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
1999-12-10
2003-04-01
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...
C502S104000, C502S158000, C502S103000, C502S117000, C502S167000
Reexamination Certificate
active
06541412
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to catalyst systems and to catalyst system components solubilized or emulsified in a Group 14 and Group 16 containing oil or amorphous solid, and to their use in polymerization processes. In a particular, preferred embodiment, the invention is directed to catalyst systems and components solubilized or emulsified with one or more siloxanes and to methods for preparing and using the same.
BACKGROUND OF THE INVENTION
Developments in polymerization technology have provided more efficient, highly productive and economically enhanced catalyst systems and processes. Especially illustrative of these advances is the development of bulky ligand metallocene-type catalysts and of Group 15 metal containing catalysts. To utilize these systems in industrial slurry or gas phases processes, it is useful that they be immobilized on a carrier or support such as, for example silica or alumina. Bulky ligand metallocene-type catalysts, however, typically exhibit lower activity when supported than in the corresponding homogeneous or non-supported catalyst systems. This “support effect” is especially dramatic when the catalyst system utilizes a stoichiometric activator, for example a bulky ligand metallocene-type
on-coordinating anion catalyst system.
In a typical method to prepare a supported catalyst system, the catalyst and activator are combined in a suitable solvent then added to the support or carrier material. However, systems utilizing stoichiometric activators are often difficult to dissolve in hydrocarbon solvents and as a result are difficult to combine with a support material. Thus, there is a need to improve the solubility of catalyst compounds, especially those utilizing stoichiometric activators, to facilitate the preparation of supported catalysts, and also to reduce the “support effect” when using such catalyst systems.
U.S. Pat. No. 5,747,404 discloses a polysiloxane supported metallocene catalyst where the metallocene-type organometallic catalyst is directly bonded to a silicon atom in a siloxane polymeric oil.
PCT WO 99/14269 discloses organopolysiloxane microgel particles, having a diameter of 5 to 200 nm, with organo-aluminum compounds immobilized thereon, which may be used as cocatalyst with metal compounds of the IV, V, VI and VIII sub-groups of the periodic table, for oligomerization cyclization or polymerization of olefins.
While these catalyst systems and methods have been described in the art, a need exists for an improved catalyst system and method for preparing it.
SUMMARY OF THE INVENTION
This invention provides a new and improved catalyst system, which include a polymerization catalyst combined with a Group 14 and Group 16 atom containing oil or amorphous solid. Preferably, the oil or amorphous solid contains alternating atoms of silicon or germanium and oxygen and most preferably, the oil or amorphous solid is a siloxane.
In another embodiment, the invention is directed to a catalyst system including a polymerization catalyst and an activator, or an activated polymerization catalyst, combined with a Group 14 and Group 16 atom containing oil or amorphous solid.
In another embodiment the invention relates to a catalyst system including a polymerization catalysts and a stoichiometric activator combined with a Group 14 and Group 16 atom containing oil or amorphous solid, where preferably, the oil or amorphous solid contains alternating atoms of silicon or germanium and oxygen.
In another aspect, the invention is directed to a catalyst system which includes a polymerization catalyst and activator combined with a polysiloxane microgel.
In another aspect the invention relates to a method for making a catalyst system which includes solubilizing or emulsifying a polymerization catalyst and/or an activator in one or more Group 14 and Group 16 atom containing oil(s) or amorphous solid(s). Optionally, the method includes further solubilizing the solution or emulsion in a hydrocarbon solvent then combining the resulting solution with a support or carrier.
In another aspect, the invention is directed to a polymerization process utilizing a catalyst system of the invention.
In another aspect, the invention is directed to pre-polymerization process utilizing a catalyst system of the invention.
DETAILED DESCRIPTION OF THE INVENTION
Introduction
The invention is directed toward a polymerization catalyst system, which includes a polymerization catalyst combined with a Group 14 and Group 16 atom containing oil or amorphous solid. Preferably, the oil or amorphous solid includes alternating atoms of silicon or germanium, and oxygen. Most preferably, the oil or amorphous solid is a siloxane or a polysiloxane, including microgels. The Group 14 and Group 16 atom containing oil or amorphous solid is used to solublize or emulsify the polymerization catalyst and/or the catalyst activator, it has been surprisingly discovered that these catalyst solutions or emulsions are highly active especially when a stoichiometric activator is utilized. The polymerization catalyst systems of the invention may be used in solution, slurry, high pressure or gas phase polymerization processes.
Polymerization Catalyst
Bulky Ligand Metallocene-Type Catalyst Compounds
The Group 14 and Group 16 atom containing oil or amorphous solid may be used to create solutions or emulsions of the bulky ligand metallocene-type polymerization catalysts described below. Generally, these catalyst compounds include half and full sandwich compounds having one or more bulky ligands bonded to at least one metal atom. Typical bulky ligand metallocene-type compounds are described as containing one or more bulky ligand(s) and one or more leaving group(s) bonded to at least one metal atom. In one preferred embodiment, at least one bulky ligands is &eegr;-bonded to the metal atom, most preferably &eegr;
5
-bonded to a transition metal atom.
The bulky ligands are generally represented by one or more open, acyclic, or fused ring(s) or ring system(s) or a combination thereof. The ring(s) or ring system(s) of these bulky ligands are typically composed of atoms selected from Groups 13 to 16 atoms of the Periodic Table of Elements. Preferably the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum or a combination thereof. Most preferably the ring(s) or ring system(s) are composed of carbon atoms such as but not limited to those cyclopentadienyl ligands or cyclopentadienyl-type ligand structures or other similar functioning ligand structure such as a pentadiene, a cyclooctatetraendiyl or an imide ligand. The metal atom is preferably selected from Groups 3 through 15 and the lanthanide or actinide series of the Periodic Table of Elements. Preferably the metal is a transition metal from Groups 4 through 12, more preferably Groups 4, 5 and 6, and most preferably the transition metal is from Group 4.
In one embodiment, the Group 14 and Group 16 atom containing non-crystalline compound may be used to create solutions or emulsions of the bulky ligand metallocene-type catalyst compounds represented by the formula:
L
A
L
B
MQ
n
(I)
where M is a metal atom from the Periodic Table of the Elements and may be a Group 3 to 12 metal or from the lanthanide or actinide series of the Periodic Table of Elements, preferably M is a Group 4, 5 or 6 transition metal, more preferably M is zirconium, hafnium or titanium. The bulky ligands, L
A
and L
B
, are open, acyclic or fused ring(s) or ring system(s) and are any ancillary ligand system, including unsubstituted or substituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom substituted and/or heteroatom containing cyclopentadienyl-type ligands. Non-limiting examples of bulky ligands include cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phos
Bell Mark L.
Faulkner Kevin
Jones Lisa Kimes
Pasterczyk J.
Univation Technologies LLC
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