Linked metallocene complexes, catalyst systems, and olefin...

Details Linked metallocene complexes, catalyst systems, and olefin... Linked metallocene complexes, catalyst systems, and olefin...

2001-09-26

2003-11-04

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S012000, C556S053000, C526S160000, C526S943000, C502S103000, C502S117000

Reexamination Certificate

active

06642400

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to polymerization catalyst complexes, catalyst systems including these catalyst complexes, and to their use in the polymerization of olefins. In particular, the present invention relates to metallocene complexes, which include two or more metallocene components linked together. Specifically, the metallocene components are linked together through the ligand structure of at least one of the metallocenes. The present invention also relates to catalyst systems containing these metallocene complexes and to their use in olefin polymerization processes.
BACKGROUND OF THE INVENTION
Use of metallocene based catalyst systems in polymerization processes to produce a diverse array of new polymers for a wide variety of applications and products is well known in the art. Polymers produced by metallocene catalysts have excellent properties such as mechanical strength and transparency. However, these polymers are typically more difficult to process.
To obtain polymer products having improved physical properties as well as easier processing polymers, the industry has focused on the physical blending of two or more polymers in the hopes that the polymer blend will exhibit the best characteristics of its component polymers. Others have looked at using two or more reactors to produce blends in situ in the reactor or at using two or more catalysts to produce the desired polymer product.
Utilizing two different catalysts, however, typically results in a polymer whose characteristics cannot be predicted from those of the polymers that each catalyst would produce if utilized separately. This unpredictability occurs, for example, from competition or other influence between the catalyst or catalyst systems used. In addition, these polymers typically do not have a preferred balance of processability and strength properties. Therefore, there is need in the art for metallocene catalyst systems capable of producing processable polymers having desirable combinations of processing, mechanical and optical properties.
U.S. Pat. No. 5,830,958 discloses a process for preparing polynuclear metallocenes by reacting a metallocene in which one of the cyclopentadienyl containing radicals has a substitutent having olefinic or acetylenic unsaturation, with a second metallocene having a metal which comes from groups VIb to Vib and a metal-hydride bond.
U.S. Pat. No. 6,153,776 discloses a Group 3-6 or Lanthanide metal complex possessing two metal centers, catalyst derived therefrom by combining the same with strong Lewis acids, Bronsted acid salts, salts containing a cationic oxidizing agent or subject to bulk electrolysis in the presence of compatible inert non-coordinating anions.
U.S. Pat. No. 6,262,197 discloses a metallocene compound containing at least two metallocene fragments L—MX
2
—L.
EP 0 953 581 A1 discloses a supported metallocene having ligands linked to R
I
OSiR
II
3
groups where R
I
is a divalent aliphatic hydrocarbon group containing from 1-20 carbon atoms optionally containing heteroatoms or a SiR
II
2
group, and R
II
is a C
1-20
alkyl, a C
3-20
cycloalkyl, C
6-20
aryl, C
3-20
alkenyl C
7-20
arylalkyl, C
8-20
arylalkenyl, or a C
7-20
alkylaryl linear or branched group.
Spalek et al., in
New Bridged Zirconocenes for Olefin Polymerization: Binuclear and Hybrid Structures,
Journal of Molecular Catalysis A: Chemical 128 (1998) 279-287, disclose bridged bisindenyl zirconocenes for the polymerization of liquid propylene.
SUMMARY OF THE INVENTION
In one aspect, the invention provides a linked metallocene complex having at least one bridged metallocene component linked to at least one unbridged metallocene component where the ligand structure of an unbridged metallocene component is connected to the bridging group of a bridged metallocene component.
In another aspect, the invention provides a linked metallocene complex having a first bridged metallocene component linked to an unbridged metallocene component linked to a second bridged metallocene component where a first ligand structure of the unbridged metallocene component is connected to the bridging group of the first bridged metallocene component, and a second ligand structure of the unbridged metallocene component is connected to the bridging group of the second bridged metallocene component.
In another aspect, the invention provides a linked metallocene complex having a first unbridged metallocene component linked to second unbridged metallocene component where a ligand structure of the first unbridged metallocene component is linked to a ligand structure of the second unbridged metallocene component.
In another aspect, the invention provides a linked metallocene complex having a first unbridged metallocene component linked to second unbridged metallocene component linked to a third unbridged metallocene component where a ligand structure of the first unbridged metallocene component is linked to a first ligand structure of the second unbridged metallocene component and where a second ligand structure of the second unbridged metallocene component is linked to a ligand structure of the third unbridged metallocene component.
In another aspect, the invention provides a linked metallocene complex containing a first bridged metallocene component linked to a unbridged metallocene component linked to a second bridged metallocene component where a ligand structure of the first bridged metallocene is linked to a first ligand structure of the unbridged metallocene and where a ligand structure of the second bridged metallocene is linked to a second ligand structure of the unbridged metallocene component.
The invention also provides methods of preparing the linked metallocene complexes described above, catalyst systems including these linked metallocene complexes, polymerization processes utilizing these complexes, and polymers made thereby.
DETAILED DESCRIPTION
New catalyst systems including structurally linked metallocenes, and synthetic routes to prepare such linked metallocenes have been discovered. Preferably, the linked metallocene includes two or more metallocene structures connected through the ligand framework of at least one of the metallocene structures.
For the purposes of this patent specification, the term “catalyst” refers to a metal compound, that when combined with an activator, polymerizes olefins. The term “activator” is used interchangeably with the term “co-catalyst”, and the term “catalyst system” refers to the combination of catalyst, activator, and optionally a support material.
Linked Metallocene Complexes of the Invention
In one embodiment, the linked metallocene complex contains at least one bridged metallocene component linked to at least one unbridged metallocene component where the ligand structure of the unbridged metallocene component is connected to the bridging group of the bridged metallocene component. In this embodiment, the two ligand structures are linked together via a linking group.
In another embodiment, the linked metallocene complex is represented by Formula I.
In Formula I, each M is independently a metal atom from the Periodic Table of the Elements and may be a Group 3 to 12 metal or a metal from the lanthanide or actinide series, preferably each M is independently a Group 3 to 10 transition metal, more preferably each M is independently a Group 4, 5 or 6 transition metal, and even more preferably each M is independently zirconium, hafnium or titanium. Most preferably, each M is zirconium.
In Formula I, each Q represents a leaving group bonded to each M. For the purposes of this patent specification and appended claims the term “leaving group” is any ligand that can be abstracted from a metallocene catalyst compound to form a metallocene catalyst cation capable of polymerizing one or more olefin(s). Each Q is independently a monoanionic ligand, or two radicals Q together form a divalent anionic chelating ligand. In one embodiment, Q is a monoanionic labile ligand having a sigma-bond to M. In a preferred embodiment, two monoanionic leaving groups Q are bond

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