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Bridged metallocene compound, olefin polymerization catalyst containing the same, and ethylene polymer obtained with the catalyst

a technology of olefin polymerization and metallocene, which is applied in the direction of catalyst activation/preparation, physical/chemical process catalysts, chemical/physical processes, etc., can solve the problems of poor high-speed film-forming properties of polymers, low mechanical strength properties of shaped articles, and low tensile strength and impact resistance strength, etc., to achieve high-speed film-forming efficiency, increase the number of terminal double bonds, and low molecular weight

Inactive Publication Date: 2010-11-18
MITSUI CHEM INC +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0063]The ethylene polymers (i to iii) may be blended with other thermoplastic resins to give thermoplastic resin compositions having excellent processability and superior mechanical strength. The ethylene polymers (i to iii) and the resin compositions containing the ethylene polymers (i to iii) may be processed with good processability into shaped articles having excellent mechanical strength, which are preferably films, and more preferably laminate films containing the films.
[0065]The olefin polymerization catalysts (a) containing the bridged metallocene compound of the invention can catalyze olefin homopolymerization or copolymerization to provide low molecular weight olefin homopolymers or copolymers having an increased number of terminal double bonds.
[0067]The olefin polymerization catalysts (b) containing the bridged metallocene compound of the invention can catalyze olefin homopolymerization or copolymerization to provide ethylene polymers having excellent shaping processability and a large number of long-chain branches. The processes of the invention can efficiently produce such polymers.

Problems solved by technology

However, shaped articles therefrom still have low mechanical strength properties such as tensile strength, tear strength and impact resistant strength.
Further, these polymers show poor high-speed film-forming properties in T-die extrusion.
However, these polymers have a low melt tension and consequent poor shaping processability.
However, the method [1] greatly increases costs in the blending of the polymers, and the ethylene polymers obtained by the methods [2], [3], [4] and [5] have a small number of long-chain branches and do not have a sufficient melt tension or shaping processability.
Further, the method [6] can deteriorate mechanical characteristics inherent to polymers or can result in gelation when the diene is used in large amounts.
However, the number of long-chain branches is still insufficient and problems remain in terms of shaping processability.
As discussed above, it has been difficult to produce resins having high melt tension and excellent mechanical strength inexpensively and efficiently by means of the conventional catalyst systems or by blending resins.
However, packaging materials that are easily opened (have easy openability) attract attention out of consideration for elderly people, infants and disabled people.

Method used

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  • Bridged metallocene compound, olefin polymerization catalyst containing the same, and ethylene polymer obtained with the catalyst
  • Bridged metallocene compound, olefin polymerization catalyst containing the same, and ethylene polymer obtained with the catalyst
  • Bridged metallocene compound, olefin polymerization catalyst containing the same, and ethylene polymer obtained with the catalyst

Examples

Experimental program
Comparison scheme
Effect test

synthetic example 1

Synthesis of dimethylsilylene (cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride (A1)

Synthesis of chloro(cyclopentadienyl)dimethylsilane

[0467]THF in a volume of 100 ml was added to 14.3 g (110 mmol) of dimethylsilyl dichloride, and the mixture was cooled to −78° C. A 2 M THF solution of sodium cyclopentadiene in a volume of 38.7 ml (77.4 mmol) was added thereto dropwise over a period of 30 minutes, and the temperature was gradually increased. The mixture was stirred at room temperature for 24 hours, and was concentrated under reduced pressure. Insolubles were removed by filtration. The filtrate was washed with hexane, and the hexane was distilled away from the filtrate under reduced pressure, thereby obtaining chloro(cyclopentadienyl)dimethylsilane. The compound was used in the next step.

Synthesis of (3-ethylcyclopentadienyl) (cyclopentadienyl) dimethylsilane

[0468]Ethylcyclopentadiene in an amount of 7.52 g (80 mmol) was dissolved in 100 ml of THF, and the solution ...

synthetic example 2

Synthesis of dimethylsilylene(3-n-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A2)

Synthesis of chloro(cyclopentadienyl)dimethylsilane

[0471]THF in a volume of 100 ml was added to 14.3 g (110 mmol) of dimethylsilyl dichloride, and the mixture was cooled to −78° C. A 2 M THF solution of sodium cyclopentadiene in a volume of 38.7 ml (77.4 mmol) was added thereto dropwise over a period of 30 minutes, and the temperature was gradually increased. The mixture was stirred at room temperature for 24 hours, and was concentrated under reduced pressure. Sodium chloride was removed by filtration. The filtrate was washed with hexane, and the hexane was distilled away from the filtrate under reduced pressure, thereby obtaining chloro(cyclopentadienyl)dimethylsilane. The compound was used in the next step.

Synthesis of dimethylsilyl (3-n-propylcyclopentadienyl) (cyclopentadienyl)

[0472]THF in a volume of 100 ml was added to 2.16 g (20 mmol) of n-propylcyclopentadiene, and the mix...

synthetic example 3

Synthesis of dimethylsilylene(cyclopentadienyl) (3-n-butylcyclopentadienyl)zirconium dichloride (A3)

Synthesis of (3-n-butylcyclopentadienyl) chlorodimethylsilane

[0476]THF in a volume of 50 ml was added to 30.1 g (61.5 mmol) of a 25 wt % THF solution of butylcyclopentadiene, and the mixture was cooled to 0° C. A 1.52 M hexane solution of n-butyllithium in a volume of 38.4 ml (58.4 mol) was added thereto dropwise. The mixture was stirred at room temperature for 2 hours and was added dropwise to 50 ml of THF containing 14.3 g (110 mmol) of dimethylsilyl dichloride at −78° C. The temperature was gradually increased, and the mixture was stirred at room temperature for 24 hours and was concentrated under reduced pressure. Insolubles were removed by filtration. The filtrate was washed with hexane and was distilled under reduced pressure, thereby obtaining 8.09 g of (3-n-butylcyclopentadienyl)chlorodimethylsilane (yield: 64%). The compound was identified by GC-MS. GC-MS: 214 (MS).

Synthesi...

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Abstract

Metallocene compounds of the invention are useful as olefin polymerization catalysts or catalyst components. Olefin polymerization processes of the invention involve an olefin polymerization catalyst containing the metallocene compound. In detail, the olefin polymerization catalysts can catalyze with high polymerization activity the production of olefin polymers having high melt tension, excellent mechanical strength and good particle properties, and the olefin polymerization processes involve the catalysts. Ethylene polymers according to the invention are obtained by the polymerization processes and have higher processability and easy-opening properties and particularly excellent mechanical strength compared to conventional ethylene polymers. Thermoplastic resin compositions of the invention contain the ethylene polymers. In more detail, shaped articles or films are obtained from the ethylene polymers or the thermoplastic resin compositions containing the ethylene polymers, and laminate films include the films.According to the invention, a single or plural kinds of bridged metallocene compounds having differing cyclopentadienyl-derived groups afford macromonomers that are a source of long-chain branches and simultaneously catalyze the repolymerization of the macromonomers into olefin polymers having a large number of long-chain branches, small neck-in in the T-die extrusion, small take-up surge and superior mechanical strength. The olefin polymerization catalysts and the polymerization processes can efficiently produce the olefin polymers.

Description

FIELD OF THE INVENTION[0001]The present invention relates to metallocene compounds useful as olefin polymerization catalysts or catalyst components, and to olefin polymerization processes with an olefin polymerization catalyst containing the metallocene compound. In detail, the invention relates to olefin polymerization catalysts that can catalyze with high polymerization activity the production of olefin polymers having high melt tension, excellent mechanical strength and good particle properties, and relates to olefin polymerization processes using the catalysts. Further, the invention relates to ethylene polymers obtained by the polymerization processes that have good processability and particularly excellent mechanical strength compared to conventional ethylene polymers, and relates to thermoplastic resin compositions containing the ethylene polymers. In more detail, the invention is concerned with shaped articles ical strength compaor films that are obtained from the ethylene p...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C08F4/42C07F17/00C08F110/02C08F210/02C08F4/52C08F4/60
CPCC07F17/00C08F4/65904C08F4/65912C08F4/65916C08F4/65927C08F110/02C08F110/06C08F210/16C08F10/00C08F2500/12C08F2500/17C08F2500/11C08F2500/10C08F2500/24C08F210/14C08F210/08
Inventor BANDO, HIDEKI
Owner MITSUI CHEM INC
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