Process and catalyst for producing isotactic polyolefins

Details Process and catalyst for producing isotactic polyolefins Process and catalyst for producing isotactic polyolefins

1998-05-29

2001-07-17

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S160000, C526S943000, C502S117000

Reexamination Certificate

active

06262199

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a metallocene catalyst component useful in preparing isotactic polyolefins. The catalyst component comprises a bridged metallocene in which the two substituted indenyl rings are complexed to a metal hydrocarbyl or metal halide. The invention further includes a process of preparing isotactic polyolefins that comprises the use of one or more of the disclosed catalyst components and also a process for preparing the catalyst components.
2. DESCRIPTION OF THE PRIOR ART
The present invention provides a catalyst and process for polymerizing olefins having three or more carbon atoms to produce a polymer with an isotactic stereochemical configuration. The catalyst and process are particularly useful in polymerizing propylene to form isotactic polypropylene. The isotactic structure is typically described as having the methyl groups attached to the tertiary carbon atoms of successive monomeric units on the same side of a hypothetical plane through the main chain of the polymer, e.g., the methyl groups are all above or all below the plane. Using the Fischer projection formula, the stereochemical sequence of isotactic polypropylene is described as follows:
Another way of describing the structure is through the use of NMR spectroscopy. Bovey's NMR nomenclature for an isotactic pentad is . . . mmmm . . . with each “m” representing a “meso” dyad or successive methyl groups on the same side in the plane. As known in the art, any deviation or inversion in the structure of the chain lowers the degree of isotacticity and crystallinity of the polymer.
In contrast to the isotactic structure, syndiotactic polymers are those in which the methyl groups attached to the tertiary carbon atoms of successive monomeric units in the chain lie on alternate sides of the plane of the polymer. Using the Fischer projection formula, the structure of a syndiotactic polymer is designated as:
In NMR nomenclature, this pentad is described as . . . rrrr . . . in which each “r” represents a “racemic” dyad, i.e., successive methyl group on alternate sides of the plane. The percentage of r dyads in the chain determines the degree of syndiotacticity of the polymer. Syndiotactic polymers are crystalline and, like the isotactic polymers, are insoluble in xylene. This crystallinity distinguishes both syndiotactic and isotactic polymers from an atactic polymer which is soluble in xylene. Atactic polymer exhibits no regular order of repeating unit configurations in the polymer chain and forms essentially a waxy product.
While it is possible for a catalyst to produce all three types of polymer, it is desirable for a catalyst to produce predominantly isotactic or syndiotactic polymer with very little atactic polymer. Catalysts that produce isotactic polyolefins are disclosed in European Patent Application No. 87870132.5 (Publication No. 0 284 708 published Oct. 5, 1988), and U.S. Pat. Nos. 4,794,096 and 4,975,403. This application and these patents disclosed chiral, stereorigid metallocene catalyst components that are used in the polymerization of olefins to form isotactic polymers and are especially useful in the preparation of a highly isotactic polypropylene.
SUMMARY OF THE INVENTION
The present invention provides an isospecific catalyst, a process for preparing the catalyst and a polymerization process for preparing isotactic polyolefins, more particularly, isotactic polypropylene, using the catalyst. The novel catalyst component provided by the present invention is a stereorigid metallocene described by the formula:
R″(CpR
2
C
4
R
4
)(CpR′
2
C
4
R′
4
)MeQ
k
wherein (CpR
2
C
4
R
4
) and (CpR
2
C
4
R
4
) are substituted indenyl rings; each R and R′ is a hydrogen or a hydrocarbyl radical having 1-20 carbon atoms; R″ is a structural bridge between the two indenyl rings imparting stereorigidity to the indenyl rings; Me is a transition metal; and each Q is a hydrocarbyl radical or is a halogen. Further, one R and R′ is a hydrocarbyl radical having 1-20 carbon atoms in a proximal position adjacent to the bridgehead carbon of the indenyl rings.
The present invention provides a process for producing isotactic polyolefins and, particularly, isotactic polypropylene, that comprises utilizing at least one of the catalyst components described by the above formula and introducing the catalyst into a polymerization reaction zone containing an olefin monomer. In addition, a cocatalyst such as alumoxane and/or an ionic compound capable of reacting with the metallocene to form a cationic metallocene may be introduced into the reaction zone. Further, the catalyst component may also be pre-polymerized prior to introducing it into the reaction zone and/or prior to the stabilization of reaction conditions in the reactor.
The present invention also includes a process for preparing a bridged metallocene component comprising contacting a substituted indenyl with an dialkylsilyldichloride followed by a second equivalent of a different substituted indenyl to produce a silicon bridged disubstituted indenyl.
The present invention further includes a process for preparing a bridged metallocene catalyst component comprising contacting a substituted indene anion having proximal substituent(s) on the indenyl ring with a substituted indene anion having proximal substituent(s) under reaction conditions sufficient to produce a bridged substituted diindene. The process further comprises contacting the bridged diindene with a metal compound of the formula MeQ
k
as defined above under reaction conditions sufficient to complex the bridged diindene to produce a bridged metallocene wherein Me is a Group IIIB, IVB, VB or VIB metal from the Periodic Table of Elements, each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen and k is the valence of Me minus 2.


REFERENCES:
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patent: 5243001 (1993-09-01), Winter et al.
patent: 5276208 (1994-01-01), Winter et al.
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Odian, Principles of Polymerization, Third Edition, John Wiley & Sons, pp. 606-619, 1991.

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