Process for producing polyolefins

Details Process for producing polyolefins Process for producing polyolefins

1999-08-31

2001-09-11

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...

C526S074000, C526S901000, C526S160000, C526S943000, C526S127000, C502S104000, C502S152000

Reexamination Certificate

active

06288181

ABSTRACT:

FIELD OF INVENTION
The present invention relates to a polymerization process for the production of polyolefins utilizing a metallocene catalyst and a compound containing an ether linkage in amounts sufficient to reduce the electrostatic charge in the polymerization reactor. The use of a compound containing an ether linkage as a catalytic agent further provides polyolefins that are suitable for molding and film applications.
BACKGROUND OF INVENTION
Polyolefins such as polyethylene are well known and are useful in many applications. In particular, linear polyethylene polymers possess properties which distinguish them from other polyethylene polymers, such as branched ethylene homopolymers commonly referred to as LDPE (low density polyethylene). Certain of these properties are described by Anderson et al, U.S. Pat. No. 4,076,698.
A particularly useful polymerization medium for producing polyethylene and polypropylene polymers is a gas phase process. Examples of such are given in U.S. Pat. Nos. 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; 5,352,749 and 5,541,270 and Canadian Patent No. 991,798 and Belgian Patent No. 839,380.
There are known various catalysts for polymerizing olefins. Exemplary of such catalysts are as follow:
1. chromium oxide catalysts which polymerize ethylene to high molecular weight high density polyethylene (HDPE),
2. organochromium catalysts used to polymerize ethylene,
3. Ziegler-Natta type catalysts which typically consist of a transition metal component and a co-catalyst that is typically an organoaluminum compound,
4. metallocene catalysts which typically consist of a transition metal having a cyclopentadienyl ligand and a co-catalyst,
5. Group 13 catalysts described in U.S. Pat. No. 5,777,120, such as cationic aluminum alkyl amidinate complexes,
6. catalysts of the type described in U.S. Pat. No. 5,866,663, such as cationic nickel alkyl diimine complexes,
7. catalysts of the type described in Organometallics, 1998, Volume 17, pages 3149-3151, such as neutral nickel alkyl salicylaldiminato complexes,
8. catalysts of the type described in the Journal of the American Chemical Society, 1998, Volume 120, pages 7143-7144, such as cationic iron alkyl pyridinebisimine complexes, and
9. catalysts of the type described in the Journal of the American Chemical Society, 1996, Volume 118, pages 10008-10009, such as cationic titanium alkyl diamide complexes.
The above catalysts are, or can be, supported on inert porous particulate carriers.
A generally encountered problem in polymerization processes, in particular gas phase polymerization processes, is the formation of agglomerates. Agglomerates can form in various places such as the polymerization reactor and the lines for recycling the gaseous stream. As a consequence of agglomerate formation it may be necessary to shut down the reactor.
When agglomerates form within the polymerization reactor there can be many adverse effects. For example, the agglomerates can disrupt the removal of polymer from the polymerization reactor by plugging the polymer discharge system. Further, if the agglomerates fall and cover part of the fluidization grid a loss of fluidization efficiency may occur. This can result in the formation of larger agglomerates which can lead to the loss of the entire fluidized bed. In either case there may be the necessity for the shutdown of the reactor.
It has been found that agglomerates may be formed as a result of the presence of very fine polymer particles in the polymerization medium. These fine polymer particles may be present as a result of introducing fine catalyst particles or breakage of the catalyst within the polymerization medium.
These fine particles are believed to deposit onto and electrostatically adhere to the inner walls of the polymerization reactor and the associated equipment for recycling the gaseous stream such as, for example, the heat exchanger. If the fine particles remain active, and the polymerization reaction continues, then the particles will grow in size resulting in the formation of agglomerates. These agglomerates when formed within the polymerization reactor tend to be in the form of sheets.
Several solutions have been proposed to resolve the problem of formation of agglomerates in gas phase polymerization processes. These solutions include the deactivation of the fine polymer particles, control of the catalyst activity and the reduction of the electrostatic charge. Exemplary of the solutions are as follows.
European Patent Application 0 359 444 A1 describes the introduction into the polymerization reactor of small amounts of an activity retarder in order to keep substantially constant either the polymerization rate or the content of transition metal in the polymer produced. The process is said to produce a polymer without forming agglomerates.
U.S. Pat. No. 4,739,015 describes the use of gaseous oxygen containing compounds or liquid or solid active-hydrogen containing compounds to prevent the adhesion of the polymer to itself or to the inner wall of the polymerization apparatus.
In U.S. Pat. No. 4,803,251 there is described a process for reducing sheeting utilizing a group of chemical additives which generate both positive and negative charges in the reactor, and which are fed to the reactor in an amount of a few parts per million (ppm) per part of the monomer in order to prevent the formation of undesired positive or negative charges.
Other processes and other additives that may be used to neutralize the electrostatic charge in the fluidized-bed reactor are found in U.S. Pat. Nos. 4,792,592; 4,803,251; 4,855,370; 4,876,320; 5,162,463; 5,194,526 and 5,200,477.
Additional processes for reducing or eliminating electrostatic charge include (1) installation of grounding devices in a fluidized bed, (2) ionization of gas or particles by electrical discharge to generate ions which neutralize the electrostatic charge on the particles and (3) the use of radioactive sources to produce radiation capable of generating ions which neutralize the electrostatic charge on the particles.
It would be desirable therefore to provide a process for producing polyolefins, particularly polyethylene, wherein the problems associated with electrostatic charge are reduced.
SUMMARY OF THE INVENTION
The polymerization process of the present invention comprises the introduction into a polymerization medium comprising an olefin, particularly ethylene, and optionally at least one or more other olefin(s), a metallocene catalyst and at least one compound comprising at least one carbon-oxygen-carbon linkage (C—O—C) of the formula R
1
—O(—R
2
—O)
m
—R
3
where m ranges from 0 to 30, and R
1
, R
2
and R
3
independently contain from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements, and further wherein R
1
, R
2
and/or R
3
can be linked and form part of a cyclic or polycyclic structure, herein referred to as the ether, wherein the ether is present in an amount sufficient to reduce the electrostatic charge in the polymerization medium to a level lower than would occur in the same polymerization process in the absence of the ether.
The present invention also relates to a process for reducing the electrostatic charge in the polymerization of an olefin, particularly ethylene, and optionally at least one or more other olefin(s) in a polymerization medium, particularly gas phase, in the presence of a metallocene catalyst, and at least one ether comprising at least one carbon-oxygen-carbon linkage (C—O—C) of the formula R
1
—O(—R
2
—O)
m
—R
3
where m ranges from 0 to 30, and R
1
, R
2
and R
3
independently contain from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements, and further wherein R
1
, R
2
and/or R
3
can be linked and form part of a cyclic or polycyclic structure, comprising introducing the ether into the polymerization medium in an amount sufficient to r

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