Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
1999-04-26
2002-01-22
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S117000, C502S152000, C502S155000, C526S134000, C526S160000, C526S943000
Reexamination Certificate
active
06340651
ABSTRACT:
BACKGROUND OF THE INVENTION
Metallocenes have been found to be useful for the polymerization of olefins. In order for metallocenes to be particularly useful in slurry type polymerization processes, it has generally been found necessary to form a catalyst system in which the metallocene and the cocatalyst are insoluble during the polymerization. Various approaches have been taken to provide insoluble heterogeneous catalyst systems that would be applicable. One technique involves the employment of metallocenes containing unsaturated substituents which can be prepolymerized in the presence of a cocatalyst to produce a solid insoluble catalyst system. An example of such a process is disclosed in U.S. Pat. No. 5,498,581. Another approach for preparing such an insoluble heterogeneous catalyst system involves the employment of a special type of metallocene referred to as a metallocycle metallocene. A metallocycle type metallocene is one in which one of the cyclic dienyl groups that is pi bonded to the metal of the metallocene also contains a substituent which is sigma bonded to the metal of the metallocene. An example of such a metallocene is disclosed in U.S. Pat. No. 5,654,454. In that case, the metallocycle was produced by a hydrozirconation type reaction. Such compounds are referred to as metallocycles for the reason that there is what can be viewed as a cyclic structure comprising the cyclic dienyl group pi bonded to the zirconium and the substituent on the cyclic dienyl group being sigma bonded to the metal.
In accordance with the present invention,there is provided a process for producing a new type of metallocene. Further there is provided an entirely new type of metallocyclic metallocene which will be referred to herein as a multicyclic metallocycle metallocene. The term multicyclic metallocycle metallocene as used herein refers to a metallocene in which a cyclic dienyl group has a substituent which is bonded to the transition metal by sigma bonds in two places to form two cyclic structures that are bonded to the transition metal in addition to the cyclic dienyl group.
An object of the present invention is to provide catalyst systems using such multicyclic metallocycle metallocenes and polymerization processes using such catalyst systems.
Another object of the present invention is to provide a metallocene which can be prepolymerized to form a solid particulate catalyst system suitable for use in slurry polymerization processes.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a process for producing metallocenes which involves reacting a first metallocene having an alkenyl group attached to a cyclodienyl group with an alkali metal alkyl. Still further in accordance with the present invention, there is provided a process for polymerizing olefins using such metallocenes. Still further in accordance with the present invention, there is provided a process for employing such metallocenes to produce catalyst systems useful for the polymerization of olefins. In a particularly preferred process, the metallocenes are used to form a prepolymerizied heterogeneous catalyst that is suitable for use in a slurry type olefin polymerization process.
In accordance with the present invention, one can produce metallocenes having the formula
wherein L is a radical having a cyclodienyl skeleton, examples of which would include cyclopentadienyl, indenyl, fluorenyl, and benzo indenyl, both substituted and unsubstituted; x is 0 or 1, Y is a structural unit connecting L to L′, if x is 1 then L′ can be selected from monovalent radicals having a cyclodienyl skeleton, examples of which would include cyclopentadienyl, indenyl,fluorenyl, and benzoindenyl, both substituted and unsubstituted and divalent radicals selected from those having the formula —NR—,—PR—, —O—, and —S—, wherein R is a hydrocarbyl group having 1 to 20 carbon atoms, preferably an alkyl group, n is 1 to 3, m is 1 to 4, and if x is 0 then L′ is selected from cyclodienyl compounds pi bonded to M, examples of which would include cyclopentadienyl, indenyl,fluorenyl, and benzoindenyl, both substituted and unsubstituted, and M is a transition metal, preferably Zr, Hf, or Ti. Examples of Z include —CH
2
—, —CR
2
—, —SiR
2
—, and the like, wherein R is as defined above.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention the new metallocenes are prepared by reacting a first metallocene having an alkenyl group attached to a cyclodienyl group with about two molar equivalents of an alkali metal alkyl having at least 4 carbon atoms. Preferably the alkenyl group has 3 to 5 carbon atoms having terminal unsaturation.
It is contemplated that the process can be applied to any metallocene in which there is a cyclodienyl group which has the required type of alkenyl group. Thus it is contemplated that the process is applicable to both bridged and unbridged sandwich bonded metallocenes and to constrained geometry monocyclodienyl metallocenes such as (3-butenylcyclopentadienyl)(t-butyl amido)dimethyl silane titanium dichloride. The currently preferred metallocenes are those of the transition metal compounds Ti, Zr, and Hf.
If L or L′ has a cyclopentadienyl skeleton, the substituents, if any, are preferably hydrocarbyl substituents having 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms.
The reaction of the first metallocene and the alkali metal alkyl can be conducted in any suitable manner. Typically the reaction would be carried out by forming a solution of the metallocene in a hydrocarbon, for example toluene, and then adding a solution of the alkali metal alkyl. The temperature employed can vary widely; however, temperatures below 0° C. are generally preferred for the combining the metallocene and the alkali metal alkyl, for example 0 to −90° C., more typically −20° C. to −80° C.
The resulting multi-cyclic metallocycle metallocene can be used for the polymerization. The inventive catalyst systems are particularly useful for the polymerization of alpha-olefins having 2 to 10 carbon atoms. Examples of such olefins include ethylene, propylene, butene-1, pentane-1, 3-methylbutene-1, hexene-1, 4-methylpentene-1, 3-methylpentene-1, heptene-1, octene-1, decene-1, 4,4-dimethyl-1-pentane, 4,4-diethyl-1-hexene, 3,4-dimethyl-1-hexene, and the like and mixtures thereof. The catalysts are also useful for preparing copolymers of ethylene and propylene and copolymers of ethylene or propylene and a higher molecular weight olefin. Monomers such as styrene and butadiene are also useful.
Polymerizations with the inventive catalyst can be carried out under a wide range of conditions depending upon the particular metallocene employed and the particular results desired. The inventive catalyst systems are considered useful for polymerization conducted under solution, slurry, or gas phase reaction conditions. Typically the inventive metallocene would be used with a suitable cocatalyst.
Examples of suitable cocatalysts include generally any of those organometallic cocatalysts which have in the past been employed in conjunction with transition metal containing olefin polymerization catalysts. Some typical examples include organometallic compounds of metals of Groups IA, IIA, and IIIB of the Periodic Table. Examples of such compounds have included organometallic halide compounds, organometallic hydrides and even metal hydrides. Some specific examples include triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diethylaluminum hydride, and the like. Other examples of known cocatalysts include the use of a stable non-coordinating counter anion cocatalyst, an example of such is disclosed in U.S. Pat. No. 5,155,080, e.g. using triphenyl carbenium tetrakis (pentafluorophenyl) boronate. Another example would be the use a mixture of trimethylaluminum and dimethylfluoroaluminum such as disclosed by Zambelli et,
Macromolecules,
22, 2186 (1989). In such counter anion systems the cocatalyst can be viewed as an ion-exchange compound comprising a cation which will irr
Alt Helmut G.
Licht Erik
Welch M. Bruce
Bell Mark L.
Bowman Edward L.
Pasterczyk J.
Phillips Petroleum Company
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