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US 7,700,699 B2Granted
Polymerization process
AssigneeExxonMobil Chemical Patents Inc.
InventorsRobert O. Hagerty, Randall B. Laird, Michael A. Risch, Pradeep P. Shirodkar, Peijun Jiang
Life of this patent
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Abstract
This invention is directed to processes of making polymer in the presence of a fluorinated hydrocarbon and recovering the polymer. The processes provided enable polymerization processes to be practiced with minimal fouling in the reaction system, and allows for the recovery of the fluorinated hydrocarbon and other hydrocarbons such as hydrocarbons for re-use in the process or hydrocarbon by-products from the polymerization process. The invention is particularly beneficial in the production of propylene polymers and copolymes using bulky ligand metallocene-type catalyst systems.
Claims63
A process for producing polymer, comprising:
- mixing together a diluent containing more than 10 weight percent of a fluorinated hydrocarbon based on the total weight of the diluent, a bulky ligand metallocene-type catalyst system, and an olefin feed containing propylene and optionally one or more comonomers;
- and
- forming a polymer wherein the fluorinated hydrocarbon in the diluent is not a perfluorinated hydrocarbon, wherein the bulky ligand metallocene-type catalyst system comprises an activator and a bulky ligand metallocene-type compound is represented by the formula:
- LALBMQn (I) or LAALBMQn (II)
- where M is a metal from Group 3 to 12 of the Periodic Table of Elements, LA and LB are selected from the group consisting of cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and hydrogenated versions thereof;
- Q is a monoanionic labile ligand having a sigma-bond to M, and depending on the oxidation state of M, the value for n is 0, 1 or 2 such that Formula I or II above represents a neutral bulky ligand metallocene-type catalyst compound;
- and
- A is a bridging group containing carbon, germanium or silicon.
5 more elements
A process for producing polymer, comprising:
- mixing together a diluent containing at least one fluorinated hydrocarbon, a bulky ligand metallocene-type catalyst system, and an olefin feed containing propylene and ethylene at not greater than 10 weight % ethylene, based on total weight of the olefin feed;
- and
- forming a polymer wherein the at least one fluorinated hydrocarbon in the diluent is not a perfluorinated hydrocarbon, wherein the bulky ligand metallocene-type catalyst system comprises an activator and a bulky ligand metallocene-type compound is represented by the formula:
- LALBMQn (I) or LAALBMQn (II)
- where M is a metal from Group 3 to 12 of the Periodic Table of Elements, LA and LB are selected from the group consisting of cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and hydrogenated versions thereof;
- Q is a monoanionic labile ligand having a sigma-bond to M, and depending on the oxidation state of M, the value for n is 0, 1 or 2 such that Formula I or II above represents a neutral bulky ligand metallocene-type catalyst compound;
- and
- A is a bridging group containing carbon, germanium or silicon.
5 more elements
A process for producing polypropylene copolymer, comprising:
- mixing together a diluent containing at least one fluorinated hydrocarbon, a bulky ligand metallocene-type catalyst system, and an olefin feed containing at least 25 weight % propylene and greater than 10 weight % ethylene, based on total weight of the feed, and forming a polypropylene copolymer wherein the at least one fluorinated hydrocarbon in the diluent is not a perfluorinated hydrocarbon, wherein the bulky ligand metallocene-type catalyst system comprises an activator and a bulky ligand metallocene-type compound is represented by the formula:
- LALBMQn (I) or LAALBMQn (II)
- where M is a metal from Group 3 to 12 of the Periodic Table of Elements, LA and LB are selected from the group consisting of cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and hydrogenated versions thereof;
- Q is a monoanionic labile ligand having a sigma-bond to M, and depending on the oxidation state of M, the value for n is 0, 1 or 2 such that Formula I or II above represents a neutral bulky ligand metallocene-type catalyst compound;
- and
- A is a bridging group containing carbon, germanium or silicon.
3 more elements
Dependencies are inferred from the claim text.