Method of polymerization

Details Method of polymerization Method of polymerization

1999-12-16

2001-08-28

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...

C526S901000, C526S172000, C526S348600, C526S131000, C526S348500, C502S155000

Reexamination Certificate

active

06281306

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to spray dried olefin polymerization catalysts and their use in gas or slu phase to produce polyolefins.
BACKGROUND OF THE INVENTION
The intense ommercialization of metallocene polyolefin catalysts (metallocene being cyclopentadienyl based transition metal catalyst compounds) has led to widespread interest in the design of non-metallocene, homogeneous catalysts, particularly for use in the economical gas and slurry phase processes. This field is more than an academic curiosity as new, non-metallocene catalysts in gas or slurry phase may provide an easier, more economical pathway to currently available products and may also provide product and process opportunities which are beyond the capability of metallocene catalysts in the gas or slurry phase.
New catalysts, however, are not automatically useable in the gas phase. Some catalysts are to active and foul the reactor. Other catalysts cannot be supported and thus cannot be introduced into the reactor in such as way that fouling does not occur. Thus there is a need in the art for a method of providing catalysts to a gas phase or slurry phase reactor, particularly catalysts that are difficult or impossible to support.
Schrock et al in U.S. Pat. No. 5,889,128 discloses a process for the living polymerization of olefins in solution using initiators having a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. In particular, the solution phase poly nerization of ethylene using {[NON]ZrMe}[MeB(C
6
F
5
)
3
] or {[NON]ZrMe(PhNMe
2
)]}[B(C
6
F
5
)
4
] is disclosed in examples 9 and 10.
EP 893 454 A1 discloses unsupported transition metal amide compounds used in combination with activators to polymerize olefins in the solution phase.
Mitsui Chemicals, Inc. in EP 0 893 454 A1 discloses transition metal amides combined with activators to polymerize olefins.
EP 0 874 005 A1 discloses phenoxide compounds with an imine substituent for use as a polymerizat ion catalyst.
EP 893 454 A1 discloses unsupported transition metal amide compounds used in combination with activators to polymerize olefins in the solution phase.
U.S. Ser. No. 09/312,878 filed May 17, 1999 discloses a gas or slurry phase polymerization process usin a supported bisamide catalyst.
Japanese Abstract JP 10330416A appears to disclose transition metal amide catalysts in combinat on with Ziegler-Natta catalysts. Japanese Abstract JP 10330412A appears to disclose transition metal amide catalysts in combination with group 4 transitiontal cyclopentadienyl catalysts.
Ethylenebis(salicylidenciminato)zirconium dichloride combined with methyl alumoxane eposited on a support and unsupported versions were used to polymerize ethylene by Repo et al in Macromolecules 1997, 30, 171-175.
U.S. Pat. No. 5,672,669, U.S. Pat. No. 5,674,795 and EP 0 668 295 B1 disclose spray dried filled metallocene catalyst compositions for use in gas phase polymerizations.
SUMMARY OF THE INVENTION
This invention relates to a catalytic molecule, and a spray dried catalyst system comprising a particulate filler, an activator, and a metal catalyst compound.
In one aspect the particulate filler may be any known particulate filler including carbon black, talc; inorganic oxides such as silica; magnesium chloride, alumina, silica-alumina; polymeric materials such as polyethylene, polypropylene, polystyrene, cross-linked polystyrene; and the like.
Preferred activators include conventional-co-catalysts, alkyl aluminum compounds (such as diethylaluminum chloride), alumoxanes, modified alumoxanes, non-coordinating anions, non-coordinating group 13 metal or metalloid anions, boranes, borates and the like. It is within the scope of this invention to use alumoxane or modified alumoxane as an activator, and/or to also use ionizing activators, neutral or ionic, such tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or a trisperfluorophenyl boron metalloid precursor which ionize the neutral metallocene compound. Other useful compounds include triphenyl boron, triethyl boron, tri-n-butyl ammonium tetraethylborate, triaryl borane and the like. Other useful compounds include aluminate salts as well.
Some of many metal catalyst compounds that may be used herein include a group 15 containing mental compound as described below and or phenoxide based catalysts as described below.


REFERENCES:
patent: 5672669 (1997-09-01), Wasserman et al.
patent: 5674795 (1997-10-01), Wasserman et al.
patent: 5889128 (1999-03-01), Schrock et al.
patent: 0 668 295 B1 (1998-06-01), None
patent: 0668295 B1 (1998-06-01), None
patent: 0874005 A1 (1998-10-01), None
patent: 0893454 A1 (1999-01-01), None
patent: 10330412 (1998-12-01), None
patent: 10330416 (1998-12-01), None
Schrock et al., Synthesis of Group 4 Complexes that Contain the Diamidoamine Ligands, J. Am. Chem. Soc. 1999, 121, 5797-5798 (date of issue: Jun. 23, 1999).

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