Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-12-29
2003-06-24
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...
C526S156000, C526S172000, C502S155000, C502S167000
Reexamination Certificate
active
06583235
ABSTRACT:
This invention relates to the use of aluminophosphate in catalyst systems comprising nickel and palladium catalysts and metal alkyl cocatalysts. This invention also relates to olefin polymerization processes using such catalyst systems to polymerize mono-1-olefins and optionally one or more co-monomers. The present invention also relates to polymers made by such processes.
BACKGROUND
It is well known that mono-1-olefins, such as ethylene and propylene, can be polymerized with catalyst systems employing transition metals such as titanium, vanadium, chromium, nickel and/or other metals, either unsupported or on a support such as alumina, silica, titania, and other refractory metals. Supported polymerization catalyst systems frequently are used with a cocatalyst, such as alkyl boron compounds and/or alkyl aluminum compounds and/or alkyl aluminoxy compounds. Organometallic catalyst systems, i.e., Ziegler-Natta-type catalyst systems, usually are unsupported and frequently are used with a cocatalyst, such as methylaluminoxane. Other components may be used in addition to the catalyst and cocatalyst.
It is also well known that, while no polymer production process is easy, slurry, or loop, polymerization processes are more commercially desirable than other polymerization processes, due to ease of operation. Furthermore, the type of polymerization process used can have an effect on the resultant polymer. For example, higher reactor temperatures can result in low catalyst activity and productivity, as well as a lower molecular weight polymer product. Higher reactor pressures also can decrease the amount of desirable branching in the resultant polymer.
Most polymer products made using slurry processes, especially polymer products made using supported chromium catalyst systems, have a broader molecular weight distribution and, therefore, the polymer product is much easier to process into a final product. Polymers made by other processes, such as, for example, higher temperature and/or higher pressure solution processes, can produce polymers having a narrow molecular weight distribution; these polymers can be much more difficult to process into an article of manufacture.
Unfortunately, many homogeneous organometallic catalyst systems have low activity, high consumption of very costly cocatalysts like methylaluminoxane (MAO), and can produce low molecular weight polymers with a narrow molecular weight distribution. Furthermore, even though MAO can be helpful or even necessary to produce a polymer with desired characteristics, an excess of MAO can result in decreased catalyst system activity. Additionally, these types of homogeneous catalyst systems preferably are used only in solution or gas phase polymerization processes.
U.S. Pat. No. 5,648,439 discloses aluminophosphate as the presently most preferred catalyst support for the chromium catalyst systems disclosed therein. The patent does not disclose that aluminophosphate can be employed in catalyst systems comprising other catalytic metals.
Polymerization processes for olefins using catalyst systems containing a nickel or palladium alpha-diimine complex, a metal containing hydrocarbylation compound, and a selected Lewis acid are disclosed in U.S. Pat. No. 5,852,145, the disclosure of which is incorporated herein by reference. In the '145 patent, the metal containing hydrocarbylation compound is defined as a compound that can transfer a hydrocarbyl group to a nickel or palladium compound. The patent states that useful alkylating agents (which are a form of the metal containing hydrocarbylation compound) have the formulas MX
2
R
n
6
or [Al(O)R
11
]
q
, which includes alkylaluminum and alkylzinc compounds which may or may not have halogen groups as well as alkyl aluminoxanes. In that patent, the selected Lewis acids are referred to as compound (II), and the group consisting of B(C
6
F
5
)
3
, AlCl
3
, AlBr
3
, Al(OTf)
3
and (R
13
R
14
R
15
C)Y is particularly disclosed and claimed. The patent states that when a hydrocarbylation compound is other than an alkylaluminum compound containing one or more halogen atoms bound to an aluminum atom or an alkyl aluminoxane, compound (II) must be present. Thus, when the hydrocarbylation compound is R
3
Al, compound (II) must be present.
U.S. Pat. No. 5,852,145 does not disclose or suggest aluminophosphate as a suitable compound (II) or a catalyst system that includes aluminophosphate. The patent states that compound (II) may optionally be present when the hydrocarbylation compound is R
2
AlBr, RAlC
2
, or “RAlO”. The patent does not indicate whether including compound (II) with those hydrocarbylation compounds will improve or alter the activity or productivity of the catalyst system.
SUMMARY OF THE INVENTION
It is an object of this invention to provide novel catalyst systems useful for polymerization.
It is another object of this invention to provide catalyst systems which are relatively simple to make, have increased activity and increased productivity.
It is a further object of this invention to provide catalyst systems which employ less costly cocatalysts.
It is an object of this invention to provide a catalyst system comprising at least diimine one nickel (II) or palladium (II) complex, at least one cocatalyst and aluminophosphate. Processes for making and using such catalyst systems are also provided.
It is also an object of this invention to provide an olefin polymerization process comprising contacting in a reaction zone under polymerization conditions an olefin monomer and a catalyst system comprising at least one diimine nickel (II) or palladium (II) complex, at least one cocatalyst and aluminophosphate.
It is further an object of this invention to provide an active olefin polymerization catalyst system comprising at least one diimine nickel (II) or palladium (II) complex, at least one cocatalyst, and an amount of aluminophosphate, where the catalyst system would not be active in the absence of aluminophosphate.
It is also an object of this invention to provide a method of making a catalyst system active or more active in the polymerization of olefins by adding an effective amount of aluminophosphate.
It is a further object of this invention to provide a process for making polyolefins employing diimine nickel or palladium catalyst systems that heretofore have been considered inactive or insufficiently active in olefins polymerization.
In accordance with this invention, catalyst systems comprising one or more nickel or palladium catalysts, at least one cocatalyst and an effective amount of aluminophosphate are provided. The nickel catalysts can be diimine nickel complexes can further comprise additional ligands selected from the group consisting of &agr;-deprotonated-&bgr;-diketones, &agr;-deprotonated-&bgr;-ketoesters, halogens and mixtures thereof. In presently preferred embodiments, the catalyst systems comprise diimine nickel complexes having a formula selected from the group consisting of Ni(NCR′C
6
R
2
H
3
)
2
(Y
2
C
3
R″
2
X)
2
and Ni(NCR′C
6
R
2
H
3
)
2
(Y
2
C
3
R″
2
X)Z, and Ni(NCR′C
6
R
2
H
3
)
2
(Y
2
C
3
R″
2
X)
2
, and the cocatalyst may be an alkyl aluminum compound or an alkyl zinc compound. Processes to make these catalyst systems also are provided.
In accordance with another embodiment of this invention, slurry polymerization processes comprising contacting ethylene, and optionally one or more higher alpha-olefins, in a reaction zone with heterogeneous catalyst systems comprising one or more nickel or palladium catalysts, at least one cocatalyst and aluminophosphate are provided. The catalyst systems preferably comprise diimine nickel complexes that may further comprise additional ligands selected from the group consisting of &agr;-deprotonated-&bgr;-diketones, &agr;-deprotonated-&bgr;-ketoesters, halogens and mixtures thereof.
In accordance with this invention, heterogeneous catalyst systems consisting essentially of at least one diimine nickel complex, at least one cocatalyst, and aluminophosphate are provided. The diimine ni
Collins Kathy S.
Eilerts Nancy W.
Guatney Lloyd W.
McDaniel Max P.
Harlan R.
Phillips Petroleum Company
Wu David W.
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