Arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and alpha-olefins

a technology of arylphenoxy catalyst and ethylene, which is applied in the direction of catalyst activation/preparation, physical/chemical process catalyst, chemical/physical process, etc., can solve the problems of difficult to produce a polymer having and unsuitable for producing a high molecular weight polymer having a weight average molecular weight of 100,000, etc., to achieve excellen

Inactive Publication Date: 2007-01-04
SK ENERGY CO LTD (KR)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0016] To overcome the above problems occurring in the prior art, the present inventors have conducted extensive studies, resulting in the finding that a non-bridged type transition metal catalyst, in which cyclopentadiene derivatives and arylphenoxide substituted with at least one aryl derivative at the ortho-position thereof are used as fixed ligands, shows an excellent thermal stability. Based on the above finding, a catalyst, which is used to produce an ethylene homopolymer or copolymers of ethylene and α-olefins having a high molecular weight, at a high activity during a solution polymerization process at high temperatures of 80° C. or higher, has been developed, thereby the present invention is accomplished.

Problems solved by technology

However, the Ziegler-Natta catalyst system is disadvantageous in that, even though it is highly active in the polymerization of ethylene, the molecular weight distribution of a resultant polymer is wide, and particularly, a compositional distribution is non-uniform in the copolymer of ethylene and α-olefin due to heterogeneous catalyst active sites.
However, it is difficult to produce a polymer having a high molecular weight using the above catalyst system.
Particularly, if it is applied to a solution polymerization process which is conducted at high temperatures of 140° C. or higher, polymerization activity is rapidly reduced and a β-hydrogen elimination reaction is dominant, thus it is unsuitable for producing a high molecular weight polymer having a weight average molecular weight (Mw) of 100,000 or more.
However, since the cyclization of the ligands along with the transition metal compound is achieved at very low yield during synthesis of the constrained geometry catalyst, it is difficult to commercialize them.
However, a limited range of phosphine compounds may be used to produce the phosphinimine ligand, and, since these compounds are harmful to the environment and to humans, it might have some difficulties in using them to produce general-purpose olefin polymers.
U.S. Pat. No. 5,079,205 discloses a catalyst having a bis-phenoxide ligand, but it has too low catalytic acitivity to be commercially used.

Method used

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  • Arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and alpha-olefins
  • Arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and alpha-olefins
  • Arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and alpha-olefins

Examples

Experimental program
Comparison scheme
Effect test

preparation example 1

Synthesis of 4-methyl-2,6-bis(2′-isopropylphenyl)phenol

[0070] A mixed solution of 1 mL of water and 4 mL of dimethoxyethane was added into a flask into which 2,6-dibromo-4-methylanisole (400 mg, 1.43 mmol), 2-isopropylphenylboronic acid (720 mg, 4.39 mmol), palladium acetate (14 mg, 0.062 mmol), triphenylphosphine (60 mg, 0.23 mmol), and potassium phosphate (940 mg, 4.43 mmol) were already added, and then refluxed at normal temperature for 6 hours. After cooling to normal temperature, an ammonium chloride aqueous solution (5 mL) and 10 mL of diethylether were added thereto to separate an organic layer and extract residues using diethylether. The separated organic layer was dried with magnesium sulfate and volatile materials were then removed to produce 670 mg of grey 4-methyl-2,6-bis(2′-isopropylphenyl)anisole solid. The anisole thus produced was dissolved in 5 mL of methylene chloride without separate purification, 3 mL of boron tribromide (1 M methylene chloride solution) was dro...

example 1

[0074] 300 mL of n-heptane was added into a stainless steel reactor which was purged with nitrogen after sufficient drying and had a volume of 500 m / L, and 0.5 mL of triisobutylaluminum (Aldrich) (200 mM n-heptane solution) was added thereto. The temperature of the reactor was then increased to 140° C., and, subsequently, 0.2 mL of (dichloro)(pentamethylcyclopentadienyl)(4-methyl-2,6-bis(2′-isopropylphenyl)phenoxy)titanium(IV) (5 mM toluene solution), produced according to preparation example 1, and 0.3 mL of triphenylmethylinium tetrakis(pentafluorophenyl)borate (99%, Boulder Scientific) (5 mM toluene solution) were sequentially added thereto. Ethylene was then injected into the reactor until the pressure in the reactor was 30 atm, and was continuously fed for polymerization. 10 min after the reaction started, 10 mL of ethanol (including 10 vol % hydrochloric acid aqueous solution) were added to finish the polymerization, agitation was conducted for 4 hours along with 1500 mL of ad...

example 2

[0075] 15 mL of 1-octene were injected into a reactor which was the same as in example 1, and polymerization was then conducted through the same procedure as in example 1 except that 0.3 mL of (dichloro)(pentamethylcyclopentadienyl)(4-methyl-2,6-bis(2′-isopropylphenyl)phenoxy)titanium(IV) (5 mM toluene solution) and 0.45 mL of triphenylmethylinium tetrakis(pentafluorophenyl)borate (Boulder Scientific) (5 mM toluene solution) were added after 0.75 mL of triisobutylaluminum (Aldrich) (200 mM n-heptane solution) were added. 4.0 g of dried polymer was obtained. The weight average molecular weight was 175,000 and a molecular weight distribution was 5.91, which were determined through gel chromatography analysis. The melt index was 0.12 g / 10 min, the melting point of the polymer was 114.7° C., the density was 0.9215 g / cc, and the content of 1-octene was 7.8 wt %.

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Abstract

The present invention relates to an arylphenoxy catalyst system producing an ethylene homopolymer or copolymers of ethylene and α-olefins, and a method of producing an ethylene homopolymer or copolymers of ethylene and α-olefins having a high molecular weight under a high temperature solution polymerization condition using the same. The catalyst system includes a group IV arylphenoxy-based transition metal catalyst and an aluminoxane cocatalyst or a boron compound cocatalyst. In the transition metal catalyst, a cyclopentadiene derivative and arylphenoxide as fixed ligands are located around the group IV transition metal, arylphenoxide is substituted with at least one aryl derivative and is located at the ortho position thereof, and the ligands are not crosslinked to each other. The catalyst includes an environmentally-friendly raw material, synthesis of the catalyst is economical, and thermal stability of the catalyst is excellent. It is useful for producing an ethylene homopolymer or copolymers of ethylene and α-olefins having various physical properties in commercial polymerization processes.

Description

INCORPORATION BY REFERENCE [0001] The present application claims priority under 35 U.S.C. §119 to Korean Patent Application No. 10-2005-0059354 filed on Jul. 1, 2005. The content of the application is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates to an arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and α-olefins. More particularly, the present invention pertains to a group IV transition metal catalyst expressed by Formula 1, a catalyst system which includes the arylphenoxy-based transition metal catalyst and an aluminoxane cocatalyst or a boron compound cocatalyst, and a method of producing an ethylene homopolymer or copolymers of ethylene and α-olefins using the same. In the transition metal catalyst, a cyclopentadiene derivative and an arylphenoxide as fixed ligands are located around a group IV transition metal, arylphenoxide ligand is su...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C08F4/44B01J31/00
CPCC07F17/00C08F4/65908C08F4/65912C08F10/00C08F110/02C08F210/16C08F2420/03C08F4/6592C08F2500/12C08F210/14C08F4/64C08F10/02
Inventor WOO, TAE WOOOK, MYUNG AHNHAHN, JONG SOKLEE, MAL OUKANG, SANG OOKKO, SUNG BOKIM, TAE JINKIM, SUNG KWAN
Owner SK ENERGY CO LTD (KR)
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