distribution is within ± 0.5 and the variation range of the melting temperature is within ± 5 ° C in the production of polyethylene using the catalyst system. to provide.

And (B) the co-catalyst compound is represented by the following formula (3).

(3)

(Wherein R ¹ is an alkyl group having 1 to 10 carbon atoms and q is an integer of 1 to 70)

The ratio of the metallocene compound (A) to the co-catalyst compound (B) is (A) the molar ratio of the metal contained in the co-catalyst compound (B) to the transition metal atom contained in the metallocene compound is 1 : 1 to 1: 500.

The carrier (C) may be at least one selected from the group consisting of silica, alumina, Bauxite, zeolite, MgCl ₂ , CaCl ₂ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, and a complex thereof, or selected from the group consisting of starch, cyclodextrin and synthetic polymers.

In the component (D), the hydrocarbyl group is preferably a n-hexyl group, an n-heptyl group, a n-octyl group, a 2-ethylhexyl group, Hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-octadecyl, n-hexadecyl, Cyclohexyl, dimethylcyclohexyl, phenyl, naphthyl, benzyl, 2-phenylethyl, naphthyl, naphthyl, naphthyl, N-nonylnaphthyl, n-decylnaphthyl, di-n-octylphenyl, n-octylphenyl, N-dodecylnaphthyl, di-n-dodecylnaphthyl, iso-tridecylnaphthyl or diisotridecylnaphthyl, or naphthyl, said organic acid being selected from the group consisting of n-nonylbenzenesulfonic acid, n-decyl-benzenesulfonic acid, n-dodecylbenzene N-decylnaphthylsulfonic acid, n-decylnaphthylsulfonic acid, n-nonylnaphthylsulfonic acid, di-n-nonylnaphthylsulfonic acid, Di-n-dodecyl-naphthylsulfonic acid, isotridecylnaphthylsulfonic acid, and diisotridecylnaphthylsulfonic acid.

And the activity control of the catalyst system satisfies the following equations (1) and (2).

[Equation 1]

A = - (6 x 10 ^-16 ) x B ⁴ + (10 ^-11 ) x B ³ - (8 x 10 ^-8 ) x B ² + (4 x 10 ^-4 ) x B + A '

A is the initial activity (kg _Polymer / g _cat ., H) when the antistatic agent is not treated, B is the antistatic agent throughput (ppm), A is the activity result _Polymer / g _cat ., H) and 0 &lt; B (ppm) < 10,000.

&Quot; (2) &quot;

^{A = (10 -29) × B} 6 - (3 × 10 -24) × B 5 + (5 × 10 -19) × B 4 - (3 × 10 -14) × B 3 + (9 × 10 -10 ) X B ² - (3 x 10 ^-5 ) x B + A '

A is the initial activity (kg _Polymer / g _cat ., H) when the antistatic agent is not treated, B is the antistatic agent throughput (ppm), A is the activity result _Polymer / g _cat ., H), and 10,000 B (ppm) &lt; 20,0000.

According to another aspect of the present invention, there is provided a process for preparing a metallocene catalyst system for olefin polymerization by reacting the metallocene catalyst system with a monomer and an activator to form a liquid phase, a gas phase, a bulk phase, Slurry Phase &quot;). &Lt; / RTI &gt;

The olefin monomer may also be a C2 to C20 alpha -olefin, a C4 to C20 diolefin, a C3 to C20 cycloolefin or a cyclodiolefin, a benzene ring of styrene or styrene, Substituted styrene in which a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a halogen group, an amine group, a silyl group or a halogenated alkyl group is bonded.

Also, the activator is represented by the following general formula (4), and is used in a molar ratio of 50 to 500 based on the metallocene catalyst.

[Chemical Formula 4]

(Wherein R ² , R ³ and R ⁴ are independently an alkyl group, an alkoxy group or a halogen group having 1 to 10 carbon atoms, and at least one of R ² , R ³ and R ⁴ is an alkyl group)

Prior art for the use of conventional antistatic agents has been mostly aimed at improving operational stability. The present invention provides a catalyst system capable of controlling the activity depending on the amount of the antistatic agent to maintain the physical properties of the polymer while controlling the desired activity, and a polyolefin manufacturing method using the catalyst system.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as "including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

The present inventors have found that when a carrier catalyst system carrying a specific metallocene compound and a cocatalyst compound is treated with a specific composition of an antistatic agent, the activity of the metallocene catalyst system can be controlled depending on the throughput of the antistatic agent, , Whereby the physical properties of the polymer product can be maintained, leading to the present invention.

(A) a metallocene compound represented by the following general formula (1) or (2), (B) a promoter compound which reacts with the metallocene compound to have catalytic activity, and (C) the metallocene compound and (D) an antistatic agent containing an antistatic functional composition comprising an organic acid compound of a hydrocarbyl group having 6 to 30 carbon atoms, and a catalyst for adsorbing an antistatic agent (D) controlling the activity of the catalyst system according to the throughput of the component.

[Chemical Formula 1]

(2)

In the general formulas (1) and (2), M is selected from Group 3 to Group 10 elements in the periodic table, and preferably selected from Group 4 elements.

Ar ¹ and Ar ² each independently represent a ligand having a cyclopentadienyl skeleton. Examples of the ligand include a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, An alkyl group having 1 to 20 carbon atoms, an alkylsilyl group, a silylalkyl group, a haloalkyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, an alkylaryl group, an arylsilyl group, a silylaryl group or a halogen atom, Group may be a substituent, and a bond may be formed between the substituents to form a ring.

X is an alkyl group having 1 to 20 carbon atoms such as an Alkyl group, a cycloalkyl group, an alkylsilyl group, a silylalkyl group, an Aryl group having 6 to 20 carbon atoms, an Arylalkyl group, An alkoxy group, an alkyloxy group, an aryloxy group, an aryloxy group, an aryloxy group, an alkylaryl group, an arylsilyl group, a silylaryl group, an alkoxy group of 1 to 20 carbon atoms, (Aryloxy) group, a halogen (Halogen) group or an amine group.

B is a component that connects the ligands Ar ¹ and Ar ² without directly coordinating to the transition metal M and is carbon (C), silicon (Si), germanium (Ge), nitrogen (N), or phosphorus (P).

And R is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkylsilyl group, a silylalkyl group, an aryl group having 6 to 20 carbon atoms, Arylalkyl group, Alkylaryl group, Arylsilyl group or Silylaryl group, n is an integer of 1 to 5, and m is 1 or 2.

The compound represented by the general formula (1) is, for example, bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (Ethylcyclopentadienyl) zirconium dichloride, bis (isopropylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (isobutylcyclopentadienyl) zirconium di Zirconium dichloride, bis (indenyl) zirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis Zirconium dichloride, bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, bis (n-butylcyclopentadienyl) hafnium dichloride As there is no ligand for connecting the cyclopentadienyl ring is selected from the group metal may be a metallocene compound.

The compound represented by the general formula (2) is, for example, 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) (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylbis (2-methyl-4-phenylindenyl) hafnium dichloride, rac-di Diphenylsilylbis (2-methyl-4-phenylindenyl) hafnium dichloride, iso-propylidene (cyclopentadienyl) (cyclopentadienyl) zirconium dichloride (9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) hafnium dichloride, diphenylmethylidene (cyclopentadienyl) (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, iso-propylidene (3-methylcyclopentadienyl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene ((3-methylcyclopentadienyl) (Cyclopentadienyl) zirconium dichloride, diphenylsilyl (cyclopentadienyl) (9-fluorenyl) hafnium dichloride, diphenylsilyl (cyclopentadienyl) -Fluorenyl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (3-tert- butyl-5-methylcyclopentadienyl) Butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (3-tert- Zirconium dichloride, hafnium dichloride, 1,2-ethylene bis (9-fluorenyl) zirconium dichloride, 1,2-ethylene bis (9-fluorenyl) hafnium dichloride, rac- [ Ylenyl) -1-phenyl-ethane] zirconium dichloride, rac- [1,2-bis (9- (5,6-cyclopenta-2-methyl-1-indenyl) -ethan] zirconium dichloride, [Ethyl] hafnium dichloride, [4- (fluorenyl) -4,6-dihydro-2H- Tetramethyl-2-phenyl-tetrahydropentene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) hafnium dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluor (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (P-tolyl) -tetrahydropentrene] zirconium dichloride, [4 (fluorenyl) -4,6,6-trimethyl- - (fluorenyl) -4,6,6-trimethyl-2- (p-tolyl) -tetrahydropentrene] hafnium dichloride, [isopropylidene- (2- (p- tolyl) -cyclopentadienyl ) - (9-fluorenyl) zirconium dichloride, [isopropylidene- (2- (p-tolyl) -cyclopentadienyl) Fluorenyl) -4,6,6-trimethyl-2- (m-tolyl) -tetrahydropentrene] zirconium dichloride (M-tolyl) -cyclohexyl) hafnium dichloride, [isopropylidene (2- (m-tolyl) -cyclopentyl] Cyclopentadienyl) - (9-fluorenyl)] hafnium dichloride, [di (m-tolyl) -cyclopentadienyl] Cyclopentadienyl) - (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (m-tolyl) -cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [isopropylidene (2- (m-tolyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium di (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [diphenylmethylidene (2- (m-tolyl) cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [diphenylmethyl (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [4- (fluorenyl) -4,6,6 -Trimethyl-2- (o-tolyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -4,6,6- Zirconium dichloride, [isopropylidene (2- (o-tolyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [isopropylidene (2- Yl) hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,3-dimethylphenyl) -tetrahydro-pentalene] zirconium dichloride , [4- (fluorenyl) -4,6-trimethyl-2- (2,3-dimethylphenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) (6-trimethyl-2- (2,4-dimethylphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) Methylphenyl) -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-fluorenyl)] 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)] hafnium dichloride, [diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [diphenylmethyl (2- (2,4-dimethylphenyl) -cyclo (2,7-di-tert-butylfluorene)] hafnium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) 9-yl) zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert- butylfluoren- (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [isopropylidene ( (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [diphenylmethylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (Dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, diphenylmethylidene (2- (2,3-dimethylphenyl) Diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopentanetriol (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, diphenylmethylidene Zirconium dichloride, [diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (2, 3-di- Yl)] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,6-dimethylphenyl) -tetrahydro-penta (4-fluorenyl) -4,6,6-trimethyl-2- (2,6-dimethylphenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) ) -4,6,6-trimethyl-2- (3,5-dimethylphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) Tetramethylphenyl) tetrahydropentene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-tetramethylphenyl-tetrahydropentalene] zirconium dichloride, [4 - (fluorenyl) -4,6,6-trimethyl-2-tetramethylphenyl-tetrahydropentene] hafnium dichloride, [4- (2,4-dimethoxyphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- - (2,4-dimethoxyphenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (3,5- dimethoxyphenyl) (4- (fluorenyl) -4,6,6-trimethyl-2- (3,5-dimethoxyphenyl) -tetrahydropentrene] hafnium dichloride, [4- Fluorenyl) zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (chlorophenyl) -tetrahydro- Phenyl) -tetrahydro-pentalene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (fluorophenyl) -tetrahydropentrene] zirconium dichloride, [4- Fluorenyl) -4,6,6-trimethyl-2- (fluorophenyl) -tetrahydropentrene] hafnium dichloride , [4- (fluorenyl) -4,6,6-trimethyl-2- (difluorophenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -Trimethyl-2- (difluorophenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (pentafluorophenyl) (Fluorenyl) -4,6,6-trimethyl-2- (difluorophenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) 4- (6-trimethyl-2- (tert-butyl-phenyl) -tetrahydro-pentalene] hafnium dichloride, [4- (fluorenyl) Phenyl) -tetrahydro-pentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (3,5- trifluoromethyl- phenyl) -Tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5-di- ) Tetrahydropentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5-di-tert- butylphenyl) tetrahydropentrene] hafnium dichloride, [(4- (fluorenyl) -4,6,6-trimethyl-2- (biphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) [4- (fluorenyl) -4,6,6-trimethyl-2-naphthyl-tetrahydropentalene] zirconium dichloride, [4- (fluorenyl) (Fluorenyl) -4,6,6-trimethyl-2- (3, 6-trimethyl-2-naphthyl-tetrahydropentrene) hafnium dichloride, [4- (fluorenyl) Phenyl) -tetrahydro-phenalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (3,5- Naphthyl dichloride, isopropylidene (2-tetramethylphenyl-cyclopentadienyl) (9-fluoro Zirconium dichloride, isopropylidene (2- (3,5-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene ) -Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,3-dimethoxyphenyl) -cyclopentane (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (dichlorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (fluorophenyl) -cyclopentadienyl) ((cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (pentafluorophenyl) -cyclopentadienyl) zirconium dichloride, isopropylidene ) -Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) (3,5-di-tert-butylphenyl) cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (tert- (Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (biphenyl) -cyclopentadienyl) (9- ) Zirconium dichloride, isopropylidene (2- (3,5-diphenyl-phenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene Zirconium dichloride, diphenylmethylidene (2-tetramethylphenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-dimethoxyphenyl) -cyclopentadienyl) Phenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2-chlorophenyl) -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 -Fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) (9-fluorenyl) Zirconium dichloride, diphenylmethylidene (2- (tert-butylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (biphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenyl Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-naphthyl-cyclopentadienyl) (9- Zirconium dichloride, isopropylidene (2-tetramethylphenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,6-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene Pentadienyl) (2,7-di-tert-butyl (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,4- dimethoxyphenyl) -cyclopentadienyl) Hafnium dichloride, isopropylidene (2- (3,5-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene Dimethoxyphenyl) cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,6- 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) Hafnium dichloride, isopropylidene (2- (trichlorophenyl) -cyclopentadienyl) (2,7-di-tert- Yl) hafnium dichloride, isopropylidene (2- (fluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, iso (2- (pentafluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5- trifluoromethyl- phenyl) -cyclopentadienyl (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (tert- butylphenyl) -cyclopentadienyl) 9-yl) hafnium dichloride, isopropylidene (2- (3,5-di-tert-butylphenyl) -cyclopentadienyl) (2,7- Yl) hafnium dichloride, isopropylidene (2- (biphenyl) -cyclopentadienyl) (2,7 (2,1-di-tert-butyl-fluorene-9-yl) hafnium dichloride, isopropylidene (2- (2-naphthyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,6-dimethylphenyl) Yl) hafnium dichloride, diphenylmethylidene (2- (3,5-dimethylphenyl) -cyclopentadienyl) (2,7-di (2,4-dimethoxyphenyl) cyclopentadienyl) (2,7-di-tert-butylfluorene-9-yl) hafnium dichloride, diphenylmethylidene (2- 9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-dimethoxyphenyl) -cyclopentadienyl) (2,7- -Butylfluorene-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (2,7- (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,6- dimethoxyphenyl) -cyclopentadienyl) Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (dichlorophenyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (trichlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) Dichloride, diphenylmethylidene (2- (difluorophenyl) -cyclopentadienyl) (2,7-di-tert- Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium di (triphenylphosphine) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) Methylidene (2- (tert-butylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (biphenyl) -cyclopentadienyl (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5- Di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-naphthyl-cyclopentadienyl) (2,7- - can be a butyl-fluoren-9-yl) hafnium dichloride, etc. group cyclopentadienyl ligand metallocene compound which connecting ring selected from the containing.

The metallocene catalyst used in the present invention is supported on a carrier, and the production process thereof may include, for example, the following steps. (1) reacting the metallocene catalyst with the cocatalyst at 0 to 50 ° C, (2) injecting the solution of step (1) into a carrier, and stirring the mixture at 20 to 120 ° C to form an activated supported catalyst (3) filtering out the supernatant after the step (2), treating the antistatic agent at 0 to 50 ° C, and (4) washing and drying the obtained supported catalyst after the step (3).

In the present invention, the (B) promoter compound may be an aluminoxane compound represented by the following formula (3).

(3)

In Formula (3), R ¹ is an alkyl group having 1 to 10 carbon atoms, and q is an integer of 1 to 70.

Examples of the aluminoxane compound include alumoxane compounds such as methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, decylaluminoxane, and the like. .

Meanwhile, the ratio of the metallocene compound (A) to the co-catalyst compound (B) in the solution formed by the reaction of the metallocene catalyst and the cocatalyst in the supported catalyst preparation is (A) It is preferable that the molar ratio of the metal contained in the co-catalyst compound (B) to the transition metal atom contained is from 1: 1 to 1: 500, more preferably from 1:10 to 1: 200, The temperature is preferably 0 to 30 ° C, and the reaction time may be 30 minutes to 4 hours, preferably 1 to 2 hours.

In the present invention, porous particulate materials may be used as a support for supporting the metallocene catalyst and cocatalyst.

As such materials, inorganic materials such as inorganic oxides, inorganic chlorides, and resinous materials such as polymers or organic materials can be used. Preferred support materials are porous inorganic oxide materials, which include materials obtained from Group 2, 3, 4, 5, 13 or Group 14 metal oxides of the Periodic Table of the Elements. For example, silica, alumina, bauxite, zeolite, MgCl ₂ , CaCl ₂ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, and a complex thereof. The organic material may be selected from starch, cyclodextrin, or a synthetic polymer.

More preferred materials for the porous inorganic oxide material are silica (SiO2), alumina (Al2O3), silica-alumina (SiO2.Al2O3), and mixtures thereof. In this case, the preferred support is a porous silica having a surface area of 100 to 700 m 2 / g, a total pore volume of 0.1 to 5.0 cc / g, an average particle size of 10 to 200 μm, an average pore size of 50 to 500 Å, Is a porous silica having a surface area of 200 to 500 m 2 / g, a total pore volume of 1.0 to 3.0 cc / g, an average particle size of 20 to 80 μm, and an average pore size of 80 to 400 Å.

In the above-mentioned step (2) of the supported catalyst production process, the supporting reaction can be preferably carried out at 50 to 100 ° C for 30 minutes to 4 hours, more preferably for 2 to 3 hours.

In the present invention, the main antistatic composition of the antistatic agent (D) contains an organic acid compound of a hydrocarbyl group having 6 to 30 carbon atoms. Preferably 8 to 28, more preferably 10 to 24 carbon atoms. Preferred organic acids are organic sulfonic acids, organic sulfinic acids or organic phosphonic acids and most preferably sulfonic acids.

Suitable hydrocarbyl groups in the present invention include linear or branched alkyl or alkenyl radicals such as n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, N-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-octadecyl, n-octadecyl, Eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, oleyl, linoleyl or linolenyl, cycloalkyl radicals such as cyclohexyl, methylcyclohexyl or dimethylcyclohexyl , An aryl radical such as phenyl or naphthyl, an aralkyl radical such as benzyl or 2-phenylethyl, or more preferably an alkaryl radical, especially a straight or branched C 1 -C 18 -alkyl group such as tolyl, xylyl, n Decylphenyl, n-decylphenyl, n-dodecylphenyl, isotridecylphenyl, n-nonylnaphthyl, di-n-nonylnaphthyl, Naphthyl, naphthyl, n-dodecylnaphthyl, di-n-dodecylnaphthyl, isotridecylnaphthyl or diisotridecylnaphthyl. In the latter monosubstituted phenyl radical, the alkyl group may be in the ortho, meta or para position relative to the sulfonic acid group and ortho orientation is preferred.

The organic acid composition preferably used in the present invention includes n-nonylbenzenesulfonic acid, n-decylbenzenesulfonic acid, n-dodecylbenzenesulfonic acid, isotridecylbenzenesulfonic acid, n-nonylnaphthylsulfonic acid, , n-decylnaphthylsulfonic acid, di-n-decylnaphthylsulfonic acid, n-dodecylnaphthylsulfonic acid, di-n-dodecyl-naphthylsulfonic acid, isotridecylnaphthylsulfonic acid or diisotridecylnaphthyl Sulfonic acid, preferably dinonylnaphthylsulfonic acid or dodecylbenzenesulfonic acid.

The antistatic agent containing the antistatic functional composition may be treated in an amount of 0.1 to 20% by weight, preferably 0.1 to 12% by weight in the whole catalyst system.

In the above-described step (3) of the supported catalyst production process, the addition reaction of the antistatic agent is carried out at a temperature of 0 to 50 ° C, preferably 20 to 30 ° C, preferably 30 minutes to 3 hours, more preferably 1 to 2 hours &Lt; / RTI &gt;

On the other hand, the solvent used for washing in the step (4) of the above-mentioned supported catalyst production process is as follows. The first washing step is preferably an aromatic hydrocarbon solvent such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene. In the second washing step, pentane It is preferable to use an aliphatic hydrocarbon-based solvent such as pentane, hexane, heptane, octane, nonane, decane, undecane or dodecane desirable.

The activity control of the catalyst system according to the present invention can satisfy the following equations (1) and (2).

[Equation 1]

A = - (6 x 10 ^-16 ) x B ⁴ + (10 ^-11 ) x B ³ - (8 x 10 ^-8 ) x B ² + (4 x 10 ^-4 ) x B + A '

In Equation 1, A 'is the initial activity of not processing the antistatic agent _{(kg Polymer / g cat.,} H), B is an antistatic agent amount (ppm), A is an active result of the antistatic agent throughput (kg _Polymer / g _cat ., h) and 0 < B (ppm) < 10,000.

&Quot; (2) &quot;

^{A = (10 -29) × B} 6 - (3 × 10 -24) × B 5 + (5 × 10 -19) × B 4 - (3 × 10 -14) × B 3 + (9 × 10 -10 ) X B ² - (3 x 10 ^-5 ) x B + A '

In equation 2, A 'is the initial activity of not processing the antistatic agent _{(kg Polymer / g cat.,} H), B is an antistatic agent amount (ppm), A is an active result of the antistatic agent throughput (kg _Polymer / g _cat ., h), and 10,000 B (ppm) < 20,0000.

According to embodiments of the present invention, at least one olefinic monomer is reacted with an activator in the presence of the metallocene catalyst system to form a liquid phase, a gas phase, a bulk phase, or a slurry A method for producing a polyolefin is provided in a slurry phase.

Examples of the alpha-olefin monomer containing a double bond used in polyolefin polymerization include ethylene, propylene, 1-butene, 1-pentene, 1- Olefin (? -Olefin) such as 1,2-butadiene (1,3-butadiene), 1,4-pentadiene, But are not limited to, C4 to C20 diolefins such as 2-methyl-1,3-butadiene, and cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, Cycloolefins such as Cyclohexadiene, Norbonene and Methyl-2-Norbonene, or Cyclodiolefins such as Cyclodiolefin, Styrene or Benzene rings of styrene, ) Substituted with a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a halogen group, an amine group, a silyl group, a halogenated alkyl group, etc., Although the monomers, and the like, and the like.

Suitable solvents for use in the polymerization include inert hydrocarbons such as propane, isobutane, butane, isopentane, pentane, hexane and the like, and the solvent is generally selected so as not to interact with the supported catalyst system.

A preferred activating agent for use in the polymerization may also be represented by the following formula (4).

[Chemical Formula 4]

In formula (4), R ² , R ³ and R ⁴ independently represent an alkyl group, an alkoxy group or a halogen group having 1 to 10 carbon atoms, and at least one of R ² , R ³ and R ⁴ is an alkyl group.

Examples of the compound represented by the formula (4) include trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, Dimethylaluminum methoxide, diethylaluminum methoxide, dibutylaluminum methoxide, dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, But are not limited to, dibutylaluminum chloride, methylaluminum dimethoxide, ethylaluminum dimethoxide, butylaluminum dimethoxide, methylaluminum dichloride, ethylaluminium Di-chloride (Ethylaluminum dichloride) and butyl aluminum dichloride at least one compound selected from the group consisting of (Butylaluminum dichloride).

In the present invention, the polymerization temperature of the olefin polymer may be selected from 0 to 200 ° C, preferably 20 to 100 ° C. The polymerization may be carried out in a batch type, a semi-continuous type or a continuous type, and the polymerization pressure may be selected from 1 to 100 bar, preferably from 5 to 60 bar Can be selected. The molar ratio of the activator to the metallocene catalyst is preferably 50-500, more preferably 100-300.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Polymerization Examples.

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 with anhydrous grade and then dried after passing through an activated molecular sieve (Molecular Sieve, 4A) or an activated alumina layer. MAO (Methylaluminoxane) was purchased from Albemarle Corporation using a 10% toluene solution (HS-MAO-10%). Silica was used by Grace without further processing.

Also, the catalytic compound of the synthesis example, racmic ethylene bis (tetrahydroindenyl) zirconium dichloride was purchased from Chemtura Organometallics GmbH and used without purification. The STATESAFE 2500 from Innospec was purchased and used as an antistatic agent.

Synthetic example  One

(0.043 g) and silica (1.0 g) of racial ethylene bis (tetrahydroindenyl) zirconium dichloride in a glove box were each charged in a 250 mL RBf (round bottom flask) , And then 10 mL of toluene was added to the catalyst compound to completely dissolve it. MAO (5.3 mL) was slowly added to the catalyst compound solution at room temperature and then stirred for 1 hour. 10 mL of toluene was added to the silica, the temperature of the silica in the slurry state was lowered to 0 ° C, and the mixed reaction solution of the catalyst and MAO was added slowly. After stirring for 1 hour, the temperature was raised to 70 ° C and the reaction was further continued for 3 hours. The antistatic agent STATSAFE 2500 at 25 ° C is quantitatively determined to be 0.1 wt% in the entire catalyst system, slowly injected, and stirred for 30 minutes. After 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 all of toluene to prepare a pale-brown free flowing powder supported catalyst.

Synthetic example  2

A supported catalyst was prepared in the same manner as in Synthesis Example 1, except that the antistatic agent in Synthesis Example 1 was quantitatively determined to be 0.2 wt% in the whole catalyst system.

Synthetic example  3

A supported catalyst was prepared in the same manner as in Synthesis Example 1 except that the antistatic agent in Synthesis Example 1 was quantitatively determined to be 0.5 wt% in the whole catalyst system.

Synthetic example  4

A supported catalyst was prepared in the same manner as in Synthesis Example 1, except that the antistatic agent in Synthesis Example 1 was quantitatively determined to be 1 wt% in the entire catalyst system.

Synthetic example  5

A supported catalyst was prepared in the same manner as in Synthesis Example 1, except that the antistatic agent in Synthesis Example 1 was quantitatively determined to have a content of 3% by weight in the whole catalyst system.

Synthetic example  6

A supported catalyst was prepared in the same manner as in Synthesis Example 1, except that the antistatic agent in Synthesis Example 1 was quantitatively determined to have a content of 5% by weight in the whole catalyst system.

Synthetic example  7

A supported catalyst was prepared in the same manner as in Synthesis Example 1, except that the antistatic agent in Synthesis Example 1 was quantified so as to have a content of 7% by weight in the whole catalyst system.

Synthetic example  8

A supported catalyst was prepared in the same manner as in Synthesis Example 1, except that the antistatic agent in Synthesis Example 1 was quantitatively determined to have a content of 9% by weight in the whole catalyst system.

Synthetic example  9

A supported catalyst was prepared in the same manner as in Synthesis Example 1, except that the antistatic agent in Synthesis Example 1 was quantitatively determined to be 12 wt% in the entire catalyst system.

Synthetic example  10

A supported catalyst was prepared in the same manner as in Synthesis Example 1, except that the antistatic agent was not treated in Synthesis Example 1.

polymerization Example

All the polymerization proceeded under constant ethylene pressure after injection of the required amount of solvent, catalyst, activator, ethylene and comonomer in an autoclave completely blocked with outside air. Solvents such as toluene and n-hexane used in the polymerization can be obtained by purchasing anhydrous grade from Sigma-Aldrich and then passing through an activated molecular sieve (Molecular Sieve, 4A) or an activated alumina layer , And 1.0 M triethylaluminum solution was purchased from Sigma Aldrich and used as is.

The molecular weight and the molecular weight distribution of the resulting polyethylene polymer were measured by GPC (Gel Permeation Chromatography, PL-GPC220) method and the melting point was measured by DSC (Differential Scanning Calorimetry, TA Instruments).

Example  One

The inside of the stainless steel reactor was replaced with nitrogen, and 1L of n-hexane was charged. Then, 0.5mmol of triethylaluminum was added and 50mg of the supported catalyst synthesized according to Synthesis Example 1 was injected in order.

Ethylene gas was introduced at a pressure of 1 bar and the prepolymerization reaction was carried out for 5 minutes while maintaining the temperature at 25 ° C. Thereafter, 10 mL of the copolymer (1-hexene) was charged in a nitrogen atmosphere, and then the temperature was raised to 80 ° C. When the temperature was reached, ethylene gas was introduced at a pressure of 8 bar and polymerization reaction was carried out for 1 hour. When the polymerization reaction was completed, the supply of ethylene was stopped, the reactor temperature was cooled to 20 DEG C, and unreacted ethylene was vented to the outside of the reactor. The reaction product was separated by filtration into a solid component, and dried at a temperature of 80 캜 under vacuum to prepare a polyethylene polymer.

Example  2

A polyethylene polymer was prepared in the same manner as in Example 1, except that the supported catalyst synthesized in Synthesis Example 2 was used in Example 1.

Example  3

A polyethylene polymer was prepared in the same manner as in Example 1, except that the supported catalyst synthesized in Synthesis Example 3 was used in Example 1.

Example  4

A polyethylene polymer was prepared in the same manner as in Example 1, except that the supported catalyst synthesized in Synthesis Example 4 was used in Example 1.

Example  5

A polyethylene polymer was prepared in the same manner as in Example 1, except that the supported catalyst synthesized in Synthesis Example 5 was used in Example 1.

Example  6

A polyethylene polymer was prepared in the same manner as in Example 1, except that the supported catalyst synthesized in Synthesis Example 6 was used.

Example  7

A polyethylene polymer was prepared in the same manner as in Example 1, except that the supported catalyst synthesized in Synthesis Example 7 was used.

Example  8

A polyethylene polymer was prepared in the same manner as in Example 1, except that the supported catalyst synthesized in Synthesis Example 8 was used in Example 1.

Example  9

A polyethylene polymer was prepared in the same manner as in Example 1, except that the supported catalyst synthesized in Synthesis Example 9 was used in Example 1.

Comparative Example  One

A polyethylene polymer was prepared in the same manner as in Example 1, except that the supported catalyst synthesized in Synthesis Example 10 was used in Example 1.

The polymerization results of the polymerization examples and comparative examples and the physical properties of the polymer were measured, and the results are shown in Table 1 below.

As shown in Table 1, the supported catalyst was treated with an antistatic agent to confirm the activity increase / decrease effect according to the throughput. When the throughput of the antistatic agent was 0.1 to 1 wt%, it increased by 24% compared with the conventional activity. When the antistatic agent treatment amount was 3 to 12 wt%, it decreased stably to 25 to 75% It is possible to obtain a polyethylene polymer product in which physical properties such as molecular weight, molecular weight distribution and melting point are maintained. Specifically, the fluctuation of the weight average molecular weight relative to the untreated antistatic agent is within ± 100,000, preferably within 50,000, the fluctuation range of the molecular weight distribution is within ± 0.5, preferably within 0.2, the variation range of the melting temperature is within ± 5 ° C, 3 &lt; 0 &gt; C.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (11)

A process for controlling the activity of the catalyst system according to the amount of the component (D) treated by treating the component (D) with a metallocene catalyst system for olefin polymerization comprising the following components (A) to (C)
When the component (D) is treated in the metallocene catalyst system, the reaction temperature is 20 to 30 ° C, the reaction time is 30 minutes to 3 hours,
When the component (D) is treated at 0.1 to 0.5 wt%, the catalytic activity of the component (D) relative to the untreated catalyst increases in proportion to the throughput of the component (D)
When the component (D) is treated at 1 to 20 wt%, the catalytic activity of the component (D) relative to the untreated catalyst decreases in inverse proportion to the throughput of the component (D)
(D) is within ± 100,000, the variation range of the molecular weight distribution is within ± 0.5 and the variation range of the melting temperature is within ± 5 ° C in the production of polyethylene using the catalyst system.
(A) racemic ethylene bis (tetrahydroindenyl) zirconium dichloride (rac-ethylenebis (tetrahydroindenyl) zirconium dichloride) compound
(B) a cocatalyst compound which reacts with the compound to have catalytic activity.
(C) a carrier carrying the compound (A) and the co-catalyst compound (B).
(D) An antistatic agent comprising an antistatic functional composition comprising an organic acid compound of a hydrocarbyl group having 6 to 30 carbon atoms. delete delete The method according to claim 1,
Wherein the co-catalyst compound (B) is represented by the following formula (3).
(3)

(Wherein R ¹ is an alkyl group having 1 to 10 carbon atoms and q is an integer of 1 to 70) The method according to claim 1,
The ratio of the compound (A) to the co-catalyst compound (B) is such that the molar ratio of the metal contained in the co-catalyst compound (B) to the transition metal atom contained in the compound (A) is from 1: &Lt; / RTI &gt; The method according to claim 1,
The carrier (C) may be selected from the group consisting of silica, alumina, Bauxite, zeolite, MgCl ₂ , CaCl ₂ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO , BaO, ThO _2, and a complex thereof, or selected from the group consisting of Starch, Cyclodextrin and synthetic polymers. The method according to claim 1,
In the component (D), the hydrocarbyl group is preferably a n-hexyl group, an n-heptyl group, a n-octyl group, a 2-ethylhexyl group, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, cyclohexyl, dimethylcyclohexyl, phenyl, naphthyl, benzyl, 2-phenylethyl, tolyl, n-octyl, N-nonylnaphthyl, n-decylnaphthyl, di-n-octylphenyl, n-octylphenyl, Decylnaphthyl, n-dodecylnaphthyl, di-n-dodecylnaphthyl, isotridecylnaphthyl or diisotridecylnaphthyl, wherein the organic acid is selected from the group consisting of n - nonylbenzenesulfonic acid, n-decylbenzenesulfonic acid, n-dodecylbenzenesulfonic acid N-octyldodecylsulfonic acid, n-octyldodecylsulfonic acid, n-octyldodecylsulfonic acid, n-octyldodecylsulfonic acid, Di-n-dodecyl-naphthylsulfonic acid, isotridecylnaphthylsulfonic acid, and diisotridecylnaphthylsulfonic acid. The method according to claim 1,
Wherein the activity control of the catalyst system satisfies the following equations (1) and (2).
[Equation 1]
A = - (6 x 10 ^-16 ) x B ⁴ + (10 ^-11 ) x B ³ - (8 x 10 ^-8 ) x B ² + (4 x 10 ^-4 ) x B + A '
A is the initial activity (kg _Polymer / g _cat ., H) when the antistatic agent is not treated, B is the antistatic agent throughput (ppm), A is the activity result _Polymer / g _cat ., H) and 0 &lt; B (ppm) < 10,000.
&Quot; (2) &quot;
^{A = (10 -29) × B} 6 - (3 × 10 -24) × B 5 + (5 × 10 -19) × B 4 - (3 × 10 -14) × B 3 + (9 × 10 -10 ) X B ² - (3 x 10 ^-5 ) x B + A '
A is the initial activity (kg _Polymer / g _cat ., H) when the antistatic agent is not treated, B is the antistatic agent throughput (ppm), A is the activity result _Polymer / g _cat ., H), and 10,000 B (ppm) < 20,0000. The metallocene catalyst system for olefin polymerization according to claim 1 is reacted with a monomer and an activator to prepare an olefin polymer in a liquid phase, a gas phase, a bulk phase or a slurry phase &Lt; / RTI &gt; 10. The method of claim 9,
The olefin monomer may be added to a benzene ring of a C2 to C20 alpha -olefin, a C4 to C20 diolefin, a C3 to C20 cycloolefin or a cyclodiolefin, styrene or styrene, Wherein the substituent is selected from the group consisting of a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a halogen group, an amine group, a silyl group or a halogenated alkyl group. 10. The method of claim 9,
Wherein the activator is represented by the following formula (4) and is used in a molar ratio of 50 to 500 based on the metallocene catalyst.
[Chemical Formula 4]

(Wherein R ² , R ³ and R ⁴ are independently an alkyl group, an alkoxy group or a halogen group having 1 to 10 carbon atoms, and at least one of R ² , R ³ and R ⁴ is an alkyl group)