Catalyst obtained by prepolymerization of polyolefin and olefin polymerization method using the same Number:7,098,285 from the United States Patent and Trademark Office (PTO) owispatent The present invention provides a prepolymerized olefin polymerization catalyst and olefin polymerization method using the same. More particularly, the present invention provides a prepolymerized catalyst that is encapsulated with macromonomers produced by polymerizing olefin monomers with a vinyl-terminated polysiloxane compound in the presence of a solid titanium catalyst for olefin polymerization having been previously surface treated with silane compounds containing two or more vinyl groups, and a method for producing polyolefin having a high melt strength using the catalyst.<H prepolymerization, polymerization, Catalyst, obtain, 7098285.html, Patent, pto, 7098285

Title: Catalyst obtained by prepolymerization of polyolefin and olefin polymerization method using the same

Abstract: The present invention provides a prepolymerized olefin polymerization catalyst and olefin polymerization method using the same. More particularly, the present invention provides a prepolymerized catalyst that is encapsulated with macromonomers produced by polymerizing olefin monomers with a vinyl-terminated polysiloxane compound in the presence of a solid titanium catalyst for olefin polymerization having been previously surface treated with silane compounds containing two or more vinyl groups, and a method for producing polyolefin having a high melt strength using the catalyst.

Patent Number: 7,098,285 Issued on 08/29/2006 to Koo, et al.

Inventors: Koo; Young-Soo (Daejon, KR), Chun; Yong (Daejon, KR), Lee; Young-Jun (Daejon, KR), Son; Ho-Sang (Seoul, KR), Ro; Ki-Su (Daejon, KR)
Assignee: Samsung Atofina Co., Ltd. (Chungnam, KR)

Appl. No.: 10/450,692

Filed: December 15, 2001

PCT Filed: December 15, 2001

PCT No.: PCT/KR01/02181

371(c)(1),(2),(4) Date: November 03, 2003

PCT Pub. No.: WO02/48206

PCT Pub. Date: June 20, 2002

Foreign Application Priority Data


Dec 16, 2000 [KR]			2000-77394

Current U.S. Class: 526/348 ; 502/103; 502/115; 502/116; 502/125; 526/124.1; 526/124.2; 526/124.3; 526/904

Current International Class: C08F 210/00 (20060101); C08F 4/42 (20060101)

Field of Search: 526/348,124.1,124.2,124.3,904 502/103,115,116,125

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Primary Examiner: Choi; Ling-Sui
Attorney, Agent or Firm: Meyertons, Hood, Kivlin, Kowert & Goetzel, P.C. Meyertons; Eric B.

Claims

What is claimed is:

1. A prepolymerized olefin polymerization catalyst encapsulated with macromonomers wherein the prepolymerized catalyst is prepared by polymerization of an olefin monomer and a vinyl-terminated polysiloxane compound in the presence of a solid titanium olefin polymerization catalyst wherein the solid titanium catalyst is prepared by surface treating a compound comprising a magnesium compound, a titanium compound, and an electron donor with a silane compound having two or more vinyl groups.

2. The prepolymerized olefin polymerization catalyst of claim 1, wherein the silane compound having two or more vinyl groups comprises divinyldimethylsilane, divinyldiphenylsilane, divinyldiethylsilane, divinyldiisobutylsilane, or divinyldihydridesilane.

3. The prepolymerized olefin polymerization catalyst of claim 1, wherein the amount of the silane compound having two or more vinyl groups is 2 200 moles per mole of magnesium compound.

4. The prepolymerized olefin polymerization catalyst of claim 1, wherein the compound comprising a magnesium compound, a titanium compound, and an electron donor is prepared by the method comprising: (i) preparing a solution of the magnesium compound by dissolving the magnesium compound in the electron donor; (ii) reacting the magnesium solution with a transition metal compound, a silicon compound, a tin compound, or a mixture thereof and thereby precipitating solid particles; and (iii) reacting the precipitated solid particles with a titanium compound and an electron donor.

5. The prepolymerized olefin polymerization catalyst of claim 1, wherein the olefin monomer used in the prepolymerization step comprises one or more monomers selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, and 1-octene.

6. The prepolymerized olefin polymerization catalyst of claim 1, wherein the vinyl-terminated polysiloxane compound has the structure: H.sub.2C.dbd.CH--SiR.sub.2--O--(SiR.sub.2--O).sub.n--SiR.sub.2--CH.dbd.CH- .sub.2 (n=0 100, R=alkyl, alkoxy, hydrogen, or phenyl).

7. The prepolymerized olefin polymerization catalyst of claim 1, wherein the macromonomers encapsulating the prepolymerized catalyst have a weight average molecular weight in the range of 500 100,000, and comprise 1 99% by weight olefin, 0.01 10% by weight vinyl-terminated polysiloxane compound, and 0.001 1% by weight silane material from the silane compound having two or more vinyl groups.

8. A method of olefin polymerization comprising contacting olefin with a catalyst system wherein the catalyst system comprises: (i) a prepolymerized olefin polymerization catalyst encapsulated with macromonomers wherein the prepolymerized catalyst is prepared by polymerization of an olefin monomer and a vinyl-terminated polysiloxane compound in the presence of a solid titanium olefin polymerization catalyst wherein the solid titanium catalyst is prepared by surface treating a compound comprising a magnesium compound, a titanium compounds and an electron donor with a silane compound having two or more vinyl groups; (ii) an organometallic compound comprising a metal of Group I or Group III of the Periodic Table; and (iii) an external electron donor.

9. The method of olefin polymerization of claim 8, wherein the organometallic compound comprises a trialkylaluminum compound.

10. The method of olefin polymerization of claim 8, wherein the external electron donor comprises an alkoxy silane compound.

11. The method of olefin polymerization of claim 8, wherein the silane compound having two or more vinyl groups comprises divinyldimethylsilane, divinyldiphenylsilane, divinyldiethylsilane, divinyldiisobutylsilane, or divinyldihydridesilane.

12. The method of olefin polymerization of claim 8, wherein the amount of the silane compound having two or more vinyl groups is 2 200 moles per mole of magnesium compound.

13. The method of olefin polymerization of claim 8, wherein the compound comprising a magnesium compound, a titanium compound, and an electron donor is prepared by the method comprising: (i) preparing a solution of the magnesium compound by dissolving the magnesium compound in the electron donor; (ii) reacting the magnesium solution with a transition metal compound, a silicon compound, a tin compound, or a mixture thereof and thereby precipitating solid particles; and (iii) reacting the precipitated solid particles with a titanium compound and an electron donor.

14. The method of olefin polymerization of claim 8, wherein the olefin monomer used in the prepolymerization step comprises one or more monomers selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, and 1-octene.

15. The method of olefin polymerization of claim 8, wherein the vinyl-terminated polysiloxane compound has the structure: H.sub.2C.dbd.CH--SiR.sub.2--O--(SiR.sub.2--O).sub.n--SiR.sub.2--CH.dbd.CH- .sub.2 (n=0 100, R=alkyl, alkoxy, hydrogen, or phenyl).

16. The method of olefin polymerization of claim 8, wherein the macromonomers encapsulating the prepolymerized catalyst have a weight average molecular weight in the range of 500 100,000, and comprise 1 99% by weight olefin, 0.01 10% by weight vinyl-terminated polysiloxane compound, and 0.001 1% by weight silane material from the silane compound having two or more vinyl groups.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a prepolymerized catalyst obtained by prepolymerization of olefin and a method for olefin polymerization using the same. More specifically, the present invention relates to a prepolymerized olefin polymerization catalyst prepared in such a way that high molecular weight macromonomers are encapsulated around the catalyst and to a method of olefin polymerization using the prepolymerized catalyst which produces polyolefin with a high melt strength.

2. Description of the Related Art

Compared to polyethylene, conventional linear polypropylenes are not suitable for melt processing (e.g., foaming, heat molding, extrusion coating, etc.) due to a low melt strength. However, a high melt strength can be achieved by introducing long chain branching into the polypropylene. Long chain branching reduces attractive forces between macromolecular chains during processing and acts to increase melt strength by crosslinking with neighboring chains during molding processes. Production of high melt strength polyolefins with long chain branching typically includes the step of forming polyolefin radicals exiting a polymerization reaction vessel by electronic radiation or by a reaction extrusion method followed by reacting these radicals to introduce long chain branching into the linear structure. If a polymerization method could be developed that was capable of directly polymerizing olefins to form a high melt strength polyolefin useful as a molding material, it is expected that the use of polyolefins as molding materials could be expanded.

SUMMARY OF THE INVENTION

In order to produce a polyolefin with a high melt strength as a polymerization product, the present invention provides a prepolymerized olefin polymerization catalyst and a method for polymerizing olefin using the catalyst. The prepolymerized olefin polymerization catalyst of the present invention has functionalized active sites that can introduce long chain branching into the polymer resulting in high melt strength.

The present invention relates to a catalyst encapsulated with macromonomers (hereinafter referred to as `prepolymerized catalyst`), which is capable of forming branches in the olefin polymers, prepared by prepolymerization of a solid titanium olefin polymerization catalyst with olefin macromonomer/multifunctional compounds and to a method for using the prepolymerized catalyst to produce polyolefins exhibiting high melt strength.

The term "polymerization" used herein includes the process of copolymerization of an olefin with other .alpha.-olefins to form a copolymer as well as the process of polymerization of an olefin to form a homopolymer.

The prepolymerized catalyst of the present invention is prepared by first surface treating a solid titanium olefin polymerization catalyst with silane compounds having two or more vinyl groups. Prepolymerization reactions are then conducted by combining the surface treated catalyst with a mixture of olefin monomer and vinyl-terminated polysiloxane. The catalyst is encapsulated by polymerizing the macromonomer around the catalyst. Compared to a non-encapsulated solid titanium catalyst, the prepolymerized catalyst, according to the present invention, exhibits good catalyst activity. The prepolymerized catalyst is capable of producing a polymer having a broad molecular weight distribution and high stereoregularity and is also capable of forming long-chain branching in polyolefins.

Any conventional solid titanium olefin polymerization catalyst may be used as the solid titanium catalyst component in the preparation of the prepolymerized catalyst of the present invention. The prepolymerized catalyst may be prepared by various methods. For example, the catalyst may be prepared by directly contacting a magnesium compound free of reducibility with a titanium compound in a liquid medium in the presence of electron donors not having active hydrogen. The catalyst may also be prepared by contacting a magnesium compound and titanium catalyst in the absence of electron donors having no active hydrogen followed by reacting the catalyst with an electron donor.

The most common methods for preparation of the solid titanium catalyst used in the preparation of the prepolymerized catalyst of the present invention include the steps of contacting a magnesium compound with a titanium compound that has at least one or more halogen atoms, and if necessary, treating the products thus obtained with an electron donor. Some of the above methods are described in German Patent Nos. 2,230,672, 2,504,036, 2,553,104, and 2,605,922, and Japanese Patent Nos. 51-28189; 51-136625, and 52-87486. In addition, a method for preparing solid titanium compounds containing electron donors from titanium compounds in a liquid state combined with magnesium compound solutions is described in Japanese Patent No. 79-40293.

The solid titanium catalyst used in the preparation of the prepolymerized catalyst of the present invention may be a conventional Ziegler-Natta catalyst, such as described in U.S. Pat. Nos. 4,482,687, 4,277,372, 3,642,746, 3,642,772, 4,158,642, 4,148,756, 4,477,639, 4,518,706, 4,946,816, 4,866,022, 5,013,702, 5,124,297, 4,330,649, European Patent No. 131,832, and Japanese Patent Shou 63-54004.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

One preferred method for preparing the solid titanium catalyst, which is also used in the examples of the present invention, forms a magnesium-supported solid titanium catalyst complex by: (i) preparing a solution by dissolving the magnesium compound having no reducibility in an electron donor; (ii) reacting the solution of step (i) with transition metal compounds, silicon compounds, tin compounds, or a mixture thereof thereby precipitating solid particles; and (iii) reacting the precipitated solid particles with a titanium compound and an electron donor followed by washing with hydrocarbon thereby preparing solid catalyst particles with controlled particle types.

The magnesium compounds having no reducibility used in the preparation of the solid titanium catalyst described above include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, and octoxy magnesium chloride; aryloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, and octoxy magnesium; aryloxy magnesium such as phenoxy magnesium and dimethyl magnesium; and magnesium salts of carboxylic acids such as lauryl magnesium and stearic acid magnesium.

The magnesium compounds may be used as a complex with other metals, with a mixture of other metals, or as mixture of two or more magnesium compounds. Preferably, the magnesium compounds are magnesium compounds containing hydrogen, magnesium chloride, alkoxy magnesium chloride, preferably alkoxy magnesium chloride having C.sub.1 C.sub.14 alkoxy groups, and aryloxy magnesium chloride, preferably aryloxy magnesium chloride having C.sub.5 C.sub.20 aryloxy groups.

Generally, the above-mentioned compounds may be represented by a simple chemical formula; however, depending on the method of preparation, the compound may not be describable by a simple chemical formula. Such compounds may generally be considered to be mixtures of the above-mentioned compounds. For example, compounds produced by a reaction of magnesium compounds with alcohols or phenols in the presence of a halosilane, phosphate pentachloride, or thionyl chloride, by pyrolysis of a Grignard reagent, or by a degradation method using hydroxyl groups, carbonyl ester bonds, ether bonds, or similar kinds of compounds are considered to be mixtures depending on the reagents or degree of reaction. These compounds may also be used in the present invention.

The magnesium compounds may be reacted with one or more electron donors that may be selected from the groups including alcohols, organic carboxylic acids, aldehydes, amines, and/or a mixture thereof, thereby producing a solution of magnesium compounds. A solution of magnesium compounds may be produced by mixing