Chemistry of hydrocarbon compounds – Unsaturated compound synthesis – By addition of entire unsaturated molecules – e.g.,...
Reexamination Certificate
2002-01-03
2004-01-20
Dang, Thuan D. (Department: 1764)
Chemistry of hydrocarbon compounds
Unsaturated compound synthesis
By addition of entire unsaturated molecules, e.g.,...
C585S521000, C585S522000, C585S525000
Reexamination Certificate
active
06680417
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to a process for the polymerization of a feedstock containing one or more C
3
to C
20
1-olefins in the presence of a solid, unsupported metallocene- and activator-containing catalyst system to form a viscous oligomer oil.
2. Discussion of the Prior Art
Slaugh et al., U.S. Pat. No. 4,658,078 (Apr. 14, 1987), discloses a process for producing relatively low molecular weight dimers by dimerizing alpha olefins to vinylidene olefins by contacting the alpha olefins with a soluble catalyst comprising a metallocene and an aluminoxane. However, the use of a soluble catalyst necessitates a wash step for the removal of catalyst from the polymerization product and the use of a hazardous solvent such as toluene generally required in soluble metallocene catalyst systems. Consequently, efforts have been made to prepare and use heterogeneous or solid metallocene catalyst systems. The solid systems employed have generally involved immobilization of the metallocene and/or aluminium compound serving as the activator on an inorganic support. Such systems suffer from the disadvantage of requiring the use of support material, and are generally of lower activity than soluble catalyst systems.
Consequently, it is highly desirable to be able to prepare and use unsupported solid metallocene catalyst systems with comparable (minimal loss) of catalyst activity. Herrmann et al., U.S. Pat. No. 5,914,376 (Jun. 22, 1999), discloses a process for the polymerization of an olefin in the presence of an unsupported heterogeneous metallocene catalyst system to form a solid polymer. The solid catalyst system is obtained by reacting a soluble metallocene with a solid aluminoxane which is obtained as a by-product obtained in the preparation of toluene-soluble aluminoxanes.
Turner, U.S. Pat. No. 4,752,597 (Jun. 21, 1988) discloses a process for preparing a solid, unsupported matellocene catalyst system. The metallocene catalyst system comprises the metallocene and aluminoxane. The metallocene and aluminoxane are contacted at a mole ratio of aluminoxane to metallocene of from about 12:1 to about 100:1 and reacted in a hydrocarbon solvent in which the metallocene and aluminoxane are each soluble but in which the resulting solid product is insoluble. The metallocene and aluminoxane are reacted at a temperature in the ranges of −78° C. to about 50° C. The resulting solid catalyst is generally sparingly soluble oils at ambient temperature in aromatic solvents, insoluble solids in aliphatic solvents, and decomposes in polar solvents. Upon recovery, the resulting catalyst system was a glassy solid in most of the patent's examples.
Kioka et al., U.S. Pat. No. 4,923,833 (May 8, 1990) discloses five methods for preparing an unsupported solid olefin polymerization catalyst containing a Group IVB metal-containing metallocene component and an aluminoxane component. Three of the methods involve the use of a solvent in which the aluminoxane is insoluble or sparingly soluble. The remaining two methods involve spray drying a solution either of the aluminoxane alone or of the metallocene and aluminoxane together. In Comparative Example 1, the preparation method of the invention is contrasted with a method of preparing an unsupported solid catalyst containing a metallocene and methylaluminoxane by combining a solution of the metallocene in toluene with a solution of methylaluminoxane in toluene and completely evaporating the toluene. Thus, Comparative Example 1 did not employ a solvent in which the methylaluminoxane was only sparingly soluble. The resulting solid catalyst particles had non-uniform shapes, a low specific surface area, and a broad particle size distribution. When used for the polymerization of ethylene to form polyethylene, the comparative catalyst had a substantially lower polymerization activity and resulted in the production of polyethylene having a substantially lower bulk density than when the catalyst of the invention was employed. There is no suggestion or recommendation in U.S. Pat. No. 4,923,833 that the comparative catalyst be used as a polymerization catalyst at all or more particularly as a polymerization catalyst for the production of a viscous oligomer oil.
OBJECTS OF THE INVENTION
It is therefore a general object of the present invention to provide an improved polymerization process employing an unsupported insoluble metallocene catalyst system that overcomes the aforesaid problems of prior art processes.
More particularly, it is an object of the present invention to provide a process for using an unsupported insoluble metallocene catalyst system it in the polymerization of one or more linear C
3
to C
20
1-olefins to produce a product mixture comprising an essentially terminally unsaturated viscous, essentially 1-olefin poly (1-olefin) or copoly (1-olefin) of molecular weight between about 300 and 10,000 that exhibits a terminal vinylidene content of more than 50%.
Other objects and advantages will become apparent upon reading the following detailed description and appended claims.
SUMMARY OF THE INVENTION
These objects are achieved by the process of the present invention for the production of an oligomer oil comprising:
(i) polymerizing a feed comprising one or more linear C
3
to C
20
1-olefins having at least one hydrogen on the 2-carbon atom, at least two hydrogens on the 3-carbon atom and at least one hydrogen on the 4-carbon (if at least 4 carbon atoms are present in the olefin), in the presence of a solid metallocene catalyst system comprising a bulky ligand transition metal complex component of the stoichiometric Formula 1 and an activator comprising an organoaluminum compound or a hydrocarbylboron compound or a mixture thereof:
L
m
MX
n
X′
p
Formula 1
wherein L is the bulky ligand, M is the transition metal, X and X′ may be the same or different and are independently selected from the group consisting of halogen or a hydrocarbyl group or hydrocarboxyl group having 1-20 carbon atoms, wherein m is 1-3, n is 0-3, p is 0-3 and the sum of the integers m+n+p corresponds to the transition metal valency, to thereby form a viscous oligomer oil product mixture comprising an essentially terminally unsaturated viscous, essentially 1-olefin-containing poly (1-olefin) or copoly (1-olefin) of molecular weight between about 300 and about 10,000 that exhibits a terminal vinylidene content of more than 50%; wherein the aforesaid solid metallocene catalyst system is formed by a process comprising:
(a) combining in an organic solvent boiling below about below 250° C. and a soluble metallocene and a soluble activator comprising at least one of an organoaluminum and a hydrocarbylboron to form a soluble metallocene- and activator-containing catalyst system; and
(b) removing the aforesaid solvent to thereby form the aforesaid catalyst system as a solid. The present invention is also the solid metallocene- and activator-containing catalyst system formed by the process of the present invention.
A preferred embodiment the present invention involves producing a viscous oligomer oil having predetermined properties by (ii) oligomerizing at least a pre-selected fraction of the product mixture formed in the aforesaid polymerization step (i) in the presence of an acidic oligormerization catalyst to thereby form the aforesaid oligomer oil, wherein the resulting product mixture comprises less than 35% oligomers that contain two or less monomeric units and at least 60% of oligomers that contain at least three monomeric units.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The metallocene catalyst employed in preparing an unsupported insoluble metallocene catalyst system in step (a) of the method of this invention, comprises a bulky ligand transition metal complex of the stoichiometric Formula 1:
L
m
MX
n
X
1
p
Formula 1
wherein L is the bulky ligand, M is the transition metal, X and X
1
are independently selected from the group consisting of halogen, hydrocarbyl group
Bagheri Vahid
Eisenberg David
Farritor Robert E.
Grzeszczak Frederic
Overstreet Andrew D.
BP Corporation North America Inc.
Dang Thuan D.
Henes James R.
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