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(12) United States Patent
Lee et al.
(io) Patent No.: (45) Date of Patent:
US 7,041,618 B2 May 9, 2006
(54) SUPPORTED METALLOCENE CATALYST AND OLEFIN POLYMERIZATION USING THE SAME
(75) Inventors: Bun-Yeoul Lee, Taejeon (KR);
Jae-Seung Oh, Taejeon (KR); Joo-Eun
Lee, Taejeon (KR); Do-Hoon Lee,
(73) Assignee: LG Chemical Ltd., Seoul (KR)
( * ) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days.
(21) Appl. No.: 10/666,618
(22) Filed: Sep. 18, 2003
(65) Prior Publication Data
US 2004/0058804 Al Mar. 25, 2004
Related U.S. Application Data
(63) Continuation-in-part of application No. 09/526,035, filed on Mar. 15, 2000, now abandoned.
(30) Foreign Application Priority Data
Jun. 22, 1999 (KR) 10-1999-0223575
Lee et al., J. Organomet. Chem., vol. 552 (1998) pp. 313-317.*
Alexaleis, et al., Tetrahedron Lett., 2951 (1988).
Andresson, et al., Angew. Int. Ed. Engl. 15, 630 (1976).
Barklay, et al., Chemistry and Industry (London), 1710
Blii mel. J. Am. Chem. Soc, 117, 2112 (1995).
Bongini, et al., A Simple and Practical Method for
Tetrahydropyranylation of Alcohols and Phenols, Synthesis,
Dubois, et al., J. Am. Chem. Soc. 115, 1190 (1993).
Soga, Makromol. Chem., Rapid Commun., 13, 221 (1992).
Soga, Makromol. Chem., Rapid Commun., 15, 139 (1994).
* cited by examiner
Primary Examiner—J. A. Lorengo
Assistant Examiner—J. Pasterczyk
(74) Attorney, Agent, or Firm—McKenna Long & Aldridge LLP
The present invention relates to a metallocene compound having a functional group that facilitates the preparation of the supported metallocene catalyst for olefin polymerization and the olefin polymerization process using the same. The metallocene compounds in this invention are strongly supported on the inorganic support due to the strong chemical bond of the ligand of the metallocene compound with the silica surface, which leads to minimize leaching of the catalyst during the activation process. Therefore, the supported catalyst of this invention allows the olefin polymerization process to proceed without any fouling in the reactor with a slurry or a gas phase process, and the morphology and bulk density of the polymer produced are much better defined than those produced by conventional methods.
11 Claims, 2 Drawing Sheets
U.S. Patent May 9,2006 Sheet 2 of 2 US 7,041,618 B2
SUPPORTED METALLOCENE CATALYST
AND OLEFIN POLYMERIZATION USING
RELATED APPLICATIONS 5
This application is a continuation-in-part of U.S. application Ser. No. 09/526,035, filed Mar. 15, 2000, now abandoned.
FIELD OF THE INVENTION
The present invention relates to a metallocene compound having a functional group that facilitates the preparation of 15 a supported metallocene catalyst for olefin polymerization and a method of olefin polymerization using the same.
BACKGROUND OF THE INVENTION
In 1976, Professor Kaminsky of Germany reported that olefin polymerization could be accomplished using a zirconocene dichloride compound as a catalyst with methylaluminoxane (MAO), which was obtained through partial 25 hydrolysis of trimethylaluminum, as a co-catalyst. See A. Anderson, et al., Angew. Chem., Int. Ed. Engl. 15, 630 (1976). Thereafter, Exxon showed that the activity of a catalyst and the molecular weight of the resulting polymer could be controlled by changing the substituents on the cyclopentadienyl ligand, and secured a patent (U.S. Pat. No. 5,324,800) on olefin polymerization utilizing the specified metallocene compounds with various substituent groups.
A homogeneous metallocene catalyst exhibits unique polymerization characteristics which cannot be obtained by conventional Ziegler-Natta catalysts. That is, the molecular weight distribution of the resulting polymer is narrow, co-polymerization is easy, and the co-monomer distribution is uniform. In the case of propylene polymerization, the tacticity of polymer can be controlled via the molecular symmetry of catalyst. These unique characteristics not only opened up a way to produce new polymers which are not attainable by conventional Ziegler-Natta catalysts, but also provided a way to make tailor-made polymers. Accordingly, there has been continuous interest in this catalyst system.
In a gas phase or a slurry process, particle morphology and the bulk density of the polymer are preferably controlled to increase the mobility of polymer and the production rate per reactor unit volume. Also, reactor fouling, a phenomenon wherein polymer sticks to the reactor wall and agitator blades, is preferably avoided for a continuous operation. To solve these problems, the catalyst is preferably anchored on a suitable support.
The following are conventional preparation methods for 55 supported metallocene catalysts: 1) a metallocene compound is adsorbed on a support, and then activated by treatment with aluminoxane (W. Kaminsky, Makromol. Chem., Rapid Commun. 14, 239 (1993); 2) aluminoxane is supported first, and then a metallocene compound is supported (K. Soga, Makromol. Chem. Rapid Commun. 13, 221 (1992); U.S. Pat. No. 5,006,500; U.S. Pat. No. 5,086,025); 3) a metallocene compound is treated with aluminoxane, and then adsorbed on a support (U.S. Pat. No. 5,240,894); and 4) the anchoring of catalyst is achieved by a chemical reaction between the ligand of a metallocene compound and a support.
In one method, the metal is ligated after the ligand is supported. (K. Soga, H. J. Kim, T. Shiono, Makromol., Rapid Commun. 15, 139 (1994), Japanese Laid-open Patent No. Heisei 6-56928, U.S. Pat. No. 5,466,766). In the other methods, a metallocene compound with suitable ligands is prepared and then it is supported on a support by chemical reaction. The suitable ligands in this case usually contain silicon based functional groups such as alkoxysilane or halosilane (European Patent No. 293815, U.S. Pat. No. 5,202,398, U.S. Pat. No. 5,767,300, European Patent No. 839836, Korean Patent Application Nos. 98-12660 and 99-06955). However, metallocene compounds with silicon containing functional group are not easy to make and do not have good stabilities. For example, European Patent No. 839836 discloses a metallocene compound having the functional group —OSiMe3. The yield in the metallation step, which is the last step in the synthesis, is only around 28 to 51% which is a disadvantage in commercial applications.
U.S. Pat. No. 5,814,574 discloses a supported polymerization catalyst which is prepared by the binding of an inorganic support with a metallocene compound containing a functional group selected from alkoxyalkyl, heterocycle oxygen group, and alkyl heterocycle oxygen group. U.S. Pat. No. 5,767,209 discloses the polymerization of olefins at a specified temperature and pressure utilizing a supported catalyst. In this patent, the metallocene compound with Lewis base functionalities, such as oxygen, silicon, phosphorus, nitrogen or sulfur atoms, is bound to an inorganic support in the absence of aluminoxane to give a supported catalyst. However, the catalyst bound to and supported on the inorganic support surface by the Lewis acid-base reaction leaches out of the surface upon activation with a Lewis acidic aluminoxane co-catalyst. The leaching of the catalyst results in reactor fouling and irregular morphology, which are detrimental in a slurry or a gas phase process.
Metallocene catalysts with suitable functional groups can be supported on a silica surface by the reaction of an alkoxysilane or halosilane functional group with a surface hydroxyl group or highly reactive siloxane group, which is formed from the dehydroxylation of the silica above 600° C, as shown in Reaction Formulas 1 through 3.